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Sample records for alkyl vinyl ethers

  1. Oil compositions containing alkyl amine or alkyl mercaptan derivatives of copolymers of an alpha olefin or an alkyl vinyl ether

    SciTech Connect

    Le, H.T.

    1990-02-13

    This patent describes an oil composition. It comprises a major amount of an oil selected from a crude oil or fuel oil and a minor amount of an alkyl amine or alkyl mercaptan derivative of an alpha olefin or alkyl vinyl ether and an unsaturated alpha, beta-dicarboxylic compound copolymer having pour point depressant ;properties. The copolymer comprising the reaction product of an alpha olefin having from about 2 to about 30 carbon atoms or mixtures of alpha olefins having from about 2 to about 30 carbon atoms or an alkyl vinyl ether or mixture of alkyl vinyl ethers.

  2. Oil compositions containing alkyl mercaptan derivatives of copolymers of an alpha olefin or an alkyl vinyl ether and an unsaturated alpha, beta-dicarboxylic compound

    SciTech Connect

    Le, H.T.

    1991-10-08

    This paper describes an oil composition. It comprises: a major amount of an oil selected from a mineral oil or synthetic oil and a manor amount of an alkyl mercaptan derivative of an alpha olefin or alkyl vinyl either and an unsaturated alpha, beta-dicarboxylic compound copolymer having pour point depressant properties, the copolymer comprising the reaction product of an alpha a olefin having from about 2 to about 30 carbon atoms or mixtures of alpha olefins having from about 2 to about 30 carbonates or an alkyl vinyl ether or mixture of alkyl vinyl ethers.

  3. Condensation of perfluoroisobutylene with perfluorinated vinyl alkyl ethers

    SciTech Connect

    Postovoi, S.A.; Zeifman, Yu.V.; Knunyants, I.L.

    1986-12-10

    Condensation of perfluoroisobutylene with perfluorovinyl aklyl ethers with CsF catalysis takes place according to a scheme of concerted nucleophilic addition, with participation of the perfluoro-tert-butyl anion as nucleophile and perfluoroisobutylene as electrophile. In the presence of CO/sub 2/ the product of concerted perfluoroalkylcarboxylation forms.

  4. Influence of Alkoxy Groups on the Photoinduced Dynamics of Organic Molecules Exemplified on Alkyl Vinyl Ethers.

    PubMed

    Schalk, O; Stenrup, M; Geng, T; Lindh, R; Thomas, R D; Feifel, R; Hansson, T

    2015-11-12

    A series of different alkyl vinyl ethers is investigated to decipher the possible reaction channels upon photoexcitation to the π3s-Rydberg and the ππ*-valence state at 200 nm using time-resolved photoelectron spectroscopy and on-the-fly time-dependent density functional theory dynamics simulations. The results indicate two possible relaxation pathways: (1) a radiationless decay through the ππ*-state back to the ground state via torsion of the C═C double bond, in accordance with the dynamics found in ethylene; and (2) a fast dissociation of the C-O bond between the alkyl and the vinoxy group in the πσ*-state. The latter state can be accessed only after excitation to the π3s-Rydberg state (quantum yield of ∼50% according to the dynamics simulations). Additionally, the excited state barrier leading to formation of a vinyl radical was found to be too high to be crossed. These results indicate that the dynamics of ethers crucially depend on the excitation wavelength and that the πσ*-state constitutes an important competitive reaction channel that leads to dissociation of the molecules. PMID:26490385

  5. Vinyl ether silicones

    SciTech Connect

    Herzig, C.; Dauth, J.; Deubzer, B.; Weis, J.

    1995-12-01

    Siloxanes with vinyl ether groups are prepared by hydrosilylation reaction of dihydrosiloxanes with divinyl ethers in excess. Different stoichiometry, produces linear copolymers of different viscosities and double bond concentrations always with an active vinyl ether group at each chain end. Polymerisations triggered by UV light were done with mixtures of these compounds and a series of onium salts. Very fast cure is observed even with low doses at 290 nm. V.E. silicones are found to cure essentially quantitative. The comparison with other highly reactive cationic monomers revealed that compounds are among the fastest curing prepolymers in cationic chemistry.

  6. The thickening additives for mineral and synthetic oils based on the copolymers of alkyl acrylates or methacrylates and butyl vinyl ether

    NASA Astrophysics Data System (ADS)

    Geraskina, Evgeniya V.; Moikin, Alexey A.; Semenycheva, Ludmila L.

    2014-05-01

    A new method for synthesizing of the copolymers of acrylic and methacrylic acid esters with butyl vinyl ether in an excess of low-boiling monomer, which has proven effective for a number of alkyl methacrylates was proposed. Tests of thickening efficiency of the obtained copolymers were carried out. The resistance to mechanical degradation of the mineral, semi synthetic and synthetic base oils doped with the copolymers was evaluated.

  7. Radical Reactions of Alkyl 2-Bromo-2,2-difluoroacetates with Vinyl Ethers: "Omitted" Examples and Application for the Synthesis of 3,3-Difluoro-GABA.

    PubMed

    Kondratov, Ivan S; Bugera, Maksym Ya; Tolmachova, Nataliya A; Posternak, Ganna G; Daniliuc, Constantin G; Haufe, Günter

    2015-12-18

    Addition reactions of perfluoroalkyl radicals to ordinary or polyfluorinated alkenes have been frequently used to synthesize perfluoroalkylated organic compounds. Here ethyl/methyl 2-bromo-2,2-difluoroacetate, diethyl (bromodifluoromethyl)phosphonate, [(bromodifluoromethyl)sulfonyl]benzene, and ethyl 2-bromo-2-fluoroacetate were involved in Na2S2O4-mediated radical additions to vinyl ethers in the presence of alcohols to give difluoro or monofluoroacetyl-substituted acetals or corresponding difluoromethylphosphonate- and (difluoromethylphenyl)sulfonyl-substituted alkyl acetals. This methodology has also been applied as a key step in the synthesis of hitherto unknown 3,3-difluoro-GABA, completing the series of isomeric difluoro GABAs. Comparison of the pKa values of 3-fluoro- and 3,3-difluoro-GABA with that of the fluorine free parent compound showed that introduction of each fluorine lead to acidification of both the amino and the carboxyl functions by approximately one unit. PMID:26550962

  8. A Mild Synthesis of New Aryl Vinyl Ethers and Diethyl 1-[(Alkyl)(cyano)methyl]vinylphosphonates via the Substitution of a 2,3-Difunctional Allyl Bromide

    PubMed Central

    Ben Kraïem, Jihène; Arfaoui, Aïcha; Amri, Hassen

    2014-01-01

    A novel class of aryl vinyl ethers 3 and diethyl 3-cyano-3-alkylprop-1-en-2-ylphosphonates 4 has been prepared, respectively, from coupling reaction of diethyl 1-(bromomethyl)-2-cyanovinylphosphonate 2 with phenols and Gilman reagents. PMID:24688373

  9. Synthetic applications of aqueous accelerated [3,3] sigmatropic rearrangements of allyl vinyl ethers. [1,3] sigmatropic rearrangements of allyl vinyl ethers in 3 M lithium perchlorate-diethyl ether at ambient temperature. New methods to effect the retro Diels-Alder reaction of N-alkyl-2-azanorbornenes

    SciTech Connect

    Clark, J.D.

    1992-01-01

    Claisen rearrangements employed in the synthesis of natural and unnatural products that were heretofore difficult or impossible using conventional means are realized through the agency of water. Allyl vinyl ether 35, the unprotected form of McMurry's aphidicolin intermediate 7, rearranged after 24 h in 2.5:1 water/methanol at 80[degrees]C, affording aldehyde 40 in 70--85% yield. Acetaldehyde elimination witnessed using conventional reaction conditions was suppressed when employing water. The application of a Claisen rearrangement within the molecular framework of fenestranes was realized for the first time. Fenestrene vinyl ethers 28 and 30 rearranged to form the fenestrenes 29 and 31, respectively. Noteworthy is fenestrene 29, the first fenestrane synthesized possessing a trans-ring fusion common to two five-membered rings. The medium of 3.0 M lithium perchlorate-diethyl ether has been found to induce the rarely witnessed rearrangement of allyl vinyl ethers, despite the fact that the corresponding sigmatropic rearrangement is energetically more favorable. Yields are very good; however, in some instances the sigmatropic rearrangement and elimination processes compete slightly. Results from the observed stereoselectivities, concentration effects on reaction rate, and a crossover study indicate that these shifts take place via dissociated ions followed by recombination, and that the observed stereoselectivities are a result of unequal steric effects in the transition states for recombination. Copper(II) and sulfonic acid ion exchange resins have been found to readily catalyze the heterocycloreversion of N-alkyl-2-azanorbornenes to the corresponding primary amines, eliminating the necessity of employing a reactive dienophile to trap out the released cyclopentadiene.

  10. Chemistry of enol ethers. LXXXIV. Condensation of acetals of saturated aldehydes with 2-trimethylsilyloxy-1,3-dienes. Synthesis of /beta/-alkoxy-alkyl vinyl and divinyl ketones

    SciTech Connect

    Makin, S.M.; Nazarova, O.N.; Dymshakova, G.M.; Kundryutskova, L.A.

    1988-11-10

    The addition of the acetals of saturated aldehydes (formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde) to 2-trimethylsilyloxy-4-methyl-1,3-pentadiene in the presence of aprotic acids (ZnCl/sub 2/, ZnBr/sub 2/, FeCl/sub 3/, SnCl/sub 4/, BF/sub 3/ /times/ OEt/sub 2/) takes place at positions 1, 2 of the diene system with the formation of /beta/-alkoxyalkyl vinyl ketones. The most effective catalysts of this reaction were stannic chloride and zinc bromide. The alkyl derivatives of divinyl ketones are formed when the obtained /beta/-alkoxyalkyl vinyl ketones are heated with p-toluenesulfonic acid.

  11. Reactions of perfluoro-1-alkylcycloalkenes with alcohols and properties of vinyl ethers formed

    SciTech Connect

    Snegirev, V.F.; Makarov, K.N.

    1986-12-10

    Perfluoro-1-alkylcycloalkenes react with alcohols to form products of vinyl and allyl substitution. Alkyl perfluorocycloakenyl ethers readily alkylate the fluoride ion and triethylamine, and by the action of SbF/sub 5/ convert into ..cap alpha.., ..beta..-unsaturated perfluoro ketones. When allyl perfluorocycloalkenyl ethers are heated, they isomerize into the corresponding ..cap alpha..-allylperfluorocycloalkanones.

  12. Elastic electron scattering by ethyl vinyl ether

    SciTech Connect

    Khakoo, M. A.; Hong, L.; Kim, B.; Winstead, C.; McKoy, V.

    2010-02-15

    We report measured and calculated results for elastic scattering of low-energy electrons by ethyl vinyl ether (ethoxyethene), a prototype system for studying indirect dissociative attachment processes that may play a role in DNA damage. The integral cross section displays the expected {pi}{sup *} shape resonance. The agreement between the calculated and measured cross sections is generally good.

  13. 1-vinyl-4-alkyl-1,2,4-triazolium salts

    SciTech Connect

    Ermakova, T.G.; Chipanina, N.N.; Gritza, A.I.; Kuznetsova, N.P.; Lopyrev, V.A.; Tatarova, L.A.

    1985-04-01

    Quaternary salts based on 1-vinyl-1,2,4-triazole have been synthesized. Alkyl iodides and bromides and dimethyl sulfate served as the quaternizing agent. Polymeric quaternary salts of 1-vinyl-1,2,4-triazole have been obtained by alkylation of its polymer.

  14. 40 CFR 721.3485 - Hydrofluorocarbon alkyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrofluorocarbon alkyl ether. 721... Substances § 721.3485 Hydrofluorocarbon alkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a hydrofluorocarbon alkyl...

  15. 40 CFR 721.3485 - Hydrofluorocarbon alkyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrofluorocarbon alkyl ether. 721... Substances § 721.3485 Hydrofluorocarbon alkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a hydrofluorocarbon alkyl...

  16. Macrocyclic polyenynes: a stereoselective route to vinyl-ether-containing skipped diene systems.

    PubMed

    Ronson, Thomas O; Voelkel, Martin H H; Taylor, Richard J K; Fairlamb, Ian J S

    2015-05-11

    The stereoselective synthesis of a challenging macrocyclic polyene scaffold, containing a sensitive vinyl ether motif, has been accomplished using O,C-dilithiation/selective C-alkylation, Pd-catalysed etherification and Wittig reactions as key steps. An end-game macrocyclisation strategy employed a regio- and stereoselective Stille cross-coupling using Pd(Br)(N-Succ)(AsPh3)2 (AsCat) as the precatalyst. PMID:25891970

  17. The millimeter and submillimeter wave spectrum of cis-methyl vinyl ether

    NASA Astrophysics Data System (ADS)

    Daly, A. M.; Kolesniková, L.; Mata, S.; Alonso, J. L.

    2014-12-01

    Among the species of potential interstellar relevance, methyl vinyl ether (CH3OCHdbnd CH2) is the simplest ether compound containing both alkyl and alkene functional groups. In order to facilitate its detection in the ISM, we have measured the millimeter and submillimeter wave spectra from 50 to 650 GHz. We present the analysis of pure rotational spectrum of the cis-methyl vinyl ether in the vibrational ground state and in the first excited states of in-plane bending mode (ν16) and methyl (ν23) and skeletal (ν24) torsional modes. Coriolis and Fermi type interactions between the v24 = 1 and v23 = 1 states have been explicitly treated using an effective two-state Hamiltonian.

  18. Alkyl Aryl Ether Bond Formation with PhenoFluor**

    PubMed Central

    Shen, Xiao; Neumann, Constanze N.; Kleinlein, Claudia; Claudia, Nathaniel W.; Ritter, Tobias

    2015-01-01

    An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation. PMID:25800679

  19. HPLC and TLC characterisation of ecdysteroid alkyl ethers.

    PubMed

    Lapenna, Silvia; Dinan, Laurence

    2009-10-01

    Semi-synthetic ecdysteroid alkyl ethers have increased potential over natural ecdysteroids as actuators of ligand-inducible gene-expression systems based on the ecdysteroid receptor for in vivo applications. However, a scalable synthesis of these compounds has yet to be developed. We report a set of reversed-phase (RP; C(18) and C(6)) and normal-phase (NP; diol) HPLC systems which can be used to analyse and separate ecdysteroid ethers with single or multiple O-methyl substitutions at the 2alpha-, 3beta-, 14alpha-, 22- and 25-positions. The elution order of methyl ether analogues of the prototypical ecdysteroid 20-hydroxyecdysone (20E) was 3-methyl<2-methyl<14-methyl<25-methyl<22-methyl with both C(18)- and C(6)-RP-HPLC, when eluted with methanol/water mixtures. Further, the elution order of 20E 22-O-alkyl ethers was methylalkyl ethers can also be adequately resolved by NP-HPLC and silica HPTLC. On the latter, detection of ecdysteroid O-alkyl ethers with the p-anisaldehyde/sulphuric acid reagent distinguishes 22-O-alkyl ethers from non-22-O-alkyl ether analogues by the colour of the resulting spot. PMID:19648067

  20. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Vinyl chloride-lauryl vinyl ether copolymers. 177.1970 Section 177.1970 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single...

  1. Semi-empirical method for calculating the activation energies of the unimolecular thermal decomposition of vinyl ethers

    NASA Astrophysics Data System (ADS)

    Sargsyan, G. N.; Shakhrokh, B.; Harutyunyan, A. B.

    2015-02-01

    A semi-empirical method is proposed for calculating the activation energy of the unimolecular decomposition of complex compounds using the example of vinyl (ethyl, propyl, and butyl) ethers. The method is based on the concept of the formation of intramolecular hydrogen bonds and the possibility of calculating the energy of deformation of ether molecules upon activation, resulting in the potential surface of the transition state undergoing distortion and the transfer of a hydrogen atom from an alkyl group to a vinyl group. The energy of deformation is calculated using the Mathcad 2001i and MM2 computer programs.

  2. Dichloromethyl alkyl ethers and sulfides in the Reformatskii reaction

    SciTech Connect

    Lapkin, I.I.; Fotin, V.V.

    1986-09-10

    A study was carried out on the reaction of dichloromethyl alkyl ethers and sulfides with ..cap alpha..-brominated esters in the presence of zinc resulting in the formation of either ..cap alpha..-alkyl-..beta..-alkoxyacrylates (or ..cap alpha..-alkyl-..beta..-alkylthioacrylates) or ..cap alpha..,..cap alpha..,..cap alpha..',..cap alpha..'-tetramethyl-..beta..-alkoxyglutaric acid (or ..cap alpha..,..cap alpha..,..cap alpha..',..cap alpha..'-tetramethyl-..beta..-alkylthioglutaric acid) depending on the structure of the starting bromoester. PMR and IR spectroscopy indicates the geometry of the ..cap alpha..-alkyl-..beta..-alkoxyacrylates and ..cap alpha..-alkyl-..beta..-alkylthioacrylates.

  3. Polymerization in the liquid crystalline state of vinyl ether monomers

    SciTech Connect

    Andersson, H.; Jonsson, H.; Gedde, U.W.; Hult, A.

    1993-12-31

    Liquid crystalline phenylbenzoate vinyl ether was polymerized cationically in both anisotropic and isotropic monomeric melts, using photochemical initiation by onium salts. High molecular mass polymers with a narrow molecular mass distribution (around 2) were produced by cationic polymerization at high temperatures ({<=}{degrees}C). The initial state of the monomer, nematic or isotropic, did not affect neither molecular mass, molecular mass distribution, nor polymerization rate. {sup 13}C-NMR studies show that the polymer formed is atactic. Ordered 30-50 {mu}m films were produced by polymerization of mesogenic vinyl ether monomers oriented in the nematic and smectic phase.

  4. Vinyl ethers containing an epoxy group. XVI. Reaction of glycidol vinyloxyethyl ether with acetals

    SciTech Connect

    Nedolya, N.A.; Khil'ko, M.Ya.; Trofimov, B.A.; Sigalov, M.V.

    1988-10-10

    In order to obtain branched acetals with epoxide groups (prospective monomers and intermediates) the authors investigated the reaction of acetaldehyde diethyl and di(1,1,3-trihydrotetrafluoropropyl) acetals with glycidol vinyloxyethyl ether. The addition of acetals to vinyl epoxy ethers was realized, and the first representative of compounds of this type, i.e., 9-glycidyloxy-6-ethoxy-4-methyl-3,7-dioxanonane, was obtained. It was also impossible to add a fluoroacetal to butyl vinyl ether (0.08-1.00 wt. % of catalyst CF/sub 3/COOH, BF/sub 3//times/ OEt/sub 2/, 20-80/degree/C, 0.5-3 h).

  5. Photoinitiated cationic polymerization with multifunctional vinyl ether monomers

    SciTech Connect

    Cribello, J.V.; Lee, J.L.; Conlon, D.A.

    1983-01-01

    Until recently, multifunctional vinyl ether monomers have not been employed in UV curing applications. The recent discovery of diaryliodonium and triarylsulfonium salts as new classes of photoinitiators for cationic polylmerization has made it possible to formulate highly photosensitive UV curable coatings based on these monomers. The syntheses of these monomers and their reactivity as a function of their structure is reviewed and evaluated.

  6. 40 CFR 721.10669 - Tertiary amine alkyl ether (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Tertiary amine alkyl ether (generic). 721.10669 Section 721.10669 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10669...

  7. 40 CFR 721.10669 - Tertiary amine alkyl ether (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Tertiary amine alkyl ether (generic). 721.10669 Section 721.10669 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10669...

  8. Antioxidant activity of alkyl hydroxytyrosyl ethers in unsaturated lipids.

    PubMed

    Cert, Rosa; Madrona, Andrés; Espartero, José Luis; Pérez-Camino, M Carmen

    2015-06-01

    The antioxidant activity of ethyl and octyl hydroxytyrosyl ethers toward lipids was determined using the Rancimat and open cup methods at high temperatures and 50 °C, respectively. The effect of the unsaturation of the matrix was evaluated using sunflower, soya, and fish refined oils. The antioxidant activities of alkyl hydroxytyrosyl ethers (HTy ethers), hydroxytyrosyl esters, and free hydroxytyrosol are similar, and are much higher than that of α-tocopherol at the same millimolar concentration. The relationship between the induction period and the concentration of the HTy ethers is a sigmoidal curve; an accurate concentration of HTy ethers is necessary to achieve maximum activity, as it increases with the level of matrix unsaturation. The presence of tocopherols in commercial oils affects the antioxidant effect of HTy ethers. Thus, the addition of a low concentration of HTy ethers results in a positive effect, whereas the effect of the addition of high amounts of ethers is slightly less than that of the phenol alone. The addition of HTy ethers to commercial refined oils increases the stability of the oils and preserves tocopherols and polyunsaturated fatty acids from oxidation, enabling the oils to maintain their nutritional properties for longer periods of time. PMID:26018773

  9. Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides.

    PubMed

    Johnson, Keywan A; Biswas, Soumik; Weix, Daniel J

    2016-05-23

    An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5 mol %) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5 mol % catalyst loading, whereas reactions at 10 mol % catalyst loading completed in as little as 20 minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2'-bipyridine) that is both air- and moisture-stable over a period of months was introduced. PMID:27017436

  10. Vibrational and VCD spectra of poly(menthyl vinyl ether)

    NASA Astrophysics Data System (ADS)

    McCann, J. L.; Bour, P.; Wieser, H.

    1998-06-01

    The detailed assignments are reported for the vibrational and VCD spectra of (1S,2R,5S)-(+)-menthol. Energy minimized geometries, harmonic force fields, and atomic polar tensors were calculated at the Becke3LYP/6-31G** level, and atomic axial tensors with the vibronic coupling theory at the HF/6-31G level. The spectra consist of contributions mainly from two isomers (70%) distinguished only by conformation of the OH group. An attempt was made to simulate the absorption and VCD spectra of poly(methyl vinyl ether) using a component approach and invoking the excitation scheme with promising though not conclusive results at this stage.

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

    PubMed Central

    Xi, Yumeng; Dong, Boliang

    2013-01-01

    Summary 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. PMID:24367417

  12. Palladium-Catalyzed Selective α-Alkenylation of Pyridylmethyl Ethers with Vinyl Bromides.

    PubMed

    Yang, Xiaodong; Kim, Byeong-Seon; Li, Minyan; Walsh, Patrick J

    2016-05-20

    An efficient palladium-catalyzed α-alkenylation of pyridylmethyl ethers with vinyl bromides is presented. A Pd/NIXANTPHOS-based catalyst system enables a mild and chemoselective coupling between a variety of pyridylmethyl ethers and vinyl bromides in good to excellent yields. Under the mild conditions, β,γ-unsaturated products are obtained without isomerization or Heck byproducts observed. PMID:27160421

  13. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... ether (generic). 721.3845 Section 721.3845 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3845 Alkyl substituted aromatic glycidyl ether (generic). (a) Chemical... as alkyl substituted aromatic glycidyl ether (PMN P-97-661) is subject to reporting under...

  14. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... ether (generic). 721.3845 Section 721.3845 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3845 Alkyl substituted aromatic glycidyl ether (generic). (a) Chemical... as alkyl substituted aromatic glycidyl ether (PMN P-97-661) is subject to reporting under...

  15. Safety Assessment of Alkyl PEG/PPG Ethers as Used in Cosmetics.

    PubMed

    Fiume, Monice M; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2016-07-01

    The Cosmetic Ingredient Review (CIR) Expert Panel assessed the safety of 131 alkyl polyethylene glycol (PEG)/polypropylene glycol ethers as used in cosmetics, concluding that these ingredients are safe in the present practices of use and concentration described in this safety assessment when formulated to be nonirritating. Most of the alkyl PEG/PPG ethers included in this review are reported to function in cosmetics as surfactants, skin-conditioning agents, and/or emulsifying agents. The alkyl PEG/PPG ethers share very similar physiochemical properties as the alkyl PEG ethers, which were reviewed previously by the CIR Expert Panel and found safe when formulated to be nonirritating. The alkyl PEG ethers differ by the inclusion of PPG repeat units, which are used to fine-tune the surfactant properties of this group. The Panel relied heavily on data on analogous ingredients, extracted from the alkyl PEG ethers and PPG reports, when making its determination of safety. PMID:27383199

  16. Dual Behavior of Iodine Species in Condensation of Anilines and Vinyl Ethers Affording 2-Methylquinolines.

    PubMed

    Le, Song Thi; Yasuoka, Chisa; Asahara, Haruyasu; Nishiwaki, Nagatoshi

    2016-01-01

    A metal-free, mild and efficient method for the synthesis of 2-methylquinolines was successfully developed by condensation of anilines with vinyl ethers in the presence of catalytic amount of iodine. Modification of both pyridine and benzene moieties was easily achieved by changing only the vinyl ether and aniline. In this reaction, the iodine species was revealed to show dual behavior; molecular iodine serves as an oxidant, while its reduced form, hydrogen iodide, activates the vinyl ether. The redox reaction between these iodine species enables the use of a catalytic amount of iodine in this synthetic method. PMID:27347919

  17. Iridium-Catalyzed Branch-Selective Hydroarylation of Vinyl Ethers via C-H Bond Activation.

    PubMed

    Ebe, Yusuke; Nishimura, Takahiro

    2015-05-13

    Iridium-catalyzed hydroarylation of vinyl ethers via a directed C-H bond activation of aromatic compounds gave high yields of the corresponding addition products with high branch selectivity. PMID:25928127

  18. 40 CFR 721.600 - 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name). 721.600 Section 721.600 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.600 3-Alkyl-2-(2-anilino)vinyl thi-azolinium...

  19. 40 CFR 721.600 - 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name). 721.600 Section 721.600 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.600 3-Alkyl-2-(2-anilino)vinyl thi-azolinium...

  20. 40 CFR 721.600 - 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name). 721.600 Section 721.600 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.600 3-Alkyl-2-(2-anilino)vinyl thi-azolinium...

  1. 40 CFR 721.600 - 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name). 721.600 Section 721.600 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.600 3-Alkyl-2-(2-anilino)vinyl thi-azolinium...

  2. 40 CFR 721.600 - 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 3-Alkyl-2-(2-anilino)vinyl thi-azolinium salt (generic name). 721.600 Section 721.600 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.600 3-Alkyl-2-(2-anilino)vinyl thi-azolinium...

  3. Competition between reaction and intramolecular energy redistribution in solution: observation and nature of nonstatistical dynamics in the ozonolysis of vinyl ethers.

    PubMed

    Quijano, Larisa Mae M; Singleton, Daniel A

    2011-09-01

    Experimental product ratios in ozonolyses of alkyl vinyl ethers in solution do not fit with expectations based on statistical rate theories. The selectivity among cleavage pathways increases with the size of the alkyl group but to an extent that is far less than RRKM theory would predict. Trajectory studies account for the observed selectivities and support a mechanism involving a competition between cleavage of the primary ozonide and intramolecular vibrational energy redistribution. A statistical model is presented that assumes that RRKM theory holds for a molecular subset of the primary ozonides, allowing the rates of energy loss from the ozonides to be estimated from the observed product ratios. PMID:21812422

  4. Competition between Reaction and Intramolecular Energy Redistribution in Solution. Observation and Nature of Nonstatistical Dynamics in the Ozonolysis of Vinyl Ethers

    PubMed Central

    Quijano, Larisa Mae M.; Singleton, Daniel A.

    2011-01-01

    Experimental product ratios in ozonolyses of alkyl vinyl ethers in solution do not fit with expectations from statistical rate theories. The selectivity among cleavage pathways increases with the size of the alkyl group but to an extent that is far less than RRKM theory would predict. Trajectory studies account for the observed selectivities and support a mechanism involving a competition between cleavage of the primary ozonide and intramolecular vibrational energy redistribution. An approximate statistical model is presented that assumes that RRKM theory holds for a molecular subset of the primary ozonides, allowing estimates of the rates of energy loss from the primary ozonides based on the observed product ratios. PMID:21812422

  5. Chemistry of enol ethers. LXXXVIII. Condensation of the tetraethylacetal of malonaldehyde with /beta/-substituted enol alkyl ethers

    SciTech Connect

    Makin, S.M.; Kruglikova, R.I.; Kharitonova, O.V.; Arshava, B.M.

    1988-03-10

    The action of /beta/-substituted enol ethers on the tetraethylacetal of malonaldehyde gave the acetals of 1,5- and 1,7-dialdehydes. The nature of the substituent in the enol ether was found to affect the regioselectivity of the reaction: condensation with ethers containing an electron-withdrawing substituent leads to 1,5-dialdehyde acetals, while condensation with ethers containing a strong electron-donor substituent leads to 1,7-dialdehyde acetals. The condensation of malonaldehyde tetraethylacetal with /beta/-substituted enol alkyl ethers was carried out at room temperature in the presence of zinc chloride as catalyst.

  6. Polymer containing pendant vinyl ether groups useful in enhanced oil recovery using

    SciTech Connect

    Irani, C.A.; Harris, T.V.; Aetzer, W.R.

    1990-08-07

    This patent describes an improvement in a method for recovering oil from an underground oil-bearing earth formation penetrated by an injection well and a producing well, in which method carbon dioxide is injected into the formation to displace oil towards the producing well from which oil is produced to the surface. It comprises: injecting into the formation carbon dioxide, the viscosity of which is increased at least three-fold by the presence of a sufficient amount of polymer containing pendant vinyl ether groups and a sufficient amount of a cosolvent to form a solution of the polymer in the carbon dioxide, wherein the minimum solubility parameter of the polymer is reduced to 6.85(cal/cc)1/1/2 or less by control of the number of pendant vinyl ether groups and by the selection of the vinyl ether groups.

  7. Preparation of ordered and crosslinked films from liquid crystalline vinyl ether monomers

    SciTech Connect

    Andersson, H.; Sahlen, F.; Gedde, U.W.; Hult, A.

    1993-12-31

    Highly ordered densely crosslinked liquid crystalline poly(vinyl ether) films have been prepared by in-situ photopolymerization of oriented bifunctional mesogenic vinyl ether monomers. Orientation was achieved either by a simple surface treatment, using an unidirectionally rubbed polyimide film or by a magnetic field. Polymerization from various monomer phases resulted in LC polymer network films with different molecular organizations. The films were analyzed with small-angle X-ray scattering, polarized light microscopy and infrared-dichroism measurements. It was shown that films with nematic, smectic A and smectic B structures were obtained, the latter having a very high degree of orientation.

  8. Diarylrhodates as promising active catalysts for the arylation of vinyl ethers with Grignard reagents.

    PubMed

    Iwasaki, Takanori; Miyata, Yoshinori; Akimoto, Ryo; Fujii, Yuuki; Kuniyasu, Hitoshi; Kambe, Nobuaki

    2014-07-01

    Anionic diarylrhodium complexes, generated by reacting [RhCl(cod)]2 with 2 equiv of aryl Grignard reagents, were found to be effective active catalysts in cross-coupling reactions of vinyl ethers with aryl Grignard reagents, giving rise to the production of vinyl arenes. In this catalytic system, vinyl-O bonds were preferably cleaved over Ar-O or Ar-Br bonds. A lithium rhodate complex was isolated, and its crystal structure was determined by X-ray crystallography. PMID:24957673

  9. Synthesize and polymerization of novel photocurable vinyl ether monomers containing perfluorinated aromatic units

    NASA Astrophysics Data System (ADS)

    Li, Wei; Zou, Ying Quan

    2012-03-01

    A series of novel UV-curable vinyl ether monomers with perfluorinated aromatic units for photoresist had been designed and synthesized. Perfluorinated vinyl ether monomer I-1was prepared from the reactions of 2-vinyloxy ethanol and hexafluorobenzene in the presence of sodium hydride in DMF. And perfluorinated vinyl ether monomer I-2 was prepared from the reactions of I-1 and 2,2,2-trifluoroethanol in the presence of sodium carbonate in DMF. The photocrosslinked perfluorinated polymers obtained by PAG201 (a kind of cationic photo-initiator) initiating. When PAG201 was introduced into the monomers, the conversion of vinyl ether double bond increased sharply. The final conversion was close to 90%, and when the light intensity was 478μW/cm2, at 25 sec, the polymerization achieved maximum. Generally, the UV-curing performance of monomers with 3wt.% PAG201 concentration is superior to 2wt.% PAG201 concentration. And their physical and chemical properties satisfied the material requirements for photoresist or UV imaging materials.

  10. Cis-METHYL Vinyl Ether: the Rotational Spectrum up to 600 GHz

    NASA Astrophysics Data System (ADS)

    Kolesniková, Lucie; Daly, Adam M.; Alonso, José L.

    2014-06-01

    Astronomical observation of dimethyl ether, methyl ethyl ether places the methyl vinyl ether among the species of potential interstellar relevance. The millimeter and submillimeter-wave transitions pertaining to the vibrational ground state and the first excited states of the methoxy, ν24, and methyl, ν23, torsional modes and the in-plane bending mode, ν16, of the cis-methyl vinyl ether have been measured and analyzed in the frequency region from 50 to 600 GHz. A significant Fermi-type and Coriolis interactions between the v24=1 and v23=1 states have been observed and the rotational spectra were analyzed using an effective two-state Hamiltonian explicitly involving corresponding coupling operators. A sets of spectroscopic constants for the ground state as well as for all three excited states reproducing the observed spectrum within the experimental uncertainty provide sufficiently precise information for the astronomical search for methyl vinyl ether. Z. Peeters, S. D. Rodgers, S. B. Charnley, L. Schriver-Mazzuoli, A. Schriver, J. V. Keane, and P. Ehrenfreund, Astron. & Astrophys. 2006, 445, 197. G. W. Fuchs, U. Fuchs, T. F. Giesen, F. Wyrowski, Astron. & Astrophys. 2005, 444, 521. B. E. Turner, A. J. Apponi, Astrophys. J. Lett. 2001, 561, 207.

  11. Maleate/vinyl ether UV-cured coatings: Effects of composition on curing and properties

    SciTech Connect

    Noren, G.K.

    1996-10-01

    The effect of the composition of the maleate polyester and the vinyl ether terminated compound on their UV-curing and properties has been investigated. Linear unsaturated polyester resins based on maleic anhydride and 1,5-pentane diol were synthesized. The molecular weight of the unsaturated polyesters was varied by changing the ratio of maleic anhydride to 1,5-pentane diol and the double bond equivalent weight was varied by replacing maleic anhydride with succinic anhydride. Coating formulations containing these unsaturated polyesters, triethylene glycol divinyl ether and a free radical photoinitiator were crosslinked in the presence of UV light. The coatings were very brittle, exhibiting tensile strengths in the range of 1.5-4.0 MPa and elongations of only 3-7%. Diethyl maleate and isobutyl vinyl ether were effective diluents for reducing viscosity but reduced the cure speed. A vinyl ether urethane oligomer was synthesized and enhanced the flexibility and toughness of the coatings when substituted for triethylene glycol divinyl ether.

  12. Copper(I)/Ligand-Catalyzed 5-endo Radical Cyclization-Aromatization of 2,2,2-Trichloroethyl Vinyl Ethers: Synthesis of 2,3-Difunctionalized 4-Chlorofurans.

    PubMed

    Ram, Ram N; Gupta, Dharmendra Kumar; Soni, Vineet Kumar

    2016-02-19

    Copper(I)/ligand-catalyzed one pot synthesis of highly substituted 2,3-difunctionalized-4-chlorofurans has been reported. The reaction proceeds via a Cu(I)-catalyzed regioselective 5-endo-trig radical cyclization of 2,2,2-trichloroethyl vinyl ethers followed by the base-promoted dehydrochlorination. The success of the kinetically disfavored 5-endo cyclization was attributed to the formation of captodatively stabilized radical intermediate in the cyclization step and relatively high reaction temperature. Synthetic application of this protocol was also demonstrated in the preparation of alkyl and aryl substituted 4-chlorofuranonapthoquinones. PMID:26796068

  13. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... determined by any suitable analytical procedure of generally accepted applicability. (ii) Inherent viscosity... D1243-79, “Standard Test Method for Dilute Solution Viscosity of Vinyl Chloride Polymers,” which...

  14. Tandem β-elimination/hetero-michael addition rearrangement of an N-alkylated pyridinium oxime to an O-alkylated pyridine oxime ether: an experimental and computational study.

    PubMed

    Picek, Igor; Vianello, Robert; Šket, Primož; Plavec, Janez; Foretić, Blaženka

    2015-02-20

    A novel OH(-)-promoted tandem reaction involving C(β)-N(+)(pyridinium) cleavage and ether C(β)-O(oxime) bond formation in aqueous media has been presented. The study fully elucidates the fascinating reaction behavior of N-benzoylethylpyridinium-4-oxime chloride in aqueous media under mild reaction conditions. The reaction journey begins with the exclusive β-elimination and formation of pyridine-4-oxime and phenyl vinyl ketone and ends with the formation of O-alkylated pyridine oxime ether. A combination of experimental and computational studies enabled the introduction of a new type of rearrangement process that involves a unique tandem reaction sequence. We showed that (E)-O-benzoylethylpyridine-4-oxime is formed in aqueous solution by a base-induced tandem β-elimination/hetero-Michael addition rearrangement of (E)-N-benzoylethylpyridinium-4-oximate, the novel synthetic route to this engaging target class of compounds. The complete mechanistic picture of this rearrangement process was presented and discussed in terms of the E1cb reaction scheme within the rate-limiting β-elimination step. PMID:25562471

  15. NMR spectroscopy of heterosubstituted alkenyl alkyl ethers. I. Fast and reliable method for determination of double bond configuration in 2-alkoxyalkenylphosphonic dihaloanhydrides

    SciTech Connect

    Lazhko, E.I.; Trostyanskaya, I.G.; Kazankova, M.A.; Ustynyuk, Yu.A.

    1986-12-20

    As criterion for determination of the geometric configuration of P(III) substituted alkyl vinyl ethers, the importance of the geminal /sup 31/P-/sup 13/C coupling constants was proposed. It was established that the ranges of /sup 2/J (CP) for the E and Z isomers of the investigated series of compounds do not overlap (120.1-40.0 and 31.8-18.6 Hz respectively). This allows the determination of the geometric configuration of a compound even from the /sup 13/C parameters of only one isomer.

