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Sample records for calix4arene telluropodant ethers

  1. Synthesis and properties of calix[4]arene telluropodant ethers as Ag+ selective sensors and Ag+, Hg2+ extractants

    Directory of Open Access Journals (Sweden)

    Yang Lu

    2009-10-01

    Full Text Available Three novel phenyltelluroalkoxyl functionalized tweezer-like calix[4]arenes 6–8 and two monophenyltelluropropoxyl functionalized calix[4]arenes 10 (cone conformer and 12 (partial cone conformer were synthesized and characterized. They are good Ag+-selective ionophores in ion-selective electrodes evaluated by electromotive force measurements of polymer membrane electrodes. The tweezer-like ionophores 6–8 showed excellent extraction ability towards Ag+ and Hg2+.

  2. Calix[4]arene daisychains.

    Science.gov (United States)

    Sameni, Soheila; Jeunesse, Catherine; Matt, Dominique; Harrowfield, Jack

    2009-07-01

    Generic calix[4]arenes became readily accessible in the late 70s. With their potential eight anchoring points, their utility for the production of sophisticated, highly functionalised macrocyclic molecules was rapidly recognised. While most studies in calixarene chemistry have focused on monocalixarene derivatives, there is now an increasing interest in developing multicalixarene compounds, especially those made of several linearly-arranged calix[4]arene units, the first examples of which were reported in 1989. This critical review will present the most important synthetic routes to such molecules together with an analysis of the properties that such cavity combinations may induce. In particular it will be shown that the nature of the links between the calixarene units plays a determinant role in the product properties and that singly-linked calixarenes can be exploited in varied applications, including those as efficient receptors of large molecules, as electrochemical and luminescent sensors in ion detection, or as new materials allowing capsule formation suitable for the storage of small guests (82 references).

  3. Conjugation, immunoreactivity, and immunogenicity of calix[4]arenes; model study to potential calix[4]arene-based Ac3+ chelators

    NARCIS (Netherlands)

    Grote Gansey, Marcel H.B.; Grote gansey, M.H.B.; de Haan, Annemarie S.; Bos, Ebo S.; Verboom, Willem; Reinhoudt, David

    1999-01-01

    For the development of calix[4]arene-based radiotherapeutic agents, the conjugation to biomolecules and immunogenicity in mice of potential 225Ac3+-chelating calix[4]arenes were studied. A calix[4]arene triethyl ester isothiocyanate and a bis(calix[4]arene) hexacarboxylic acid, containing a masked

  4. Calix[4]arene rhenium(V) complexes as potential radiopharmaceuticals

    NARCIS (Netherlands)

    Bommel, K.J.C.; Verboom, Willem; Hulst, A.J.R.L.; Kooijman, Huub; Spek, Anthony L.; Reinhoudt, David

    2000-01-01

    The calix[4]arene platform was used for the syntheses of novel rhenium(V) complexes, that may have potential applications as radiopharmaceuticals. The reaction of ReO(PPh3)2Cl3 with tetradentate N2O2-calix[4]arene ligand 8 in ethanol gave the novel mixed-ligand rhenium complex 9 with the structure

  5. Polymer inclusion membrane containing a diglycolamide-functionalized calix[4]arene for actinide ion uptake and transport

    NARCIS (Netherlands)

    Mahanty, B.N.; Mohapatra, P.K.; Raut, D.R.; Das, D.K.; Behere, P.G.; Afzal, M.; Verboom, Willem

    2016-01-01

    Cellulose triacetate (CTA) -based polymer inclusion membranes (PIM) containing a diglycolamide-functionalized calix[4]arene (C4DGA) as the carrier extractant and 2-nitrophenyl octyl ether (NPOE) as the plasticizer were evaluated for the separation of actinides such as Am3+, Pu4+, UO22+, and Th4+

  6. Head-to-head linked double calix[4]arenes: convenient synthesis and complexation properties

    NARCIS (Netherlands)

    Struck, O.; Struck, Oliver; Chrisstoffels, L.A.J.; Lugtenberg, R.J.W.; Verboom, Willem; van Hummel, G.J.; Harkema, Sybolt; Reinhoudt, David

    1997-01-01

    Combination of calix[4]arenes functionalized at the upper rim at the 5- and 17-positions with amino and formyl groups, respectively, gives a new series of "head-to-head" linked double calix[4]arenes in nearly quantitative yield. The X-ray structure of a modified double calix[4]arene is reported. The

  7. Novel upper rim functionalizations of calix[4]arenes using the Tscherniac-Einhorn amidomethylation reaction

    NARCIS (Netherlands)

    Bommel, K.J.C.; Westerhof, Folke; Verboom, Willem; Reinhoudt, David; Hulst, A.J.R.L.

    1999-01-01

    A variety of novel upper rim functionalized calix-[4]arenes have been synthesized, using the Tscherniac-Einhorn amidomethylation reaction. Partially or fully alkylated calix [4]arenes bearing propyl or ethoxyethyl substituents could be easily condensed with various N-methylol-amides and -imides

  8. Binucleating behaviour of a proximally-diphosphinated calix[4]arene.

    Science.gov (United States)

    Awada, Mouhamad; Jeunesse, Catherine; Matt, Dominique; Toupet, Loic; Welter, Richard

    2011-10-21

    The long diphosphine 5,11-diphenylphosphanyl-25,26-dipropyloxy-27,28-bis(2-propenyloxy) calix[4]arene (cone) (5), in which the two phosphorus atoms are separated by a semi-rigid linking unit, was prepared in four steps starting from calix[4]arene. Reaction of 5 with AuCl(SEt(2)) or [RuCl(2)(p-cymene)](2) led to calixarenes bearing two metallated pendant arms, [5·(AuCl)(2)] and [5·{RuCl(2)(p-cymene)}(2)], respectively. In the presence of AgBF(4) or [Ni(C(5)H(5))(1,5-cyclooctadiene)]BF(4), diphosphine 5 displayed a marked tendency to form oligomeric material, but under high dilution conditions dimeric species were obtained selectively. The inability of 5 to form chelate complexes was further illustrated by its reaction with [PdCl(2)(1,5-cyclooctadiene)(2)], which led quantitatively to a rare complex in which a diphosphine spans across the dinuclear [PdCl(μ-Cl)(2)PdCl] unit. This journal is © The Royal Society of Chemistry 2011

  9. Calix[4]arene Based Single-Molecule Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Karotsis, Georgios; Teat, Simon J.; Wernsdorfer, Wolfgang; Piligkos, Stergios; Dalgarno, Scott J.; Brechin, Euan K.