  16. High absorbing resists based on trifluoromethacrylate-vinyl ether copolymers for EUV lithography

    NASA Astrophysics Data System (ADS)

    Christianson, Matthew D.; Meyer, Matthew M.; Ongayi, Owendi; Valeri, David; Wagner, Michael

    2013-03-01

    Highly sensitive EUV photoresists remain a critical challenge to enable high volume manufacturing with EUV lithography. Chemically amplified resists continue to provide the best sensitivity for EUV photoresists, but the high EUV transparency of most resists continues to waste a large percentage of EUV photons that pass through the resist film without photochemically generating acid. Highly fluorinated polymers have been proposed as more sensitive resist materials because fluorine increases EUV absorption of a material. Thus, methacrylate-like polymers with fluorinated backbones are an attractive possibility for new EUV resist materials. Trifluoromethacrylates are known to undergo free radical polymerization with electron rich comonomers such as vinyl ethers. The resulting polymers have backbone trifluoromethyl groups that enhance the absorption of EUV photons while retaining the potential for solubility change by acid-catalyzed tertiary ester deprotection similar to methacrylate-based chemically amplified resists. Interestingly, copolymerizations of trifluoromethacrylates and vinyl ethers are not particularly sensitive to traditional experimental parameters that influence polymer molecular weight. Instead, we have found that the structure of the vinyl ether comonomer has a profound impact on polymer molecular weight with acyclic vinyl ethers generating very high molecular weight polymers (Mw exceeding 100,000 g/mol) and cyclic vinyl ethers generating very low molecular weight polymers (Mw less than 10,000 g/mol) under similar conditions. Combination of cyclic and non-cyclic vinyl ethers in the monomer feed enables the synthesis of polymers at a desired molecular weight with a narrow polydispersity (PDI less than 2). Initial EUV contrast curves demonstrate potential for highly sensitive photoresists using these backbone-fluorinated polymers. A variety of polymers have been prepared to determine optimum compositions of leaving group, sensitizing, and etch resistant

  17. Infrared absorption and vibrational circular dichroism spectra of poly(vinyl ether) containing diastereomeric menthols as pendants

    NASA Astrophysics Data System (ADS)

    McCann, Jennifer L.; Rauk, Arvi; Wieser, Hal

    1997-06-01

    The absorption and vibrational circular dichroism (VCD) spectra in the 1700 to 830 cm -1 region are reported and qualitatively interpreted for poly(vinyl ether) with (+)-menthol (I), (+)-isomenthol (II) and (+)-neomenthol (III) as pendants.

  18. Unique Curing Properties through Living Polymerization in Crosslinking Materials: Polyurethane Photopolymers from Vinyl Ether Building Blocks.

    PubMed

    Kirschbaum, Stefan; Landfester, Katharina; Taden, Andreas

    2015-05-01

    Photopolymers with unique curing capabilities were produced by combining living cationic polymerization with network formation and restricted polymer motion. A vinyl ether diol was synthesized as a functional building block and reacted with isophorone diisocyanate to form a highly functionalized vinyl ether polyurethane as a model system with high crosslinking ability. When using a cationic photoinitiator, fast polymerization is observed upon short UV irradiation. Curing proceeds in the absence of light and under ambient conditions without oxygen inhibition. Cationic active sites become trapped dormant species upon network-induced vitrification and surprisingly remain living for several days. The polymerization can be reactivated by additional UV irradiation and/or raised temperature. The curing behavior was studied in detail by using UV and FT-NIR coupled rheology and photo-DSC to simultaneously study spectroscopic and mechanical information, as well as thermal effects. PMID:25776255

  19. NMR study of products of the reaction of fulvenes with vinyl butyl ether

    SciTech Connect

    Yashtulov, N.A.; Dobrovinskii, L.A.; Cherkasov, A.N.; Kamyshina, L.G.; Livshits, R.M.

    1987-08-20

    The formation of copolymers with conjugated double bonds was proven by /sup 1/H and /sup 13/C NMR in cationic copolymerization of 6,6-disubstituted pentafulvenes with vinyl butyl ether. The composition and structure of the copolymers were determined. It was shown that it is possible to find the constants of copolymerization and distribution of the microblock nature in relation to the composition of the copolymers.

  20. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... as alkyl substituted aromatic glycidyl ether (PMN P-97-661) is subject to reporting under this... in § 721.125 (a), (b), (c),(d),(e), (f), (g), (h),(i), and (k) are applicable to manufacturers... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses...

  1. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... as alkyl substituted aromatic glycidyl ether (PMN P-97-661) is subject to reporting under this... in § 721.125 (a), (b), (c),(d),(e), (f), (g), (h),(i), and (k) are applicable to manufacturers... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses...

  2. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of alkylphenyl... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10059 Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

  3. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of alkylphenyl... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10059 Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

  4. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of alkylphenyl... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10059 Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

  5. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenyl... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10059 Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

  6. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenyl... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10059 Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

  7. Composites of vinyl polystyrylpyridine/bismaleimide-aliphatic ether copolymers

    NASA Technical Reports Server (NTRS)

    Heimbuch, Alvin H.; Rosser, Robert W.; Hsu, Ming-Ta S.

    1989-01-01

    An aliphatic ether bismaleimide was prepared and coreacted with a polyvinylstyrylpyridine (VPSP) oligomer. Studies showed that a controlled ratio of aliphatic to aromatic units in the polymer backbone improved both processibility and interlaminar shear properties for the carbon-fiber composite system. This modified resin was readily soluble in tetrahydrofuran, allowing for better fiber impregnation and thus enhancing adhesive properties and reproducibility. DSC studies have shown a lower cure temperature for the copolymer than for the neat aliphatic bismaleimide, and a glass transition temperature of 260 C, which is more than adequate for most applications. Limited measurements indicated an improvement in toughness (impact resistance).

  8. Visible-light-promoted iminyl radical formation from vinyl azides: synthesis of 6-(fluoro)alkylated phenanthridines.

    PubMed

    Sun, Xiaoyang; Yu, Shouyun

    2016-09-18

    An efficient strategy assisted by visible-light-promoted iminyl radical formation has been developed for the synthesis of 6-(fluoro)alkylated phenanthridine derivatives. In the reactions, addition of alkyl and trifluoromethyl radicals onto vinyl azides gives iminyl radicals, which then undergo intramolecular homolytic aromatic substitution leading to phenanthridines. These reactions can be carried out under mild conditions with high chemical yields and broad substrate scope. PMID:27530901

  9. Photoinitiated polymerization of new hybrid monomer containing vinyl ether and (methyl) acryloyl groups

    NASA Astrophysics Data System (ADS)

    Diao, Cuimei; Zou, Yingquan

    2011-04-01

    The photopolymerization kinetics of 4-(vinyloxy)butyl methacrylate containing cationic and free radical polymerizable vinyl groups was studied by real-time Fourier transform infrared spectra (RT-FTIR) .The cationic polymerizable vinyl ether moieties(Vc) of the hybrid monomer in solution polymerized rapidly by exposure to UV light in presence of a cationic photoinitiator such as an iodonium salt or suflonium salt .High conversions, of 90%, were obtained for most of the systems investigated. The efficiency of the cationic photoinitiators in initiating the polymerization of the vinyl ether moieties (Vc) of the hybrid monomer was in the order: suflonium salt > iodonium salt . The free radical polymerizable methacrylate groups (Vr) of the hybrid monomer in solution polymerized by exposure to UV light in presence of a radical photoinitiator such as 2,4,6-trimethyl benzoyl diphenylphoshine oxide (TPO), 2-isopropyl thioxanthone (ITX) , Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Irgaure 819), 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone (Irgaure 907). Among the photoinitiators , the best effect in initiating the polymerization of methacrylate groups (Vr) of the hybrid monomer is initiator Irgaure 907.

  10. Synthesis and biological evaluation of vinyl ether-containing azole derivatives as inhibitors of Trichophyton rubrum.

    PubMed

    Wang, Lulu; Yang, Wenge; Wang, Kai; Zhu, Jing; Shen, Fei; Hu, Yonghong

    2012-07-15

    In an attempt to search for many target compounds with excellent activities, a series of vinyl ether-containing azole derivatives were designed, synthesized, and evaluated as antifungal agents. Results of preliminary antifungal tests against Trichophyton rubrum in vitro indicated that most of the synthesized compounds showed excellent activities. In comparison with fluconazole, itraconazole, voriconazole, omoconazole and amphotericin B, several compounds (such as 7d, 7g and 7h) exhibited more potent inhibitory activities, suggesting that they were promising leads for the development of novel antifungal agents. PMID:22683344

  11. Ac conduction in conducting poly pyrrole-poly vinyl methyl ether polymer composite materials

    SciTech Connect

    Saha, S.K.; Mandal, T.K.; Mandal, B.M.; Chakravorty, D.

    1997-03-01

    Composite materials containing conducting polypyrrole and insulating poly (vinyl methyl ether) (PVME) have been synthesized by oxidative polymerization of pyrrole in ethanol using FeCl{sub 3} oxidant in the presence of PVME. The ac conductivity measurements have been carried out in the frequency range of 100 Hz to 10 MHz and in the temperature range of 110 to 350 K. The frequency dependent conductivity has been explained on the basis of a small polaron tunnelling mechanism. {copyright} {ital 1997 American Institute of Physics.}

  12. Mechanism of iridium-catalysed branched-selective hydroarylation of vinyl ethers: a computational study.

    PubMed

    Zhang, Mei; Huang, Genping

    2016-02-16

    The iridium-catalysed branched-selective hydroarylation of vinyl ethers represents a rare example of the branched-selective hydroarylation involving the non-styrene-type alkenes. Herein, we report our DFT calculations on the mechanism of this reaction. The results show that after C-H oxidative addition, instead of the widely accepted Chalk-Harrod type mechanism, the branched-selective hydroarylation may proceed through an unconventional modified Chalk-Harrod type mechanism, involving the migratory insertion into the Ir-C bond and C-H reductive elimination. Both steric and electronic effects of the alkoxy group were found to account for the complete branched selectivity. PMID:26804666

  13. Ether complexes of tungsten with two different binding modes: An O-bound ether and an {eta}{sup 2}-(C=C) vinyl ether. Evidence for C-H...O hydrogen bonding of vinylic C-H groups

    SciTech Connect

    Song, J.S.; Szalda, D.J.; Bullock, R.M.

    1996-11-13

    The reaction of PhCH(OCH{sup 3}){sup 2} with Cp(CO){sup 3}WH and HOTf gives [Cp(CO){sup 3}W(PhCH{sup 2}OCH{sup 3})]{sup +}OTf{sup -}. The structure of this benzyl methyl ether complex was determined by single crystal X-ray diffraction and was shown to have the ether bonded to tungsten through the oxygen. This compound was isolated as a kinetic product of the reaction; it decomposes in solution by releasing free PhCH{sup 2}OCH{sup 3} and forming Cp(CO){sup 3}WOTf. An analog with the BAr`{sup 4}{sup -} counterion [Ar` = 3, 5-bis(trifluoromethyl)phenyl] is more stable. The reaction of the vinyl acetal CH{sup 2}=CHCH(OEt){sup 2} with Cp(CO){sup 3}WH and HOTf produces [Cp(CO){sup 3}W({eta}{sup 2}-EtOCH=CHCH{sup 3})]{sup +} OTf{sup -}, in which the ether is bonded to tungsten through the C=C bond of the vinyl ether. The crystal structure of this compound shows that the W-C(OEt) distance (2.69(3) A) is significantly longer than the W-C(CH{sup 3}) distance (2.37(3) A). There are weak C-H...O hydrogen bonds between both vinyl CH`s and oxygens of the triflate counterions. Evidence is presented that some of these weak hydrogen bonds are maintained in CD{sup 2}Cl{sup 2} solution but not in CD{sup 3}CN. 44 refs., 4 figs., 3 tabs.

  14. Effect of solvents on the radiation-induced polymerization of ethyl and isopropyl vinyl ethers. [gamma rays

    SciTech Connect

    Hsieh, W.C.; Kubota, H.; Squire, D.R.; Stannett, V.

    1980-09-01

    The radiation-induced cationic polymerization of ethyl and isopropyl vinyl ethers was studied in a variety of solvents. The propagation rate constants were estimated and found to vary widely with the nature of the solvent. In particular, a good linear relationship existed between the logarithms of the rate constants and the reciprocal of the dielectric constants. The lowest rates were those of the highest dielectric constant solvents. These results have been interpreted in terms of the Laidler and Eyring theory of ion-molecule reactions. Isopropyl vinyl ether polymerizes much faster than ethyl vinyl ether, although the rates approach the same value at infinite dielectric constant. In contrast, free carbenium ion polymerizations initiated by stable carbenium ion salts in methylene chloride solution had similar values for both monomers. A comparison is made between the rate constants obtained with both methods of initiation.

  15. Complexation between poly(maleic acid/octyl vinyl ether) and poly(vinyl caprolactam) in aqueous solution and at the alumina/water interface.

    PubMed

    Qiu, Q; Somasundaran, P

    2002-09-01

    Solution and interfacial properties of binary polymer mixtures of poly(maleic acid/octyl vinyl ether) (PMAOVE) and poly(vinyl caprolactam) (PVCAP) have been studied for the alumina/water system. To test the hydrophobic effect, mixtures of poly(maleic acid/methyl vinyl ether) (PMAMVE) and PVCAP are also investigated and compared to the behavior of PMAOVE/PVCAP. At low pH, both polymer mixtures become turbid upon mixing. The turbidity increases at low mixing ratios of PVCAP to the vinyl ether component, reaches a maximum, and then decreases at higher mixing ratios. Upon shifting the pH to the alkaline range, i.e., pH 7.5 and above, the turbid solution becomes clear for both the polymer mixtures. Cloud point measurements indicate the absence of complexation of PVCAP with PMAMVE under the alkaline conditions, but strong interaction with PMAOVE. This is attributed to the different forces involved in the complexation among the polymers: H bonding for PVCAP/PMAMVE and both H bonding and hydrophobic effects for PVCAP/PMAOVE. At the alumina/water interface, the normally nonadsorbing PVCAP is triggered to adsorb by PMAOVE, attributed to the hydrophobic complexation between the two. However, the adsorption of PVCAP shows a maximum as a function of the concentration of PMAOVE. At concentrations of PMAOVE above the onset of its own plateau adsorption, the amount of PVCAP triggered to adsorb is reduced possibly due to the polymer complex formation in solution. PMID:16290852

  16. Propargyl Vinyl Ethers and Tertiary Skipped Diynes: Two Pluripotent Molecular Platforms for Diversity-Oriented Synthesis.

    PubMed

    Tejedor, David; López-Tosco, Sara; Méndez-Abt, Gabriela; Cotos, Leandro; García-Tellado, Fernando

    2016-04-19

    During the last years, we have been involved in the development of a diversity-oriented synthetic strategy aimed at transforming simple, linear, and densely functionalized molecular platforms into collections of topologically diverse scaffolds incorporating biologically relevant structural motifs such as N- and O- heterocycles, multifunctionalized aromatic rings, fused macrocycles, etc. The strategy merges the concepts of pluripotency (the property of an array of chemical functionalities to express different chemical outcomes under different chemical environments) and domino chemistry (chemistry based on processes involving two or more bond-forming transformations that take place while the initial reaction conditions are maintained, with the subsequent reaction resulting as a consequence of the functionality installed in the previous one) to transform common multifunctional substrates into complex and diverse molecular frameworks. This design concept constitutes the ethos of the so-called branching cascade strategy, a branch of diversity-oriented synthesis focused on scaffold diversity generation. Two pluripotent molecular platforms have been extensively studied under this merging (branching) paradigm: C4-O-C3 propargyl vinyl ethers (PVEs) and C7 tertiary skipped diynes (TSDs). These are conveniently constructed from simple and commercially available raw materials (alkyl propiolates, ketones, aldehydes, acid chlorides) through multicomponent manifolds (ABB' three-component reaction for PVEs; A2BB' four-component reaction for TSDs) or a simple two-step procedure (for PVEs). Their modular origin facilitates their structural/functional diversification without increasing the number of synthetic steps for their assembly. These two pluripotent molecular platforms accommodate a well-defined and dense array of through-bond/through-space interrelated functionalities on their structures, which defines their primary reactivity principles and establishes the reactivity profile

  17. Effect of solvents on the radiation-induced polymerization of ethyl and isopropyl vinyl ethers

    SciTech Connect

    Hsieh, W.C.

    1981-01-01

    The effect of solvents on the radiation-induced cationic polymerization of ethyl and isopropyl vinyl ethers (EVE and IPVE, respectively) was investigated. EVE and IPVE polymerizations were carried out in bulk and in solution under superdry conditions in which polar impurities, especially water, have been reduced to negligible levels. This was accomplished by means of a sodium mirror technique using joint free baked out glass equipment and high vacuum. Plots of the monomer conversions and irradiation times were obtained for EVE and IPVE polymerizations in bulk and in benzene solution at constant monomer concentrations. The monomer concentration dependence of the polymerization rate was studied for EVE polymerization in bulk and in benzene, diethlyl ether, diglyme and methylene chloride, and for IPVE polymerization in bulk and in benzene. Solvent effect on the estimated propagating rate constants was examined for EVE and IPVE polymerization in bulk and in solution. The effect of temperature on the polymerization rate was also investigated for EVE polymerization in bulk ad in benzene, diethyl and diisopropyl ethers, methylene chloride and nitromethane, and for IPVE ploymerization in bulk and in benzene.

  18. Oxazolidines. 2. Synthesis of 2-methyloxazolidines by cyclization of vinyl ethers of 1,2-amino alcohols

    SciTech Connect

    Kukharev, B.F.; Stankevich, V.K.; Klimenko, G.R.; Terent'eva, V.P.; Kukhareva, V.A.

    1986-10-01

    A study has been made of the catalytic activity of a number of proton acids and Lewis acids, amongst which mercury salts were particularly active, in the cyclization of N-phenylethanolamine vinyl ether to 2-methyl-3-phenyloxazolidine. A method for the preparative synthesis of 2-methyloxazolidines has been developed.

  19. Microemulsion formed by alkyl polyglucoside and an alkyl glycerol ether with weakly charged films.

    PubMed

    Fukuda; Olsson; Ueno

    2001-02-01

    We have studied the effects on phase equilibria of a nonionic surfactant mixture-water-oil system when replacing small amount of surfactant molecules by ionic surfactant, sodium dodecyl sulfate (SDS). The nonionic surfactant system contains dodecyl-beta-D-maltoside (C(12)AG2) and iso-octyl glyceryl ether (i-C(8)GE) as cosurfactant, water and cyclohexane at constant water to oil ratio of 60/40 (w/w). Adding a small amount of SDS has large impact on the phase behavior. Clear liquid crystalline phase and upper microemulsion phase are added to the phase sequence at high i-C(8)GE/(C(12)AG2+i-C(8)GE) ratio. We also compare the phase equilibria of pure dodecyl maltoside system with polyglucosides mixture system. PMID:11087985

  20. Investigation of quantitative structure-reactivity relationships in the aliphatic Claisen rearrangement of bis-vinyl ethers reveals a dipolar, dissociative mechanism.

    PubMed

    O'Rourke, Natasha F; Wulff, Jeremy E

    2014-02-28

    Kinetic investigations of substituent effects in the thermal rearrangement of bis-vinyl ether substrates are reported. Findings indicate that the influence of the various substituent patterns on the rate of rearrangement in these compounds differs from that documented in the literature for the analogous [3,3]-sigmatropic rearrangement of allyl vinyl ethers. In addition, the thermochemical data collected suggests the existence of a dissociative transition state with significant dipolar character. These findings provide a unique contribution to the already extensive body of literature dedicated to mechanistic investigation of the Claisen rearrangement of aliphatic allyl vinyl ethers. PMID:24424964

  1. 40 CFR 721.10044 - Metal oxide, modified with alkyl and vinyl terminated polysiloxanes (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... vinyl terminated polysiloxanes (generic). 721.10044 Section 721.10044 Protection of Environment... and vinyl terminated polysiloxanes (generic). (a) Chemical substance and significant new uses subject... and vinyl terminated polysiloxanes (PMN P-02-698) is subject to reporting under this section for...

  2. Synthesis, spectroscopy and computational studies of some novel π-conjugated vinyl N-alkylated quinolinium salts and their precursor's

    NASA Astrophysics Data System (ADS)

    Nycz, Jacek E.; Czyż, Karolina; Szala, Marcin; Malecki, Jan G.; Shaw, George; Gilmore, Brendan; Jon, Marek

    2016-02-01

    A series of π-conjugated vinyl N-methylated quinolinium salts (3) and their precursor's N-alkylated quinolinium salts (2) were prepared and characterized by NMR, IR, UV-Vis and MS spectroscopy. It was confirmed that the hydroxyl and amino derivatives of vinyl N-methylated quinolinium salts lead to spiro type compounds (4). The syntheses of N-alkylated quinolinium salts were successful, and even multigram scale was achievable. The structures of 1,2-dimethylquinolinium iodide (2a) and 1-ethyl-2-methylquinolinium iodide (2b) were determined by single crystal X-ray diffraction method. NMR spectra showed readily diagnostic H-1 and C-13 signals from methyl and N-alkyl groups for both 2 and 3. The geometries of the studied compounds were optimized in singlet states using the density functional theory (DFT) method with B3LYP functional. In general, the predicted bond lengths and angles are in a good agreement with the values based on the X-ray crystal structure data.

  3. Coupled torsional and bending motions in s-cis methyl vinyl ether

    NASA Astrophysics Data System (ADS)

    Meyer, Rolf; Ha, Tae-Kyu; Oldani, Markus; Caminati, Walther

    1987-02-01

    New microwave measurements on s-cis methyl vinyl ether and a study of the interactions among skeletal and methyl torsions and COC bending are reported. Using pulsed microwave Fourier transform spectroscopy, the small methyl torsional A-E splitting (0.16 MHz) in the vibrational ground state has been resolved for the first time. Large splittings are observed in the first excited states of skeletal torsion and COC bending. Ab initio results on the torsional coupling, allowing for structural relaxation, are reported and used to specify, in part, a flexible model for the torsional and bending motions. The spectroscopic properties of this three-dimensional model sytem, as estimated from the results for the one-dimensional and two-dimensional subsystems, explain the relevant experimental data. The gearing type torsional interaction predicted ab initio is confirmed by this treatment. The adjusted potential function as well as the structural relaxations upon torsion suggest repulsive interaction between the methyl hydrogen atoms and the methylenic hydrogen atom next to the methyl group.

  4. Tuning the Miscibility of Polystyrene / Poly(vinyl methyl ether) Blends with Electric Fields

    NASA Astrophysics Data System (ADS)

    Kriisa, Annika; Roth, Connie

    2014-03-01

    Application of electric fields seem experimentally simple, as they can be switched on and off instantly and effortlessly. Nevertheless the influence of electric fields on the phase separation temperature Ts in small molecules and polymeric mixtures is not yet well understood. Available theoretical calculations use thermodynamic arguments for adding an electrostatic free energy term to the total free energy of mixing and predict changes in Ts due to external electric fields that are much smaller than what most experimental results report. To date, neither theory or experiments have found a clear consensus on whether uniform electric fields enhance mixing or demixing. As only a few experimental results have been published over the past several decades with typically only small shifts in Ts, more experiments with unambiguously large shifts in Ts are needed to better understand this effect. Using a fluorescence technique we have developed for measuring the phase separation temperature Ts of polystyrene (PS) / poly(vinyl methyl ether) (PVME) blends [J. Polym. Sci., Part B 2012, 50, 250-256], we investigate the change in Ts due to the presence of electric fields. We show that electric fields strongly enhance mixing in PS/PVME polymer blends. For example, for a 50/50 PS/PVME blend composition, Ts is increased by over 10 K for electric fields of 18 kV/mm.

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

    SciTech Connect

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

    1987-08-10

    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 /sup 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-..pi.. conjugation is concurrent in nature and depends on the position of the vinyloxy group in the heterocycle.

  6. 40 CFR 721.10044 - Metal oxide, modified with alkyl and vinyl terminated polysiloxanes (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Metal oxide, modified with alkyl and... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10044 Metal oxide, modified with alkyl... to reporting. (1) The chemical substance identified generically as metal oxide, modified with...

  7. 40 CFR 721.10044 - Metal oxide, modified with alkyl and vinyl terminated polysiloxanes (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Metal oxide, modified with alkyl and... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10044 Metal oxide, modified with alkyl... to reporting. (1) The chemical substance identified generically as metal oxide, modified with...

  8. 40 CFR 721.10044 - Metal oxide, modified with alkyl and vinyl terminated polysiloxanes (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal oxide, modified with alkyl and... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10044 Metal oxide, modified with alkyl... to reporting. (1) The chemical substance identified generically as metal oxide, modified with...

  9. Electric fields enhance miscibility of polystyrene/poly(vinyl methyl ether) blends

    NASA Astrophysics Data System (ADS)

    Kriisa, Annika; Roth, Connie B.

    2014-10-01

    How the presence of electric fields alters the miscibility of mixtures has been studied since the 1960s with conflicting reports on both the magnitude and direction of the shift in the phase separation temperature Ts. Theoretical understanding of the phenomenon has been hampered by the lack of experimental data with unambiguously large shifts in Ts outside of experimental error. Here, we address these concerns by presenting data showing that uniform electric fields strongly enhance the miscibility of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends. Reliable shifts in Ts of up to 13.5 ± 1.4 K were measured for electric fields strengths of E = 1.7 × 107 V/m in a 50/50 PS/PVME mixture. By using a sensitive fluorescence method to measure Ts, the PS/PVME blend can be quenched back into the one phase region of the phase diagram when the domains are still small allowing the blend to be remixed such that Ts can be measured repeatedly on the same sample. In this manner, highly reproducible Ts values at non-zero and zero electric field can be ascertained on the same sample. Our results agree with the vast majority of existing experimental data on various mixtures finding that electric fields enhance miscibility, but are opposite to the one previous study on PS/PVME blends by Reich and Gordon [J. Polym. Sci.: Polym. Phys. Ed. 17, 371 (1979)] reporting that electric fields induce phase separation, a study which has been considered anomalous in the field.

  10. Quasielastic neutron scattering study of hydrogen motions in an aqueous poly(vinyl methyl ether) solution

    NASA Astrophysics Data System (ADS)

    Capponi, S.; Arbe, A.; Cerveny, S.; Busselez, R.; Frick, B.; Embs, J. P.; Colmenero, J.

    2011-05-01

    We present a quasielastic neutron scattering (QENS) investigation of the component dynamics in an aqueous Poly(vinyl methyl ether) (PVME) solution (30% water content in weight). In the glassy state, an important shift in the Boson peak of PVME is found upon hydration. At higher temperatures, the diffusive-like motions of the components take place with very different characteristic times, revealing a strong dynamic asymmetry that increases with decreasing T. For both components, we observe stretching of the scattering functions with respect to those in the bulk and non-Gaussian behavior in the whole momentum transfer range investigated. To explain these observations we invoke a distribution of mobilities for both components, probably originated from structural heterogeneities. The diffusive-like motion of PVME in solution takes place faster and apparently in a more continuous way than in bulk. We find that the T-dependence of the characteristic relaxation time of water changes at T ≲ 225 K, near the temperature where a crossover from a low temperature Arrhenius to a high temperature cooperative behavior has been observed by broadband dielectric spectroscopy (BDS) [S. Cerveny, J. Colmenero and A. Alegría, Macromolecules, 38, 7056 (2005), 10.1021/ma050811t]. This observation might be a signature of the onset of confined dynamics of water due to the freezing of the PVME dynamics, that has been selectively followed by these QENS experiments. On the other hand, revisiting the BDS results on this system we could identify an additional "fast" process that can be attributed to water motions coupled with PVME local relaxations that could strongly affect the QENS results. Both kinds of interpretations, confinement effects due to the increasing dynamic asymmetry and influence of localized motions, could provide alternative scenarios to the invoked "strong-to-fragile" transition.

  11. Gold-catalyzed annulations of 2-alkynyl benzaldehydes with vinyl ethers: synthesis of dihydronaphthalene, isochromene, and bicyclo[2.2.2]octane derivatives.

    PubMed

    Malhotra, Deepika; Liu, Le-Ping; Mashuta, Mark S; Hammond, G B

    2013-03-18

    With the suitable selection of a gold catalyst as well as the appropriate control of the reaction conditions, various new gold-catalyzed cyclizations of 2-alkynyl benzaldehyde with acyclic or cyclic vinyl ethers have been developed. Acetal-tethered dihydronaphthalene and isochromenes were obtained from the reactions of 2-alkynyl benzaldehydes with acyclic vinyl ethers under mild conditions. And, more interestingly, the gold-catalyzed reactions of 2-alkynyl benzaldehyde with a cyclic vinyl ether afforded the bicyclo[2.2.2]octane derivative involving two molecules of cyclic vinyl ethers. These products contain interesting substructures that have been found in many biologically active molecules and natural products. In addition, a gold-catalyzed homo-dimerization of 2-phenylethynyl benzaldehyde 1a was observed when the reaction was carried out in the absence of vinyl ether, affording a set of separable diastereomeric products. Plausible mechanisms for these transformations are discussed; a gold-containing benzopyrylium was regarded as the crucial intermediate by which a number of these new transformations took place. PMID:23362089

  12. 40 CFR 721.10556 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Poly(oxy-1,2-ethanediyl), .alpha.- (2...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers (PMN P-06-450; CAS...

  13. 40 CFR 721.10557 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Poly(oxy-1,2-ethanediyl), .alpha.- (2...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers (PMN P-06-451; CAS...

  14. 40 CFR 721.10556 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Poly(oxy-1,2-ethanediyl), .alpha.- (2...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers (PMN P-06-450; CAS...

  15. 40 CFR 721.10558 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Poly(oxy-1,2-ethanediyl), .alpha.- (2...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS...

  16. 40 CFR 721.10557 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Poly(oxy-1,2-ethanediyl), .alpha.- (2...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers (PMN P-06-451; CAS...

  17. 40 CFR 721.10558 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Poly(oxy-1,2-ethanediyl), .alpha.- (2...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS...

  18. Asymmetric synthesis of α,α-disubstituted amino acids by cycloaddition of (E)-ketonitrones with vinyl ethers.

    PubMed

    Zhang, Xiaofei; Cividino, Pascale; Poisson, Jean-François; Shpak-Kraievskyi, Pavlo; Laurent, Mathieu Y; Martel, Arnaud; Dujardin, Gilles; Py, Sandrine

    2014-04-01

    Original acyclic (E)-α,α-dialkylketonitrones bearing a chiral auxiliary on their nitrogen atom were synthesized and successfully employed for the asymmetric synthesis of α,α-disubstituted amino acids using regio- and stereocontrolled 1,3-dipolar cycloaddition reactions with vinyl ethers. N-Glycosyl chiral auxiliaries were found to provide excellent exo- and π-facial stereocontrol. The obtained enantiopure cycloadducts were selectively transformed into functional α,α-disubstituted amino acids and related β-peptides through the highly regioselective opening of an intermediate quaternary anhydride. PMID:24650145

  19. Vinyl ethers containing a cyclic carbonate group. I. Synthesis of 3-(/omega/-vinyloxyalkoxy)propylene 1,2-carbonates

    SciTech Connect

    Nedolya, N.A.; Tatarova, T.F.; Vyalykh, E.P.; Trofimov, B.A.

    1989-01-10

    In order to synthesize 3-(/omega/-vinyloxyalkoxy)propylene 1,2-carbonates the authors studied the reaction of /omega/-vinyloxyalkoxymethyloxiranes with carbon dioxide at 140-180/degree/C, catalyzed by a tertiary amine (triethylamine). The main results from this reaction are described. The effect of the reaction conditions (solvent, concentration of catalyst, ratio of reagents, state of aggregation of the carbon dioxide, process temperature and time) on the result were studied for the case of 2-vinyloxyethoxymethyloxirane. The reaction leads with high yields to functional vinyl ethers of a new type - 3-(/omega/-vinyloxyalkoxy)propylene 1,2-carbonates.

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

    SciTech Connect

    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.

  1. [Occupational lung cancer after inhalation of alkylating compounds: dichlordimethyl ether, monochlordimethyl ether and dimethyl sulphate (author's transl)].

    PubMed

    Bettendorf, U

    1977-03-18

    A 42-year-old chemist died from extensive pulmonary carcinoma, having inhaled for over seven years dichlordimethyl ether, monochlordimethyl ether and small amounts of dimethyl sulphate. This exposure took place in circumstances which, in animal experiments, have led to the development of cancer. A causal connection between the occupational exposure to these chemicals and carcinogenesis has to be accepted. PMID:844406

  2. 40 CFR 721.10044 - Metal oxide, modified with alkyl and vinyl terminated polysiloxanes (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10044 Metal oxide, modified with alkyl... to reporting. (1) The chemical substance identified generically as metal oxide, modified with...

  3. The Absolute Rates of the Solution Phase Addition of Atomic Hydrogen to a Vinyl Ether and a Vinyl Ester. The Effect of Oxygen Substitution on Hydrogen Atom Reactivity with Olefins

    SciTech Connect

    Tanner, D. D.; Kandanarachchi, P.; Das, N. C.; Franz, James A.

    2003-04-08

    The reactions of vinyl butyl ether and vinyl butyrate with atomic hydrogen and deuterium lead to addition of atomic hydrogen to the terminal position of the olefins. This observation is consistent with the reactions carried out earlier with other olefins. Both the absolute rates of addition to vinylbutyl ether and vinyl butyrate in acetone and hexane were carried out at several temperatures. The relative rates are consistent with only modest stabilization of the transition state of the radical adduct by the ??-o substituent compared with hydrogen atom addition to 1-octene. The relative rates measured in acetone and hexane indicate no significant differential solvation of ground state relative to the transition structures of the hydrogen atom addition. The kinetics reveal that the early transition states of hydrogen atom addition exhibit little selectivity (vinyl ether versus simple olefin) in either abstraction of hydrogen ??- to the oxygen or by terminal addition to the olefinic ether, reflecting the modest influence of the increased enthalpy of reaction associated with resonance stabilization by the oxygen substituent at the developing radical site.

  4. Absolute Rates of the Solution-Phase Addition of Atomic Hydrogen to a Vinyl Ether and a Vinyl Ester: Effect of Oxygen Substitution on Hydrogen Atom Reactivity with Olefins

    SciTech Connect

    Tanner, D D.; Kandanarachchi, P; Das, N. C.; Franz, James A.

    2003-04-08

    The reactions of vinyl butyl ether and vinyl butyrate with atomic hydrogen and deuterium lead to addition at the terminal position of the olefins. This observation is consistent with the reactions carried out earlier with other olefins. Both of the absolute rates of addition to vinylbutyl ether and vinyl butyrate, in acetone and hexane, were measured at several temperatures. The relative rates are consistent with only modest stabilization of the transition state of the radical adduct by the R-O substituent compared with that of hydrogen atom addition to 1-octene. The relative rates measured in acetone and hexane indicate no significant differential solvation of the ground state relative to the transition structures of the hydrogen atom addition. The kinetics reveal that the early transition states for hydrogen atom addition exhibit little selectivity (vinyl ether versus simple olefin) in either the abstraction of hydrogen R to the oxygen or by terminal addition to the olefinic ether and reflects the modest influence of the increased enthalpy of reaction associated with resonance stabilization by the oxygen substituent at the developing radical site.

  5. Gold(I)-Catalyzed Angle Strain Controlled Strategy to Furopyran Derivatives from Propargyl Vinyl Ethers: Insight into the Regioselectivity of Cycloisomerization.

    PubMed

    Jin, Shengfei; Jiang, Chongguo; Peng, Xiaoshi; Shan, Chunhui; Cui, Shanshan; Niu, Yuanyuan; Liu, Yang; Lan, Yu; Liu, Yongxiang; Cheng, Maosheng

    2016-02-19

    A unique strategy for the regiospecific synthesis of bicyclic furopyran derivatives has been developed via a gold(I)-catalyzed propargyl-Claisen rearrangement/6-endo-trig cyclization of propargyl vinyl ethers. The introduction of angle strain into the substrates significantly altered the reaction's regioselectivity. Insight into the regioselectivity of the cycloisomerization was obtained with density functional theory calculations. PMID:26841301

  6. 40 CFR 721.5960 - N,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt (generic name). 721.5960 Section 721.5960...,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt... methyl sulfate double salt (PMN P-84-913) is subject to reporting under this section for the...

  7. 40 CFR 721.5960 - N,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt (generic name). 721.5960 Section 721.5960...,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt... methyl sulfate double salt (PMN P-84-913) is subject to reporting under this section for the...

  8. 40 CFR 721.5960 - N,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt (generic name). 721.5960 Section 721.5960...,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt... methyl sulfate double salt (PMN P-84-913) is subject to reporting under this section for the...

  9. 40 CFR 721.5960 - N,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt (generic name). 721.5960 Section 721.5960...,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt... methyl sulfate double salt (PMN P-84-913) is subject to reporting under this section for the...

  10. 40 CFR 721.5960 - N,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt (generic name). 721.5960 Section 721.5960...,N′-Bis(2-(2-(3-alkyl)thia- zoline) vinyl)-1,4-pheny-lene-dia-mine methyl sulfate double salt... methyl sulfate double salt (PMN P-84-913) is subject to reporting under this section for the...

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

    PubMed

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

    2016-08-18

    We report the influence of adding five short-chain glycol ethers (SCGEs) on the structure, stability, and viscoelastic properties of aqueous dispersions of partially hydrolyzed poly(vinyl acetate) and borax. The properties of these gel-like materials have been investigated as a function of the structure of the added SCGE both below and above the critical aggregation (or micellar) concentrations using (11) B and (13) C NMR, rheology, and small-angle neutron scattering. The results indicate that the SCGE aggregation behavior is not affected by incorporation into the gel-like network. However, changes in the viscoelasticity and structural properties of the dispersions were detected that can be correlated to the nature of the solvent system. Also, the ability of these materials to clean an unvarnished acrylic paint surface coated with synthetic soil has been evaluated using colorimetery, and the surface of the dispersion after cleaning was visualized with scanning electron microscopy. PMID:27387383

  12. Catalytic asymmetric Claisen rearrangement of Gosteli-type allyl vinyl ethers: total synthesis of (-)-9,10-dihydroecklonialactone B.

    PubMed

    Becker, Julia; Butt, Lena; von Kiedrowski, Valeska; Mischler, Elisabeth; Quentin, Florian; Hiersemann, Martin

    2014-04-01

    The enantioselective synthesis of (-)-9,10-dihydroecklonialactone B is described. The catalytic asymmetric Claisen rearrangement of a Gosteli-type allyl vinyl ether was utilized to afford an acyclic α-keto ester building block endowed with functionality amenable to the preparation of the carbocyclic target molecule by suitable postrearrangement transformations: A highly diastereoselective Corey-Bakshi-Shibata reduction of a β-chiral α-keto ester and a reductive homologation of an α-hydroxy ester. A transprotection tactic by a chemoselective intramolecular 6-exo-trig iodoetherification enabled regioselective ring-closing alkene metatheses to afford the 5- as well as the 14-membered ring, however, with mixed success in terms of E/Z selectivity. PMID:24621347

  13. Microwave-Assisted Organocatalyzed Rearrangement of Propargyl Vinyl Ethers to Salicylaldehyde Derivatives: An Experimental and Theoretical Study.

    PubMed

    Tejedor, David; Cotos, Leandro; Márquez-Arce, Daniel; Odriozola-Gimeno, Mikel; Torrent-Sucarrat, Miquel; Cossío, Fernando P; García-Tellado, Fernando

    2015-12-01

    The microwave-assisted imidazole-catalyzed transformation of propargyl vinyl ethers (PVEs) into multisubstituted salicylaldehydes is described. The reaction is instrumentally simple, scalable, and tolerates a diverse degree of substitution at the propargylic position of the starting PVE. The generated salicylaldehyde motifs incorporate a broad range of topologies, spanning from simple aromatic monocycles to complex fused polycyclic systems. The reaction is highly regioselective and takes place under symmetry-breaking conditions. The preparative power of this reaction was demonstrated in the first total synthesis of morintrifolin B, a benzophenone metabolite isolated from the small tree Morinda citrifolia L. A DFT study of the reaction was performed with full agreement between calculated values and experimental results. The theoretically calculated values support a domino mechanism comprising a propargyl Claisen rearrangement, a [1,3]-H shift, a [1,7]-H shift (enolization), a 6π electrocyclization, and an aromatization reaction. PMID:26515241

  14. Versatile assembly of p-carboxylatocalix[4]arene-O-alkyl ethers

    SciTech Connect

    Kennedy, Stuart; Teat, Simon J.; Dalgarno, Scott J.

    2009-07-08

    Crystallisation of lower-rim tetra-O-alkylated p-carboxylatocalix[4]arenes from pyridine results in the formation of both bi-layer and pillar type supramolecular motifs. Full alkylation at the calixarene lower rim has significant influence over the supramolecular self-assembly motif, including preclusion of pyridine guest molecules from the calixarene cavity in the solid state.

  15. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO(2)(111) Model Catalysts

    SciTech Connect

    Calaza, Florencia C; Chen, Tsung-Liang; Mullins, David R; Overbury, Steven {Steve} H

    2011-01-01

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  16. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts

    SciTech Connect

    F Calaza; T Chen; D Mullins; S Overbury

    2011-12-31

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  17. Iron-Catalyzed Cross-Coupling of Unactivated, Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

    PubMed Central

    Denmark, Scott E.; Cresswell, Alexander J.

    2013-01-01

    The first systematic investigation of unactivated aliphatic sulfur compounds as electrophiles in transition metal-catalyzed cross-coupling are described. Initial studies focused on discerning the structural and electronic features of the organosulfur substrate which enable the challenging oxidative addition to the C(sp3)–S bond. Through extensive optimization efforts, an Fe(acac)3-catalyzed cross-coupling of unactivated alkyl aryl thio ethers with aryl Grignard reagents was realized, in which a nitrogen “directing group” on the S-aryl moiety of the thio ether served a critical role in facilitating the oxidative addition step. In addition, alkyl phenyl sulfones were found to be effective electrophiles in the Fe(acac)3-catalyzed cross-coupling with aryl Grignard reagents. For the latter class of electrophile, a thorough assessment of the various reaction parameters revealed a dramatic enhancement in reaction efficiency with an excess of TMEDA (8.0 equiv). The optimized reaction protocol was used to evaluate the scope of the method with respect to both the organomagnesium nucleophile and sulfone electrophile. PMID:24256193

  18. Development of a Vinyl Ether-Functionalized Polyphosphoester as a Template for Multiple Postpolymerization Conjugation Chemistries and Study of Core Degradable Polymeric Nanoparticles

    PubMed Central

    2015-01-01

    A novel polyphosphoester (PPE) with vinyl ether side chain functionality was developed as a versatile template for postpolymerization modifications, and its degradability and biocompatibility were evaluated. An organocatalyzed ring-opening polymerization of ethylene glycol vinyl ether-pendant cyclic phosphotriester monomer allowed for construction of poly(ethylene glycol vinyl ether phosphotriester) (PEVEP). This vinyl ether-functionalized PPE scaffold was coupled with hydroxyl- or thiol-containing model small molecules via three different types of conjugation chemistries—thiol–ene “click” reaction, acetalization, or thio-acetalization reaction—to afford modified polymers that accommodated either stable thio–ether or hydrolytically labile acetal or thio–acetal linkages. Amphiphilic diblock copolymers of poly(ethylene glycol) and PEVEP formed well-defined micelles with a narrow and monomodal size distribution in water, as confirmed by dynamic light scattering (DLS), transmission electron microscopy, and atomic force microscopy. The stability of the micelles and the hydrolytic degradability of the backbone and side chains of the PEVEP block segment were assessed by DLS and nuclear magnetic resonance spectroscopy (1H and 31P), respectively, in aqueous buffer solutions at pH values of 5.0 and 7.4 and at temperatures of 25 and 37 °C. The hydrolytic degradation products of the PEVEP segments of the block copolymers were then identified by electrospray ionization, gas chromatography, and matrix-assisted laser desorption/ionization mass spectrometry. The parent micelles and their degradation products were found to be non-cytotoxic at concentrations up to 3 mg/mL, when evaluated with RAW 264.7 mouse macrophages and OVCAR-3 human ovarian adenocarcinoma cells. PMID:25601803

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

    PubMed

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

    2016-05-10

    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. PMID:27062726

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

    PubMed

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

    2015-07-01

    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. PMID:26067375

  1. Bismuth-catalyzed synthesis of polycyclic aromatic hydrocarbons (PAHs) with a phenanthrene backbone via cyclization and aromatization of 2-(2-arylphenyl)vinyl ethers.

    PubMed

    Murai, Masahito; Hosokawa, Naoki; Roy, David; Takai, Kazuhiko

    2014-08-15

    The reaction of 2-(2-arylphenyl)vinyl ethers in the presence of a catalytic amount of bismuth(III) triflate gave substituted phenanthrenes in excellent yields under mild reaction conditions. The reaction was also applied to the construction of other polycyclic aromatic hydrocarbons (PAHs), such as chrysene, helicene, and pyrene having a phenanthrene backbone, via regioselective cyclization. This method has the advantages of easy availability of the cyclization precursors, operational simplicity, and high reaction efficiency. PMID:25076204

  2. Neuroprotective effect of alkyl hydroxytyrosyl ethers in rat brain slices subjected to a hypoxia-reoxygenation model.

    PubMed

    Guerrero, A; De la Cruz, J P; Muñoz-Marín, J; López-Villodres, J A; Madrona, A; Espartero, J L; González-Correa, J A

    2012-10-15

    The aim of the present study was to investigate the antioxidant and possible neuroprotective and antioxidant effects of five alkyl hydroxytyrosyl (HT) ethers (ethyl, butyl, hexyl, octyl and dodecyl) in rat brain slices. None of the compounds modified lipid peroxidation or glutathione concentrations (GSH) in oxygenated samples. The effects of oxidative stress were investigated with ferrous salts to induce lipid peroxidation and diethylmaleate (DEM) to reduce GSH. All compounds inhibited lipid peroxidation with an inhibitory concentration 50% (IC(50)) one tenth that of HT. These compounds, especially the butyl derivative, prevented GSH depletion after incubation with DEM. We also explored the neuroprotective effect of these compounds in an experimental model of hypoxia-reoxygenation in rat brain slices. All compounds showed neuroprotective and antioxidant effects. Our results established a relationship between these effects and the length of the carbon chain (maximum effect in the range of C4-C8). PMID:23442672

  3. 40 CFR 721.10060 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, alkyl diglycidyl dibenzene...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Specific Chemical Substances § 721.10060 Reaction product of alkylphenyl glycidyl ether... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of...

  4. 40 CFR 721.10060 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, alkyl diglycidyl dibenzene...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Specific Chemical Substances § 721.10060 Reaction product of alkylphenyl glycidyl ether... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of...

  5. 40 CFR 721.10060 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, alkyl diglycidyl dibenzene...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Specific Chemical Substances § 721.10060 Reaction product of alkylphenyl glycidyl ether... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of...

  6. 40 CFR 721.10060 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, alkyl diglycidyl dibenzene...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Specific Chemical Substances § 721.10060 Reaction product of alkylphenyl glycidyl ether... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of...

  7. 40 CFR 721.10060 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, alkyl diglycidyl dibenzene...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Specific Chemical Substances § 721.10060 Reaction product of alkylphenyl glycidyl ether... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of...

  8. Digestion of the 1-O-alkyl diacylglycerol ethers of Atlantic dogfish liver oils by Atlantic salmon Salmo salar.

    PubMed

    Kang, S J; Lall, S P; Ackman, R G

    1997-01-01

    Dogfish (Squalus acanthias) liver poses a waste disposal problem in Canada because it is not utilized for any commercial purpose. The liver of Atlantic dogfish, which is often up to 20% of the weight of the fish, contains 40-70% oil. The oil contains about 30-40% 1-O-alkyl diacylglycerol ethers (DAGE) which render it unacceptable for human use, and it has also not been considered satisfactory for animal feed use. Polyunsaturated fatty acids (20:5n-3 and 22:6n-3) are present in dogfish liver oils at levels comparable to those in herring oil. Dogfish liver oil could be a source of essential fatty acids for Atlantic salmon (Salmo salar), but their ability to hydrolyze DAGE from dogfish oil has not been examined. Experiments were designed to measure the digestibility of fatty acids of DAGE in salmon. The fatty acid moieties were liberated by the digestive enzymes of the fish and made readily available as a source of energy. The 1-O-alkylglycerol ether moiety was absorbed to a small extent but should not constitute a health problem in either the fish or the human fish consumer. The long-chain polyunsaturated fatty acids were particularly well absorbed, with an apparent digestibility in salmon of 87-95% when feeding on dogfish liver oil. The total fatty acids and other lipids were in fact both absorbed to the extent of approximately 85%. PMID:9075189

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

    PubMed Central

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

    2014-01-01

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

  10. Immobilization of saccharides and peptides on 96-well microtiter plates coated with methyl vinyl ether-maleic anhydride copolymer.

    PubMed

    Satoh, A; Kojima, K; Koyama, T; Ogawa, H; Matsumoto, I

    1998-06-15

    We have previously reported a method to immobilize protein ligands on microtiter plates coated with methyl vinyl ether-maleic anhydride copolymer (MMAC) [Isosaki, K., et al. (1992) J. Chromatogr. 597, 123-128]. In this study, we improved the MMAC method to efficiently immobilize not only small ligands such as peptides and oligosaccharides, which could not be efficiently immobilized previously, but also heparin via its reducing end. Amino and hydrazino groups were introduced to MMAC-coated microtiter plate wells by coupling to acid anhydride groups of MMAC with 1,6-hexamethylenediamine and adipic acid dihydrazide, respectively. The amino groups introduced were allowed to react with peptides by use of divalent cross-linkers. Hydrazino groups were allowed to react with formyl groups of saccharides by reductive amination. Peptides and oligosaccharides were immobilized in a dose-dependent manner by these methods. In the case of the angiotensin peptide thus immobilized, the detection limit by monoclonal antibodies was as low as 0.1-1 fmol peptide per well. Application of 20-200 nmol oligosaccharides to the well was sufficient to immobilize and subsequently detect lectins. Furthermore, heparin immobilized on the hydrazinocoated wells was successfully used for the binding assay of annexin IV. PMID:9648659

  11. Understanding How the Presence of Uniform Electric Fields Can Shift the Miscibility of Polystyrene/Poly(vinyl methyl ether) Blends

    NASA Astrophysics Data System (ADS)

    Kriisa, Annika; Roth, Connie B.

    2015-03-01

    Techniques which can externally control and manipulate the phase behavior of polymeric systems, without altering chemistry on a molecular level, have great practical benefits. One such possible mechanism is the use of electric fields, shown to cause interfacial instabilities, orientation of morphologies, and phase transitions in polymer blends and block copolymers. We have recently demonstrated that the presence of uniform electric fields can also strongly enhance the miscibility of polystyrene (PS) / poly(vinyl methyl ether) (PVME) blends [J. Chem. Phys. 2014, 141, 134908]. Using fluorescence to measure the phase separation temperature Ts of PS/PVME blends with and without electric fields, we show that Ts can be reproducibly and reversibly increased by 13.5 +/- 1.4 K for electric fields of 17 kV/mm for this lower critical solution temperature (LCST) blend. This increase in blend miscibility with electric fields represents some of the largest absolute shifts in Ts ever recorded, well outside of experimental error. The best theoretical prediction for the expected shift in Ts with electric field for this system is still two orders of magnitude smaller than that observed experimentally. We discuss the limitations of this theoretical prediction and consider possible factors affecting miscibility that may need to be also included.

  12. Computational study on the mechanisms and rate constants of the OH-initiated oxidation of ethyl vinyl ether in atmosphere.

    PubMed

    Han, Dandan; Cao, Haijie; Li, Jing; Li, Mingyue; He, Maoxia; Hu, Jingtian

    2014-09-01

    The hydroxylation reactions of ethyl vinyl ether (EVE) in the present of O2 and NO are analyzed by using MPWB1K/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) level of theory. According to the calculated thermodynamic data, the detailed reaction mechanisms of EVE and OH are proposed. All of the ten possible reaction pathways are discussed. The major products of the title reaction are ethyl formate and formaldehyde, which is in accordance with experimental detection. The rate constants of the primary reactions over the temperature of 250-400K and the pressure range of 100-2000Torr are computed by employing MESMER program. At 298K and 760Torr, OH-addition channels are predominate and the total rate constant is ktot=4.53×10(-11)cm(3)molecule(-1)s(-1). The Arrhenius equation is obtained as ktot=6.27×10(-12)exp(611.5/T), according to the rate constants given at different temperatures. Finally, the atmospheric half life of EVE with respect to OH is estimated to be 2.13h. PMID:24997901

  13. Electrophilic Metal Alkyl Chemistry in New Ligand Environments

    SciTech Connect

    Jordan, Richard F.

    2013-06-30

    The goals of this project were to design new electrophilic metal alkyl complexes and to exploit these systems in fundamental studies of olefin polymerization and other important and new catalytic reactions. A key target reaction is insertion copolymerization of olefins and polar CH2=CHX vinyl monomers such as vinyl halides and vinyl ethers. During the period covered by this report we (i) investigated the properties of ortho-alkoxy-arylphosphine ligands in Ni-based olefin polymerization catalysts, (ii) studied the synthesis of double-end-capped polyethylene using group 4 metal catalysts that contain tris-pyrazolylborate ligands, (iii) explored the ethylene insertion reactivity of group 4 metal tris-pyrazolyl-borate complexes, (iv) showed that (α-diimine)PdMe{sup +} species undergo multiple insertion of silyl vinyl ethers, (v) synthesized and explored the reactivity of base-free Ni benzyl complexes that contain ortho-phosphino-arene sulfonate ligands, (vi) established the mechanism of the reaction of vinyl chloride with (α-diimine)PdMe{sup +} catalysts, (vii) explored the role of cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (α-diimine)PdMe{sup +} species, (viii) discovered a new class of self-assembled tetranuclear Pd catalysts that produce high molecular weight linear polyethylene and copolymerize ethylene and vinyl fluoride, and (ix) developed model systems that enabled investigation of cis-trans isomerization of {phosphine-sulfonate}Pd(II) complexes.

  14. Kinetic study of the OH-initiated photo-oxidation of four unsaturated (allyl and vinyl) ethers under simulated atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Peirone, Silvina A.; Aranguren Abrate, Juan P.; Taccone, Raúl A.; Cometto, Pablo M.; Lane, Silvia I.

    2011-09-01

    Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with n-propyl vinyl ether ( k1), 2-chloroethyl vinyl ether ( k2), allyl ether ( k3) and allyl ethyl ether ( k4) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using N 2 and ultra pure air as bath gas. Using isoprene, 1-methyl-1-cyclohexene, 2-methyl-2-butene, 3-buten-1-ol and 2-methyl-2-propen-1-ol as reference compounds, the following rate constants were derived: k1 = (11.0 ± 0.4) × 10 -11, k2 = (9 ± 1) × 10 -11, k3 = (6.8 ± 0.7) × 10 -11 and k4 = (4.2 ± 0.7) × 10 -11, in units of cm 3 molecule -1 s -1. This is the first experimental detcermination of k2- k4. The rate constants obtained are compared with the previous literature data for corresponding alkenes reactions with OH and the observed reactivity trends are discussed. The atmospheric implications of the results are considered.

  15. N-alkyl pyrrolidone ether podands as versatile alkali metal ion chelants.

    PubMed

    Perrin, Andrea; Myers, Dominic; Fucke, Katharina; Musa, Osama M; Steed, Jonathan W

    2014-02-28

    This work explores the coordination chemistry of a bis(pyrrolidone) ether ligand. Pyrrolidones are commercially important functional groups because of the high polarity and hence high hydrophilicity and surface affinity. An array of alkali metal ion complexes of a podand bearing two pendant pyrrolidone functionalities, namely 1-{2-[2-(2-oxo-pyrrolid-1-yl)-ethoxy]-ethyl}-pyrrolid-2-one (1) are reported. Reaction of this ligand with sodium hexafluorophosphate gives two discrete species of formulae [Na(1)2]PF6 (3) and [Na3(H2O)2(μ-1)2](PF6)3 (4), and a coordination polymer {[Na3(μ3-1)3(μ2-1)](PF6)3}n (5). The same reaction in methanol gives a 1 : 1 complex, namely [Na2(μ-1)2(MeOH)2](PF6)2 (6). Use of tetraphenyl borate as a less coordinating counter ion gives [Na2(1)2(H2O)4](BPh4)2 (7) and [Na2(1)4](BPh4)2 (8). Two potassium complexes have also been isolated, a monomer [K(1)2]PF6 (9) and a cyclic tetramer [K4(μ4-H2O)2(μ-1)4](PF6)4 (10). The structures illustrate the highly polar nature of the amide carbonyl moiety within bis(pyrrolidone) ethers with longer interactions to the ether oxygen atom. The zinc complex is also reported and {[ZnCl2(μ-1)]}n (11) exhibits bonding only to the carbonyl moieties. The ether oxygen atom is not necessary for Na(+) complexation as exemplified by the structure of the sodium complex of the analogue 1,3-bis(pyrrolid-2-on-1-yl)butane (2). Reaction of compound 1 with lithium salts results in isolation of the protonated ligand. PMID:24336897

  16. Hydroxytyrosyl alkyl ether derivatives inhibit platelet activation after oral administration to rats.

    PubMed

    Muñoz-Marín, Javier; De la Cruz, José Pedro; Reyes, José Julio; López-Villodres, Juan Antonio; Guerrero, Ana; López-Leiva, Inmaculada; Espartero, José Luis; Labajos, María Teresa; González-Correa, José Antonio

    2013-08-01

    The low lipophilicity of hydroxytyrosol (HT) has motivated efforts to synthesize homologous series with better lipid solubility, such as the ethers, which are more lipophilic than HT. Because HT inhibits platelet aggregation, the aim of the study was to assess the possible anti-platelet effect of five HT ether derivatives (ethyl, butyl, hexyl, octyl and dodecyl) after oral administration to rats. Whole blood collagen-induced platelet aggregation and calcium-induced thromboxane B2 (TxB2), aortic 6-keto-prostaglandin F1α (6-keto-PGF1α) and nitrites+nitrates, plasma concentration of lipid peroxides (TBARS) and red blood cell content of reduced glutathione (GSH) were measured. The administration of 20 mg/kg/day inhibited platelet aggregation, TxB2 and TBARS in a non-linear manner related to the length of the carbon chain, with a cut-off effect in the hexyl derivative. Aortic nitrite and red blood cell GSH production were also increased. The aortic production of 6-keto-PGF1α was unaltered except in the group treated with the dodecyl derivative. The administration of 50 mg/kg/day showed a similar pharmacodynamic profile but without the non-linear effect. In conclusion, HT ethers, especially the hexyl derivative, are a potential alternative to hydroxytyrosol, and their effect merits additional research to determine their role in the prophylaxis of vascular disease. PMID:23643702

  17. Stabilization of alkylated azacrown ether by fatty acid at the air-water interface.

    PubMed

    Zarbakhsh, Ali; Campana, Mario; Webster, John R P; Wojciechowski, Kamil

    2010-12-01

    The adsorbed amount of partially deuterated dihexadecyl-diaza-18-crown-6 ether (d-ACE16) in the presence of different chain length fatty acids as a function of surface pressure was determined by neutron reflectometry technique. The highest adsorbed amount of the azacrown ether was observed for the mixture of ACE16 with hexadecanoic (palmitic) acid, pointing to the importance of chain length matching between the two species for optimum stabilization of the mixed monolayer. The contrast variation technique was used to estimate the contribution to the total adsorbed amount from stearic acid and ACE16. It was found that the mixed Langmuir monolayer is stable against dissolution up to a surface pressure of 20 mN m(-1). Above this pressure, however, the spread and adsorbed amounts start to deviate, indicative of partial dissolution into the aqueous subphase. The consequences of this behavior for the transport of metal ions through the interfaces of permeation liquid membranes (PLMs) are discussed. PMID:21049946

  18. Characterization and quantitation of mixtures of alkyl ether sulfates and carboxylic acids by capillary electrophoresis with indirect photometric detection.

    PubMed

    Bernabé-Zafón, Virginia; Ortega-Gadea, Silvia; Simó-Alfonso, Ernesto F; Ramis-Ramos, Guillermo

    2003-08-01

    The separation, characterization, and determination of mixtures of alkyl ether sulfates (AES) and fatty acids (C10-C16) in background electrolytes (BGEs) containing acetonitrile (ACN)-water mixtures is addressed. Due to inhibition of the ionization of the carboxylate groups, the migration time and the resolution between the fatty acids decreased when the water content of the BGE was reduced, but efficiency and resolution between the AES oligomers improved. The migration times increased and resolution improved by substituting 5% ACN by an equivalent amount of dioxane. A complete separation of the two surfactant classes, up to the AES oligomers with 8 ethylene oxide units (EOs) with respect to C10, with excellent resolution between the AES oligomers, while preserving a satisfactory resolution between the fatty acids, was achieved with a BGE containing 5 mM trimethoxybenzoic acid, 7 mM dipentylamine, 85% ACN, 5% dioxane, and 10% water. The two surfactant classes were increasingly resolved by further reducing the water content of the BGE. Thus, C2 (acetate) was resolved from the AES oligomers up to 7 EOs using 90% ACN and 5% dioxane, but the resolution between the heavier fatty acids was poor with this BGE. Identification of the AES oligomers was eased by the excellent regularity of the successive migration times; thus, within each AES subclass or series of oligomers with the same number of carbon atoms in the alkyl chain, the migration times decreased following a mild curve as the number of EOs increased. The way how the data obtained by indirect photometry (corrected peak areas that are proportional to the molar concentrations) should be managed to avoid systematic error when the calibration curve is constructed using an AES standard with an oligomer distribution different from that of the samples is discussed and equations are given. Decyl sulfate was successfully used as internal standard. The detection limits (S/N = 3) were of ca. 2 microM for individual AES

  19. Asymmetric Total Synthesis of (+)- and (−)-Clusianone and (+)- and (−)Clusianone Methyl Enol Ether via ACC Alkylation and Evaluation of their Anti-HIV Activity

    PubMed Central

    Garnsey, Michelle R.; Matous, James A.; Kwiek, Jesse J.; Coltart, Don M.

    2011-01-01

    The total asymmetric synthesis of (+)- and (−)-clusianone and (+)- and (−)-clusianone methyl enol ether is reported. Asymmetric induction is achieved through the use of ACC alkylation, providing the key intermediates with an er of 99:1. The four synthetic compounds were evaluated for their anti-HIV activity. Both (+)- and (−)-clusianone displayed significant anti-HIV activity. PMID:21414776

  20. Spontaneous Emulsification of Triolein Induced by Mixed Micellar Solutions of Sodium Polyoxyethylene Alkyl Ether Sulfate and Dodecyldimethyl Amine Oxide.

    PubMed

    Endo, Chika; Ito, Yoshiko; Akabane, Chika; Kaneko, Yukihiro; Sakai, Hideki

    2015-01-01

    A new mechanism of spontaneous emulsification without any salts or co-solvents is described, and is related to the dilatational behavior. Spontaneous emulsification can reduce the time required to remove oily soils from hard surfaces and enhance the detergency, because this type of emulsification requires no external mechanical work. In this paper, we focused on triolein, the main component of food oils and human sebum soil, and tried to induce spontaneous emulsification by using mixed micellar solutions of sodium polyoxyethylene alkyl ether sulfate and N, N-dimethyldodecylamine oxide (AES/DDAO). We characterized the dilatation of the oil/water interface using dynamic interfacial tension and elasticity measurements. This study confirmed that the degree of spontaneous emulsification can be enhanced by controlling the molar ratio of DDAO to AES. This enhancement can be attributed to an increased rate of decrease in the dynamic interfacial tension (i.e., a decreased interface dilatational elasticity), allowing for much greater suppression of the Marangoni effect. Further, we determined that one of the reasons for the decrease in the interface dilatational elasticity is the increasing number of micelles near the oil drop interface, which results from a decrease in the electrostatic repulsion between the micelles and the drop interface. Therefore, controlling the molar ratio of a mixed anionic/amphoteric surfactant solution is an effective way to induce spontaneous emulsification in the absence of salts or co-solvents. PMID:26250425

  1. Reaction products and mechanisms for the reaction of n-butyl vinyl ether with the oxidants OH and Cl: Atmospheric implications

    NASA Astrophysics Data System (ADS)

    Colmenar, Inmaculada; Martín, Pilar; Cabañas, Beatriz; Salgado, Sagrario; Tapia, Araceli; Martínez, Ernesto

    2015-12-01

    A reaction product study for the degradation of butyl vinyl ether (CH3(CH2)3OCHdbnd CH2) by reaction with chlorine atoms (Cl) and hydroxyl radicals (OH) has been carried out using Fourier Transform Infrared absorption spectroscopy (FTIR) and/or Gas Chromatography-Mass Spectrometry with a Time of Flight analyzer (GC-TOFMS). The rate coefficient for the reaction of butyl vinyl ether (BVE) with chlorine atoms has also been evaluated for the first time at room temperature (298 ± 2) K and atmospheric pressure (708 ± 8) Torr. The rate coefficient obtained was (9.9 ± 1.5) × 10-10 cm3 molecule-1 s-1 and this indicates the high reactivity of butyl vinyl ether with Cl atoms. However, this value may be affected by the dark reaction of BVE with Cl2. The results of a qualitative study of the Cl reaction show that the main oxidation products are butyl formate (CH3(CH2)3OC(O)H), butyl chloroacetate (CH3(CH2)3OC(O)CH2Cl and formyl chloride (HCOCl). Individual yields in the ranges ∼16-40% and 30-70% in the absence and presence of NOx, respectively, have been estimated for these products. In the OH reaction, butyl formate and formic acid were identified as the main products, with yields of around 50 and 20%, respectively. Based on the results of this work and a literature survey, the addition of OH radicals and Cl atoms at the terminal C atom of the double bond in CH3(CH2)3OCHdbnd CH2 has been proposed as the first step in the reaction mechanism for both of the studied oxidants. The tropospheric lifetime of butyl vinyl ether is very short and, as a consequence, it will be rapidly degraded and will only be involved in tropospheric chemistry at a local level. The degradation products of these reactions should be considered when evaluating the atmospheric impact.

  2. Volumetric Properties of the Mixture Propan-1-ol C3H8O + C5H10O Propyl vinyl ether (VMSD1111, LB5079_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Propan-1-ol C3H8O + C5H10O Propyl vinyl ether (VMSD1111, LB5079_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  3. Volumetric Properties of the Mixture Propan-1-ol C3H8O + C5H10O Propyl vinyl ether (VMSD1212, LB5078_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Propan-1-ol C3H8O + C5H10O Propyl vinyl ether (VMSD1212, LB5078_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  4. Vapor-Liquid Equilibrium in the Mixture Propyl vinyl ether C5H10O + C6H6 Benzene (EVLM1121, LB5723_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume B 'Binary Liquid Systems of Nonelectrolytes II' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-liquid Equilibrium in the Mixture Propyl vinyl ether C5H10O + C6H6 Benzene (EVLM1121, LB5723_E)' providing data from direct measurement of mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

  5. Volumetric Properties of the Mixture Propyl vinyl ether C5H10O + C6H6 Benzene (VMSD1212, LB5077_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume B 'Binary Liquid Systems of Nonelectrolytes II' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Propyl vinyl ether C5H10O + C6H6 Benzene (VMSD1212, LB5077_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  6. Vapor-Liquid Equilibrium in the Mixture Propan-1-ol C3H8O + C5H10O Propyl vinyl ether (EVLM1121, LB5724_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture Propan-1-ol C3H8O + C5H10O Propyl vinyl ether (EVLM1121, LB5724_E)' providing data from direct measurement of mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

  7. Volumetric Properties of the Mixture Propyl vinyl ether C5H10O + C6H6 Benzene (VMSD1111, LB5076_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume B 'Binary Liquid Systems of Nonelectrolytes II' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Propyl vinyl ether C5H10O + C6H6 Benzene (VMSD1111, LB5076_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  8. Structures and Surface Properties of "Cyclic" Polyoxyethylene Alkyl Ethers: Unusual Behavior of Cyclic Surfactants in Water.

    PubMed

    Hirose, Yuki; Taira, Toshiaki; Sakai, Kenichi; Sakai, Hideki; Endo, Akira; Imura, Tomohiro

    2016-08-23

    The cyclization of amphiphiles has emerged as an attractive strategy for inducing remarkable properties in these materials without changing their chemical composition. In this study, we successfully synthesized three cyclic polyoxyethylene dodecyl ethers (c-POEC12's) with different ring sizes and explored the effects of their topology on their surface and self-assembly properties related to their function, comparing them with those of their linear counterparts (l-POEC12's). The surface activity of the c-POEC12's remained almost constant despite the change in their hydrophobic and hydrophilic balance (HLB) value, while that of the l-POEC12's decreased with an increase in the HLB value as general surfactants. In contrast to the normal micelles seen in the case of the l-POEC12's (3.4-9.7 nm), the cyclization of the POEC12's resulted in the formation of large spherical structures 72.8-256.8 nm in size. It also led to a dramatic decrease of 28 °C in the cloud point temperature. Furthermore, the cyclization of the POEC12's markedly suppressed the rate of protease hydrolysis caused by the surfactants. The initial rate of reduction of a detergent enzyme from Bacillus licheniformis was increased by more than 40% in the case of c-POE600C12 and c-POE1000C12, even though they exhibited surface activities almost equal to or higher than those of their linear counterparts. These results suggest that cyclization induces unusual aqueous behaviors in POEC12, making the surfactant milder with respect to detergent enzymes while ensuring it exhibits increased surface activity. PMID:27462805

  9. Regioselective hydroformylation of cylic vinyl and allyl ethers with rhodium catalysts. Crucial influence of the size of the phosphorous cocatalyst

    SciTech Connect

    Polo, A.; Claver, C.; Castillon, S.

    1992-11-01

    The authors have explored the possibilities offered by the modification of thiolato bridges in dinuclear rhodium complexes on the selective hydroformylation of cylic vinyl and allyl ethers. The dinuclear complex [Rh{sub 2}({mu}-S(CH{sub 2}){sub 3}NMe{sub 2}){sub 2}(cod){sub 2}] (cod = 1,5-cyclooctadiene) has been prepared, and its reactivity with CO, phospines, and phosphites has been investigated. The complex crystallizes in the monoclinic space group C2/c with Z = 8, {alpha} = 22.543 (4) A, B = 12.040 (2) A, c = 21.547 (3) A, and {Beta} = 98.77 (1){degrees}. For the determination of the structure 4091 unique reflections were used, and the final refinement gave R = 4.1% and R{sub w} = 4.4%. The molecular structure reveals that the two rhodium atoms are bridged by the two thiolato ligands, and the cyclooctadiene completes the coordination of the metal atoms. The amine groups are not bonded to the rhodium. The dinuclear complex has been used in the hydroformylation of 2,3-di-hydrofuran, 2,5-dihydrofuran, 3,4-dihydro-2H-pyran or 3,6-dihydro-2H-pyran was tetrahydropyran-2-carbaldehyde. A systematic study of the influence of the reaction parameters on the selectivity of the hydroformylation of 2,3-dihydroformylation of 3,4-dihydro-2H-pyran or 3,6-dihydro-2H-pyran was tetrahydropyran-2-carbaldehyde. A systematic study of the influence of the reaction parameters on the selectivity of the hydroformylation of 2,3-dihydrofuran and 2,5-dihydrofuran was undertaken. The study allowed the rationalization of the observed selectivity and the optimization of the yields and regioselectivities. Thus, by modification of the reaction parameters, tetrahydrofuran-3-carbaldehyde was obtained in quantitative yields from 2,5-dihydrofuran and tetrahydrofuran-2-carbaldehyde can be prepared from either 2,3-dihydrofuran or 2,5-dihydrofuran in approximately 75% yield. 33 refs., 3 figs., 9 tabs.

  10. Cross-Linked Hydrogels Formed through Diels-Alder Coupling of Furan- and Maleimide-Modified Poly(methyl vinyl ether-alt-maleic acid).

    PubMed

    Stewart, S Alison; Backholm, Matilda; Burke, Nicholas A D; Stöver, Harald D H

    2016-02-23

    The Diels-Alder [4 + 2] cycloaddition between furan- and maleimide-functional polyanions was used to form cross-linked synthetic polymer hydrogels. Poly(methyl vinyl ether-alt-maleic anhydride) was reacted with furfurylamine or N-(2-aminoethyl)maleimide in acetonitrile to form pairs of furan- and maleimide-functionalized poly(methyl vinyl ether-alt-maleic acid)s. Mixtures of these mutually reactive polyanions in water gelled within 15 min to 18 h, depending on degree of functionalization and polymer concentrations. Solution and magic-angle spinning (1)H NMR were used to confirm the formation of the Diels-Alder adduct, to analyze competing hydrolytic side reactions, and demonstrate postgelation functionalization. The effect of the degree of furan and maleimide functionalization, polymer concentration, pH, and calcium ion concentration, on gelation time, gel mechanical properties, and equilibrium swelling, are described. Release of dextran as a model drug was studied using fluorescence spectroscopy, as a function of gel composition and calcium treatment. PMID:26800849

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

    PubMed

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

    2014-01-01

    Water interacting with a polymer reveals a number of properties very different to bulk water. These interactions lead to the redistribution of hydrogen bonds in water. It results in modification of thermodynamic properties of water and the molecular dynamics of water. That kind of water is particularly well observable at temperatures below the freezing point of water, when the bulk water crystallizes. In this work, we determine the amount of water bound to the polymer and of the so-called pre-melting water in poly(vinyl methyl ether) hydrogels with the use of Raman spectroscopy, dielectric spectroscopy, and calorimetry. This analysis allows us to compare various physical properties of the bulk and the pre-melting water. We also postulate the molecular mechanism responsible for the pre-melting of part of water in poly(vinyl methyl ether) hydrogels. We suggest that above -60 °C, the first segmental motions of the polymer chain are activated, which trigger the process of the pre-melting. PMID:25100897

  12. Activity of organophosphorus insecticides in bacterial tests for mutagenicity and DNA repair--direct alkylation versus metabolic activation and breakdown. II. O,O-dimethyl-O-(1,2-dibromo-2,2-dichloroethyl)-phosphate and two O-ether derivatives of trichlorfon.

    PubMed

    Braun, R; Schöneich, J; Weissflog, L; Dedek, W

    1983-03-01

    The following organophosphates were tested for their ability to induce DNA damage in a rec-type repair test with Proteus mirabilis strains PG713 (rec- hcr-) and PG273 (wild-type) and point mutations in the his- strain TA100 of Salmonella typhimurium: O,O-dimethyl-O-(1,2-dibromo-2,2-dichloroethyl)-phosphate (NALED); trichlorfon-O-methyl ether (TCP-O-ME), O,O-dimethyl-(1-methoxy-2,2,2-trichlorethyl)-phosphonate; trichlorfon-O-methyl ether vinyl derivative (TCP-O-MEVD), O,O-dimethyl-(1-methoxy-2,2-dichlorovinyl)-phosphonate. All compounds were negative in the repair test but induced base pair substitutions in S. typhimurium. The mutagenicity of NALED is due to the direct alkylating ability of the parental molecule and to mutagenic metabolites generated by enzymatic splitting of the side chain. Glutathion-dependent enzymes in the S9-mix eliminate the mutagenic activity of NALED completely. Mutation induction by TCP-O-ME and TCP-O-MEVD is predominantly caused by the reactive O-methyl ether configuration of the side chain and is resistant to metabolic inactivation by NADPH- or glutathion-dependent enzymatic pathways in the S9-mix of mice. PMID:6337735

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

    PubMed

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

    2009-11-28

    Quasielastic neutron scattering experiments (time-of-flight, neutron spin echo, and backscattering) on protonated poly(vinyl methyl ether) (PVME) have revealed the hydrogen dynamics above the glass-transition temperature. Fully atomistic molecular dynamics simulations properly validated with the neutron scattering results have allowed further characterization of the atomic motions accessing the correlation functions directly in real space. Deviations from Gaussian behavior are found in the high-momentum transfer range, which are compatible with the predictions of mode coupling theory (MCT). We have applied the MCT phenomenological version to the self-correlation functions of PVME atoms calculated from our simulation data, obtaining consistent results. The unusually large value found for the lambda-exponent parameter is close to that recently reported for polybutadiene and simple polymer models with intramolecular barriers. PMID:19947703

  14. Optical and dielectric properties of fluorinated ethylene propylene and tetrafluoroethylene-perfluoro(alkoxy vinyl ether) copolymer films modified by low energy N 4+ and C 4+ ion beams

    NASA Astrophysics Data System (ADS)

    Šiljegović, M.; Kačarević-Popović, Z. M.; Bibić, N.; Jovanović, Z. M.; Maletić, S.; Stchakovsky, M.; Krklješ, A. N.

    2011-12-01

    Fluorinated ethylene propylene (FEP) and tetrafluoroethylene-perfluoro(alkoxy vinyl ether) (PFA) copolymer films were irradiated in vacuum with 60 keV C 4+ and N 4+ ions to fluences ranging from 1.0×10 12 to 5.0×10 15 cm -2. Changes in optical and dielectric properties were analyzed by spectroscopic ellipsometry and ultraviolet-visible (UV-vis), Raman and dielectric relaxation spectroscopies. Direct and indirect energy band gap values were determined from the absorption edge in the 200-800 nm region using Tauc's relation. The values of the direct energy gap have been found to be greater than the corresponding values of the indirect energy gap. Significant changes in the index of refraction, and β and γ dielectric relaxations were observed in the case of N 4+ irradiated FEP and PFA samples.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Acid-Triggered Release via dePEGylation of Fusogenic Liposomes Mediated by Heterobifunctional Phenyl Substituted Vinyl Ethers with Tunable pH-Sensitivity

    PubMed Central

    Kim, Hee-Kwon; Van den Bossche, Jeroen; Hyun, Seok-Hee; Thompson, David H

    2012-01-01

    A new family of heterobifunctional phenyl-substituted vinyl ether (PIVE) coupling agents with tunable acid-sensitivity has been developed. The PIVE compounds are designed to hydrolyze under acidic conditions with hydrolysis rates that can be varied by rational selection of the phenyl ring substituent. These reagents were incorporated within 2-methoxypoly(ethylene glycol) PEG-conjugated 1,3-dioctadecyl-rac-glycerol lipids to produce the acid-cleavable lipopolymers mPEG-[H-PIVE]-DOG, mPEG-[F-PIVE]-DOG, mPEG-[Me-PIVE]-DOG, and mPEG-[MeO-PIVE]-DOG. These lipopolymers were hydrolyzed under acidic conditions (pH 3.5 or 4.5) at rates that were dependent on the electron donating or withdrawing character of the α-phenyl vinyl ether substituent, while remaining stable at pH 7.4. Blending of these compounds with 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) in a 10:90 mPEG-PIVE-Lipid:DOPE ratio produced stable liposomes at neutral pH; however, acidification of the solution led to dePEGylation and release of the liposomal cargo in a manner that correlated with the PIVE proton affinity. Specifically, we observed 70 % calcein release within 12 h from mPEG-[MeO-PIVE]-DOG-containing liposomes at pH 4.5, whereas only 22% calcein release was observed from mPEG-[F-PIVE]-DOG:DOPE liposomes over this same timescale and pH. These results indicate that dePEGylation following acidification is a triggering mechanism that can be rationally designed and controlled through the appropriate selection of PIVE moieties. PMID:22988941

  17. Human platelets respond differentially to lysophosphatidic acids having a highly unsaturated fatty acyl group and alkyl ether-linked lysophosphatidic acids.

    PubMed Central

    Tokumura, Akira; Sinomiya, Junya; Kishimoto, Seishi; Tanaka, Tamotsu; Kogure, Kentaro; Sugiura, Takayuki; Satouchi, Kiyoshi; Waku, Keizo; Fukuzawa, Kenji

    2002-01-01

    Lysophosphatidic acid (LPA) is a physiological agonist that is produced by lysophospholipase D, phospholipase A(1) and phospholipase A(2) in the blood of animals. It exerts diverse biological actions on a broad range of animal cells. Specific receptors for this important agonist have been characterized. In this investigation, for the first time we prepared LPAs having a highly unsaturated fatty acyl group, such as the eicosapentaenoyl or docosahexaenoyl residue, and their acetylated derivatives. Human platelets aggregated more potently in response to the highly unsaturated acyl-LPAs than to LPAs with a C(18) fatty acyl group, such as an oleoyl group, while alkyl ether-linked LPAs (alkyl-LPA) had much stronger aggregating activity. Two positional isomers of LPAs with an arachidonoyl, eicosapentaenoyl or docosahexaenoyl group had equipotent aggregatory activity as well as the positional isomers of their acetylated analogues, indicating that putative LPA receptors could not distinguish the difference between the positional isomers. We found that platelet preparations from two individuals showed no aggregatory response to alkyl-LPAs, although they contained mRNAs for known LPA receptors in the following order of expression level: endothelial differentiation gene (Edg)-4>Edg-7>Edg-2. We also obtained evidence that 2-(p-amylcinnamoyl)amino-4-chlorobenzoic acid (ONO-RS-082), a phospholipase A(2) inhibitor, potentiated alkyl-LPA-induced platelet aggregation, but inhibited highly unsaturated acyl-LPA-induced platelet aggregation. These results indicated that human platelets express acyl-LPA-selective and alkyl-LPA-selective receptors on their plasma membrane. PMID:11982483

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

    NASA Astrophysics Data System (ADS)

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

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

  19. Radiolytic preparation of poly(styrene sulfonic acid) - grafted poly(tetrafluoroethylene- co-perfluorovinyl vinyl ether) membranes with highly cross-linked networks

    NASA Astrophysics Data System (ADS)

    Kang, Sung-A.; Shin, Junhwa; Fei, Geng; Ko, Beom-Seok; Kim, Chong-Yeal; Nho, Young-Chang

    2010-11-01

    In this study, various amounts of a divinylbenzene (DVB) cross-linking agent (5˜30%) were introduced during a simultaneous irradiation grafting of styrene onto a PFA film of a 25 μm thickness in order to prepare a series of poly(styrene sulfonic acid)-grafted poly(tetrafluoroethylene- co-perfluorovinyl vinyl ether) (PFA) membranes with various degrees of cross-linking and grafting (29˜74%). The effects of the DVB cross-linking agent on the properties of the prepared membranes, such as water uptake, proton conductivity, methanol permeability, and chemical stability, were also investigated in this study. The results indicated that the ion exchange capacity (IEC) slightly decreased with increasing DVB content, whereas the water uptake, proton conductivity, and methanol permeability of the membrane greatly decreased. The chemical stability of the prepared membranes was found to be significantly improved with increasing DVB content. The results indicated that the cross-linked network membranes are promising for application in a direct methanol fuel cell.

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

    PubMed Central

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

    2014-01-01

    Photodynamic therapy is generally considered to be safer than conventional anticancer therapies, and it is effective against different kinds of cancer. However, its clinical application has been significantly limited by the hydrophobicity of photosensitizers. In this work, a system composed of the hydrophobic photosensitizer aluminum–phthalocyanine chloride (AlPc) associated with water dispersible poly(methyl vinyl ether-co-maleic anhydride) nanoparticles is described. AlPc was associated with nanoparticles produced by a method of solvent displacement. This system was analyzed for its physicochemical characteristics, and for its photodynamic activity in vitro in cancerous (murine mammary carcinoma cell lineage 4T1, and human mammary adenocarcinoma cells MCF-7) and noncancerous (murine fibroblast cell lineage NIH/3T3, and human mammary epithelial cell lineage MCF-10A) cell lines. Cell viability and the elicited mechanisms of cell death were evaluated after the application of photodynamic therapy. This system showed improved photophysical and photochemical properties in aqueous media in comparison to the free photosensitizer, and it was effective against cancerous cells in vitro. PMID:24634582

  1. Computational study on the mechanisms and rate constants of the Cl-initiated oxidation of methyl vinyl ether in the atmosphere.

    PubMed

    Han, Dandan; Cao, Haijie; Li, Mingyue; Li, Xin; Zhang, Shiqing; He, Maoxia; Hu, Jingtian

    2015-01-29

    The Cl-initiated oxidation reactions of methyl vinyl ether (MVE) are analyzed by using the high-level composite method CBS-QB3. Detailed chemistry for the reactions of MVE with chlorine atoms is proposed according to the calculated thermodynamic data. The primary eight channels, including two Cl-addition reactions and six H-abstraction reactions, are discussed. In accordance with the further investigation of the two dominant additional routes, formyl chloride and formaldehyde are the major products. Over the temperature range of 200-400 K and the pressure range of 100-2000 Torr, the rate constants of primary reactions are calculated by employing the MESMER program. H-abstraction channels are negligible according to the value of rate constants. During the studied temperature range, the Arrhenius equation is obtained as ktot = 5.64 × 10(-11) exp(215.1/T). The total rate coefficient is ktot = 1.25 × 10(-10) cm(3) molecule(-1) s(-1) at 298 K and 760 Torr. Finally, the atmospheric lifetime of MVE with respect to Cl is estimated to be 2.23 h. PMID:25565072

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

    PubMed

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

    2016-08-01

    The purpose of this study was to design a targeted anti-cancer drug delivery system for breast cancer. Therefore, doxorubicin (DOX) loaded poly(methyl vinyl ether maleic acid) nanoparticles (NPs) were prepared by ionic cross-linking method using Zn(2+) ions. To optimise the effect of DOX/polymer ratio, Zn/polymer ratio, and stirrer rate a full factorial design was used and their effects on particle size, zeta potential, loading efficiency (LE, %), and release efficiency in 72 h (RE72, %) were studied. Targeted NPs were prepared by chemical coating of tiptorelin/polyallylamin conjugate on the surface of NPs by using 1-ethyl-3-(3-dimethylaminopropyl) carboiimid HCl as cross-linking agent. Conjugation efficiency was measured by Bradford assay. Conjugated triptorelin and targeted NPs were studied by Fourier-transform infrared spectroscopy (FTIR). The cytotoxicity of DOX loaded in targeted NPs and non-targeted ones were studied on MCF-7 cells which overexpress luteinizing hormone-releasing hormone (LHRH) receptors and SKOV3 cells as negative LHRH receptors using Thiazolyl blue tetrazolium bromide assay. The best results obtained from NPs prepared by DOX/polymer ratio of 5%, Zn/polymer ratio of 50%, and stirrer rate of 960 rpm. FTIR spectrum confirmed successful conjugation of triptorelin to NPs. The conjugation efficiency was about 70%. The targeted NPs showed significantly less IC50 for MCF-7 cells compared to free DOX and non-targeted NPs. PMID:27463791

  3. Self-assembly behavior of amphiphilic C₆₀-end-capped poly(vinyl ether)s in water and dissociation of the aggregates by the complexing of the C₆₀ moieties with externally added γ-cyclodextrins.

    PubMed

    Motoyanagi, Jin; Kurata, Akihiro; Minoda, Masahiko

    2015-03-01

    C60-end-capped polymers consisting of an amphiphilic poly(2-methoxyethyl vinyl ether) (PMOVE) main chain were synthesized by living cationic polymerization using a C60-functionalized initiator (C60VE-TFA) in the presence of EtAlCl2 as an activator and dioxane as an added base. The obtained polymers (C60-PMOVE) dissolved in a wide range of solvents including water and exhibited solvatochromism depending on the polarity of the media employed. This phenomenon was attributed to self-assembly in polar media due to hydrophobicity of the C60 moieties at the terminus of the amphiphilic polymer chain. Furthermore, the addition of γ-cyclodextrin (γ-CD), a strong host molecule for fullerenes, to the self-assembled system brought about the dissociation of the aggregates into molecularly dispersed free polymer chains. Titration of the aqueous solution of the self-assembly of C60-PMOVE with γ-CD indicated the possible formation of inclusion complexes of C60-PMOVE and γ-CD, and this binding process occurs in a positive cooperative manner. PMID:25658224

  4. 40 CFR 721.10523 - Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (generic). 721... methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (PMN P... Substances § 721.10523 Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide,...

  5. 40 CFR 721.10523 - Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (generic). 721... methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (PMN P... Substances § 721.10523 Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide,...

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  7. Thermodynamic properties and ideal-gas enthalpies of formation for butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol

    SciTech Connect

    Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.; Smith, N.K.

    1996-11-01

    Ideal-gas enthalpies of formation of butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo-[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol are reported. Enthalpies of fusion were determined for bicyclo[2.2.1]hept-2-ene and trans-azobenzene. Two-phase (solid + vapor) or (liquid + vapor) heat capacities were determined from 300 K to the critical region or earlier decomposition temperature for each compound studied. Liquid-phase densities along the saturation line were measured for bicyclo[2.2.1]hept-2-ene. For butyl vinyl ether and 1,2-dimethoxyethane, critical temperatures and critical densities were determined from the dsc results and corresponding critical pressures derived from the fitting procedures. Fitting procedures were used to derive critical temperatures, critical pressures, and critical densities for bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, and di-tert-butyl ether. Group-additivity parameters or ring-correction terms useful in the application of the Benson group-contribution correlations were derived.

  8. Interactions of water with the nonionic surfactant polyoxyethylene glycol alkyl ethers studied by phase-sensitive sum frequency generation and molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Mafi, Amirhossein; Hu, Dan; Chou, Keng C.

    2016-06-01

    Phase-sensitive sum frequency generation (SFG) vibrational spectroscopy and molecular dynamics (MD) simulation were used to study the interactions between water molecules and the surfactant polyoxyethylene glycol alkyl ether (C12E4) at its critical micelle concentration. The surfactant enhanced the positive peak of water's SFG spectrum suggesting that C12E4 was more anionic-like, even though the surfactant was overall neutral. MD simulations showed that the surfactant increased the depth of the surface anisotropic layer from 0.31 to 1.82 nm and the average number of hydrogen bonds per water molecule from 2.7 to 3.1. For water molecules near the surfactant, their H and O atoms are confined in well-separated shells. Both the O and C atoms in the head group of the surfactant are surrounded by the H atoms, instead of the O atoms, of water indicating that the negatively charged O atoms of the surfactant play a more important role than the C atoms in determining the orientation of water. The simulation also showed that the orientation of surface water molecules was flipped in the presence of the surfactant, which was consistent with the observed SFG spectra.

  9. Acid-labile mPEG-Vinyl Ether-1,2-Dioleylglycerol Lipids with Tunable pH Sensitivity: Synthesis and Structural Effects on Hydrolysis Rates, DOPE Liposome Release Performance and Pharmacokinetics

    PubMed Central

    Shin, Junhwa; Shum, Pochi; Grey, Jessica; Fujiwara, Shin-ichi; Malhotra, Guarov S.; González-Bonet, Andres; Hyun, Seok-Hee; Moase, Elaine; Allen, Theresa M.; Thompson, David H.

    2012-01-01

    A family of 3-methoxypoly(ethylene glycol)-vinyl ether-1,2-dioleylglycerol (mPEG-VE-DOG) lipopolymer conjugates, designed on the basis of DFT calculations to possess a wide range of proton affinities, was synthesized and tested for their hydrolysis kinetics in neutral and acidic buffers. Extruded ~100 nm liposomes containing these constructs in ≥90 mol% 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) produced dispersions that retained their calcein cargo for more than 2 days at pH 7.5, but released the encapsulated contents over a wide range of timescales as a function of the electronic properties of the vinyl ether linkage, the solution pH and the mPEG-VE-DOG composition in the membrane. The in vivo performance of two different 90:10 DOPE:mPEG-VE-DOG compositions was also evaluated for blood circulation time and biodistribution in mice, using 125I-tyraminylinulin as a label. The pharmacokinetic profiles gave a T1/2 of 7 h and 3 h for 90:10 DOPE:ST302 and 90:10 DOPE:ST502, respectively, with the liposomes being cleared predominantly by liver and spleen uptake. The behavior of these DOPE:mPEG-VE-DOG formulations is consistent with their relative rates of vinyl ether hydrolysis, i.e., the more acid-sensitive mPEG-VE-DOG derivatives produce faster leakage rates from DOPE:mPEG-VE-DOG liposomes, but decreased the blood circulation times in mice. These findings suggest that the vinyl ether-based PEG-lipid derivatives are promising agents for stabilizing acid-sensitive DOPE liposomes to produce formulations with a priori control over their pH-responsiveness in vitro. Our data also suggest, however, that the same factors that contribute to enhanced acid-sensitivity of the DOPE:mPEG-VE-DOG dispersions are also likely responsible for their reduced pharmacokinetic profiles. PMID:23030381

  10. Acid-labile mPEG-vinyl ether-1,2-dioleylglycerol lipids with tunable pH sensitivity: synthesis and structural effects on hydrolysis rates, DOPE liposome release performance, and pharmacokinetics.

    PubMed

    Shin, Junhwa; Shum, Pochi; Grey, Jessica; Fujiwara, Shin-ichi; Malhotra, Guarov S; González-Bonet, Andres; Hyun, Seok-Hee; Moase, Elaine; Allen, Theresa M; Thompson, David H

    2012-11-01

    A family of 3-methoxypoly(ethylene glycol)-vinyl ether-1,2-dioleylglycerol (mPEG-VE-DOG) lipopolymer conjugates, designed on the basis of DFT calculations to possess a wide range of proton affinities, was synthesized and tested for their hydrolysis kinetics in neutral and acidic buffers. Extruded ∼100 nm liposomes containing these constructs in ≥90 mol % 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) produced dispersions that retained their calcein cargo for more than 2 days at pH 7.5, but released the encapsulated contents over a wide range of time scales as a function of the electronic properties of the vinyl ether linkage, the solution pH, and the mPEG-VE-DOG composition in the membrane. The in vivo performance of two different 90:10 DOPE:mPEG-VE-DOG compositions was also evaluated for blood circulation time and biodistribution in mice, using (125)I-tyraminylinulin as a label. The pharmacokinetic profiles gave a t(1/2) of 7 and 3 h for 90:10 DOPE:ST302 and 90:10 DOPE:ST502, respectively, with the liposomes being cleared predominantly by liver and spleen uptake. The behavior of these DOPE:mPEG-VE-DOG formulations is consistent with their relative rates of vinyl ether hydrolysis, i.e., the more acid-sensitive mPEG-VE-DOG derivatives produced faster leakage rates from DOPE:mPEG-VE-DOG liposomes, but decreased the blood circulation times in mice. These findings suggest that the vinyl ether-based PEG-lipid derivatives are promising agents for stabilizing acid-sensitive DOPE liposomes to produce formulations with a priori control over their pH responsiveness in vitro. Our data also suggest, however, that the same factors that contribute to enhanced acid sensitivity of the DOPE:mPEG-VE-DOG dispersions are also likely responsible for their reduced pharmacokinetic profiles. PMID:23030381

  11. Formation and cleansing performance of bicontinuous microemulsions in water/poly (oxyethylene) alkyl ether/ester-type oil systems.

    PubMed

    Aramaki, Kenji; Tawa, Kosuke; Shrestha, Lok Kumar; Iwanaga, Tetsuro; Kamada, Miho

    2013-01-01

    Phase behaviors in water/poly(oxyethylene) dodecyl ether (C₁₂EO(n), n = 4, 6, 8)/cetyl isooctanoate (CIO) systems were studied. In the C₁₂EO₆ and C₁₂EO₈ systems, self-assembled structures with positive curvatures, such as O/W microemulsions, and micellar cubic and hexagonal phases, were observed. A wider region of a lamellar liquid-crystalline phase, which included a narrow microemulsion region joined by a miscibility gap, was observed in the C₁₂EO₄ system. The structure of the microemulsion phase in the C₁₂EO₄ system was characterized by pulsed-field-gradient NMR (PFG-NMR) and small angle X-ray scattering (SAXS) techniques. PFG-NMR measurements indicated that the structure of the microemulsion was bicontinuous; both water and oil phases were continuous within the microemulsion. Pair-distance distribution function, p (r), and structure factors obtained by Generalized Indirect Fourier Transformation (GIFT) analysis of the SAXS data showed that the microemulsion domain sizes decreased with an increase in the oil content. The structure of the bicontinuous microemulsion was consistent with the results of a detergency test, in which the microemulsion samples were applied to lipstick dirt on an artificial skin plate. Detergency was observed to be better for the microemulsion at lower oil contents because of the larger oil domain size at these low concentrations. PMID:24088518

  12. Multifunctional Poly(methyl vinyl ether-co-maleic anhydride)-graft-hydroxypropyl-β-cyclodextrin Amphiphilic Copolymer as an Oral High-Performance Delivery Carrier of Tacrolimus.

    PubMed

    Zhang, Dong; Pan, Xiaolei; Wang, Shang; Zhai, Yinglei; Guan, Jibin; Fu, Qiang; Hao, Xiaoli; Qi, Wanpeng; Wang, Yingli; Lian, He; Liu, Xiaohong; Wang, Yongjun; Sun, Yinghua; He, Zhonggui; Sun, Jin

    2015-07-01

    In order to improve oral bioavailability of tacrolimus (FK506), a novel poly(methyl vinyl ether-co-maleic anhydride)-graft-hydroxypropyl-β-cyclodextrin amphiphilic copolymer (CD-PVM/MA) is developed, combining the bioadhesiveness of PVM/MA, P-glycoprotein (P-gp), and cytochrome P450-inhibitory effect of CD into one. The FK506-loaded nanoparticles (CD-PVM/MA-NPs) were obtained by solvent evaporation method. The physiochemical properties and intestinal absorption mechanism of FK506-loaded CD-PVM/MA-NPs were characterized, and the pharmacokinetic behavior was investigated in rats. FK506-loaded CD-PVM/MA-NPs exhibited nanometer-sized particles of 273.7 nm, with encapsulation efficiency as high as 73.3%. FK506-loaded CD-PVM/MA-NPs maintained structural stability in the simulated gastric fluid, and about 80% FK506 was released within 24 h in the simulated intestinal fluid. The permeability of FK506 was improved dramatically by CD-PVM/MA-NPs compared to its solution, probably due to the synergistic inhibition effect of P-gp and cytochrome P450 3A (CYP3A). The intestinal biodistribution of fluorescence-labeled CD-PVM/MA-NPs confirmed its good bioadhesion to the rat intestinal wall. Two endocytosis pathways, clathrin- and caveolae-mediated endocytosis, were involved in the cellular uptake of CD-PVM/MA-NPs. The important role of lymphatic transport in nanoparticles' access to the systemic circulation, about half of the contribution to oral bioavailability, was observed in mesenteric lymph duct ligated rats. The AUC0-24 of FK506 loaded in nanoparticles was enhanced up to 20-fold compared to FK506 solutions after oral administration. The present study suggested that the novel multifunctional CD-PVM/MA is a promising efficient oral delivery carrier for FK506, due to its ability in solubilization, inhibitory effects on both P-gp and CYP 3A, high bioadhesion, and sustained release capability. PMID:26024817

  13. Rh(I)-catalyzed transformation of propargyl vinyl ethers into (E,Z)-dienals: stereoelectronic role of trans effect in a metal-mediated pericyclic process and a shift from homogeneous to heterogeneous catalysis during a one-pot reaction.

    PubMed

    Vidhani, Dinesh V; Krafft, Marie E; Alabugin, Igor V

    2014-01-01

    The combination of experiments and computations reveals unusual features of stereoselective Rh(I)-catalyzed transformation of propargyl vinyl ethers into (E,Z)-dienals. The first step, the conversion of propargyl vinyl ethers into allene aldehydes, proceeds under homogeneous conditions via a "cyclization-mediated" mechanism initiated by Rh(I) coordination at the alkyne. This path agrees well with the small experimental effects of substituents on the carbinol carbon. The key feature revealed by the computational study is the stereoelectronic effect of the ligand arrangement at the catalytic center. The rearrangement barriers significantly decrease due to the greater transfer of electron density from the catalytic metal center to the CO ligand oriented trans to the alkyne. This effect increases electrophilicity of the metal and lowers the calculated barriers by 9.0 kcal/mol. Subsequent evolution of the catalyst leads to the in situ formation of Rh(I) nanoclusters that catalyze stereoselective tautomerization. The intermediacy of heterogeneous catalysis by nanoclusters was confirmed by mercury poisoning, temperature-dependent sigmoidal kinetic curves, and dynamic light scattering. The combination of experiments and computations suggests that the initially formed allene-aldehyde product assists in the transformation of a homogeneous catalyst (or "a cocktail of catalysts") into nanoclusters, which in turn catalyze and control the stereochemistry of subsequent transformations. PMID:24304338

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  15. Vinyl stilbazoles

    NASA Technical Reports Server (NTRS)

    Parker, John A. (Inventor); Heimbuch, Alvin H. (Inventor); Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)

    1986-01-01

    Vinyl pyridines including vinyl stilbazole materials and vinyl styrylpyridine oligomer materials are disclosed. These vinylpyridines form copolymers with bismaleimides which copolymers have good fire retardancy and decreased brittleness. The cure temperatures of the copolymers are substantially below the cure temperatures of the bismaleimides alone. Reinforced composites made from the cured copolymers are disclosed as well.

  16. Synthesis of alkenyl sulfides through the iron-catalyzed cross-coupling reaction of vinyl halides with thiols.

    PubMed

    Lin, Yun-Yung; Wang, Yu-Jen; Lin, Che-Hung; Cheng, Jun-Hao; Lee, Chin-Fa

    2012-07-20

    We report here the iron-catalyzed cross-coupling reaction of alkyl vinyl halides with thiols. While many works are devoted to the coupling of thiols with alkyl vinyl iodides, interestingly, the known S-vinylation of vinyl bromides and chlorides is limited to 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene. Investigation on the coupling reaction of challenging alkyl vinyl bromides and chlorides with thiols is rare. Since the coupling of 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene with thiols can be performed in the absence of any catalyst, here we focus on the coupling of thiols with alkyl vinyl halides. This system is generally reactive for alkyl vinyl iodides and bromides to provide the products in good yields. 1-(Chloromethylidene)-4-tert-butyl-cyclohexane was also coupled with thiols, giving the targets in moderate yields. PMID:22708836

  17. Alkylating potential of oxetanes.

    PubMed

    Gómez-Bombarelli, Rafael; Palma, Bernardo Brito; Martins, Célia; Kranendonk, Michel; Rodrigues, Antonio S; Calle, Emilio; Rueff, José; Casado, Julio

    2010-07-19

    Small, highly strained heterocycles are archetypical alkylating agents (oxiranes, beta-lactones, aziridinium, and thiirinium ions). Oxetanes, which are tetragonal ethers, are higher homologues of oxiranes and reduced counterparts of beta-lactones, and would therefore be expected to be active alkylating agents. Oxetanes are widely used in the manufacture of polymers, especially in organic light-emitting diodes (OLEDs), and are present, as a substructure, in compounds such as the widely used antimitotic taxol. Whereas the results of animal tests suggest that trimethylene oxide (TMO), the parent compound, and beta,beta-dimethyloxetane (DMOX) are active carcinogens at the site of injection, no studies have explored the alkylating ability and genotoxicity of oxetanes. This work addresses the issue using a mixed methodology: a kinetic study of the alkylation reaction of 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilicity similar to that of DNA bases, by three oxetanes (TMO, DMOX, and methyloxetanemethanol), and a mutagenicity, genotoxicity, and cell viability study (Salmonella microsome test, BTC E. coli test, alkaline comet assay, and MTT assay). The results suggest either that oxetanes lack genotoxic capacity or that their mode of action is very different from that of epoxides and beta-lactones. PMID:20550097

  18. Vinyl chloride

    Integrated Risk Information System (IRIS)

    Vinyl chloride ; CASRN 75 - 01 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Eff

  19. Vinyl acetate

    Integrated Risk Information System (IRIS)

    Vinyl acetate ; CASRN 108 - 05 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Eff

  20. Vinyl bromide

    Integrated Risk Information System (IRIS)

    Vinyl bromide ; CASRN 593 - 60 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Eff

  1. Rearrangements of Cycloalkenyl Aryl Ethers.

    PubMed

    Törincsi, Mercedesz; Nagy, Melinda; Bihari, Tamás; Stirling, András; Kolonits, Pál; Novak, Lajos

    2016-01-01

    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. PMID:27104504

  2. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-09-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  3. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-05-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  4. Formation of secondary organic aerosol and oligomers from the ozonolysis of enol ethers

    NASA Astrophysics Data System (ADS)

    Sadezky, A.; Chaimbault, P.; Mellouki, A.; Römpp, A.; Winterhalter, R.; Le Bras, G.; Moortgat, G. K.

    2006-06-01

    Formation of secondary organic aerosol has been observed in the gas phase ozonolysis of a series of enol ethers, among them several alkyl vinyl ethers (AVE, ROCH=CH2), such as ethyl, propyl, n-butyl, iso-butyl, t-butyl vinyl ether, and ethyl propenyl ether (EPE, C2H5OCH=CHCH3). The ozonolysis has been studied in a 570 l spherical glass reactor at atmospheric pressure (730 Torr) and temperature (296 K). Gas phase reaction products were investigated by in-situ FTIR spectroscopy, and secondary organic aerosol (SOA) formation was monitored by a scanning mobility particle sizer (SMPS). The chemical composition of the formed SOA was analysed by a hybrid mass spectrometer using electrospray ionization (ESI). The main stable gas phase reaction product is the respective alkyl formate ROC(O)H, formed with yields of 60 to 80%, implying that similar yields of the corresponding Criegee Intermediates (CI) CH2O2 for the AVE and CH3CHO2 for EPE are generated. Measured SOA yields are between 2 to 4% for all enol ethers. Furthermore, SOA formation is strongly reduced or suppressed by the presence of an excess of formic acid, which acts as an efficient CI scavenger. Chemical analysis of the formed SOA by ESI(+)/MS-TOF allows to identify oligomeric compounds in the mass range 200 to 800 u as its major constituents. Repetitive chain units are identified as CH2O2 (mass 46) for the AVE and C2H4O2 (mass 60) for EPE and thus have the same chemical compositions as the respective major Criegee Intermediates formed during ozonolysis of these ethers. The oligomeric structure and chain unit identity are confirmed by HPLC/ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF experiments, whereby successive and systematic loss of a fragment with mass 46 for the AVE (and mass 60 for EPE) is observed. It is proposed that the oligomer has the following basic structure of an oligoperoxide, -[CH(R)-O-O]n-, where R=H for the AVE and R=CH3 for the EPE. Oligoperoxide formation is thus suggested to be another, so far

  5. Formation of secondary organic aerosol and oligomers from the ozonolysis of enol ethers

    NASA Astrophysics Data System (ADS)

    Sadezky, A.; Chaimbault, P.; Mellouki, A.; Römpp, A.; Winterhalter, R.; Le Bras, G.; Moortgat, G. K.

    2006-10-01

    Formation of secondary organic aerosol has been observed in the gas phase ozonolysis of a series of enol ethers, among them several alkyl vinyl ethers (AVE, ROCH=CH2), such as ethyl, propyl, n-butyl, iso-butyl, t-butyl vinyl ether, and ethyl propenyl ether (EPE, C2H5OCH=CHCH3). The ozonolysis has been studied in a 570 l spherical glass reactor at ambient pressure (730 Torr) and room temperature (296 K). Gas phase reaction products were investigated by in-situ FTIR spectroscopy, and secondary organic aerosol (SOA) formation was monitored by a scanning mobility particle sizer (SMPS). The chemical composition of the formed SOA was analysed by a hybrid mass spectrometer using electrospray ionization (ESI). The main stable gas phase reaction product is the respective alkyl formate ROC(O)H, formed with yields of 60 to 80%, implying that similar yields of the corresponding excited Criegee Intermediates (CI) CH2O2 for the AVE and CH3CHO2 for EPE are generated. Measured SOA yields are between 2 to 4% for all enol ethers. Furthermore, SOA formation is strongly reduced or suppressed by the presence of an excess of formic acid, which acts as an efficient CI scavenger. Chemical analysis of the formed SOA by ESI(+)/MS-TOF allows to identify oligomeric compounds in the mass range 200 to 800 u as its major constituents. Repetitive chain units are identified as CH2O2 (mass 46) for the AVE and C2H4O2 (mass 60) for EPE and thus have the same chemical compositions as the respective major Criegee Intermediates formed during ozonolysis of these ethers. The oligomeric structure and chain unit identity are confirmed by HPLC/ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF experiments, whereby successive and systematic loss of a fragment with mass 46 for the AVE (and mass 60 for EPE) is observed. It is proposed that the oligomer has the following basic structure of an oligoperoxide, -[CH(R)-O-O]n-, where R=H for the AVE and R=CH3 for the EPE. Oligoperoxide formation is thus suggested to be another, so

  6. Allene ether Nazarov cyclization.

    PubMed

    Tius, Marcus A

    2014-05-01

    The ease of synthesis and the exceptional reactivity of alkoxyallenes has led to their use in a large number of highly diverse applications. This Report describes their use in various versions of the allene ether Nazarov cyclization. Following a brief introduction to the Nazarov cyclization (Section 1), the oxidative cyclization of vinyl alkoxyallenes is discussed first (Section 2). Nazarov cyclizations of α-alkoxyallenyl vinyl ketones and of α-alkoxyallenyl vinyl tertiary carbinols are covered (Section 3). The discovery and the subsequent rational design of acetals that serve as chiral auxiliaries on the allene in highly enantioselective Nazarov cyclizations is explained (Section 4). Interrupted Nazarov cyclizations of alkoxyallenes that are generated in situ from the isomerization of propargyl ethers on solid supports are discussed, including the evolution of a highly diastereoselective, chiral auxiliary controlled version of the reaction. Some applications of the methodology to natural products total synthesis have been included so as to provide the reader with benchmarks with which to judge the utility of the methodology. PMID:24196585

  7. Light induced controlled release of fragrances by Norrish type II photofragmentation of alkyl phenyl ketones.

    PubMed

    Levrand, Barbara; Herrmann, Andreas

    2002-11-01

    The use of alkyl phenyl ketones as delivery systems for the controlled release of fragrances was investigated by photoirradiation of undegassed solutions with a xenon lamp as well as natural sunlight. A large variety of precursor compounds was prepared efficiently in a few reaction steps from commercially available starting materials. The Norrish type II photofragmentation was found to be the predominant reaction pathway to yield the desired perfumery alkenes and acetophenones in polar and apolar solution. Systematic GC-MS analysis of the irradiated solutions allowed identification of a series of side products that are due to the presence of oxygen. A detailed analysis of the product distribution after irradiation was carried out for a series of 4-alkoxy-1-phenylbutanone derivatives. Besides the expected acetophenones, vinyl ethers and phenylcyclobutanols, the formation of alkyl formates, alcohols and 4-oxo-4-phenylbutanoates was observed. The product distribution as influenced by solvent polarity, precursor concentration and substituent effects was investigated. The utility of alkyl phenyl ketones as precursors for the light induced controlled release of fragrances under natural daylight conditions was also demonstrated. PMID:12659532

  8. Reactions involving shifting of the double bond in cyclic ethers

    SciTech Connect

    Ibatullin, U.G.; Petrushina, T.F.; Akhmadeeva, A.A.; Safarov, M.G.

    1985-09-01

    4-Methylenetetrahydropyran undergoes isomerization to 4-methyl-5,6-dihydropyran in the presence of sodium on aluminum oxide. Both pyrans are converted to a vinyl ether, viz., 4-methyl-2,3-dihydropyran, under the influence of iron pentacarbonyl.

  9. Motor fuel alkylation process utilizing low acid

    SciTech Connect

    Kocal, J.A.; Imai, T.

    1987-01-06

    A process is described for the alkylation of an isoparaffin with an olefin acting agent comprising contacting the isoparaffin with the olefin acting agent at alkylation conditions in the presence of a catalyst. The catalyst consists essentially of an anhydrous, nonalcoholic mixture of from about 5 to 15 wt. % methyl tert-butyl ether and from 85 to 95 wt. % hydrofluoric acid. The volumetric ratio of hydrofluoric acid to isoparaffin and olefin acting agent is less than 0.75.

  10. Reactivity of hydroxy- and aquo(hydroxy)-λ3-iodane-crown ether complexes.

    PubMed

    Miyamoto, Kazunori; Yokota, Yukie; Suefuji, Takashi; Yamaguchi, Kentaro; Ozawa, Tomoyuki; Ochiai, Masahito

    2014-04-25

    We have designed a series of hydroxy(aryl)-λ(3)-iodane-[18]crown-6 complexes, prepared from the corresponding iodosylbenzene derivatives and superacids in the presence of [18]crown-6, and have investigated their reactivities in aqueous media. These activated iodosylbenzene monomers are all non-hygroscopic shelf-storable reagents, but they maintain high oxidizing ability in water. The complexes are effective for the oxidation of phenols, sulfides, olefins, silyl enol ethers, and alkyl(trifluoro)borates under mild conditions. Furthermore, hydroxy-λ(3)-iodane-[18]crown-6 complexes serve as efficient progenitors for the synthesis of diaryl-, vinyl-, and alkynyl-λ(3)-iodanes in water. Other less polar organic solvents, such as methanol, acetonitrile, and dichloromethane, are also usable in some cases. PMID:24644216

  11. An efficient copper-catalyzed cross-coupling reaction of alkyl-triflates with alkyl-Grignard reagents

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A highly efficient method for the formation of C-C covalent bonds by cross-coupling reaction between alkyl-triflates and alkyl-Grignard reagents catalyzed by copper catalyst, Li2CuCl4, is described. The reaction works with most primary triflates in diethyl ether at low temperature within 0.5-3 h an...

  12. Reactivity of vinyl phosphonate containing diazoesters: formation, reactivity, and utility.

    PubMed

    Wang, Jin; Rainier, Jon D

    2015-01-16

    Treatment of diazo vinyl phosphonate with alcohols, amines, and thiols in the presence of Rh(II) results in the chemo- and stereoselective generation of enol ethers, enamines and vinyl sulfides via an X-H insertion process. The utility of the products from these reactions was demonstrated through their conversion into quaternary substituted heterocycles including furans and oxetanes as highlighted by the generation of a bicyclic phosphonate analogue of neodysiherbaine. PMID:25534147

  13. Mono- and Dialkyl Glycerol Ether Lipids in Anaerobic Bacteria: Biosynthetic Insights from the Mesophilic Sulfate Reducer Desulfatibacillum alkenivorans PF2803T

    PubMed Central

    Mollex, Damien; Vinçon-Laugier, Arnauld; Hakil, Florence; Pacton, Muriel; Cravo-Laureau, Cristiana

    2015-01-01

    Bacterial glycerol ether lipids (alkylglycerols) have received increasing attention during the last decades, notably due to their potential role in cell resistance or adaptation to adverse environmental conditions. Major uncertainties remain, however, regarding the origin, biosynthesis, and modes of formation of these uncommon bacterial lipids. We report here the preponderance of monoalkyl- and dialkylglycerols (1-O-alkyl-, 2-O-alkyl-, and 1,2-O-dialkylglycerols) among the hydrolyzed lipids of the marine mesophilic sulfate-reducing proteobacterium Desulfatibacillum alkenivorans PF2803T grown on n-alkenes (pentadec-1-ene or hexadec-1-ene) as the sole carbon and energy source. Alkylglycerols account for one-third to two-thirds of the total cellular lipids (alkylglycerols plus acylglycerols), depending on the growth substrate, with dialkylglycerols contributing to one-fifth to two-fifths of the total ether lipids. The carbon chain distribution of the lipids of D. alkenivorans also depends on that of the substrate, but the chain length and methyl-branching patterns of fatty acids and monoalkyl- and dialkylglycerols are systematically congruent, supporting the idea of a biosynthetic link between the three classes of compounds. Vinyl ethers (1-alken-1′-yl-glycerols, known as plasmalogens) are not detected among the lipids of strain PF2803T. Cultures grown on different (per)deuterated n-alkene, n-alkanol, and n-fatty acid substrates further demonstrate that saturated alkylglycerols are not formed via the reduction of hypothetic alken-1′-yl intermediates. Our results support an unprecedented biosynthetic pathway to monoalkyl/monoacyl- and dialkylglycerols in anaerobic bacteria and suggest that n-alkyl compounds present in the environment can serve as the substrates for supplying the building blocks of ether phospholipids of heterotrophic bacteria. PMID:25724965

  14. Mono- and dialkyl glycerol ether lipids in anaerobic bacteria: biosynthetic insights from the mesophilic sulfate reducer Desulfatibacillum alkenivorans PF2803T.

    PubMed

    Grossi, Vincent; Mollex, Damien; Vinçon-Laugier, Arnauld; Hakil, Florence; Pacton, Muriel; Cravo-Laureau, Cristiana

    2015-05-01

    Bacterial glycerol ether lipids (alkylglycerols) have received increasing attention during the last decades, notably due to their potential role in cell resistance or adaptation to adverse environmental conditions. Major uncertainties remain, however, regarding the origin, biosynthesis, and modes of formation of these uncommon bacterial lipids. We report here the preponderance of monoalkyl- and dialkylglycerols (1-O-alkyl-, 2-O-alkyl-, and 1,2-O-dialkylglycerols) among the hydrolyzed lipids of the marine mesophilic sulfate-reducing proteobacterium Desulfatibacillum alkenivorans PF2803T grown on n-alkenes (pentadec-1-ene or hexadec-1-ene) as the sole carbon and energy source. Alkylglycerols account for one-third to two-thirds of the total cellular lipids (alkylglycerols plus acylglycerols), depending on the growth substrate, with dialkylglycerols contributing to one-fifth to two-fifths of the total ether lipids. The carbon chain distribution of the lipids of D. alkenivorans also depends on that of the substrate, but the chain length and methyl-branching patterns of fatty acids and monoalkyl- and dialkylglycerols are systematically congruent, supporting the idea of a biosynthetic link between the three classes of compounds. Vinyl ethers (1-alken-1'-yl-glycerols, known as plasmalogens) are not detected among the lipids of strain PF2803T. Cultures grown on different (per)deuterated n-alkene, n-alkanol, and n-fatty acid substrates further demonstrate that saturated alkylglycerols are not formed via the reduction of hypothetic alken-1'-yl intermediates. Our results support an unprecedented biosynthetic pathway to monoalkyl/monoacyl- and dialkylglycerols in anaerobic bacteria and suggest that n-alkyl compounds present in the environment can serve as the substrates for supplying the building blocks of ether phospholipids of heterotrophic bacteria. PMID:25724965

  15. Merging Photoredox and Nickel Catalysis: Decarboxylative Cross-Coupling of Carboxylic Acids with Vinyl Halides

    PubMed Central

    2015-01-01

    Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of α-oxy and α-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions. PMID:25521443

  16. Method for making aromatic ethers using diorganoamino pyridinium salt catalyst

    SciTech Connect

    Brunelle, D. J.; Singleton, D. A.

    1985-04-23

    A method is provided for making aromatic ethers by effecting the displacement of reactive radicals on an activated aromatic nucleus such as a phthalimide with a mono or bisalkali metal phenoxide in the presence of an organic solvent and a dialkylamino branched alkyl substituted pyridinium salt as a phase transfer catalyst. Improved yields of bis(aromatic ethers) are achieved without the production of undesirable by-products, such as alkylated phenols.

  17. Catalytic cleavage of ether C-O bonds by pincer iridium complexes.

    PubMed

    Haibach, Michael C; Lease, Nicholas; Goldman, Alan S

    2014-09-15

    The development of efficient catalytic methods to cleave the relatively unreactive C-O bonds of ethers remains an important challenge in catalysis. Building on our group's recent work, we report the dehydroaryloxylation of aryl alkyl ethers using pincer iridium catalysts. This method represents a rare fully atom-economical method for ether C-O bond cleavage. PMID:25060043

  18. Vinyl capped addition polyimides

    NASA Technical Reports Server (NTRS)

    Vannucci, Raymond D. (Inventor); Malarik, Diane C. (Inventor); Delvigs, Peter (Inventor)

    1990-01-01

    Polyimide resins having improved thermo-oxidative stability are provided having aromatic vinyl end-caps. The polyimides are prepared by the reaction of a mixture of monomers comprising (1) a diamine, (2) an ester of tetracarboxylic acid and (3) an aromatic vinyl compound in a molar ratio of 1:2:3 of n: (n + 1):2 when the aromatic vinyl compound contains nitrogen and in a ratio of (n + 1):n:2 when the aromatic vinyl compound does not contain nitrogen, wherein n ranges from about 5 to about 20.

  19. Nickel-Catalyzed Intramolecular C-O Bond Formation: Synthesis of Cyclic Enol Ethers.

    PubMed

    Han, Seo-Jung; Doi, Ryohei; Stoltz, Brian M

    2016-06-20

    An efficient and exceptionally mild intramolecular nickel-catalyzed carbon-oxygen bond-forming reaction between vinyl halides and primary, secondary, and tertiary alcohols has been achieved. Zinc powder was found to be an essential additive for obtaining high catalyst turnover and yields. This operationally simple method allows direct access to cyclic vinyl ethers in high yields in a single step. PMID:27159831

  20. Preparation of vinyl acetate

    DOEpatents

    Tustin, Gerald Charles; Zoeller, Joseph Robert; Depew, Leslie Sharon

    1998-01-01

    This invention pertains to the preparation of vinyl acetate by contacting a mixture of hydrogen and ketene with a heterogeneous catalyst containing a transition metal to produce acetaldehyde, which is then reacted with ketene in the presence of an acid catalyst to produce vinyl acetate.

  1. Preparation of vinyl acetate

    DOEpatents

    Tustin, G.C.; Zoeller, J.R.; Depew, L.S.

    1998-03-24

    This invention pertains to the preparation of vinyl acetate by contacting a mixture of hydrogen and ketene with a heterogeneous catalyst containing a transition metal to produce acetaldehyde, which is then reacted with ketene in the presence of an acid catalyst to produce vinyl acetate.

  2. Certain glycol ethers eliminated from toxic chemical release reporting requirements

    SciTech Connect

    1994-09-01

    Effective June 28, 1994, the U.S. Environmental Protection Agency (EPA) eliminated high molecular weight glycol ethers from the reporting requirements of section 313 of the Emergency Planning and Community Right-To-Know Act of 1986 (EPCRA). EPCRA (42 U.S.C. 11023) is also referred to as Title III of the Superfund Amendments and Reauthorization Act (SARA) of 1986. EPA redefined the glycol ethers category list of chemicals subject to reporting based on an EPA review of available human health data on short-chain glycol ethers. EPA is removing only the surfactant glycol ethers, which are high molecular weight glycol ethers, i.e., those with pendant alkyl groups and that typically have eight or more carbon atoms. The redefinition retains certain glycol ethers (i.e., ethylene glycol ethers where there are 1,2, or 3 repeating ethylene oxide groups) in the category. These are reasonably anticipated to cause adverse human health effects.

  3. Catalytic alkylation apparatus

    SciTech Connect

    Hann, P.D.; VanPool, J.

    1989-09-05

    This patent describes an apparatus. It comprises alkylation reactor means for producing alkylate product; acid catalyst settler means having an upper portion, an intermediate portion and a lower portion; means for withdrawing alkylate product from the alkylation reactor means and for providing alkylate product from the alkylation reactor means to a point of introduction in the intermediate portion of the acid catalyst settler means; and means for establishing a temperature gradient in the upper the gas lines to the detector so that a flow rate of a sample gas passing through the detector is constant.

  4. Pentabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Pentabromodiphenyl ether ; CASRN 32534 - 81 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncar

  5. Hexabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Hexabromodiphenyl ether ; CASRN 36483 - 60 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

  6. Ethyl ether

    Integrated Risk Information System (IRIS)

    Ethyl ether ; CASRN 60 - 29 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  7. Tetrabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Tetrabromodiphenyl ether ; CASRN 40088 - 47 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncar

  8. Nonabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Nonabromodiphenyl ether ; CASRN 63936 - 56 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

  9. Tribromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Tribromodiphenyl ether ; CASRN 49690 - 94 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarci

  10. Octabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Octabromodiphenyl ether ; CASRN 32536 - 52 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

  11. Vinyl capped addition polyimides

    NASA Technical Reports Server (NTRS)

    Vannucci, Raymond D. (Inventor); Malarik, Diane C. (Inventor); Delvigs, Peter (Inventor)

    1991-01-01

    Polyimide resins (PMR) are generally useful where high strength and temperature capabilities are required (at temperatures up to about 700 F). Polyimide resins are particularly useful in applications such as jet engine compressor components, for example, blades, vanes, air seals, air splitters, and engine casing parts. Aromatic vinyl capped addition polyimides are obtained by reacting a diamine, an ester of tetracarboxylic acid, and an aromatic vinyl compound. Low void materials with improved oxidative stability when exposed to 700 F air may be fabricated as fiber reinforced high molecular weight capped polyimide composites. The aromatic vinyl capped polyimides are provided with a more aromatic nature and are more thermally stable than highly aliphatic, norbornenyl-type end-capped polyimides employed in PMR resins. The substitution of aromatic vinyl end-caps for norbornenyl end-caps in addition polyimides results in polymers with improved oxidative stability.

  12. Alkylated lariat ethers as solvent extraction reagents: Surveying the extraction of alkali metals by bis-t-octylbenzo-14-crown-4-acetic acid by use of potentiometric two-phase titration

    SciTech Connect

    Sachleben, R.A.; Moyer, B.A.; Case, F.I.; Garmon, S.A.

    1993-01-01

    Two-phase potentiometric titrimetry was used to survey the extraction of alkali metal cations from aqueous chloride solution by the lipophilic, ionizable lariat ether bis-(t-octylbenzo)-14-crown-4-acetic acid (BOB14C4AA) in o-xylene. Analysis of the data indicates that ion-exchange extraction by the crown-carboxylic acid at low loading (i.e., low conversion of BOB14C4AA to its salt form) is stronger for lithium ion than for the other alkali metals. Little or no selectivity occurs at high loadings. In comparison with the long-chain carboxylic acid 2-methyl-2-heptylnonanoic acid (HMHN), BOB14C4AA extracts lithium and sodium at significantly lower pH; in the loading range of 0.1 to 0.7, the pH shift is 1.4-1.8 pH units for sodium ion and 1.7-2.3 pH units for lithium ion. The titration data are interpreted in terms of aggregated organic-phase species. In the case of lithium extraction, clear evidence was found for a species in which neutral BOB14C4AA participates in the organic-phase complexation of the metal cation.

  13. PROCESS FOR PRODUCING ALKYL ORTHOPHOSPHORIC ACID EXTRACTANTS

    DOEpatents

    Grinstead, R.R.

    1962-01-23

    A process is given for producing superior alkyl orthophosphoric acid extractants for use in solvent extraction methods to recover and purify various metals such as uranium and vanadium. The process comprises slurrying P/sub 2/O/ sub 5/ in a solvent diluent such as kerosene, benzene, isopropyl ether, and the like. An alipbatic alcohol having from nine to seventeen carbon atoms, and w- hcrein ihc OH group is situated inward of the terminal carbon atoms, is added to the slurry while the reaction temperature is mainiained below 60 deg C. The alcohol is added in the mole ratio of about 2 to l, alcohol to P/sub 2/O/sub 5/. A pyrophosphate reaotion product is formed in the slurry-alcohol mixture. Subsequently, the pyrophosphate reaction product is hydrolyzed with dilute mineral acid to produce the desired alkyl orthophosphoric aeid extractant. The extraetant may then be separated and utilized in metal-recovery, solvent- extraction processes. (AEC)

  14. Polygas spells relief from alkylation ills

    SciTech Connect

    Weismantel, G.E.

    1980-06-16

    Tight supplies and soaring prices of isobutane (for olefin alkylation), are causing renewed interest in the olefin ''polymerization'' (i.e., dimerization), route to high-octane gasoline-blending components. Modern polymerization processes, intended to supplement rather than replace alkylation offer considerable energy and capital savings, compared with alkylation-only schemes. In addition to the Institut Francais du Petrole's Dimersol ''polymerization'' tecnique which is already being used or will be used by 1981 in at least five U.S. refineries, with six more units in the planning stage, a low-cost process to ''polymerize'' excess refinery olefins, developed by International Energy Consultants Inc., is nearing commercialization. A third route to process C/sub 3//C/sub 4/ refinery streams with high conversion rates has been proposed by UOP Inc. The low motor octane number (MON) of the product gasoline (approx. 13 numbers lower than a typical alkylate), was recently confirmed in Total Petroleum Inc.'s studies, but Good Hope Refineries Inc. plans to increase its polymer gasoline MON by adding methyl tert.-butyl ether.

  15. The direct polymerization of vinyl alcohol and vinyl alcohol derivatives

    SciTech Connect

    Novak, B.M.; Cederstav, A.K.

    1995-12-01

    The copolymerization of vinyl alcohol with a number of electron deficient olefins is reported. Vinyl alcohol was formed through the acid catalyzed hydrolysis of ketene methyl vinyl acetal. Under water starved conditions, the kinetics of tautomerization have a zero order dependence upon the concentration of vinyl alcohol (k{sub obs} = 3.5 x 10{sup -6} M/s). Hence, under these conditions, the half life of vinyl alcohol can be several hours at room temperature. We found that this meta-stable species could be quantitatively polymerized in a copolymerization (AIBN, h{upsilon}, -10 to 25{degrees}C) with maleic anhydride, maleimide or acrylonitrile.

  16. Vintage Vinyl Record Design

    ERIC Educational Resources Information Center

    Sacco, Michael

    2008-01-01

    In this article, the author describes a project in which his ninth-grade art students utilized a vinyl record as an unusual medium to create a work that exhibited solid design, great creativity, and strong craftsmanship. Students presented their pieces to the class for critique, explained the process, the media, and their feelings about their…

  17. A Caenorhabditis elegans model for ether lipid biosynthesis and function[S

    PubMed Central

    Shi, Xun; Tarazona, Pablo; Brock, Trisha J.; Browse, John; Feussner, Ivo; Watts, Jennifer L.

    2016-01-01

    Ether lipids are widespread in nature, and they are structurally and functionally important components of membranes. The roundworm, Caenorhabditis elegans, synthesizes numerous lipid species containing alkyl and alkenyl ether bonds. We isolated C. elegans strains carrying loss-of-function mutations in three genes encoding the proteins required for the initial three steps in the ether lipid biosynthetic pathway, FARD-1/FAR1, ACL-7/GNPAT, and ADS-1/AGPS. Analysis of the mutant strains show that they lack ether lipids, but possess the ability to alter their lipid composition in response to lack of ether lipids. We found that increases in de novo fatty acid synthesis and reduction of stearoyl- and palmitoyl-CoA desaturase activity, processes that are at least partially regulated transcriptionally, mediate the altered lipid composition in ether lipid-deficient mutants. Phenotypic analysis demonstrated the importance of ether lipids for optimal fertility, lifespan, survival at cold temperatures, and resistance to oxidative stress.Caenorhabditis PMID:26685325

  18. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... borosilicate flask, and for each gram of sample add 3 milliliters of solvent previously heated to 150 °F. Maintain the temperature of the contents of the flask at 150 °F for 2 hours using a hot plate while also maintaining gentle mechanical agitation. Filter the contents of the flask rapidly through No. 42...

  19. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... borosilicate flask, and for each gram of sample add 3 milliliters of solvent previously heated to 150 °F. Maintain the temperature of the contents of the flask at 150 °F for 2 hours using a hot plate while also maintaining gentle mechanical agitation. Filter the contents of the flask rapidly through No. 42...

  20. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... borosilicate flask, and for each gram of sample add 3 milliliters of solvent previously heated to 150 °F. Maintain the temperature of the contents of the flask at 150 °F for 2 hours using a hot plate while also maintaining gentle mechanical agitation. Filter the contents of the flask rapidly through No. 42...

  1. Safety Assessment of Alkyl PEG Sulfosuccinates as Used in Cosmetics.

    PubMed

    Johnson, Wilbur; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2015-09-01

    The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) reviewed the safety of alkyl polyethylene glycol (PEG) sulfosuccinates, which function in cosmetics mostly as surfactants/cleansing agents. Although these ingredients may cause ocular and skin irritation, dermal penetration is unlikely because of the substantial polarity and molecular size of these ingredients. The Panel considered the negative oral carcinogenicity and reproductive and developmental toxicity data on chemically related laureths (PEG lauryl ethers) and negative repeated dose toxicity and skin sensitization data on disodium laureth sulfosuccinate supported the safety of these alkyl PEG sulfosuccinates in cosmetic products, but. The CIR Expert Panel concluded that the alkyl PEG sulfosuccinates are safe in the present practices of use and concentration when formulated to be nonirritating. PMID:26362121

  2. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOEpatents

    Smith, Jr., Lawrence A.; Jones, Jr., Edward M.; Hearn, Dennis

    1984-01-01

    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.degree. to 250.degree. 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.

  3. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOEpatents

    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.

  4. Synthesis of amphiphilic 6-carboxypullulan ethers.

    PubMed

    Pereira, Junia M; Mahoney, Michelle; Edgar, Kevin J

    2014-01-16

    Hydrophobically modified polysaccharides that contain carboxyl groups possess exceptional features for drug delivery and other applications. Carboxyl groups were introduced at C-6 in the pullulan backbone by applying the well-established oxidation with TEMPO and NaOCl/NaBr. The oxidized product, 6-carboxypullulan, is even more water-soluble than pullulan. Consequently, further chemical modifications have been mainly restricted to reactions that can be performed in water or under heterogeneous conditions. We find that the TBA salt of 6-carboxypullulan is soluble in a range of organic solvents and can be reacted homogeneously with various alkyl halides in DMSO and sodium hydroxide at 40 °C to yield 6-carboxypullulan ethers. Complete substitution (DS 7 per trisaccharide repeat unit) was achieved upon reaction with iodoethane, while products from reaction with longer chain alkyl halides (propyl and butyl derivatives) achieved DS up to about 3. The amphiphilic products have impressive surfactant properties. PMID:24188839

  5. Synthesis and Cytotoxicity of Silicon and Germanium Containing Pyridine Oxime O-Ethers

    PubMed Central

    Abele, Edgars; Abele, Ramona; Arsenyan, Pavel; Shestakova, Irina; Kanepe, Iveta; Antonenko, Inga; Popelis, Juris; Lukevics, Edmunds

    2003-01-01

    Silicon and germanium containing pyridine aldoxime, ketoxime and amidoxime O-ethers have been prepared using phase transfer catalytic systems oxime alkyl halide solid KOH 18-crown-6 benzene and oxime alkyl halide solid K2CO3 or Cs2CO3 18-crown-6 toluene. Cytotoxic activity of silicon and germanium containing pyridine oxime O-ethers was tested in vitro on two monolayer tumor cell lines: MG- 22A (mouse hepatoma) and HT-1080 (human fibrosarcoma). O-[3-Yriethylsilylpropyl]- and O-[3-(1-methyl- 1-silacyclopentyl)propyl] oximes of pyridine aldehydes and ketones exhibit high cytotoxicity. Presence of methyl group in the pyridine ring considerably decreased activity of amidoxime O-ethers. Oxime ethers containing two elements are essentially inactive. For 2-acetylpyridine oxime ethers the activity increases in order of alkyl substituents: Et3GeCH2CH2SiMe2CH2 < Et3SiCH2CH2CH2 < (CH2)4SiCH2CH2CH2. Cytotoxicity of ketoxime O-ethers is considerably lower in comparison with aldoxime O-ethers. PMID:18365061

  6. KOAc-promoted alkynylation of α-C-H bonds of ethers with alkynyl bromides under transition-metal-free conditions.

    PubMed

    Zhang, Jiajun; Li, Pinhua; Wang, Lei

    2014-05-14

    A novel KOAc-promoted α-position C-H activation and alkynylation of ethers with alkynyl bromides to 2-alkynyl ethers has been developed under transition-metal-free and simple reaction conditions. In addition, this methodology can also be extended to the vinylation of ethers with vinyl bromides in excellent regio- and stereo-selectivity. A wide range of direct C(sp)-C(sp(3)) and C(sp(2))-C(sp(3)) bonds has been formed through this protocol, which offers a new and alternative route. PMID:24691678

  7. 21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies may be obtained from the Office of... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethylene-vinyl acetate-vinyl alcohol copolymers... acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No....

  8. 21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies may be obtained from the Office of Food... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethylene-vinyl acetate-vinyl alcohol copolymers... acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No....

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

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  10. Metal-catalyzed activation of ethers via C-O bond cleavage: a new strategy for molecular diversity.

    PubMed

    Cornella, Josep; Zarate, Cayetana; Martin, Ruben

    2014-12-01

    In 1979, the seminal work of Wenkert set the standards for the utilization of aryl and vinyl ethers as coupling partners via C-O bond-cleavage. Although the topic remained dormant for almost three decades, the last few years have witnessed a renaissance in this area of expertise, experiencing an exponential growth and becoming a significant discipline within the cross-coupling arena. The means to utilize readily accessible aryl or vinyl ethers as counterparts does not only represent a practical, powerful and straightforward alternative to organic halides, but also constitutes an excellent opportunity to improve our chemical knowledge about a relatively unexplored area of expertise. This review summarizes the most significant developments in the area of C-O bond-cleavage when employing aryl or vinyl ethers, providing a detailed overview of the current state of the art and including future aspects, when applicable. PMID:25157613

  11. A novel biobased plasticizer of epoxidized cardanol glycidylether: Synthesis and application in soft poly(vinyl chloride) films

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A novel plasticizer derived from cardanol, epoxied cardanol glycidyl ether (ECGE), was synthesized and characterized by 1H-NMR and 13C-NMR. Effects of the ECGE combined with dioctyl phthalate (DOP), a commercial plasticizer, in soft poly(vinyl chloride) (PVC) films were studied. Dynamic mechanical a...

  12. Rhodium(III)-catalyzed C-H activation/annulation with vinyl esters as an acetylene equivalent.

    PubMed

    Webb, Nicola J; Marsden, Stephen P; Raw, Steven A

    2014-09-19

    The behavior of electron-rich alkenes in rhodium-catalyzed C-H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed. PMID:25165993

  13. Thermolysis of phenethyl phenyl ether: A model of ether linkages in low rank coal

    SciTech Connect

    Britt, P.F.; Buchanan, A.C. III; Malcolm, E.A.

    1994-09-01

    Currently, an area of interest and frustration for coal chemists has been the direct liquefaction of low rank coal. Although low rank coals are more reactive than bituminous coals, they are more difficult to liquefy and offer lower liquefaction yields under conditions optimized for bituminous coals. Solomon, Serio, and co-workers have shown that: in the pyrolysis and liquefaction of low rank coals, a low temperature cross-linking reaction associated with oxygen functional groups occurs before tar evolution. A variety of pretreatments (demineralization, alkylation, and ion-exchange) have been shown to reduce these retrogressive reactions and increase tar yields, but the actual chemical reactions responsible for these processes have not been defined. In order to gain insight into the thermochemical reactions leading to cross-linking in low rank coal, we have undertaken a study of the pyrolysis of oxygen containing coal model compounds. Solid state NMR studies suggest that the alkyl aryl ether linkage may be present in modest amounts in low rank coal. Therefore, in this paper, we will investigate the thermolysis of phenethyl phenyl ether (PPE) as a model of 0-aryl ether linkages found in low rank coal, lignites, and lignin, an evolutionary precursor of coal. Our results have uncovered a new reaction channel that can account for 25% of the products formed. The impact of reaction conditions, including restricted mass transport, on this new reaction pathway and the role of oxygen functional groups in cross-linking reactions will be investigated.

  14. Oxidative acetoxylation of the silyl ethers of ketone enols

    SciTech Connect

    Brunovlenskaya, I.I.; Kusainova, K.M.; Kashin, A.K.

    1988-07-20

    The authors studied the reaction of (dicarboxyiodo)benzenes with the trimethylsilyl ethers of ketone enols having various structures. They also undertook a comparative investigation of the oxidation of these compounds with lead tetraacetate. The reaction of (diacetoxyiodo)benzene with the trimethylsilyl ethers of ketone enols takes place with retention of the (CH/sub 3/)/sub 3/Si group in two directions, i.e., substitution of the vinylic hydrogen or diacetoxylation of the double bond. The reaction can be used for the regioselective synthesis of /alpha/-acetoxy ketones, since the trimethylsilyl group is readily eliminated from the obtained products by the action of fluoride ion or boron trifluoride etherate with the formation of the corresponding substituted ketones.

  15. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether

    PubMed Central

    Andrews, Ian P.; Kwon, Ohyun

    2008-01-01

    The palladium-catalyzed hydrostannation of acetylenes is widely exploited in organic synthesis as a means of forming vinyl stannanes for use in palladium-catalyzed cross-coupling reactions. Application of this methodology to ethyl ethynyl ether results in an enol ether that is challenging to isolate from the crude reaction mixture because of incompatibility with typical silica gel chromatography. Reported here is a highly efficient procedure for the palladium-catalyzed hydrostannation of ethyl ethynyl ether using 0.1% palladium(0) catalyst and 1.0 equiv of tributyltin hydride. The product obtained is a mixture of regioisomers that can be carried forward with exclusive reaction of the β-isomer. This method is highly reproducible; relative to previously reported procedures, it is more economical and involves a more facile purification procedure. PMID:20011027

  16. Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

    PubMed Central

    2015-01-01

    Although transfer of electrophilic alkoxyl (“RO+”) from organic peroxides to organometallics offers a complement to traditional methods for etherification, application has been limited by constraints associated with peroxide reactivity and stability. We now demonstrate that readily prepared tetrahydropyranyl monoperoxyacetals react with sp3 and sp2 organolithium and organomagnesium reagents to furnish moderate to high yields of ethers. The method is successfully applied to the synthesis of alkyl, alkenyl, aryl, heteroaryl, and cyclopropyl ethers, mixed O,O-acetals, and S,S,O-orthoesters. In contrast to reactions of dialkyl and alkyl/silyl peroxides, the displacements of monoperoxyacetals provide no evidence for alkoxy radical intermediates. At the same time, the high yields observed for transfer of primary, secondary, or tertiary alkoxides, the latter involving attack on neopentyl oxygen, are inconsistent with an SN2 mechanism. Theoretical studies suggest a mechanism involving Lewis acid promoted insertion of organometallics into the O–O bond. PMID:26560686

  17. Studies Update Vinyl Chloride Hazards.

    ERIC Educational Resources Information Center

    Rawls, Rebecca

    1980-01-01

    Extensive study affirms that vinyl chloride is a potent animal carcinogen. Epidemiological studies show elevated rates of human cancers in association with extended contact with the compound. (Author/RE)

  18. Boost refining profits by converting surplus butadiene to valuable feedstocks for MTBE and/or alkylation

    SciTech Connect

    Nocca, J.L. ); Hennico, A.; Cosyns, J.; Torck, B. )

    1994-01-01

    Ethylene plants produce a C4 butadiene-rich cut as a by-product. Although it has been a highly valued chemical intermediate for a long time, butadiene is now in over supply due to the installation of new steam cracking plants and the growing use of naphtha, the main butadiene generator, as feedstock. In the meantime, the demand for alkylate and ethers has increased steadily to produce environmentally friendly gasoline. This paper presents processes developed by IFP to convert surplus butadiene into ethers or alkylate for gasoline production. The first process transforms the butadiene-rich stream into a butenes-rich stream, an ideal alkylation feedstock. The second process generates isobutene from the butenes stream by skeletal isomerization for MTBE production.

  19. Copper-assisted nickel catalyzed ligand-free C(sp2)-O cross-coupling of vinyl halides and phenols.

    PubMed

    Kundu, Debasish; Maity, Pintu; Ranu, Brindaban C

    2014-02-21

    A convenient and efficient protocol has been achieved for the cross-coupling of phenols and vinyl halides by a unique Ni/Cu catalytic system for the first time, where the reaction is catalyzed by Ni and Cu is involved in the transmetalation process. This procedure provides an easy access to a library of aryl-vinyl and aryl-styrenyl ethers. PMID:24502267

  20. Palladium-Catalyzed Decarbonylative Dehydration for the Synthesis of α-Vinyl Carbonyl Compounds and Total Synthesis of (-)-Aspewentins A, B, and C.

    PubMed

    Liu, Yiyang; Virgil, Scott C; Grubbs, Robert H; Stoltz, Brian M

    2015-09-28

    The direct α-vinylation of carbonyl compounds to form a quaternary stereocenter is a challenging transformation. It was discovered that δ-oxocarboxylic acids can serve as masked vinyl compounds and be unveiled by palladium-catalyzed decarbonylative dehydration. The carboxylic acids are readily available through enantioselective acrylate addition or asymmetric allylic alkylation. A variety of α-vinyl quaternary carbonyl compounds are obtained in good yields, and an application in the first enantioselective total synthesis of (-)-aspewentins A, B, and C is demonstrated. PMID:26230413

  1. Crown ethers in graphene

    SciTech Connect

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I.; Gallego, Nidia C.; Pantelides, Sokrates T.; Pennycook, Stephen J.; Moyer, Bruce A.; Chisholm, Matthew F.

    2014-11-13

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basic structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.

  2. Crown ethers in graphene

    DOE PAGESBeta

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I.; Gallego, Nidia C.; Pantelides, Sokrates T.; Pennycook, Stephen J.; Moyer, Bruce A.; Chisholm, Matthew F.

    2014-11-13

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basicmore » structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.« less

  3. Crown ethers in graphene

    NASA Astrophysics Data System (ADS)

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I.; Gallego, Nidia C.; Pantelides, Sokrates T.; Pennycook, Stephen J.; Moyer, Bruce A.; Chisholm, Matthew F.

    2014-11-01

    Crown ethers are at their most basic level rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted attention for their ability to selectively incorporate various atoms or molecules within the cavity formed by the ring. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity. Here we present atomic-resolution images of the same basic structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar. First-principles calculations show that the close similarity of the structures should also extend to their selectivity towards specific metal cations. Crown ethers in graphene offer a simple environment that can be systematically tested and modelled. Thus, we expect that our finding will introduce a new wave of investigations and applications of chemically functionalized graphene.

  4. Stereospecific Ni-Catalyzed Cross-Coupling of Potassium Alkenyltrifluoroborates with Alkyl Halides

    PubMed Central

    2015-01-01

    A general method for the alkenylation of alkyl electrophiles using nearly stoichiometric amounts of the air- and moisture-stable potassium organotrifluoroborates has been developed. Various functional groups were tolerated on both the nucleophilic and electrophilic partner. Reactions of highly substituted E- and Z-alkenyltrifluoroborates, as well as vinyl- and propenyltrifluoroborates, were successful, and no loss of stereochemistry or regiochemistry was observed. PMID:24666316

  5. Method of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-09-14

    Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about 70.degree. C. to about 120.degree. C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.

  6. Synthesis and Antioxidant Activity of Alkyl Nitroderivatives of Hydroxytyrosol.

    PubMed

    Gallardo, Elena; Palma-Valdés, Rocío; Sarriá, Beatriz; Gallardo, Irene; de la Cruz, José P; Bravo, Laura; Mateos, Raquel; Espartero, José L

    2016-01-01

    A series of alkyl nitrohydroxytyrosyl ether derivatives has been synthesized from free hydroxytyrosol (HT), the natural olive oil phenol, in order to increase the assortment of compounds with potential neuroprotective activity in Parkinson's disease. In this work, the antioxidant activity of these novel compounds has been evaluated using Ferric Reducing Antioxidant Power (FRAP), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), and Oxygen Radical Scavenging Capacity (ORAC) assays compared to that of nitrohydroxytyrosol (NO₂HT) and free HT. New compounds showed variable antioxidant activity depending on the alkyl side chain length; compounds with short chains (2-4 carbon atoms) maintained or even improved the antioxidant activity compared to NO₂HT and/or HT, whereas those with longer side chains (6-8 carbon atoms) showed lower activity than NO₂HT but higher than HT. PMID:27213306

  7. 46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34 Section 151.50-34 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-34 Vinyl chloride (vinyl chloride monomer). (a)...

  8. Palladium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Vinyl Aziridines with Nitrogen Heterocycles: Rapid Access to Biologically Active Pyrroles and Indoles

    PubMed Central

    Trost, Barry M.; Osipov, Maksim; Dong, Guangbin

    2010-01-01

    We report that nitrogen heterocycles can serve as competent nucleophiles in the palladium-catalyzed dynamic kinetic asymmetric alkylation of vinyl aziridines. The resulting alkylated products were obtained with high regio-, chemo-, and enantioselectivity. Both substituted 1H-pyrroles and 1H-indoles were successfully employed to give exclusively the branched N-alkylated products. The synthetic utility of this process was demonstrated by applying this method to the preparation of several medicinal chemistry lead compounds and bromopyrrole alkaloids including longamide B, longamide B methyl ester, hanishin, agesamides A and B, and cyclooroidin. PMID:20949972

  9. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  10. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  11. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  12. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  13. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  14. Microbial reductive dehalogenation of vinyl chloride

    DOEpatents

    Spormann, Alfred M [Stanford, CA; Muller, Jochen A [Baltimore, MD; Rosner, Bettina M [Berlin, DE; Von Abendroth, Gregory [Mannheim, DE; Meshulam-Simon, Galit [Los Angeles, CA; McCarty, Perry L [Stanford, CA

    2014-02-11

    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.

  15. Microbial reductive dehalogenation of vinyl chloride

    DOEpatents

    Spormann, Alfred M.; Muller, Jochen A.; Rosner, Bettina M.; Von Abendroth, Gregory; Meshulam-Simon, Galit; McCarty, Perry L

    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.

  16. INTRAVENOUS ETHER ANESTHESIA

    PubMed Central

    Eger, Edmond I.; Johnson, Edward A.

    1963-01-01

    From a study of intravenous ether anesthesia, it was concluded that ether diluted to a 5 per cent solution in 5 per cent dextrose and water may be used to induce and maintain a smooth and easily controlled anesthetic state similar to that obtained with inhalation ether but without the dependence of the latter technique on ventilation. Cough and laryngospasm were absent. Adequate spontaneous respiration can be maintained with this technique. The technique is particularly useful in endoscopy during which the airway is often not available for anesthetic administration. PMID:14051486

  17. Genotoxicity of glycol ethers.

    PubMed Central

    McGregor, D B

    1984-01-01

    The genetic toxicology of glycol ethers is reviewed. Ethylene glycol monomethyl ether (EGME) and diglyme have been more extensively studied than other members of this series. Most results indicate a lack of genotoxic potential, but certain tests have yielded positive responses with certain compounds. Ethylene glycol monoethyl ether (EGEE) induced sister chromatid exchanges and chromosomal aberrations in cultured cells. Both EGME and diglyme induced mouse sperm head morphological changes, male rat weak dominant lethal mutations and marked, but reversible, loss of male rat fertility. PMID:6541999

  18. Catalytic oxidation of dimethyl ether

    DOEpatents

    Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

    2016-05-10

    A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

  19. Synthesis and Evaluation of Alpha-Hydroxy Ethers as Potential Biodiesel Additives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Several novel alpha-hydroxy ethers were synthesized by treatment of alkyl 9,10-epoxystearates with a number of alcohols in the presence of acid catalyst in good yield from oleic acid. The low temperature behavior of each material was analyzed through cloud point (CP) and pour point (PP) determinati...

  20. Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

    PubMed Central

    Malysheva, Svetlana F; Artem’ev, Alexander V; Gusarova, Nina K; Belogorlova, Nataliya A; Albanov, Alexander I; Liu, C W

    2015-01-01

    Summary Secondary phosphine oxides react with vinyl sulfides (both alkyl- and aryl-substituted sulfides) under aerobic and solvent-free conditions (80 °C, air, 7–30 h) to afford 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides in 70–93% yields. PMID:26664618

  1. Polyimides with pendant alkyl groups

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Young, P. R.

    1982-01-01

    The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

  2. CHEMILUMINESCENT MONITOR FOR VINYL CHLORIDE

    EPA Science Inventory

    A monitor for vinyl chloride monomer (VCM) in ambient air was constructed using commercially available components of a gas chromatograph (GC) coupled with a chemiluminescence ozone analyzer slightly modified to make it suitable for use as a GC detector. The specificity for VCM is...

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

    SciTech Connect

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

    1988-01-01

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

  4. Serum albumin as a probe for testing the selectivity of irreversible cysteine protease inhibitors: The case of vinyl sulfones.

    PubMed

    Regazzoni, Luca; Colombo, Simone; Mazzolari, Angelica; Vistoli, Giulio; Carini, Marina

    2016-05-30

    Vinyl sulfones are used for drug design of irreversible inhibitors of cysteine proteases since they are able to alkylate cysteine thiols inside the catalytic pocket of this class of enzymes. Some authors have reported the lack of reactivity towards glutathione as sufficient evidence of the selectivity of such a mechanism. Herein, we demonstrate that some simple molecules containing a vinyl sulfone moiety are not thiol-specific alkylants since they react with some albumin nucleophiles including side chains of Cys34 and His146. Such side-reactions are not desirable for any drug candidate since they limit serum stability, bioavailability and they possibly trigger toxicity mechanisms. In silico predictions, indicate that the compounds tested share similar structural features with reported inhibitors of cysteine proteases, as well as similar poses around the main albumin nucleophiles. Altogether, the data suggest that albumin is better than glutathione for the setup of early in vitro tests probing the selectivity of cysteine protease inhibitors. PMID:26970985

  5. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  6. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  7. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  8. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  9. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  10. Alkylation and acylation of cyclotriphosphazenes.

    PubMed

    Benson, Mark A; Zacchini, Stefano; Boomishankar, Ramamoorthy; Chan, Yuri; Steiner, Alexander

    2007-08-20

    Phosphazenes (RNH)6P3N3 (R = n-propyl, isobutyl, isopropyl, cyclohexyl, tert-butyl, benzyl) are readily alkylated at ring N sites by alkyl halides forming N-alkyl phosphazenium cations. Alkylation of two ring N sites occurred after prolonged heating in the presence of methyl iodide or immediately at room temperature with methyl triflate yielding N,N'-dimethyl phosphazenium dications. Geminal dichloro derivatives Cl2(RNH)4P3N3 are methylated by methyl iodide at the ring N site adjacent to both P centers carrying four RNH groups. X-ray crystal structures showed that the alkylation of ring N sites leads to substantial elongation of the associated P-N bonds. Both N-alkyl and N,N'-dialkyl phosphazenium salts form complex supramolecular networks in the solid state via NH...X interactions. Systems carrying less-bulky RNH groups show additional NH...N bonds between N-alkyl phosphazenium ions. N-Alkyl phosphazenium halides form complexes with silver ions upon treatment with silver nitrate. Depending on the steric demand of RNH substituents, either one or both of the vacant ring N sites engage in coordination to silver ions. Treatment of (RNH)6P3N3 (R = isopropyl) with acetyl chloride and benzoyl chloride, respectively, yielded N-acyl phosphazenium ions. X-ray crystal structures revealed that elongation of P-N bonds adjacent to the acylated ring N site is more pronounced than it is in the case of N-alkylated species. Salts containing N-alkyl phosphazenium ions are stable toward water and other mild nucleophiles, while N,N'-dialkyl and N-acyl phosphazenium salts are readily hydrolyzed. The reaction of (RNH)6P3N3 with bromoacetic acid led to N-alkylation at one ring N site in addition to formation of an amide via condensation of an adjacent RNH substituent with the carboxylic acid group. The resulting bromide salt contains mono cations of composition (RNH)5P3N3CH2CONR in which a CH2-C(O) unit is embedded between a ring N and an exocyclic N site of the phosphazene. PMID

  11. In vivo biocompatibility studies of poly( n-vinyl 2-pyrrolidone/itaconic acid) hydrogels synthesized by γ-rays

    NASA Astrophysics Data System (ADS)

    Özdemir, S.; Özdemir, E.; Tunca, R.; Hazıroǧlu, R.; Şen, M.; Kantoǧlu, Ö.; Güven, O.

    2003-08-01

    In this study, poly( n-vinyl 2-pyrrolidone/itaconic acid) hydrogels have been synthesized by γ-rays in different compositions and their biocompatibility have been investigated as in vivo and some biochemical parameters of mice serum and histology of their tissues have been examined. By these purposes, poly( n-vinyl 2-pyrrolidone/itaconic acid) (P(VP/IA)) hydrogels were implanted to hypersensitive mice (BALB/c). One and a half months after implantation, hydrogel implanted animals were sacrificed by ether anesthesia and the area hydrogel contacted with tissue was investigated by light microscope for histopathological identification of the tissue. Then the total immunoglobulin E (IgE) level was determined by ELISA. Differential white cell count was also made to better understanding of reaction between hydrogel and tissue. These poly( n-vinyl 2-pyrrolidone/itaconic acid) hydrogels can be directly used as biomedical materials.

  12. Aqueous DMSO Mediated Conversion of (2-(Arylsulfonyl)vinyl)iodonium Salts to Aldehydes and Vinyl Chlorides.

    PubMed

    Zawia, Eman; Moran, Wesley J

    2016-01-01

    Vinyl(aryl)iodonium salts are useful compounds in organic synthesis but they are under-utilized and their chemistry is under-developed. Herein is described the solvolysis of some vinyl(phenyl)iodonium salts, bearing an arylsulfonyl group, in aqueous DMSO leading to aldehyde formation. This unusual process is selective and operates under ambient conditions. Furthermore, the addition of aqueous HCl and DMSO to these vinyl(aryl)iodonium salts allows their facile conversion to vinyl chlorides. PMID:27537866

  13. Bio-based alternative to the diglycidyl ether of bisphenol A with controlled materials properties.

    PubMed

    Maiorana, Anthony; Spinella, Stephen; Gross, Richard A

    2015-03-01

    A series of biobased epoxy monomers were prepared from diphenolic acid (DPA) by transforming the free acid into n-alkyl esters and the phenolic hydroxyl groups into diglycidyl ethers. NMR experiments confirmed that the diglycidyl ethers of diphenolates (DGEDP) with methyl and ethyl esters have 6 and 3 mol % of glycidyl ester. Increasing the chain length of DGEDP n-alkyl esters from methyl to n-pentyl resulted in large decreases in epoxy resin viscosity (700-to-11 Pa·s). Storage modulus of DPA epoxy resins, cured with isophorone diamine, also varied with n-alkyl ester chain length (e.g., 3300 and 2100 MPa for the methyl and n-pentyl esters). The alpha transition temperature of the cured materials showed a linear decrease from 158 to 86 °C as the ester length increases. The Young's modulus and tensile strengths were about 1150 and 40 MPa, respectively, for all the cured resins tested (including DGEBA) and varied little as a function of ester length. Degree of cure for the different epoxy resins, determined by FTIR and DSC, closely approached the theoretical maximum. The result of this work demonstrates that diglycidyl ethers of n-alkyl diphenolates represent a new family of biobased liquid epoxy resins that, when cured, have similar properties to those from DGEBA. PMID:25633466

  14. Ruthenium Vinyl Carbene Intermediates in Enyne Metathesis

    PubMed Central

    Diver, Steven T.

    2009-01-01

    This review provides an overview of ruthenium vinyl carbene reactivity as it relates to enyne metathesis. Methods for the synthesis of metathesis-active and metathesis-inactive complexes are also summarized. Some of the early hypotheses about vinyl carbene intermediates in enyne metatheses were tested in the arena of synthetic chemistry and subsequently led to mechanistic studies. In these two areas, studies from the author's labs are described. There are still many unresolved questions in enyne metathesis that trace back to vinyl carbene reactivity. Hopefully this review will stimulate further investigation into vinyl carbene reactivity which should further refine our understanding of catalytic enyne metathesis. PMID:19590747

  15. Triethylene glycol monoethyl ether

    Integrated Risk Information System (IRIS)

    Triethylene glycol monoethyl ether ; CASRN 112 - 50 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  16. Triethylene glycol monobutyl ether

    Integrated Risk Information System (IRIS)

    Triethylene glycol monobutyl ether ; CASRN 143 - 22 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  17. Propylene glycol monoethyl ether

    Integrated Risk Information System (IRIS)

    Propylene glycol monoethyl ether ; CASRN 52125 - 53 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  18. p-Bromodiphenyl ether

    Integrated Risk Information System (IRIS)

    p - Bromodiphenyl ether ; CASRN 101 - 55 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcin

  19. Chloromethyl methyl ether (CMME)

    Integrated Risk Information System (IRIS)

    Chloromethyl methyl ether ( CMME ) ; CASRN 107 - 30 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  20. Synthesis and biological evaluation of arctigenin ester and ether derivatives as activators of AMPK.

    PubMed

    Shen, Sida; Zhuang, Jingjing; Chen, Yijia; Lei, Min; Chen, Jing; Shen, Xu; Hu, Lihong

    2013-07-01

    A series of new arctigenin and 9-deoxy-arctigenin derivatives bearing different ester and ether side chains at the phenolic hydroxyl positions are designed, synthesized, and evaluated for activating AMPK potency in L6 myoblasts. Initial biological evaluation indicates that some alkyl ester and phenethyl ether arctigenin derivatives display potential activities in AMPK phosphorylation improvement. Further structure-activity relationship analysis shows that arctigenin ester derivatives 3a, 3h and 9-deoxy-arctigenin phenethyl ether derivatives 6a, 6c, 6d activate AMPK more potently than arctigenin. Moreover, the 2-(3,4-dimethoxyphenyl)ethyl ether moiety of 6c has been demonstrated as a potential functional group to improve the effect of AMPK phosphorylation. The structural optimization of arctigenin leads to the identification of 6c as a promising lead compound that exhibits excellent activity in AMPK activation. PMID:23673223

  1. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    SciTech Connect

    Vicic, David A

    2009-08-10

    Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride

  2. Intermolecular Photocatalyzed Heck-like Coupling of Unactivated Alkyl Bromides by a Dinuclear Gold Complex.

    PubMed

    Xie, Jin; Li, Jian; Weingand, Vanessa; Rudolph, Matthias; Hashmi, A Stephen K

    2016-08-26

    A practical protocol for a photocatalyzed alkyl-Heck-like reaction of unactivated alkyl bromides and different alkenes promoted by dinuclear gold photoredox catalysis in the presence of an inorganic base is reported. Primary, secondary, and tertiary unactivated alkyl bromides with β-hydrogen can be applied. Esters, aldehydes, ketones, nitriles, alcohols, heterocycles, alkynes, alkenes, ethers, and halogen moieties are all well tolerated. In addition to 1,1-diarylalkenes, silylenolethers and enamides can also be applied, which further increases the synthetic potential of the reaction. The mild reaction conditions, broad substrate scope, and an excellent functional-group tolerance deliver an ideal tool for synthetic chemists that can even be used for challenging late-stage modifications of complex natural products. PMID:27348503

  3. Propenyl ether monomers for photopolymerization

    DOEpatents

    Crivello, J.V.

    1996-10-22

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

  4. Propenyl ether monomers for photopolymerization

    DOEpatents

    Crivello, James V.

    1996-01-01

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

  5. Synthesis and Characterization of bis(Tetrahydrofurfuryl) Ether.

    PubMed

    Stenger-Smith, John D; Baldwin, Lawrence; Chafin, Andrew; Goodman, Paul A

    2016-08-01

    Despite the availability of a large number of alkyl tetrahydrofurfuryl ethers that have a wide range of applications, pure bis(tetrahydrofurfuryl) ether (BTHFE) has not been previously synthesized. Here, we report the synthesis of BTHFE (consisting of the RR, SS, and meso stereoisomers) at greater than 99 % purity from tetrahydrofurfuryl alcohol, using (tetrahydrofuran-2-yl)methyl methanesulfonate as an intermediate. Additionally, we demonstrate that BTHFE can be used as a non-volatile solvent in poly(3,4-propylenedioxythiophene)-based supercapacitors. Supercapacitor devices employing solutions of the ionic liquid 1-ethyl-3-methyl-imidizolium bis(trifluoromethylsulfonyl)imide in BTHFE display similar performances to those prepared by using the neat ionic liquid as an electrolyte, although solution-based devices exhibit a somewhat higher resistance. PMID:27547636

  6. Synthesis and Characterization of bis(Tetrahydrofurfuryl) Ether

    PubMed Central

    Stenger‐Smith, John D.; Baldwin, Lawrence; Chafin, Andrew

    2016-01-01

    Abstract Despite the availability of a large number of alkyl tetrahydrofurfuryl ethers that have a wide range of applications, pure bis(tetrahydrofurfuryl) ether (BTHFE) has not been previously synthesized. Here, we report the synthesis of BTHFE (consisting of the RR, SS, and meso stereoisomers) at greater than 99 % purity from tetrahydrofurfuryl alcohol, using (tetrahydrofuran‐2‐yl)methyl methanesulfonate as an intermediate. Additionally, we demonstrate that BTHFE can be used as a non‐volatile solvent in poly(3,4‐propylenedioxythiophene)‐based supercapacitors. Supercapacitor devices employing solutions of the ionic liquid 1‐ethyl‐3‐methyl‐imidizolium bis(trifluoromethylsulfonyl)imide in BTHFE display similar performances to those prepared by using the neat ionic liquid as an electrolyte, although solution‐based devices exhibit a somewhat higher resistance. PMID:27547636

  7. Anodic polymerization of vinyl ethylene carbonate in Li-Ion battery electrolyte

    SciTech Connect

    Chen, Guoying; Zhuang, Guorong V.; Richardson, Thomas J.; Gao, Liu; Ross Jr., Philip N.

    2005-02-28

    A study of the anodic oxidation of vinyl ethylene carbonate (VEC) was conducted with post-mortem analysis of reaction products by ATR-FTIR and gel permeation chromatography (GPC). The half-wave potential (E1/2) for oxidation of VEC is ca. 3.6 V producing a resistive film on the electrode surface. GPC analysis of the film on a gold electrode produced by anodization of a commercial Li-ion battery electrolyte containing 2 percent VEC at 4.1 V showed the presence of a high molecular weight polymer. IR analysis indicated polycarbonate with alkyl carbonate rings linked by aliphatic methylene and methyl branches.

  8. Catalytic Dealkylation of Ethers to Alcohols on Metal Surfaces.

    PubMed

    Yang, Biao; Lin, Haiping; Miao, Kangjian; Zhu, Pan; Liang, Liangbo; Sun, Kewei; Zhang, Haiming; Fan, Jian; Meunier, Vincent; Li, Youyong; Li, Qing; Chi, Lifeng

    2016-08-16

    On-surface synthesis has prompted much interest in recent years because it provides an alternative strategy for controlling chemical reactions and allows for the direct observation of reaction pathways. Herein, we combined scanning tunneling microscopy and density functional theory to provide extensive evidence for the conversion of alkoxybenzene-containing ethers into alcohols by means of surface synthesis. The reported dealkylation reactions are finely controlled by the annealing parameters, which govern the onset of successive alkyl chains dissociations. Moreover, density functional theory calculations elucidate the details of the reaction pathways, showing that dealkylation reactions are surface-assisted and very different from their homogeneous analogues in solution. PMID:27432690

  9. Glycol Ethers As Groundwater Contaminants

    NASA Astrophysics Data System (ADS)

    Ross, Benjamin; Johannson, Gunnar; Foster, Gregory D.; Eckel, William P.

    1992-01-01

    Ether derivatives of dihydroxy alcohols, which are formed from ethylene or propylene, comprise an important group of groundwater contaminants known as glycol ethers. Compounds in this group are used as solvents, cleaning agents, and emulsifiers in many chemical products and manufacturing operations. Glycol ethers have been associated with a variety of toxic effects, and some compounds in the group are relatively potent teratogens. The limited information available suggests that glycol ethers are contaminants in groundwater, especially in anaerobic plumes emanating from disposal of mixed industrial and household waste. Most methods used to analyze groundwater samples cannot adequately detect μg/? (ppb) concentrations of glycol ethers, and the existing methods perform worst for the most widely used and toxic species. A new method capable of analyzing μg/? concentrations of glycol ethers was recently developed, and its use is recommended for groundwater samples where glycol ethers are likely to be present.

  10. Selective, nickel-catalyzed hydrogenolysis of aryl ethers.

    PubMed

    Sergeev, Alexey G; Hartwig, John F

    2011-04-22

    Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from competing hydrogenolysis of aliphatic C-O bonds and hydrogenation of the arene. Here, we report hydrogenolyses of aromatic C-O bonds in alkyl aryl and diaryl ethers that form exclusively arenes and alcohols. This process is catalyzed by a soluble nickel carbene complex under just 1 bar of hydrogen at temperatures of 80 to 120°C; the relative reactivity of ether substrates scale as Ar-OAr>Ar-OMe>ArCH(2)-OMe (Ar, Aryl; Me, Methyl). Hydrogenolysis of lignin model compounds highlights the potential of this approach for the conversion of refractory aryl ether biopolymers to hydrocarbons. PMID:21512027

  11. 29 CFR 1910.1017 - Vinyl chloride.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 29 Labor 6 2012-07-01 2012-07-01 false Vinyl chloride. 1910.1017 Section 1910.1017 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED) OCCUPATIONAL SAFETY AND HEALTH STANDARDS (CONTINUED) Toxic and Hazardous Substances § 1910.1017 Vinyl chloride. (a) Scope and...

  12. 29 CFR 1915.1017 - Vinyl chloride.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 7 2011-07-01 2011-07-01 false Vinyl chloride. 1915.1017 Section 1915.1017 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1017 Vinyl chloride. Note: The requirements applicable to shipyard employment under this...

  13. 29 CFR 1926.1117 - Vinyl chloride.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 29 Labor 8 2013-07-01 2013-07-01 false Vinyl chloride. 1926.1117 Section 1926.1117 Labor... (CONTINUED) SAFETY AND HEALTH REGULATIONS FOR CONSTRUCTION Toxic and Hazardous Substances § 1926.1117 Vinyl chloride. Note: The requirements applicable to construction work under this section are identical to...

  14. 29 CFR 1915.1017 - Vinyl chloride.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 7 2010-07-01 2010-07-01 false Vinyl chloride. 1915.1017 Section 1915.1017 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1017 Vinyl chloride. Note: The requirements applicable to shipyard employment under this...

  15. 29 CFR 1926.1117 - Vinyl chloride.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 8 2010-07-01 2010-07-01 false Vinyl chloride. 1926.1117 Section 1926.1117 Labor... (CONTINUED) SAFETY AND HEALTH REGULATIONS FOR CONSTRUCTION Toxic and Hazardous Substances § 1926.1117 Vinyl chloride. Note: The requirements applicable to construction work under this section are identical to...

  16. 29 CFR 1926.1117 - Vinyl chloride.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 8 2011-07-01 2011-07-01 false Vinyl chloride. 1926.1117 Section 1926.1117 Labor... (CONTINUED) SAFETY AND HEALTH REGULATIONS FOR CONSTRUCTION Toxic and Hazardous Substances § 1926.1117 Vinyl chloride. Note: The requirements applicable to construction work under this section are identical to...

  17. 29 CFR 1915.1017 - Vinyl chloride.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 29 Labor 7 2012-07-01 2012-07-01 false Vinyl chloride. 1915.1017 Section 1915.1017 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1017 Vinyl chloride. Note: The requirements applicable to shipyard employment under this...

  18. 29 CFR 1915.1017 - Vinyl chloride.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 29 Labor 7 2013-07-01 2013-07-01 false Vinyl chloride. 1915.1017 Section 1915.1017 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1017 Vinyl chloride. Note: The requirements applicable to shipyard employment under this...

  19. 29 CFR 1926.1117 - Vinyl chloride.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 8 2014-07-01 2014-07-01 false Vinyl chloride. 1926.1117 Section 1926.1117 Labor... (CONTINUED) SAFETY AND HEALTH REGULATIONS FOR CONSTRUCTION Toxic and Hazardous Substances § 1926.1117 Vinyl chloride. Note: The requirements applicable to construction work under this section are identical to...

  20. 29 CFR 1915.1017 - Vinyl chloride.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 7 2014-07-01 2014-07-01 false Vinyl chloride. 1915.1017 Section 1915.1017 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1017 Vinyl chloride. Note: The requirements applicable to shipyard employment under this...

  1. 29 CFR 1926.1117 - Vinyl chloride.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 29 Labor 8 2012-07-01 2012-07-01 false Vinyl chloride. 1926.1117 Section 1926.1117 Labor... (CONTINUED) SAFETY AND HEALTH REGULATIONS FOR CONSTRUCTION Toxic and Hazardous Substances § 1926.1117 Vinyl chloride. Note: The requirements applicable to construction work under this section are identical to...

  2. Alkylation of toluene with ethanol

    SciTech Connect

    Walendziewski, J.; Trawczynski, J.

    1996-10-01

    A series of Y and ZSM-5 zeolite based catalysts was prepared. Zeolites were cation exchanged and formed with 50% of aluminum hydroxide as a binder, and the obtained catalysts were finally thermally treated. Activity tests in alkylation of toluene with ethanol were carried out in the temperature range of 325--400 C, in nitrogen or hydrogen stream, and a pressure up to 3 MPa. The feed consisted of toluene and ethanol mixed in a mole ratio 1/1 or 2/1. The obtained results showed that among the studied catalysts the highest activity in the alkylation reaction was attained by ZSM-5 zeolite based catalyst with a moderate acidity and medium silica to alumina ratio, i.e., {approximately}50. Activity and selectivity of the most active catalyst as well as conversion of the feed components were similar to those reported in other papers. The content of p-ethyltoluene in alkylation products attained ca. 60%.

  3. A biological source of oceanic alkyl nitrates

    NASA Astrophysics Data System (ADS)

    Dahl, E. E.; Lewis, C. B.; Velasco, F. L.; Escobar, C.; Kellogg, D.; Velcamp, M.

    2013-12-01

    Alkyl nitrates are an important component of reactive nitrogen in the troposphere. The oceans are a source of alkyl nitrates to the atmosphere, however the source of alkyl nitrates in the oceans is unknown. It has been demonstrated that the reaction of alkyl peroxy radicals (ROO) with nitric oxide (NO) produces alkyl nitrates in the aqueous phase. We hypothesize that alkyl nitrates may be formed by organisms through the same reaction and therefore biological production could be a source of alkyl nitrates to the troposphere. This work focuses on the production of alkyl nitrates by the diatoms Chaetoceros muelleri and Thalassiosira weisfloggi. Using chemostats, we measure alkyl nitrates formed under nitrate limited conditions. We also use triggers and inhibitors of nitric oxide formation to determine if alkyl nitrate formation is affected by changes in NO production. To date, the rates of production of alkyl nitrates in our cultures, lead us to estimate a production rate on the order of femtomolar/day for C1-C3 alkyl nitrates by diatom species in the equatorial Pacific Ocean. This suggests that diatoms may contribute to the overall ocean source of alkyl nitrates; however, it is possible that other types of phytoplankton, such as cyanobacteria, that are more abundant in the open ocean, may contribute to a greater extent.

  4. Phosphine-alkene ligand-mediated alkyl-alkyl and alkyl-halide elimination processes from palladium(II).

    PubMed

    Tuxworth, Luke; Baiget, Lise; Phanopoulos, Andreas; Metters, Owen J; Batsanov, Andrei S; Fox, Mark A; Howard, Judith A K; Dyer, Philip W

    2012-10-28

    N-Diphenylphosphino-7-aza-benzobicyclo[2.2.1]hept-2-ene (2) behaves as a chelating phosphine-alkene ligand for Pd(0) and Pd(II), promoting direct alkyl-alkyl and indirect alkyl-halide reductive elimination reactions due to the stabilisation of the resulting bis(phosphine-alkene)Pd(0) complex. PMID:22986447

  5. Comparison of surface modifications of poly(ether urethanes) by chemical infusion and graft polymerization

    SciTech Connect

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

    1988-01-01

    Our approach to surface modification uses the chemical infusion process to introduce materials into the outermost layer of the polymeric material, thereby altering the surface without changing the bulk properties of the polymer. The infused materials may slowly diffuse out of the infusion layer if they are volatile or highly mobile. However, if polymeric infusant materials are employed, they may become chain entangled with the host polymer and result in a permanently modified surface. A second approach utilizes photo-initiated graft polymerization of poly(ether urethanes) with an appropriate monomer. We have explored both of these methods by examining the infusion of polyvinylpyrrolidone (PVP) and poly(ethylene glycol) (PEG) into commercially available poly(ether urethanes) and the graft polymerization of N-vinyl pyrrolidone onto poly(ether urethanes). Results are presented here. 7 refs., 1 tab.

  6. Bacterial degradation of glycol ethers.

    PubMed

    Kawai, F

    1995-12-01

    Assimilation of ethyleneglycol (EG) ethers by polyethyleneglycol-utilizing bacteria was examined. Ethyleneglycol ether-utilizing bacteria were also isolated from soil and activated sludge samples by enrichment-culture techniques. Three strains (4-5-3, EC 1-2-1 and MC 2-2-1) were selected and characterized as Pseudomonas sp. 4-5-3, Xanthobacter autotrophicus, and an unidentified gram-negative, non-spore-forming rod respectively. Their growth characteristics were examined: Pseudomonas sp. 4-5-3 assimilated EG (diethyleneglycol, DEG) monomethyl, monoethyl and monobutyl ethers, DEG, propanol and butanol. X. autotrophicus EC 1-2-1 grew well on EG monoethyl and monobutyl ethers, EG and primary alcohols (C1-C4), and slightly on EG monomethyl ether. The strain MC 2-2-1 grew on EG monomethyl ether, EG, primary alcohols (C1-C4), and 1,2-propyleneglycol (PG). The mixed culture of Pseudomonas sp. 4-5-3 and X. autotrophicus EC 1-2-1 showed better growth and improved degradation than respective single cultures towards EG monomethyl, monoethyl or monobutyl ethers. Intact cells of Pseudomonas sp. 4-5-3 degraded various kinds of monoalkyl ethers, which cannot be assimilated by the strain. Metabolic products were characterized from reaction supernatants of intact cells of Pseudomonas sp. 4-5-3 with EG or DEG monoethyl ethers: they were analyzed by thin-layer chromatography and GC-MS and found to be ethoxyacetic acid and ethoxyglycoxyacetic acid. Also, PG monoalkyl ethers (C1-C4), dipropyleneglycol monoethyl and monomethyl ethers and tripropyleneglycol monomethyl ether were assimilated by polypropyleneglycol-utilizing Corynebacterium sp. 7. PMID:8597556

  7. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  8. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  9. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  10. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  11. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  12. Facile heme vinyl posttranslational modification in a hemoglobin.

    PubMed

    Preimesberger, Matthew R; Wenke, Belinda B; Gilevicius, Lukas; Pond, Matthew P; Lecomte, Juliette T J

    2013-05-21

    Iron-protoporphyrin IX, or b heme, is utilized as such by a large number of proteins and enzymes. In some cases, notably the c-type cytochromes, this group undergoes a posttranslational covalent attachment to the polypeptide chain, which adjusts the physicochemical properties of the holoprotein. The hemoglobin from the cyanobacterium Synechocystis sp. PCC 6803 (GlbN), contrary to the archetypical hemoglobin, modifies its b heme covalently. The posttranslational modification links His117, a residue that does not coordinate the iron, to the porphyrin 2-vinyl substituent and forms a hybrid b/c heme. The reaction is an electrophilic addition that occurs spontaneously in the ferrous state of the protein. This apparently facile type of heme modification has been observed in only two cyanobacterial GlbNs. To explore the determinants of the reaction, we examined the behavior of Synechocystis GlbN variants containing a histidine at position 79, which is buried against the porphyrin 4-vinyl substituent. We found that L79H/H117A GlbN bound the heme weakly but nevertheless formed a cross-link between His79 Nε2 and the heme 4-Cα. In addition to this linkage, the single variant L79H GlbN also formed the native His117-2-Cα bond yielding an unprecedented bis-alkylated protein adduct. The ability to engineer the doubly modified protein indicates that the histidine-heme modification in GlbN is robust and could be engineered in different local environments. The rarity of the histidine linkage in natural proteins, despite the ease of reaction, is proposed to stem from multiple sources of negative selection. PMID:23607716

  13. 42 CFR 84.250 - Vinyl chloride respirators; description.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Vinyl chloride respirators; description. 84.250... Respirators § 84.250 Vinyl chloride respirators; description. Vinyl chloride respirators, including all... escape from vinyl chloride atmospheres containing adequate oxygen to support life, are...

  14. 42 CFR 84.250 - Vinyl chloride respirators; description.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Vinyl chloride respirators; description. 84.250... Respirators § 84.250 Vinyl chloride respirators; description. Vinyl chloride respirators, including all... escape from vinyl chloride atmospheres containing adequate oxygen to support life, are...

  15. 42 CFR 84.250 - Vinyl chloride respirators; description.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 42 Public Health 1 2012-10-01 2012-10-01 false Vinyl chloride respirators; description. 84.250... Respirators § 84.250 Vinyl chloride respirators; description. Vinyl chloride respirators, including all... escape from vinyl chloride atmospheres containing adequate oxygen to support life, are...

  16. 42 CFR 84.250 - Vinyl chloride respirators; description.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Vinyl chloride respirators; description. 84.250... Respirators § 84.250 Vinyl chloride respirators; description. Vinyl chloride respirators, including all... escape from vinyl chloride atmospheres containing adequate oxygen to support life, are...

  17. 42 CFR 84.250 - Vinyl chloride respirators; description.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Vinyl chloride respirators; description. 84.250... Respirators § 84.250 Vinyl chloride respirators; description. Vinyl chloride respirators, including all... escape from vinyl chloride atmospheres containing adequate oxygen to support life, are...

  18. 21 CFR 175.270 - Poly(vinyl fluoride) resins.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... polymerization of vinyl fluoride. (b) The poly(vinyl fluoride) basic resins have an intrinsic viscosity of not... Dilute Solution Viscosity of Vinyl Chloride Polymers,” which is incorporated by reference. Copies may be... Solution Viscosity of Vinyl Chloride Polymers,” which is incorporated by reference; see paragraph (b)...

  19. 21 CFR 175.270 - Poly(vinyl fluoride) resins.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... polymerization of vinyl fluoride. (b) The poly(vinyl fluoride) basic resins have an intrinsic viscosity of not... Dilute Solution Viscosity of Vinyl Chloride Polymers,” which is incorporated by reference. Copies may be... Solution Viscosity of Vinyl Chloride Polymers,” which is incorporated by reference; see paragraph (b)...

  20. 21 CFR 175.270 - Poly(vinyl fluoride) resins.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... polymerization of vinyl fluoride. (b) The poly(vinyl fluoride) basic resins have an intrinsic viscosity of not... Dilute Solution Viscosity of Vinyl Chloride Polymers,” which is incorporated by reference. Copies may be... Solution Viscosity of Vinyl Chloride Polymers,” which is incorporated by reference; see paragraph (b)...

  1. 21 CFR 175.270 - Poly(vinyl fluoride) resins.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... polymerization of vinyl fluoride. (b) The poly(vinyl fluoride) basic resins have an intrinsic viscosity of not... Dilute Solution Viscosity of Vinyl Chloride Polymers,” which is incorporated by reference. Copies may be... Solution Viscosity of Vinyl Chloride Polymers,” which is incorporated by reference; see paragraph (b)...

  2. Cel vinyls: materials and methods.

    PubMed

    Harrison, S J

    1983-12-01

    Many commercial uses of media are applicable to medical/scientific media production and illustration, not the least of which are techniques pioneered in the commercial cartooning field. Whether or not the illustrative effort culminates in a "cartoon," the production techniques of the cartooning industry cannot be overlooked by the illustrator faced with providing projection graphics, whether animated or still, for slides, motion pictures, television or even print media. When Walt Disney introduced Mickey Mouse as "Steamboat Willie" in 1928, his technology opened the door for exploration of cartooning media by all artists. Only in comparatively recent years have these tools been used by the scientific illustrator. In this article cel vinyl acrylics or cartoon colors will be discussed: the rationale for the use of this medium, materials and methods, and considerations related to the photography of this art form. PMID:6677644

  3. Positron scattering from vinyl acetate

    NASA Astrophysics Data System (ADS)

    Chiari, L.; Zecca, A.; Blanco, F.; García, G.; Brunger, M. J.

    2014-09-01

    Using a Beer-Lambert attenuation approach, we report measured total cross sections (TCSs) for positron scattering from vinyl acetate (C4H6O2) in the incident positron energy range 0.15-50 eV. In addition, we also report an independent atom model with screening corrected additivity rule computation results for the TCSs, differential and integral elastic cross sections, the positronium formation cross section and inelastic integral cross sections. The energy range of these calculations is 1-1000 eV. While there is a reasonable qualitative correspondence between measurement and calculation for the TCSs, in terms of the energy dependence of those cross sections, the theory was found to be a factor of ˜2 larger in magnitude at the lower energies, even after the measured data were corrected for the forward angle scattering effect.

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  5. Ether and Relativity

    NASA Astrophysics Data System (ADS)

    Farhoudi, Mehrdad; Yousefian, Maysam

    2016-05-01

    We consider one of the fundamental debates in performing the relativity theory, namely, the ether and the relativity points of view, in a way to aid the learning of the subjects. In addition, we present our views and prospects while describing the issues that being accessible to many physicists and allowing broader views. Also, we very briefly review the two almost recent observations of the Webb redshift and the ultra high energy cosmic rays, and the modified relativity models that have been presented to justify them, wherein we express that these justifications have not been performed via a single model with a single mechanism.

  6. Carbonylation reactions of alkyl iodides through the interplay of carbon radicals and Pd catalysts.

    PubMed

    Sumino, Shuhei; Fusano, Akira; Fukuyama, Takahide; Ryu, Ilhyong

    2014-05-20

    Numerous methods for transition metal catalyzed carbonylation reactions have been established. Examples that start from aryl, vinyl, allyl, and benzyl halides to give the corresponding carboxylic acid derivatives have all been well documented. In contrast, the corresponding alkyl halides often encounter difficulty. This is inherent to the relatively slow oxidative addition step onto the metal center and subsequent β-hydride elimination which causes isomerization of the alkyl metal species. Radical carbonylation reactions can override such problems of reactivity; however, carbonylation coupled to iodine atom transfer (atom transfer carbonylation), though useful, often suffers from a slow iodine atom transfer step that affects the outcome of the reaction. We found that atom transfer carbonylation of primary, secondary, and tertiary alkyl iodides was efficiently accelerated by the addition of a palladium catalyst under light irradiation. Stereochemical studies support a mechanistic pathway based on the synergic interplay of radical and Pd-catalyzed reaction steps which ultimately lead to an acylpalladium species. The radical/Pd-combined reaction system has a wide range of applications, including the synthesis of carboxylic acid esters, lactones, amides, lactams, and unsymmetrical ketones such as alkyl alkynyl and alkyl aryl ketones. The design of unique multicomponent carbonylation reactions involving vicinal C-functionalization of alkenes, double and triple carbonylation reactions, in tandem with radical cyclization reactions, has also been achieved. Thus, the radical/Pd-combined strategy provides a solution to a longstanding problem of reactivity involving the carbonylation of alkyl halides. This novel methodology expands the breadth and utility of carbonylation chemistry over either the original radical carbonylation reactions or metal-catalyzed carbonylation reactions. PMID:24712759

  7. Pure Rotational Spectroscopy of Vinyl Mercaptan

    NASA Astrophysics Data System (ADS)

    Martin-Drumel, Marie-Aline; Zingsheim, Oliver; Thorwirth, Sven; Müller, Holger S. P.; Lewen, Frank; Schlemmer, Stephan

    2014-06-01

    Vinyl mercaptan (ethenethiol, CH_2=CHSH) exists in the gas phase in two distinct rotameric forms, syn (planar) and anti (quasi-planar in the ground vibrational state). The microwave spectra of these two isomers were investigated previously, however not exceeding frequencies of about 65 GHz. In the present investigation, the pure rotational spectra of both species have been investigated at millimeter wavelengths. Vinyl mercaptan was produced in a radiofrequency discharge through a constant flow of ethanedithiol at low pressure. Both syn and anti rotamers were observed and new extensive sets of molecular parameters were obtained. Owing to its close structural relationship to vinyl alcohol and the astronomical abundance of complex sulfur-bearing molecules, vinyl mercaptan is a plausible candidate for future radio astronomical searches. M. Tanimoto et al. J. Mol. Spectrosc. 78, 95--105 & 106--119 (1979)

  8. Methods of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-08-03

    A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.

  9. Vinyl chloride loss during laboratory holding time

    SciTech Connect

    Soule, R.G.; Jones, D.B.A.; Symonik, D.M.; Gerbec, B.A.; Turgeon, D.W.

    1995-12-31

    Because vinyl chloride is a potent human carcinogen, it`s important that analytical results from groundwater samples accurately reflect levels of exposure. This study investigated the current allowable sample holding time of 14 days to determine if vinyl chloride is lost from samples during this time. In addition to lab spiked samples, groundwater was collected from a well known to contain vinyl chloride. A statistically significant (a = 0.05) decrease in vinyl chloride concentrations was observed over the 14-day holding time. The most significant loss was seen for those samples held the maximum length of time (14 days). No differences in degradation pattern were noted between analytical detectors used (PID versus Hall) or sample type (lab versus field). There also was a loss of vinyl chloride observed during the sampling and handling process. Analytical variability at low concentrations and the establishment of health-based guidelines near the analytical detection limit require that multiple samples be collected from a single location when highly accurate results are required. These findings have implications for the accurate generation of public health exposure assessments and the implementation of health-based recommendations at sites with vinyl chloride groundwater contamination.

  10. PREPARATION OF ALKYL PYROPHOSPHATE EXTRACTANTS

    DOEpatents

    Levine, C.A.; Skiens, W.E.; Moore, G.R.

    1960-08-01

    A process for providing superior solvent extractants for metal recovery processes is given wherein the extractant comprises an alkyl pyrophosphoric acid ester dissolved in an organic solvent diluent. Finely divided solid P/sub 2/O/ sub 5/ is slurried in an organic solvent-diluent selected from organic solvents such as kerosene, benzene, chlorobenzene, toluene, etc. An alcohol selected from the higher alcohols having 4 to 17 carbon atoms. e.g.. hexanol-1. heptanol-3, octanol-1. 2.6-dimethyl-heptanol-4, and decanol-1, is rapidly added to the P/sub 2/O/sub 5/ slurry in the amount of about 2 moles of alcohol to 1 mole of P/sub 2/ O/sub 5/. The temperature is maintained below about 110 deg C during the course of the P/sub 2/O/sub 5/-alcohol reaction. An alkyl pyrophosphate extractant compound is formed as a consequence of the reaction process. The alkyl pyrophosphate solvent-diluent extractant phase is useful in solvent extraction metal recovery processes.

  11. Precursor of ether phospholipids is synthesized by a flavoenzyme through covalent catalysis

    PubMed Central

    Nenci, Simone; Piano, Valentina; Rosati, Sara; Aliverti, Alessandro; Pandini, Vittorio; Fraaije, Marco W.; Heck, Albert J. R.; Edmondson, Dale E.; Mattevi, Andrea

    2012-01-01

    The precursor of the essential ether phospholipids is synthesized by a peroxisomal enzyme that uses a flavin cofactor to catalyze a reaction that does not alter the redox state of the substrates. The enzyme crystal structure reveals a V-shaped active site with a narrow constriction in front of the prosthetic group. Mutations causing inborn ether phospholipid deficiency, a very severe genetic disease, target residues that are part of the catalytic center. Biochemical analysis using substrate and flavin analogs, absorbance spectroscopy, mutagenesis, and mass spectrometry provide compelling evidence supporting an unusual mechanism of covalent catalysis. The flavin functions as a chemical trap that promotes exchange of an acyl with an alkyl group, generating the characteristic ether bond. Structural comparisons show that the covalent versus noncovalent mechanistic distinction in flavoenzyme catalysis and evolution relies on subtle factors rather than on gross modifications of the cofactor environment. PMID:23112191

  12. 75 FR 50926 - 2-propenoic acid, 2-methyl-, C12-16-alkyl esters, telomers with 1-dodecanethiol, polyethylene...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ...This regulation establishes an exemption from the requirement of a tolerance for residues of 2-propenoic acid, 2-methyl-, C12-16- alkyl esters, telomers with 1-dodecanethiol, polyethylene-polypropylene glycol ether with propylene glycol monomethacrylate (1:1), and styrene 2,2'-(1,2-diazenediyl)bis[2-methylbutanenitrile]-initiated, number average molecular weight (in AMU) 4000; when used as an......

  13. Thermal Conductivity of Ethylene Vinyl Acetate Copolymer/Nanofiller Blends

    NASA Technical Reports Server (NTRS)

    Ghose, S.; Watson, K. A.; Working, D. C.; Connell, J. W.; Smith, J. G., Jr.; Lin, Y.; Sun, Y. P.

    2007-01-01

    To reduce weight and increase the mobility, comfort, and performance of future spacesuits, flexible, thermally conductive fabrics and plastic tubes are needed for the Liquid Cooling and Ventilation Garment. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As an approach to raise the thermal conductivity (TC) of an ethylene vinyl acetate copolymer (Elvax 260), it was compounded with three types of carbon based nanofillers: multi-walled carbon nanotubes (MWCNTs), vapor grown carbon nanofibers (CNFs), and expanded graphite (EG). In addition, other nanofillers including metallized CNFs, nickel nanostrands, boron nitride, and powdered aluminum were also compounded with Elvax 260 in the melt at various loading levels. In an attempt to improve compatibility between Elvax 260 and the nanofillers, MWCNTs and EG were modified by surface coating and through noncovalent and covalent attachment of organic molecules containing alkyl groups. Ribbons of the nanocomposites were extruded to form samples in which the nanofillers were aligned in the direction of flow. Samples were also fabricated by compression molding to yield nanocomposites in which the nanofillers were randomly oriented. Mechanical properties of the aligned samples were determined by tensile testing while the degree of dispersion and alignment of nanoparticles were investigated using high-resolution scanning electron microscopy. TC measurements were performed using a laser flash (Nanoflash ) technique. TC of the samples was measured in the direction of, and perpendicular to, the alignment direction. Additionally, tubing was also extruded from select nanocomposite compositions and the TC and mechanical flexibility measured.

  14. Gasoline range ether synthesis from light naphtha products of fluid catalytic cracking of Fischer-Tropsch wax

    SciTech Connect

    Reagan, W.J.

    1994-12-31

    The Fluid Catalytic Cracking of Fischer-Tropsch wax (C{sub 20}{sup +} paraffins) produces two to four time the concentration of reactive iso-olefins (isobutylene, isoamylenes, isohexenes) than observed from conventional gas oil feedstocks. Methanol reacts with these olefins to form the corresponding tertiary alkyl ethyl ethers: MTBE, TAME and MTHE`s. These etherification reactions are mildly exothermic and equilibrium limited. The reaction temperature and the olefin molecular structure are important variables for maximum ether yields. The base naphtha research octane number increases by 2-4 numbers after the etherification reaction. The presence of hydrogen has a detrimental affect on ether yields because of hydrogenation of reactive olefins to paraffins. The catalytic cracking of Fischer-Tropsch wax provides a non-conventional source of olefins for ether synthesis that can supplement existing and dwindling petroleum supplies.

  15. Lubricant compositions containing antioxidant mixtures comprising substituted thiazoles and substituted thiadiazole compounds

    SciTech Connect

    Shim, J.

    1981-04-07

    Lubricants are described containing oleaginous materials and, in an amount sufficient to impart oxidation stability and corrosion resistance, an adduct of a benzotriazole compound and an alkyl vinyl ether or a vinyl ester of a carboxylic acid in combination with an alkyl dimercapto thiadiazole.

  16. 21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethylene-vinyl acetate-vinyl alcohol copolymers. 177.1360 Section 177.1360 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single...

  17. Some like it pungent and vile. TRPA1 as a molecular target for the malodorous vinyl disulfides from asafoetida.

    PubMed

    Shokoohinia, Yalda; Chianese, Giuseppina; Appendino, Giovanni; Di Marzo, Vincenzo; De Petrocellis, Luciano; Ghannadi, Alireza; Taghvayi, Roshanak; Fattahian, Khadijeh; Soltani, Reza; Taglialatela-Scafati, Orazio

    2013-10-01

    Ferula assa-foetida L. is a major source of asafoetida, a foul-smelling gum-resin of dietary and medicinal relevance. Investigation of the roots and latex of F. assa-foetida yielded various mixed vinyl disulfides, including two novel asadisulfide-type esters. The reactivity of asadisulfide was investigated in the cysteamine NMR assay, where it behaved as disulfide shuffling agents due to the high mobility of the vinyl sulfide moiety. In accordance with their transthiolation capacity, these compounds potently activated TRPA1, the target of mustard oil and the pungent sulfur compounds from onion and garlic, qualifying S-alkyl-S-alkenyldisulfides, a rare class of natural products, as a novel class of dietary TRPA1 activators. These observations provide a mechanistic basis for rationalizing some of the sensory properties and potential beneficial health claims associated to the use of asafoetida as a spice and as a medicine. PMID:23954176

  18. Synthesis of prostaglandins by conjugate addition and alkylation of a directed enolate ion. 4,5-allenyl prostaglandins

    SciTech Connect

    Patterson, J.W. )

    1990-09-28

    Over the previous two decades many elegant syntheses of prostaglandins, which in more sophisticated forms, allow the stereospecific introduction of the various asymmetric carbons have been accomplished. However, among these approaches the cuprate addition/enolate alkylation of suitable cyclopentenone {sup 2} stands out because of brevity and convergence. The recent reports by Noyori{sup 3} and Corey{sup 4} and their colleagues have reduced to practice the conversion of 4-alkoxycyclopentenones to prostaglandin E{sub 2} (PGE{sub 2}) by conjugate addition of an organocopper derivative of the lower side chain followed by alkylation of the resulting carbanion with methyl 7-halohept-2-enoate. The subject of this paper is application of the Tardella tin enolate alkylation developed by Noyori to the synthesis of 4, 5-allenic prostaglandins, a pharmacologically important class of compounds. The authors results demonstrate that the tandem alkylation of an enone precursor with a cuprate reagent followed by alkylation of the corresponding tin enolate with bromide reagent is a viable synthetic method for 4,5-didehydro-PGE{sub 2}. Because the optically active forms of 1 and the vinyl iodide precursor of the PGE{sub 2} lower side chain have been employed to produce a single enantiomer of PGE{sub 2}, the extension of the methodology described here to the synthesis of single enantiomers of 4a awaits only the preparation of the separate enantiomers of allene 14.

  19. Functionalization of poly(aryl ether ether ketone)

    SciTech Connect

    Wang, Fei; Roovers, J.

    1993-12-31

    Bromomethyl and dibromomethyl substituted poly(aryl ether ether ketone) have been prepared from methyl poly(aryl ether ether ketone) by bromination with bromine. These brominated polymers are intermediates that can be further functionalized by: hydrolysis, oxidation, substitution etc. A series of new functionalized PEEK polymers has been prepared. The functional group includes -CH{sub 2}OH, -CH{sub 2}OCH{sub 3}, -CHO, -COOH, -COOCH{sub 3}, -CH{sub 2}CN, -CH{sub 2}COOH, -CH{sub 2}OCOCH{sub 3}, -CH{sub 2}N{sup +}H(CH{sub 2}CH{sub 3}){sub 2}Br{sup {minus}}, -CH{sub 2}N(CH{sub 2}CH{sub 3}){sub 2}, -CH{sub 2}N{sup +}H(CH{sub 2}CH{sub 3}){sub 3}Br{sup {minus}}.

  20. Polyarylene Ethers with Improved Properties

    NASA Technical Reports Server (NTRS)

    Hergenrother, P. M. (Inventor); Jensen, B. J. (Inventor); Havens, S. J. (Inventor)

    1986-01-01

    This invention relates to novel polyarylene ethers which possess the combination of high strength, toughness, and high use temperature with ease of extrusion and formation into complex objects. These polyarylene ethers are suitable for use in adhesives, coatings, films, membranes, and composite matrices. The polyarylene ethers of this invention are the polycondensation products from the reaction of either 1,3-bis (4-chloro or fluorobenzoyl) benzene with any one of the following bisphenolic compounds: bis (3-hydroxyphenyl) methane; bis (4-hydroxyphenyl) methane; 1,1-dimethyl-bis (4-hydroxyphenyl)methane, or 9,9-bis (4-hydroxyphenyl) fluorene. Random and block copolymers are also comprehended.

  1. Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  2. An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

    NASA Astrophysics Data System (ADS)

    Neale, Alex R.; Murphy, Sinead; Goodrich, Peter; Schütter, Christoph; Hardacre, Christopher; Passerini, Stefano; Balducci, Andrea; Jacquemin, Johan

    2016-09-01

    A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent-free, IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

  3. Tetrabutylammonium decatungstate-photosensitized alkylation of electrophilic alkenes: Convenient functionalization of aliphatic C-H bonds.

    PubMed

    Dondi, Daniele; Fagnoni, Maurizio; Albini, Angelo

    2006-05-15

    Tetrabutylammonium decatungstate (TBADT, 2 x 10(-3) m) is an effective photocatalyst for the alkylation of electrophilic alkenes (0.1 m, alpha,beta-unsaturated nitriles, esters, ketones) by alkanes, alcohols, and ethers. The products are in most cases obtained in >70 % isolated yields, through an experimentally very simple procedure. The kinetics of the radical processes following initial hydrogen abstraction by excited TBADT in deoxygenated MeCN have been studied. In the absence of a trap, back hydrogen transfer from reduced tungstate is the main pathway for alkyl radicals, while alpha-hydroxyalkyl radicals are oxidized to ketones by ground-state TBADT. With both radical types the reaction ceases at a few percent conversion. However, trapping by electrophilic alkenes is followed by reduction of the radical adduct and regeneration of the catalyst, which allows the alkylation to proceed up to complete alkene conversion with the mentioned good yields of products. With a nucleophilic (alpha-hydroxyalkyl) radical, alkylation is efficient (Phi = 0.58) and can also be carried out when degassing is omitted, the only difference being a short induction period. With a less reactive (cyclohexyl) radical, the quantum yield is lower (Phi = 0.06) and the reaction is considerably slowed in aerated solutions, but the chemical yield remains good. PMID:16521134

  4. Masked N-Heterocyclic Carbene-Catalyzed Alkylation of Phenols with Organic Carbonates.

    PubMed

    Lui, Matthew Y; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

    2016-09-01

    An easily prepared masked N-heterocyclic carbene, 1,3-dimethylimidazolium-2-carboxylate (DMI-CO2 ), was investigated as a "green" and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low-toxicity and renewable alkylating agents, such as dimethyl- and diethyl carbonate, in a focused microwave reactor. DMI-CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8-diazabicycloundec-7-ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N-heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo-soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs. PMID:27528488

  5. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  6. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  7. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  8. Imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  9. Aerobic vinyl chloride metabolism in Mycobacterium aurum L1

    SciTech Connect

    Hartmans, S.; Bont, J.A.M. de )

    1992-04-01

    Mycobacterium aurum L1, capable of growth on vinyl chloride as a sole carbon and energy source, was previously isolated from soil contaminated with vinyl chloride. The initial step in vinyl chloride metabolism in strain L1 is catalyzed by alkene monooxygenase, transforming vinyl chloride into the reactive epoxide chlorooxirane. The enzyme responsible for chlorooxirane degradation appeared to be very unstable and thus hampered the characterization of the second step in vinyl chloride metabolism. Dichloroethenes are also oxidized by vinyl chloride-grown cells of strain L1, but they are not utilized as growth substrates. Three additional bacterial strains which utilize vinyl chloride as a sole carbon and energy source were isolated from environments with no known vinyl chloride contamination. The three new isolates were similar to strain L1 and were also identified as Mycobacterium aurum.

  10. Degradable vinyl polymers for biomedical applications

    NASA Astrophysics Data System (ADS)

    Delplace, Vianney; Nicolas, Julien

    2015-10-01

    Vinyl polymers have been the focus of intensive research over the past few decades and are attractive materials owing to their ease of synthesis and their broad diversity of architectures, compositions and functionalities. Their carbon-carbon backbones are extremely resistant to degradation, however, and this property limits their uses. Degradable polymers are an important field of research in polymer science and have been used in a wide range of applications spanning from (nano)medicine to microelectronics and environmental protection. The development of synthetic strategies to enable complete or partial degradation of vinyl polymers is, therefore, of great importance because it will offer new opportunities for the application of these materials. This Review captures the most recent and promising approaches to the design of degradable vinyl polymers and discusses the potential of these materials for biomedical applications.

  11. Space, Time, Ether, and Kant

    NASA Astrophysics Data System (ADS)

    Wong, Wing-Chun Godwin

    This dissertation focused on Kant's conception of physical matter in the Opus postumum. In this work, Kant postulates the existence of an ether which fills the whole of space and time with its moving forces. Kant's arguments for the existence of an ether in the so-called Ubergang have been acutely criticized by commentators. Guyer, for instance, thinks that Kant pushes the technique of transcendental deduction too far in trying to deduce the empirical ether. In defense of Kant, I held that it is not the actual existence of the empirical ether, but the concept of the ether as a space-time filler that is subject to a transcendental deduction. I suggested that Kant is doing three things in the Ubergang: First, he deduces the pure concept of a space-time filler as a conceptual hybrid of the transcendental object and permanent substance to replace the category of substance in the Critique. Then he tries to prove the existence of such a space-time filler as a reworking of the First Analogy. Finally, he takes into consideration the empirical determinations of the ether by adding the concept of moving forces to the space -time filler. In reconstructing Kant's proofs, I pointed out that Kant is absolutely committed to the impossibility of action-at-a-distance. If we add this new principle of no-action-at-a-distance to the Third Analogy, the existence of a space-time filler follows. I argued with textual evidence that Kant's conception of ether satisfies the basic structure of a field: (1) the ether is a material continuum; (2) a physical quantity is definable on each point in the continuum; and (3) the ether provides a medium to support the continuous transmission of action. The thrust of Kant's conception of ether is to provide a holistic ontology for the transition to physics, which can best be understood from a field-theoretical point of view. This is the main thesis I attempted to establish in this dissertation.

  12. Occupational asthma due to alkyl cyanoacrylate

    SciTech Connect

    Nakazawa, T. )

    1990-08-01

    A case of bronchial asthma induced by occupational exposure to alkyl cyanoacrylate, an adhesive, occurred in an assembly operation. Provocative exposure testing induced immediate and delayed asthmatic responses. Alkyl cyanoacrylate seemed to act as an allergen or as an irritant, resulting in the development of asthma.

  13. Stabilized dialkyl aluminum complexes as alkylating agents

    SciTech Connect

    Blum, J.; Baidossi, W.; Rosenfeld, A.

    1995-12-31

    Although trialkylaluminum derivatives are widely used as Ziegler-Natta polymerization co-catalysts, their application as routine alkylating agents is limited owing to their pyrophoric nature. The authors have now found that substitution of one of the alkyl moieties by a chelating group reduces the sensitivity of the organoaluminum compounds to air, and enables one to utilize them under normal laboratory conditions.

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

    DOEpatents

    Hofmann, Michael A.

    2006-11-14

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

  15. 46 CFR 154.1740 - Vinyl chloride: Inhibiting and inerting.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Vinyl chloride: Inhibiting and inerting. 154.1740... Operating Requirements § 154.1740 Vinyl chloride: Inhibiting and inerting. When a vessel is carrying vinyl chloride, the master shall ensure that: (a) Section 154.1818 is met; or (b) Section 154.1710 is met,...

  16. 46 CFR 154.1745 - Vinyl chloride: Transferring operations.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Vinyl chloride: Transferring operations. 154.1745 Section 154.1745 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS... Operating Requirements § 154.1745 Vinyl chloride: Transferring operations. A vessel carrying vinyl...

  17. 46 CFR 154.1745 - Vinyl chloride: Transferring operations.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Vinyl chloride: Transferring operations. 154.1745 Section 154.1745 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS... Operating Requirements § 154.1745 Vinyl chloride: Transferring operations. A vessel carrying vinyl...

  18. 46 CFR 154.1740 - Vinyl chloride: Inhibiting and inerting.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride: Inhibiting and inerting. 154.1740... Operating Requirements § 154.1740 Vinyl chloride: Inhibiting and inerting. When a vessel is carrying vinyl chloride, the master shall ensure that: (a) Section 154.1818 is met; or (b) Section 154.1710 is met,...

  19. 46 CFR 154.1745 - Vinyl chloride: Transferring operations.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Vinyl chloride: Transferring operations. 154.1745 Section 154.1745 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS... Operating Requirements § 154.1745 Vinyl chloride: Transferring operations. A vessel carrying vinyl...

  20. 46 CFR 154.1745 - Vinyl chloride: Transferring operations.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Vinyl chloride: Transferring operations. 154.1745 Section 154.1745 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS... Operating Requirements § 154.1745 Vinyl chloride: Transferring operations. A vessel carrying vinyl...

  1. 46 CFR 154.1745 - Vinyl chloride: Transferring operations.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride: Transferring operations. 154.1745 Section 154.1745 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS... Operating Requirements § 154.1745 Vinyl chloride: Transferring operations. A vessel carrying vinyl...

  2. 46 CFR 154.1740 - Vinyl chloride: Inhibiting and inerting.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Vinyl chloride: Inhibiting and inerting. 154.1740... Operating Requirements § 154.1740 Vinyl chloride: Inhibiting and inerting. When a vessel is carrying vinyl chloride, the master shall ensure that: (a) Section 154.1818 is met; or (b) Section 154.1710 is met,...

  3. 46 CFR 154.1740 - Vinyl chloride: Inhibiting and inerting.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Vinyl chloride: Inhibiting and inerting. 154.1740... Operating Requirements § 154.1740 Vinyl chloride: Inhibiting and inerting. When a vessel is carrying vinyl chloride, the master shall ensure that: (a) Section 154.1818 is met; or (b) Section 154.1710 is met,...

  4. 46 CFR 154.1740 - Vinyl chloride: Inhibiting and inerting.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Vinyl chloride: Inhibiting and inerting. 154.1740... Operating Requirements § 154.1740 Vinyl chloride: Inhibiting and inerting. When a vessel is carrying vinyl chloride, the master shall ensure that: (a) Section 154.1818 is met; or (b) Section 154.1710 is met,...

  5. 49 CFR 179.102-4 - Vinyl fluoride, stabilized.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 3 2013-10-01 2013-10-01 false Vinyl fluoride, stabilized. 179.102-4 Section 179... Specifications for Pressure Tank Car Tanks (Classes DOT-105, 109, 112, 114 and 120) § 179.102-4 Vinyl fluoride, stabilized. Each tank used to transport vinyl fluoride, stabilized, must comply with the following...

  6. 49 CFR 179.102-4 - Vinyl fluoride, stabilized.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 3 2014-10-01 2014-10-01 false Vinyl fluoride, stabilized. 179.102-4 Section 179... Specifications for Pressure Tank Car Tanks (Classes DOT-105, 109, 112, 114 and 120) § 179.102-4 Vinyl fluoride, stabilized. Each tank used to transport vinyl fluoride, stabilized, must comply with the following...

  7. 49 CFR 179.102-4 - Vinyl fluoride, stabilized.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 3 2012-10-01 2012-10-01 false Vinyl fluoride, stabilized. 179.102-4 Section 179... Specifications for Pressure Tank Car Tanks (Classes DOT-105, 109, 112, 114 and 120) § 179.102-4 Vinyl fluoride, stabilized. Each tank used to transport vinyl fluoride, stabilized, must comply with the following...

  8. 21 CFR 175.270 - Poly(vinyl fluoride) resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...(vinyl fluoride) basic resins have an intrinsic viscosity of not less than 0.75 deciliter per gram as determined by ASTM method D1243-79, “Standard Test Method for Dilute Solution Viscosity of Vinyl Chloride... (ASTM method D1243-79, “Standard Test Method for Dilute Solution Viscosity of Vinyl Chloride...

  9. 40 CFR 721.3140 - Vinyl epoxy ester.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Vinyl epoxy ester. 721.3140 Section... Substances § 721.3140 Vinyl epoxy ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance vinyl epoxy ester (PMN P-85-527) is subject to reporting under...

  10. 40 CFR 721.3140 - Vinyl epoxy ester.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Vinyl epoxy ester. 721.3140 Section... Substances § 721.3140 Vinyl epoxy ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance vinyl epoxy ester (PMN P-85-527) is subject to reporting under...

  11. 40 CFR 721.3140 - Vinyl epoxy ester.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Vinyl epoxy ester. 721.3140 Section... Substances § 721.3140 Vinyl epoxy ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance vinyl epoxy ester (PMN P-85-527) is subject to reporting under...

  12. 40 CFR 721.10262 - Oxime, Me vinyl silane (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Oxime, Me vinyl silane (generic). 721... Substances § 721.10262 Oxime, Me vinyl silane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as oxime, Me vinyl silane (PMN...

  13. 40 CFR 721.10262 - Oxime, Me vinyl silane (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Oxime, Me vinyl silane (generic). 721... Substances § 721.10262 Oxime, Me vinyl silane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as oxime, Me vinyl silane (PMN...

  14. 40 CFR 721.10262 - Oxime, Me vinyl silane (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Oxime, Me vinyl silane (generic). 721... Substances § 721.10262 Oxime, Me vinyl silane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as oxime, Me vinyl silane (PMN...

  15. Discovery of Inhibitors for the Ether Lipid-Generating Enzyme AGPS as Anti-Cancer Agents

    PubMed Central

    Piano, Valentina; Benjamin, Daniel I; Valente, Sergio; Nenci, Simone; Mai, Antonello; Aliverti, Alessandro; Nomura, Daniel K; Mattevi, Andrea

    2015-01-01

    Dysregulated ether lipid metabolism is an important hallmark of cancer cells. Previous studies have reported that lowering ether lipid levels by genetic ablation of the ether lipid-generating enzyme alkyl-glycerone phosphate synthase (AGPS) lowers key structural and oncogenic ether lipid levels and alters fatty acid, glycerophospholipid, and eicosanoid metabolism to impair cancer pathogenicity, indicating that AGPS may be a potential therapeutic target for cancer. In this study, we have performed a small-molecule screen to identify candidate AGPS inhibitors. We have identified several lead AGPS inhibitors and have structurally characterized their interactions with the enzyme and show that these inhibitors bind to distinct portions of the active site. We further show that the lead AGPS inhibitor 1a selectively lowers ether lipid levels in several types of human cancer cells and impairs their cellular survival and migration. We provide here the first report of in situ-effective pharmacological tools for inhibiting AGPS, which may provide chemical scaffolds for future AGPS inhibitor development for cancer therapy. PMID:26322624

  16. Alkylating reactivity and herbicidal activity of chloroacetamides.

    PubMed

    Jablonkai, Istvan

    2003-04-01

    The relationship between S- and N-alkylating reactivity and herbicidal activity within a series of chloroacetamides, including several commercial herbicides and newly synthesised analogues was studied. The S-alkylating reactivity of selected chloroacetamides, as well as those of atrazine and chlorfenprop-methyl, was determined by in vitro GSH conjugation at a ratio of GSH to alkylating agent of 25:1. A spectrophotometric reaction using 4-(4-nitrobenzyl)pyridine was used to characterise the N-alkylating reactivity of the chemicals. Our results indicate that a reduced level of N-alkylating reactivity correlates with an improved herbicidal efficacy at a practical rate. However, the phytoxicity of the molecules is not simply dependent on chemical reactivities, but strictly related to the molecular structure, indicating that lipophilicity, uptake, mobility and induction of detoxifying enzymes may also be decisive factors in the mode of action. PMID:12701706

  17. C-Alkylation by Hydrogen Autotransfer Reactions.

    PubMed

    Obora, Yasushi

    2016-04-01

    The development of practical, efficient, and atom-economical methods for the formation of carbon-carbon bonds remains a topic of considerable interest in current synthetic organic chemistry. In this review, we have summarized selected topics from the recent literature with particular emphasis on C-alkylation processes involving hydrogen transfer using alcohols as alkylation reagents. This review includes selected highlights concerning recent progress towards the modification of catalytic systems for the α-alkylation of ketones, nitriles, and esters. Furthermore, we have devoted a significant portion of this review to the methylation of ketones, alcohols, and indoles using methanol. Lastly, we have also documented recent advances in β-alkylation methods involving the dimerization of alcohols (Guerbet reaction), as well as new developments in C-alkylation methods based on sp (3) C-H activation. PMID:27573136

  18. Theory Of Alkyl Terminated Silicon Quantum Dots

    SciTech Connect

    Reboredo, F; Galli, G

    2004-08-19

    We have carried out a series of ab-initio calculations to investigate changes in the optical properties of Si quantum dots as a function of surface passivation. In particular, we have compared hydrogen passivated dots with those having alkyl groups at the surface. We find that, while on clusters with reconstructed surfaces a complete alkyl passivation is possible, steric repulsion prevents full passivation of Si dots with unreconstructed surfaces. In addition, our calculations show that steric repulsion may have a dominant effect in determining the surface structure, and eventually the stability of alkyl passivated clusters, with results dependent on the length of the carbon chain. Alkyl passivation weakly affects optical gaps of silicon quantum dots, while it substantially decreases ionization potentials and electron affinities and affect their excited state properties. On the basis of our results we propose that alkyl terminated quantum dots may be size selected taking advantage of the change in ionization potential as a function of the cluster size.

  19. Revisiting ether-derivatized imidazolium-based ionic liquids.

    PubMed

    Fei, Zhaofu; Ang, Wee Han; Zhao, Dongbin; Scopelliti, Rosario; Zvereva, Elena E; Katsyuba, Sergey A; Dyson, Paul J

    2007-08-30

    A series of ether-derivatized imidazolium halides have been prepared and characterized. Contrary to literature reports, they are all crystalline solids and have melting points well above room temperature (50-100 degrees C). Single crystals of the imidazolium salts, obtained in situ by slow cooling from their molten state to room temperature, were analyzed by X-ray crystallography, revealing various anion-cation interactions in the solid state. Exchange of the halides with [Tf(2)N]- yielded room temperature ionic liquids with viscosities that are comparable to related 1-alkyl-3-methylimidazolium ionic liquids. Density functional theory combined with IR spectroscopy has been used to analyze the role of functionalization of the imidazolium side chain on the formation of the molecular and supramolecular structure of the compounds and its possible impact on their physical properties. PMID:17676796

  20. Functionalization of immunostimulating complexes (ISCOMs) with lipid vinyl sulfones and their application in immunological techniques and therapy

    PubMed Central

    Cruz-Bustos, Teresa; González-González, Gloria; Morales-Sanfrutos, Julia; Megía-Fernández, Alicia; Santoyo-González, Francisco; Osuna, Antonio

    2012-01-01

    Background Immunostimulating complexes (ISCOM)-type nanocapsules have been functionalized with lipid vinyl sulfones that anchor to them via the hydrophobic zone of their structure and can be charged with pharmacologically active molecules or macromolecules. These functionalized nanocapsules can incorporate protein A and bind to G immunoglobulins (IgGs) to make vehicles directed at the surface antigens of infectious agents, tumor cells, or receptor cells and deliver the encapsulated molecules in a highly specific way. They may be of particular use in pharmacological treatments with highly toxic molecules that should not be used in solution whenever it can be avoided. When bound to antibodies they can be used in biological processes that require the delivery or presentation of macromolecules to certain specific cells, in immunization processes for instance, or in diagnostic immunological techniques, as they are able to transport both the secondary antibodies and the reaction labels. Methods and results We describe the preparation of ISCOMs, the binding to the ISCOMS of newly synthesized compounds composed of chain alkyl vinyl sulfone, and the subsequent binding of the vinyl-sulfone compounds to IgGs. Within this context, a compound deriving from cholesterol functionalized with vinyl sulfone and used together with cholesterol in varying proportions has been linked to the structure of the ISCOMs and bound to protein A–IgG. This functionalization in no way altered the form or structure of the ISCOMs and allowed the nanocapsules carrying the specific IgGs to bind to forms of Trypanosoma cruzi against which antibodies had been developed. The fact that functionalized ISCOMs containing antibodies could deliver actinomycin D directly to the parasite meant that the effective dose of the antibiotic could be reduced very significantly. Conclusion We have developed ISCOM-type nanocapsules functionalized with lipid vinyl sulfone capable of anchoring to the surface of functional

  1. 21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...., which is incorporated by reference in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies may be... alcoholysis or hydrolysis of those ethylene-vinyl acetate copolymers complying with § 177.1350. (1)...

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

    USGS Publications Warehouse

    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

  3. Role of alkyl alcohol on viscosity of silica-based chemical gels for decontamination of highly radioactive nuclear facilities

    SciTech Connect

    Choi, B. S.; Yoon, S. B.; Jung, C. H.; Lee, K. W.; Moon, J. K.

    2012-07-01

    Silica-based chemical gel for the decontamination of nuclear facilities was prepared by using fumed silica as a viscosifier, a 0.5 M Ce (IV) solution dissolved in concentrated nitric acid as a chemical decontamination agent, and tripropylene glycol butyl ether (TPGBE) as a co-viscosifier. A new effective strategy for the preparation of the chemical gel was investigated by introducing the alkyl alcohols as organic solvents to effectively dissolve the co-viscosifier. The mixture solution of the co-viscosifier and alkyl alcohols was more effective in the control of viscosity than that of the co-viscosifier only in gel. Here, the alkyl alcohols played a key role as an effective dissolution solvent for the co-viscosifier in the preparation of the chemical gel, resulting in a reducing of the amount of the co-viscosifier and gel time compared with that of the chemical gel prepared without the alkyl alcohols. It was considered that the alkyl alcohols contributed to the effective dissolution of the co-viscosifier as well as the homogeneous mixing in the formation of the gel, while the co-viscosifier in an aqueous media of the chemical decontamination agent solution showed a lower solubility. The decontamination efficiency of the chemical gels prepared in this work using a multi-channel analyzer (MCA) showed a high decontamination efficiency of over ca. 94% and ca. 92% for Co-60 and Cs-137 contaminated on surface of the stainless steel 304, respectively. (authors)

  4. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-01-05

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70 C and 500 C and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  5. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-09-07

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

  6. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1994-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  7. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1994-06-14

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  8. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.

    1989-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  9. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70.degree. C. and 500.degree. C. and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  10. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  11. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.

    1989-07-18

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  12. The Reaction between a Vinylic Ether and 2,4-Dinitrobenzenesulfenyl Chloride.

    ERIC Educational Resources Information Center

    Silversmith, Ernest F.

    1979-01-01

    This reaction can form the basis of a laboratory experiment for students who have mastered basic spectroscopy. The structure of the product can be assigned from four reasonable possibilities on the basis of the nmr spectrum. (BB)

  13. Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement.

    PubMed

    Souza, Frederico B; Shamim, Anwar; Argomedo, Luiz M Z; Pimenta, Daniel C; Stefani, Hélio A

    2015-11-01

    An efficient methodology for the synthesis of aryl-substituted vinyl sulfoxides through direct substitution of aryl-substituted alkynyl grignard reagents on menthyl-p-toluenesulfinate followed by Suzuki-Miyaura cross-coupling reaction has been developed. It has also been described that the reaction of alkyl-substituted and cycloalkyl-substituted alkynyl grignard reagents with menthyl-p-toluenesulfinate led to two products, i.e., alkynyl sulfoxide derivatives, as a result of substitution, and enyne sulfoxide derivatives, which resulted from substitution followed by Michael type addition. It was possible to selectively synthesize the enyne sulfoxide derivatives by changing the concentration of the grignard reagent. These alkenyl sulfoxides were transformed into the corresponding [Formula: see text]-thio aldehydes in high yields via additive Pummerer rearrangement. PMID:26232026

  14. Heat Bonding of Irradiated Ethylene Vinyl Acetate

    NASA Technical Reports Server (NTRS)

    Slack, D. H.

    1986-01-01

    Reliable method now available for joining parts of this difficult-tobond material. Heating fixture encircles ethylene vinyl acetate multiplesocket part, providing heat to it and to tubes inserted in it. Fixtures specially designed to match parts to be bonded. Tube-and-socket bonds made with this technique subjected to tensile tests. Bond strengths of 50 percent that of base material obtained consistently.

  15. Process for the preparation of vinyl acetate

    DOEpatents

    Tustin, G.C.; Zoeller, J.R.; Depew, L.S.

    1998-02-17

    This invention pertains to the preparation of vinyl acetate by contacting within a contact zone a mixture of ketene and acetaldehyde with an acid catalyst at about one bar pressure and between about 85 and 200 C and removing the reaction products from the contact zone.

  16. Process for the preparation of vinyl acetate

    DOEpatents

    Tustin, Gerald Charles; Zoeller, Joseph Robert; Depew, Leslie Sharon

    1998-01-01

    This invention pertains to the preparation of vinyl acetate by contacting within a contact zone a mixture of ketene and acetaldehyde with an acid catalyst at about one bar pressure and between about 85.degree. and 200.degree. C. and removing the reaction products from the contact zone.

  17. Advanced asymmetric synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid by alkylation/cyclization of newly designed axially chiral Ni(II) complex of glycine Schiff base.

    PubMed

    Kawashima, Aki; Shu, Shuangjie; Takeda, Ryosuke; Kawamura, Akie; Sato, Tatsunori; Moriwaki, Hiroki; Wang, Jiang; Izawa, Kunisuke; Aceña, José Luis; Soloshonok, Vadim A; Liu, Hong

    2016-04-01

    Asymmetric synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid (vinyl-ACCA) is in extremely high demand due to the pharmaceutical importance of this tailor-made, sterically constrained α-amino acid. Here we report the development of an advanced procedure for preparation of the target amino acid via two-step SN2 and SN2' alkylation of novel axially chiral nucleophilic glycine equivalent. Excellent yields and diastereoselectivity coupled with reliable and easy scalability render this method of immediate use for practical synthesis of (1R,2S)-vinyl-ACCA. PMID:26661034

  18. Isolation of a Bacterial Culture That Degrades Methyl t-Butyl Ether

    PubMed Central

    Salanitro, J. P.; Diaz, L. A.; Williams, M. P.; Wisniewski, H. L.

    1994-01-01

    We have isolated a mixed bacterial culture (BC-1) which is capable of degrading the gasoline oxygenate methyl t-butyl ether (MTBE). BC-1 was developed from seed microorganisms present in a chemical plant biotreater sludge. This enrichment culture has been maintained in continuous culture treating high concentrations of MTBE (120 to 200 mg/liter) as the sole carbon source in a simple feed containing NH4+, PO43-, Mg2+, and Ca2+ nutrients. The unit had a stable MTBE removal rate when maintained with a long cell retention time (ca. 80 to 90 days); however, when operated at a ≤50-day cell waste rate, loss of MTBE-degrading activity was observed. The following three noteworthy experimental data show that MTBE is biodegraded extensively by BC-1: (i) the continuous (oxygen-sparged) culture was able to sustain a population of autotrophic ammonia-oxidizing bacteria which could nitrify influent NH4+ concentrations at high rates and obtain CO2 (sole carbon source for growth) from the metabolism of the alkyl ether, (ii) BC-1 metabolized radiolabeled either (14CH3O-MTBE) to 14CO2 (40%) and 14C-labeled cells (40%), and (iii) cell suspensions of the culture were capable of degrading (substrate depletion experiments) MTBE to t-butyl alcohol, a primary metabolite of MTBE. BC-1 is a mixed culture containing several bacterial species and is the first culture of its kind which can completely degrade an alkyl ether. PMID:16349335

  19. Investigate the morphology and chemical properties of nanoengineered vinyl ester clay nanocomposite

    NASA Astrophysics Data System (ADS)

    Yebassa, Desta L.

    In recent years the area of nanocomposites has received considerable attention with the expectation that nanoclay filled polymers can be useful as matrix materials for composite applications. Although considerable progress has been made in understanding structure-property relationship of nanocomposites, consistent improvement in properties of nanocomposites remains elusive. This is because the addition of hydrophilic clay sheets to a hydrophobic polymeric resin can cause aggregation of clay sheets with and the aggregated clay sheets acting as stress concentration sites in the polymer matrix. The primary objective of this study was to improve the clay platelet separation in vinyl ester resin matrix by organically modifying the nanoclay platelet with a partially reactive onium salt. An approach to improving the compatibility of hydrophilic clay with the polymeric resin, is to chemically functionalize the clay with short and long chain cations, so as to increase the organophilicity of the clay surface layer and provide sufficient layer separation for polymer chains to infiltrate during curing. For our research purpose we selected medium and long chain length alkyl ammonium salts to functionalize clay. The medium chain length reactive onium salt (o-undecylenyl amine hydrochloride) was synthesized from commercial o-undecylenyl alcohol through a series of synthetic conversions which include bromination, azide formation, and azide reduction. The clay was ion exchanged with both reactive and non-reactive medium and long chain onium salts to form partially reactive clay. When the partially reactive clay and vinyl ester resin was sonicated with styrene, we obtained a variety of exfoliated/intercalated vinyl ester nanocomposite. Monomer styrene and high intensity ultrasonic mixing produces vinyl ester nanocomposite with the highest degree of clay platelet exfoliation. We also investigated the degradation of filled and unfilled polymer film exposed in alkali medium at various

  20. Thermal Conductivity of Ethylene Vinyl Acetate Copolymer/Nanofiller Blends

    NASA Technical Reports Server (NTRS)

    Ghose, Sayata; Watson, Kent A.; Working, Dennis C.; Connell, John W.; Smith, Joseph G., Jr.; Lin, Y.; Sun, Y. P.

    2007-01-01

    To reduce weight and increase the mobility, comfort, and performance of future spacesuits, flexible, thermally conductive fabrics and plastic tubes are needed for the Liquid Cooling and Ventilation Garment. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As an approach to raise the thermal conductivity (TC) of an ethylene vinyl acetate copolymer (Elvax(TM)260), it was compounded with three types of carbon based nanofillers: multi-walled carbon nanotubes (MWCNTs), vapor grown carbon nanofibers (CNFs), and expanded graphite (EG). In addition, other nanofillers including metallized CNFs, nickel nanostrands, boron nitride, and powdered aluminum were also compounded with Elvax(TM) 260 in the melt at various loading levels. In an attempt to improve compatibility between Elvax 260 and the nanofillers, MWCNTs and EG were modified by surface coating and through noncovalent and covalent attachment of organic molecules containing alkyl groups. Ribbons of the nanocomposites were extruded to form samples in which the nanofillers were aligned in the direction of flow. Samples were also fabricated by compression molding to yield nanocomposites in which the nanofillers were randomly oriented. Mechanical properties of the aligned samples were determined by tensile testing while the degree of dispersion and alignment of nanoparticles were investigated using high-resolution scanning electron microscopy. TC measurements were performed using a laser flash (Nanoflash(TM)) technique. TC of the samples was measured in the direction of, and perpendicular to, the alignment direction. Additionally, tubing was also extruded from select nanocomposite compositions and the TC and mechanical flexibility measured.

  1. Nanocomposites prepared from acrylonitrile butadiene rubber and organically modified montmorillonite with vinyl groups

    NASA Astrophysics Data System (ADS)

    Han, Mijeong; Kim, Hoonjung; Kim, Eunkyoung

    2006-01-01

    Nanocomposites were prepared from acrylonitrile-butadiene rubber (NBR), vinyl groups containing organically modified montmorillonite and additives, such as zinc oxide, stearic acid, and sulfur. The organically modified montmorillonites used in these nanocomposites were prepared by ion exchange reactions of N,N'-dimethylalkyl-(p-vinylbenzyl)-ammonium chlorides (DAVBAs, alkyl = octyl, dodecyl, and octadecyl) with sodium montmorillonite (Na+-MMT). NBR nanocomposites were obtained by controlling both the mixing and vulcanization conditions, by using a Brabender mixer and hot-press process. X-ray diffraction (XRD) analysis shows that, depending on the amount of montmorillonite that is added, both exfoliated and intercalated nanocomposite structures are formed. The NBR/DAVBA-MMT nanocomposites exhibit much higher mechanical properties (e.g., tensile strength, Young's modulus, 300% modulus, and hardness) as well as gas barrier properties as compared to NBR Na+-MMT or NBR composites generated from modified montmorillonites without vinyl groups. Consistent with the results of XRD, transmission electron microscopy (TEM) reveals that the intercalation and exfoliation structures of the nanocomposites coexist and that the DAVBA-MMT layers are well dispersed in NBR.

  2. 40 CFR 721.3380 - Anilino ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Anilino ether. 721.3380 Section 721... Anilino ether. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as anilino ether (P-83-910) is subject to reporting under this section...

  3. 40 CFR 721.3364 - Aliphatic ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic ether. 721.3364 Section 721... Aliphatic ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an aliphatic ether (PMN P-93-1381) is subject to reporting under...

  4. 40 CFR 721.3364 - Aliphatic ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aliphatic ether. 721.3364 Section 721... Aliphatic ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an aliphatic ether (PMN P-93-1381) is subject to reporting under...

  5. 40 CFR 721.3374 - Alkylenediolalkyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylenediolalkyl ether. 721.3374... Substances § 721.3374 Alkylenediolalkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an alkylenediolalkyl ether (PMN P-93-362) is subject...

  6. 40 CFR 721.3437 - Dialkyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Dialkyl ether. 721.3437 Section 721... Dialkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as dialkyl ether (PMN P-93-1308) is subject to reporting under this...

  7. 40 CFR 721.3374 - Alkylenediolalkyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylenediolalkyl ether. 721.3374... Substances § 721.3374 Alkylenediolalkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an alkylenediolalkyl ether (PMN P-93-362) is subject...

  8. 40 CFR 721.3437 - Dialkyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Dialkyl ether. 721.3437 Section 721... Dialkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as dialkyl ether (PMN P-93-1308) is subject to reporting under this...

  9. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a...

  10. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a...

  11. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a...

  12. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a...

  13. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a...

  14. Lacinilene C 7-methyl ether

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lacinilene C 7-methyl ether is an antimicrobial compound produced by the cotton plant in response to attack by pathogens. For the first time, we now report the crystal structure of this compound. This may prove useful in studies on the interaction of the compound with pathogenic fungal cells....

  15. Desoxyhemigossypol-6-methyl-ether

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Desoxyhemigossypol-6-methyl ether is an antimicrobial compound produced by the cotton plant in response to attack by pathogens. For the first time, we now report the crystal structure of this compound. This may prove useful in studies on the interaction of the compound with pathogenic fungal cells...

  16. Bis(chloromethyl)ether (BCME)

    Integrated Risk Information System (IRIS)

    Bis ( chloromethyl ) ether ( BCME ) ; CASRN 542 - 88 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

  17. Propylene glycol monomethyl ether (PGME)

    Integrated Risk Information System (IRIS)

    Propylene glycol monomethyl ether ( PGME ) ; CASRN 107 - 98 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

  18. Bis(chloroethyl)ether (BCEE)

    Integrated Risk Information System (IRIS)

    Bis ( chloroethyl ) ether ( BCEE ) ; CASRN 111 - 44 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  19. p,p\\'-Dibromodiphenyl ether

    Integrated Risk Information System (IRIS)

    p , p ' - Dibromodiphenyl ether ; CASRN 2050 - 47 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for

  20. Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

    PubMed

    Song, Yingying; Cheng, Chen; Jing, Huanwang

    2014-09-26

    Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. PMID:25154312

  1. Preparation of hydrophilic vinyl chloride copolymer hollow fiber membranes with antifouling properties

    NASA Astrophysics Data System (ADS)

    Rajabzadeh, Saeid; Sano, Rie; Ishigami, Toru; Kakihana, Yuriko; Ohmukai, Yoshikage; Matsuyama, Hideto

    2015-01-01

    Hydrophilic vinyl chloride copolymer hollow fiber membranes with antifouling properties were prepared from brominated vinyl chloride-hydroxyethyl methacrylate copolymer (poly(VC-co-HEMA-Br)). The base membrane was grafted with two different zwitterionic monomers, (2-methacryloyloxyethylphosphorylcholine) (MPC) and [2-(methacryloyloxy) ethyl] dimethyl (3-sulfopropyl) ammonium hydroxide) (MEDSAH), and poly(ethylene glycol) methyl ether methacrylate (PEGMA). The effect of the grafting on the base membrane hydrophilicity and antifouling properties was investigated. For comparison of the results, the pure water permeabilities and pore sizes at the outer surfaces of the grafted hollow fiber membranes were controlled to be similar. A poly(VC-co-HEMA-Br) hollow fiber membrane with similar pure water permeability and pore size was also prepared as a control membrane. A BSA solution was used as a model fouling solution for evaluation of the antifouling properties. Grafting with zwitterionic monomers and PEGMA improved the antifouling properties compared with the control membrane. The PEGMA grafted membrane showed the best antifouling properties among the grafted membranes

  2. Thermally induced alkylation of diamond.

    PubMed

    Hoeb, Marco; Auernhammer, Marianne; Schoell, Sebastian J; Brandt, Martin S; Garrido, Jose A; Stutzmann, Martin; Sharp, Ian D

    2010-12-21

    We present an approach for the thermally activated formation of alkene-derived self-assembled monolayers on oxygen-terminated single and polycrystalline diamond surfaces. Chemical modification of the oxygen and hydrogen plasma-treated samples was achieved by heating in 1-octadecene. The resulting layers were characterized using X-ray photoelectron spectroscopy, thermal desorption spectroscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and water contact angle measurements. This investigation reveals that alkenes selectively attach to the oxygen-terminated sites via covalent C-O-C bonds. The hydrophilic oxygen-terminated diamond is rendered strongly hydrophobic following this reaction. The nature of the process limits the organic layer growth to a single monolayer, and FTIR measurements reveal that such monolayers are dense and well ordered. In contrast, hydrogen-terminated diamond sites remain unaffected by this process. This method is thus complementary to the UV-initiated reaction of alkenes with diamond, which exhibits the opposite reactivity contrast. Thermal alkylation increases the range of available diamond functionalization strategies and provides a means of straightforwardly forming single organic layers in order to engineer the surface properties of diamond. PMID:21090790

  3. Radiation-resistant vinyl halide resin compositions and a process for their production

    SciTech Connect

    Ejk, A.J.; Jachym, M.A.

    1988-02-23

    A method of sterilizing a packaging material is described comprising (I) providing a packaging material comprising a resinous composition consisting essentially of a mixture of: (a) a vinyl halide resin; (b) an organotin mercaptoacid ester having the formula R/sub x/Sn(SR'COOR'')/sub y/ wherein: R represents an alkyl group having 1-8 carbon atoms, R' represents an alkylene group having 1 to 4 carbon atoms; R'' represents an alkyl, aryl, alkaryl or aralkyl group having 1 to 18 carbon atoms, and x and y represent numbers in the range of 1 to 3 whose total is 4; and (c) an epoxy compound; the organotin mercaptoacid ester and the epoxy compound being present in an amount effective to stabilize the composition against the deteriorative effects of ionizing radiation wherein the epoxy compound is present in an amount of from about 3 to about 5 parts by weight percent by weight of the organotion mercaptoacid ester; and (II) subjecting the material to ionizing radiation for a period of time sufficient to substantially sterilize the packaging.

  4. N-Alkylation by Hydrogen Autotransfer Reactions.

    PubMed

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed. PMID:27573267

  5. Degradation kinetics of poly(ether-urethane) Estane® induced by electron irradiation

    NASA Astrophysics Data System (ADS)

    Dannoux, A.; Esnouf, S.; Begue, J.; Amekraz, B.; Moulin, C.

    2005-07-01

    Radiation effects on a segmented aromatic poly(ether-urethane) induced by electron beam irradiation under oxygen atmosphere were investigated using Fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance (EPR) in order to determine the degradation mechanisms. Thin films have been irradiated under a dose rate of 1 MGy/h with absorbed doses varying from 25 to 1000 kGy under O2. FTIR spectra have shown the formation of hydroperoxides, carboxylic acids, primary amines, alcohols, esters and formates. Moreover, the decrease of urethane and ether absorbances revealed the degradation of both soft and hard segments. Spin-trapping technique was used to monitor the evolution of short-lived peroxy and alkyl radicals at room temperature. Finally, a mechanism of degradation for electron irradiated polyurethane is proposed.

  6. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOEpatents

    Diebold, J.P.; Scahill, J.W.; Chum, H.L.; Evans, R.J.; Rejai, B.; Bain, R.L.; Overend, R.P.

    1996-04-02

    A process is described for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols. 35 figs.

  7. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOEpatents

    Diebold, James P.; Scahill, John W.; Chum, Helena L.; Evans, Robert J.; Rejai, Bahman; Bain, Richard L.; Overend, Ralph P.

    1996-01-01

    A process for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols.

  8. Ether analogues of DPA-714 with subnanomolar affinity for the translocator protein (TSPO).

    PubMed

    Banister, Samuel D; Beinat, Corinne; Wilkinson, Shane M; Shen, Bin; Bartoli, Cecilia; Selleri, Silvia; Da Pozzo, Eleonora; Martini, Claudia; Chin, Frederick T; Kassiou, Michael

    2015-03-26

    Sixteen new phenyl alkyl ether derivatives (12, 14-28) of the 5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylacetamide (DPA) class were synthesized and evaluated in a competition binding assay against [(3)H]PK11195 using 18 kDa translocator protein (TSPO) derived from rat kidney mitochondrial fractions. All analogues showed superior binding affinities for TSPO compared to DPA-713 (5) and DPA-714 (6). Picomolar affinities were observed for this class of TSPO ligands in this assay for the first time, with phenethyl ether 28 showing the greatest affinity (Ki = 0.13 nM). Additionally, all analogues increased pregnenolone biosynthesis (134-331% above baseline) in a rat C6 glioma cell steroidogenesis assay. PMID:25725375

  9. Liquid exfoliation of alkyl-ether functionalised layered metal-organic frameworks to nanosheets.

    PubMed

    Foster, Jonathan A; Henke, Sebastian; Schneemann, Andreas; Fischer, Roland A; Cheetham, Anthony K

    2016-08-18

    We report the synthesis of a 2D-layered metal-organic framework incorporating weakly interacting chains designed to aid exfoliation of the layers into nanosheets. Dispersion of the nanosheets exposes labile metal-sites which are shown to exchange solvent molecules allowing the nanosheets to act as sensors in suspension. PMID:27452790

  10. Sodium-oxygen batteries with alkyl-carbonate and ether based electrolytes.

    PubMed

    Kim, Jinsoo; Lim, Hee-Dae; Gwon, Hyeokjo; Kang, Kisuk

    2013-03-14

    Recently, metal-air batteries, such as lithium-air and zinc-air systems, have been studied extensively as potential candidates for ultra-high energy density storage devices because of their exceptionally high capacities. Here, we report such an electrochemical system based on sodium, which is abundant and inexpensive. Two types of sodium-oxygen batteries were introduced and studied, i.e. with carbonate and non-carbonate electrolytes. Both types could deliver specific capacities (2800 and 6000 mA h g(-1)) comparable to that of lithium-oxygen batteries but with slightly lower discharge voltages (2.3 V and 2.0 V). The reaction mechanisms of sodium-oxygen batteries in carbonate and non-carbonate electrolytes were investigated and compared with those of lithium-oxygen batteries. PMID:23386220

  11. Low pour crude oil compositions

    SciTech Connect

    Motz, K.L.; Latham, R.A.; Statz, R.J.

    1990-05-22

    This patent describes and improvement in the process of transporting waxy crude oils through a pipeline. It comprises: incorporating into the crude oil an effective pour point depressant amount of an additive comprising a polymer selected from the group consisting of copolymers of ethylene and acrylonitrile, and terpolymers of ethylene, acrylonitrile and a third monomer selected from the group consisting of vinyl acetate, carbon monoxide, alkyl acrylates, alkyl methacrylates, alkyl vinyl ethers, vinyl chloride, vinyl fluoride, acrylic acid, and methacrylic acid, wherein the amount of third monomer in the terpolymer ranges from about 0.1 to about 10.0 percent by weight.

  12. Separation of gases through gas enrichment membrane composites

    DOEpatents

    Swedo, R.J.; Kurek, P.R.

    1988-07-19

    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.

  13. Separation of gases through gas enrichment membrane composites

    DOEpatents

    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.

  14. Alkyl rearrangement processes in organozirconium complexes. Observation of internal alkyl complexes during hydrozirconation

    SciTech Connect

    Chirik, P.J.; Day, M.W.; Labinger, J.A.; Bercaw, J.E.

    1999-11-10

    Isotopically labeled alkyl zirconocene complexes of the form (CpR{sub n}){sub 2}Zr(CH{sub 2}CDR{sub 2}{prime})(X) (CpR{sub n} = alkyl-substituted cyclopentadienyl; R{prime} = H, alkyl group; X = H, D, Me) undergo isomerization of the alkyl ligand as well as exchange with free olefin in solution under ambient conditions. Increasing the substitution on the Cp ring results in slower isomerization reactions, but these steric effects are small. In contrast, changing X has a very large effect on the rate of isomerization. Pure {sigma}-bonding ligands such as methyl and hydride promote rapid isomerization, whereas {pi}-donor ligands inhibit {beta}-H elimination and hence alkyl isomerization. For ({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}Zr(R)(Cl), internal alkyl complexes have been observed for the first time. The rate of isomerization depends on the length of the alkyl group: longer alkyl chains (heptyl, hexyl) isomerize faster than shorter chains (butyl). The transient intermediate species have been identified by a combination of isotopic labeling and {sup 1}H, {sup 2}H, and {sup 13}C NMR experiments. The solid-state structure of the zirconocene cyclopentyl chloride complex, Cp{sub 2}Zr(cyclo-C{sub 5}H{sub 9})(Cl), has been determined by X-ray diffraction.

  15. Blend of alkyl phenol ethoxylates and alkyl phenol glycoxylates and their use as surfactants

    SciTech Connect

    Grolitzer, M. A.

    1985-11-12

    Nonionic surfactant compositions useful in forming stable emulsions with oil in saline solutions comprising a blend of: at least one alkyl phenol ethoxylate and at least one alkyl phenol glycoxylate. These surfactant compositions may be employed in enhanced oil recovery processes and other applications where good emulsification and high salinity tolerances are required such as textiles, leather, dairy, concrete grinding aids and drilling muds.

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

    PubMed

    Demir, Teyfik

    2015-05-01

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

  17. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    SciTech Connect

    Albright, L.F.; Kranz, K.E.; Masters, K.R.

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  18. 77 FR 12328 - Agency Information Collection Activities; Submission for OMB Review; Comment Request; Vinyl...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-02-29

    ...; Vinyl Chloride Standard ACTION: Notice. SUMMARY: The Department of Labor (DOL) is submitting the... . SUPPLEMENTARY INFORMATION: The purpose of the Vinyl Chloride Standard and its information collection... exposure to vinyl chloride. Employers must monitor worker exposure, reduce worker exposure to...

  19. Liquid Densities of Fluorinated Ethers

    NASA Astrophysics Data System (ADS)

    Nakazawa, Noriaki; Sako, Takeshi; Nakane, Takashi; Sekiya, Akira; Kawamura, Mitsutaka; Sato, Masahito; Mochizuki, Yuji; Takada, Naoto; Yasumoto, Masahiko

    The liquid densities of thirteen fluorinated ethers which are expected as promising candidates of CFC alternatives were measured at temperatures from 278 K to 323 K and atmospheric pressure. The fluorinated ethers used in this study are 1-difluoromethoxy-1,1, 2- trifluoroethane, 1-methoxy-1, 1,2,2-tetrafluoroethane, 1-methoxy-2,2 ,3 ,3- tetrafluoropropane, 1-methoxy-1-trifluoromethy1-2,2 ,2- trifluoroethane, 1-methoxy-1,1,2,2, 3-hexafluoropropane,1-difluoromethoxy-2,2, 3, 3 -tetrafluoropropane, 1-methoxy-heptafluoropropane,1-difluoromethoxy-2, 2, 3, 3, 3-pentafluoropropane, 1- (2, 2, 2-trifruoroethoxy) -1, 1, 2,2-tetrafluoroethane, 1-pentafluoroethoxy-1, 1, 2, 2-tetrafluoroethane,2-trifluoromethoxy-1, 1, 1,2-tetrafluorobutane, 1-proxynonafluorobutane, and 1-ethoxy-undecafluoropentane. The liquid density has been measured by the vibrating tube densitometer (ANTON PARR, DMA 602) within an error of 0.07%. The liquid densities decrease monotonically with increase of temperature.

  20. 4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall; Bugga, Ratnakumar

    2006-01-01

    investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

  1. 3-O-Alkyl-2,3-dehydrosilibinins: Two synthetic approaches and in vitro effects toward prostate cancer cells.

    PubMed

    Zhang, Sheng; Vue, Bao; Huang, Michael; Zhang, Xiaojie; Lee, Timmy; Chen, Guanglin; Zhang, Qiang; Zheng, Shilong; Wang, Guangdi; Chen, Qiao-Hong

    2016-07-15

    Eight 3-O-alkyl-2,3-dehydrosilibinins have been synthesized from commercially available silibinin through two synthetic approaches. A one-pot reaction, starting with aerobic oxidation of silibinin followed by direct alkylation of the phenolic hydroxyl group in the subsequent 2,3-dehydrosilibinin, furnishes the desired derivatives in 11-16% yields. The three-step procedure employing benzyl ether to protect 7-OH in silibinin generates the desired derivatives in 30-46% overall yields. The antiproliferative activity of the 2,3-dehydrosilibinin derivatives against both androgen-sensitive and androgen-insensitive prostate cancer cells have been assessed using a WST-1 cell proliferation assay. All derivatives exhibited greater antiproliferative potency than silibinin, with 2,3-dehydrosilibinins each possessing a three- to five-carbon linear alkyl group to 3-OH (IC50 values in a range of 1.71-3.06μM against PC-3 and LNCaP cells) as the optimal derivatives. The optimal potency was reached with three- to five-carbon alkyl groups. Our findings suggest that 3-O-propyl-2,3-dehydrosilibinin effectively inhibits the growth of PC-3 prostate cancer cells by arresting cell cycle in the G0/G1 phase, but not by activating PC-3 cell apoptosis. PMID:27261177

  2. Measuring exposures to glycol ethers.

    PubMed

    Clapp, D E; Zaebst, D D; Herrick, R F

    1984-08-01

    In 1981, NIOSH began investigating the potential reproductive health effects resulting from exposures to a class of organic solvents known generically as glycol ethers (GE). This research was begun as a result of the NIOSH criteria document development program which revealed little data available on the health effects of glycol ether exposure. Toxicologic research was begun by NIOSH and other researchers which suggested substantial reproductive effects in animals. These animal data motivated a study of human exposures in the occupational setting. In 1981 and 1982 NIOSH conducted several walk-through surveys which included preliminary measurements of exposures in a variety of industries including painting trades, coal mining, production blending and distribution facilities, aircraft fueling, and communications equipment repair facilities. The human exposure data from these surveys is summarized in this paper with most results well below 1 parts per million (ppm) and only a few values approaching 10 ppm. Blood samples were collected at one site resulting in GE concentrations below the limit of detection. Exposures to airborne glycol ethers, in the industries investigated during the collection of this data, revealed several problems in reliably sampling GE at low concentrations. It became apparent, from the data and observations of work practices, that air monitoring alone provided an inadequate index of GE exposure. Further field studies of exposure to GE are anticipated, pending location of additional groups of exposed workers and development of more reliable methods for characterizing exposure, especially biological monitoring. PMID:6499824

  3. Reactions of Vinyl Groups on a Model Chromia Surface: Vinyl Chloride on Stoichiometric Alpha-Cr2O3 (1012)

    SciTech Connect

    McKee, M.; Ma, Q; Mullins, D; Neurock, M; Cox, D

    2009-01-01

    The thermal reaction of vinyl chloride on nearly-stoichiometric ?-Cr2O3 View the MathML source produces gas phase acetylene, ethylene, 1,3-butadiene, and dihydrogen, and results in the deposition of chlorine adatoms. No surface carbon or combustion products (CO, CO2, H2O) are observed. Thermal desorption and spectroscopic studies indicate that the surface reaction of vinyl chloride proceeds through C-Cl bond cleavage to form Cl adatoms and surface vinyl groups which dehydrogenate to acetylene, hydrogenate to ethylene, and couple to form butadiene. Cl adatoms affect surface reactivity in two ways: (1) by increasing the barrier to vinyl dehydrogenation from 145 to 160 kJ/mol, and (2) by blocking Cr3+ sites which shuts down the surface chemistry. Selectivity to butadiene is dependent on Cl adatom coverage, where the increased stability of vinyl intermediates at lower Cl coverages gives rise to more butadiene coupling product. At higher Cl coverages, Cl appears to inhibit the mobility of surface vinyl and decreases the reaction probability for coupling. Photoemission and near edge X-ray absorption fine structure (NEXAFS) spectra show that a mixed monolayer of molecular and dissociated vinyl chloride is formed at 130 K. The polarization dependence of the NEXAFS indicates that vinyl chloride ?-bonds with the molecular plane nominally parallel to the surface, while vinyl intermediates ?-bond at Cr centers with the molecular plane nominally perpendicular to the surface, in agreement with DFT predictions of the adsorption geometries.

  4. Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, George W.; Onwo, Wilfred M.; Cronin, John R.

    1992-01-01

    Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.

  5. A STUDY OF FUNDAMENTAL REACTION PATHWAYS FOR TRANSITION METAL ALKYL COMPLEXES. I. THE REACTION OF A NICKEL METHYL COMPLEX WITH ALKYNES. II. THE MECHANISM OF ALDEHYDE FORMATION IN THE REACTION OF A MOLYBDENUM HYDRIDE WITH MOLYBDENUM ALKYLS

    SciTech Connect

    Huggins, John Mitchell

    1980-06-01

    I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl~ acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve initial cis addition. However, a coordinatively unsaturated vinylnickel complex is initially formed which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted kinetic reaction products. II. The reaction of CpMo(CO){sub 3}H (1a) with CpMo(CO){sub 3}R (2, R= CH{sub 3}, C{sub 2}H{sub 5}) at 50{degrees} C in THF gives the aldehyde RCHO and the dimers [CpMo(CO){sub 3}]{sub 2} (3a) and [CpMo(CO){sub 2}]{sub 2} (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand it was possible to show that the

  6. Toxicity of vinyl chloride and poly(vinyl chloride): a critical review.

    PubMed Central

    Wagoner, J K

    1983-01-01

    In 1974, vinyl chloride (VC) was first reported in the open scientific literature to induce angiosarcoma of the liver both in humans and in animals. Additional research has now demonstrated the carcinogenicity of VC to other organs and at lower concentrations. The target organs for VC now clearly include the liver, brain and the lung, and probably the lymphohematopoietic system. The evidence for a carcinogenic risk has been extended to jobs associated with poly(vinyl chloride) exposure. Cases of liver angiosarcoma have been reported among individuals employed in PVC fabrication facilities and an epidemiological study has demonstrated a significant association between exposure to PVC dust and the risk of lung cancer mortality. Cases of angiosarcoma of the liver also have been reported among individuals living in near proximity to vinyl chloride-poly(vinyl chloride) plants. An association between PVC dust and pneumoconiosis also has been demonstrated. On the basis of findings, prudent control of PVC dust in the industrial setting is indicated. PMID:6360677

  7. Crystalline Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    Series of imide/arylene ether block copolymers prepared by using arylene ether blocks to impart low melt viscosity, and imide blocks to provide high strength and other desirable mechanical properties. Work represents extension of LAR-14159 on imide/arylene ether copolymers in form of films, moldings, adhesives, and composite matrices. Copolymers potentially useful in variety of high-temperature aerospace and microelectronic applications.

  8. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  9. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  10. Aerobic biodegradation of vinyl chloride in groundwater samples

    SciTech Connect

    Davis, J.W.; Carpenter, C.L. )

    1990-12-01

    Studies were conducted to examine the biodegradation of {sup 14}C-labeled vinyl chloride in samples taken from a shallow aquifer. Under aerobic conditions, vinyl chloride was readily degraded, with greater than 99% of the labeled material being degraded after 108 days and approximately 65% being mineralized to {sup 14}CO{sub 2}.

  11. 40 CFR 721.3140 - Vinyl epoxy ester.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Vinyl epoxy ester. 721.3140 Section 721.3140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3140 Vinyl epoxy ester. (a)...

  12. AIR TOXICS EMISSIONS FROM A VINYL SHOWER CURTAIN

    EPA Science Inventory

    The paper reports results of both static and dynamic chamber tests conducted to evaluate emission characteristics of air toxics from a vinyl shower Curtain. (NOTE: Due to the relatively low price and ease of installation, vinyl shower curtains have been widely used in bathrooms i...

  13. ASSOCIATION BETWEEN BIRTH DEFECTS AND EXPOSURE TO AMBIENT VINYL CHLORIDE

    EPA Science Inventory

    To better define the association between exposure to vinyl chloride monomer (VCM) and the occurrence of birth defects, this epidemiological study was made in Shawinigan, Quebec, Canada, where a vinyl chloride polymerization plant has operated since 1943. Birth-defect rates in Sha...

  14. 40 CFR 721.10255 - Vinyl carboxylic acid ester (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Vinyl carboxylic acid ester (generic... Specific Chemical Substances § 721.10255 Vinyl carboxylic acid ester (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  15. 40 CFR 721.10255 - Vinyl carboxylic acid ester (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Vinyl carboxylic acid ester (generic... Specific Chemical Substances § 721.10255 Vinyl carboxylic acid ester (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  16. 40 CFR 721.10255 - Vinyl carboxylic acid ester (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Vinyl carboxylic acid ester (generic... Specific Chemical Substances § 721.10255 Vinyl carboxylic acid ester (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  17. Production of methyl-vinyl ketone from levulinic acid

    DOEpatents

    Dumesic, James A.; West; Ryan M.

    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.

  18. LaRC-ITPI/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Working, Dennis C.

    1991-01-01

    As part of an effort to develop high performance structural resins for aerospace applications, work has continued on block copolymers containing imide and arylene ether segments. The arylene ether block used in this study contains a bulky fluorene group in the polymer backbone while the imide block contains an arylene ketone segment similar to that in the arylene ether block and has been named LaRC-ITPI. A series of imide/arylene ether block and segmented copolymers were prepared and characterized. Films were prepared from these copolymers and mechanical properties were measured.

  19. Palladium-Catalyzed, Ring-Forming Aromatic C–H Alkylations with Unactivated Alkyl Halides

    PubMed Central

    Venning, Alexander R. O.; Bohan, Patrick T.; Alexanian, Erik J.

    2015-01-01

    A catalytic C–H alkylation using unactivated alkyl halides and a variety of arenes and heteroarenes is described. This ring-forming process is successful with a variety of unactivated primary and secondary alkyl halides, including those with β-hydrogens. In contrast to standard polar or radical cyclizations of aromatic systems, electronic activation of the substrate is not required. The mild, catalytic reaction conditions are highly functional group tolerant and facilitate access to a diverse range of synthetically and medicinally important carbocyclic and heterocyclic systems. PMID:25746442

  20. Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases

    SciTech Connect

    He, Jiayue; Lu, Lu; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-03-01

    Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO2, the selective hydrogenolysis dominates for cleaving the Caliphatic-O bond. Catalyzed by the dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO2 or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.

  1. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia

    2009-09-22

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  2. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  3. The identification of Isopar H in vinyl flooring.

    PubMed

    Wells, Sharee Booke

    2005-07-01

    Vinyl flooring manufacturers use plasticizers to decrease the viscosity and increase the pliability of vinyl. Several ignitable liquid plasticizers used in the manufacture of vinyl flooring were identified and investigated in this study. Twenty-nine collections from five major vinyl manufacturers, a total of 72 samples, were analyzed using passive headspace concentration in accordance with the American Society for Testing and Materials (ASTM E 1412-00) and gas chromatographic-mass spectrometric (GC-MS) analysis as described in ASTM E 1618-01 (1,2). Norpar products and TXIB (2,2,4-trimethyl-1,3-pentanediol diisobutyrate) are ignitable liquids common to the manufacture of vinyl flooring and were identified in all recently obtained samples. Isopar H is an ignitable liquid found in various products such as charcoal starters, copier toners, and some solvents (2). Of the 29 collections analyzed, Isopar H was only identified in Armstrong's Interflex-Traditions pattern. PMID:16078489

  4. Organocatalytic Aerobic Oxidation of Benzylic sp(3) C-H Bonds of Ethers and Alkylarenes Promoted by a Recyclable TEMPO Catalyst.

    PubMed

    Zhang, Zhiguang; Gao, Yuan; Liu, Yuan; Li, Jianjun; Xie, Hexin; Li, Hao; Wang, Wei

    2015-11-01

    An entirely metal-free catalyst system consisting of an easily prepared recyclable new TEMPO derived sulfonic salt catalyst, and mineral acids (NaNO2 and HCl) has been developed for selective aerobic oxidation of structurally diverse benzylic sp(3) C-H bonds of ethers and alkylarenes. The mild reaction conditions allow for the generation of synthetically and biologically valued isochromanones and xanthones from readily accessible alkyl aromatic precursors in good yields. PMID:26513695

  5. Ether-linked diglycerides inhibit vascular smooth muscle cell growth via decreased MAPK and PI3K/Akt signaling.

    PubMed

    Houck, Kristy L; Fox, Todd E; Sandirasegarane, Lakshman; Kester, Mark

    2008-10-01

    Diglycerides (DGs) are phospholipid-derived second messengers that regulate PKC-dependent signaling pathways. Distinct species of DGs are generated from inflammatory cytokines and growth factors. Growth factors increase diacyl- but not ether-linked DG species, whereas inflammatory cytokines predominately generate alkyl, acyl- and alkenyl, acyl-linked DG species in rat mesenchymal cells. These DG species have been shown to differentially regulate protein kinase C (PKC) isotypes. Ester-linked diacylglycerols activate PKC-epsilon and cellular proliferation in contrast to ether-linked DGs, which lead to growth arrest through the inactivation of PKC-epsilon. It is now hypothesized that ether-linked DGs inhibit mitogenesis through the inactivation of ERK and/or Akt signaling cascades. We demonstrate that cell-permeable ether-linked DGs reduce vascular smooth muscle cell growth by inhibiting platelet-derived growth factor-stimulated ERK in a PKC-epsilon-dependent manner. This inhibition is specific to the ERK pathway, since ether-linked DGs do not affect growth factor-induced activation of other family members of the MAPKs, including p38 MAPK and c-Jun NH(2)-terminal kinases. We also demonstrate that ether-linked DGs reduce prosurvival phosphatidylinositol 3-kinase (PI3K)/Akt signaling, independent of PKC-epsilon, by diminishing an interaction between the subunits of PI3K and not by affecting protein phosphatase 2A or lipid (phosphatase and tensin homologue deleted in chromosome 10) phosphatases. Taken together, our studies identify ether-linked DGs as potential adjuvant therapies to limit vascular smooth muscle migration and mitogenesis in atherosclerotic and restenotic models. PMID:18723771

  6. Flow-Induced Crystallization of Poly(ether ether ketone)

    NASA Astrophysics Data System (ADS)

    Nazari, Behzad; Rhoades, Alicyn; Colby, Ralph

    The effects of an interval of shear above the melting temperature Tm on subsequent isothermal crystallization below Tm is reported for the premier engineering thermoplastic, poly(ether ether ketone) (PEEK). The effect of shear on the crystallization rate of PEEK is investigated by means of rheological techniques and differential scanning calorimetry (DSC) under a protocol of imposing shear in a rotational cone and plate rheometer and monitoring crystallization after quenching. The rate of crystallization at 320 °C was not affected by shear for shear rates <7 s-1 at 350 °C, whereas intervals of adequate shear at higher shear rates prior to the quench to 320 °C accelerated crystallization significantly. As the duration of the interval of shear above 7 s-1 is increased, the crystallization time decreases but at each shear rate eventually saturates once the applied specific work exceeds ~120 MPa. The annealing of the flow-induced precursors was also investigated. The nuclei were fairly persistent at temperatures close to 350 °C, however very unstable at temperatures above 375 °C. This suggests that the nanostructures formed under shear might be akin to crystalline lamellae of greater thickness, compared to quiescently crystallized lamellae.

  7. MECHANICAL PROPERTIES OF BLENDS OF PAMAM DENDRIMERS WITH POLY(VINYL CHLORIDE) AND POLY(VINYL ACETATE)

    EPA Science Inventory

    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 ...

  8. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  9. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  10. 40 CFR 721.575 - Substituted alkyl halide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  11. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  12. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  13. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  14. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  15. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl amino nitriles (generic)....

  16. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  17. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  18. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  19. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  20. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  1. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl amino nitriles (generic)....

  2. IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

    EPA Science Inventory

    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  3. 40 CFR 721.1852 - Di-alkyl borane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Di-alkyl borane (generic). 721.1852... Substances § 721.1852 Di-alkyl borane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as di-alkyl borane (PMN P-00-1087) is...

  4. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl phosphine oxide... Specific Chemical Substances § 721.10087 Substituted alkyl phosphine oxide (generic). (a) Chemical... as substituted alkyl phosphine oxide (PMN P-06-332) is subject to reporting under this section...

  5. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted alkyl phosphine oxide... Specific Chemical Substances § 721.10087 Substituted alkyl phosphine oxide (generic). (a) Chemical... as substituted alkyl phosphine oxide (PMN P-06-332) is subject to reporting under this section...

  6. 40 CFR 721.9720 - Disubstituted alkyl triazines (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Disubstituted alkyl triazines (generic... Specific Chemical Substances § 721.9720 Disubstituted alkyl triazines (generic name). (a) Chemical... as disubstituted alkyl triazines (PMNs P-85-932 and P-85-933) are subject to reporting under...

  7. 40 CFR 721.10506 - Alkylated phenols (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkylated phenols (generic). 721.10506... Substances § 721.10506 Alkylated phenols (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkylated phenols (PMNs...

  8. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  9. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  10. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  11. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  12. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  13. 40 CFR 721.10506 - Alkylated phenols (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkylated phenols (generic). 721.10506... Substances § 721.10506 Alkylated phenols (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkylated phenols (PMNs...

  14. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  15. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  16. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  17. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  18. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  19. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  20. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...