    2009-06-04

    Single-molecule magnets (SMMs) have been the subject of much interest in recent years because their molecular nature and inherent physical properties allow the crossover between classical and quantum physics to be observed. The macroscopic observation of quantum phenomena - tunneling between different spin states, quantum interference between tunnel paths - not only allows scientists to study quantum mechanical laws in great detail, but also provides model systems with which to investigate the possible implementation of spin-based solid state qubits and molecular spintronics. The isolation of small, simple SMMs is therefore an exciting prospect. To date almost all SMMs have been made via the self-assembly of 3d metal ions in the presence of bridging/chelating organic ligands. However, very recently an exciting new class of SMMs, based on 3d metal clusters (or single lanthanide ions) housed within polyoxometalates, has appeared. These types of molecule, in which the SMM is completely encapsulated within (or shrouded by) a 'protective' organic or inorganic sheath have much potential for design and manipulation: for example, for the removal of unwanted dipolar interactions, the introduction of redox activity, or to simply aid functionalization for surface grafting. Calix[4]arenes are cyclic (typically bowl-shaped) polyphenols that have been used extensively in the formation of versatile self-assembled supramolecular structures. Although many have been reported, p-{sup t}But-calix[4]arene and calix[4]arene (TBC4 and C4 respectively, Figure 1A) are frequently encountered due to (a) synthetic accessibility, and (b) vast potential for alteration at either the upper or lower rim of the macrocyclic framework. Within the field of supramolecular chemistry, TBC4 is well known for interesting polymorphic behavior and phase transformations within anti-parallel bi-layer arrays, while C4 often forms self-included trimers. The polyphenolic nature of calix[n]arenes (where

  10. Research on Synthesis of New Azo Calix[4]arene and its Dyeing Properties

    OpenAIRE

    Tang Jun; Sun Yu; Li Lingling; Xu Zhen; Lv Zaosheng

    2015-01-01

    With the raw materials of calix[4]arene, benzocaine, tricaine and procaine hydrochloride, three new azo calix[4]arene derivatives—6a, 6b and 6c are synthesized by diazotization–coupling reaction of an aromatic amine, with its yield of 83%, 81% and 83% respectively. The structural characterization is in a way of IR, 1H NMR and elemental analysis. This paper investigates the spectral properties of azo calix[4]arene derivatives under different solution pH conditions through the UV–visible spectr...

  11. Calix[4]arene-cholic acid conjugates: a new class of efficient synthetic ionophores.

    Science.gov (United States)

    Maulucci, Nakia; De Riccardis, Francesco; Botta, Cinzia Barbara; Casapullo, Agostino; Cressina, Elena; Fregonese, Massimo; Tecilla, Paolo; Izzo, Irene

    2005-03-14

    The synthesis of a new class of amphiphilic calix[4]arene-based ionophores, relying on direct reductive amination as a key step, and the evaluation of their H+ and Na+ transporting properties is described.

  12. CONFORMATIONAL EQUILIBRIUM AND SPECTROSCOPIC PROPERTIES OF CALIX[4]ARENE: THEORETICAL STUDY USING AB INITIO METHOD

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    Hanggara Sudrajat

    2010-06-01

    Full Text Available Molecular structures were optimized for the calix[4]arene by ab initio method at the Hartree-Fock level of theory using LANL2DZ and 6-311G basis sets. Conformational equilibrium of four calix[4]arene conformers are reported. The results are compared with experiment, force field, and semiempirical molecular orbital calculations. General trends in relative stabilities of calix[4]arene decrease in following order: cone > partial-cone > 1,2-alternate > 1,3-alternate. The most stable conformer is the cone conformer that is stabilized by an array of four hydrogen bonds and these results agree with the reported experimental observations. All structures were analyzed using theoretical IR, UV-Vis, and 1H NMR spectra attributed to the conformational equilibrium at the Hartree-Fock level of theory using LANL2DZ basis set.     Keywords: ab initio calculation, calix[4]arene, conformations, cone

  13. CALIX[4]ARENE C-145 EFFECTS ON СELLULAR HAEMOSTASIS

    Directory of Open Access Journals (Sweden)

    V. O. Chernyshenko

    2016-06-01

    Full Text Available The aim of the research was to study a potential antithrombotic sodium salt of calix[4]arene-methylene-bis-phosphonic acid (С-145 — on activation and aggregation of platelets in vivo, as well as on proliferation and apoptosis of endothelial cells in the cell culture. Effects of calix[4]arene С-145 estimated in vitro after addition to the platelet rich plasma, and in vivo after intravenous injection into rabbit bloodstream in equivalent amounts (46 μM. Aggregation of platelets was induced by adenosine diphosphate and detected using aggregometer Solar AP2110. Platelet shape and cytoplasmic granularity were monitored on COULTER EPICS XL Flow Cytometer. The level of tissuetype plasminogen activator — tPA — was estimated using enzyme-linked immunosorbent assay ELISA. Effects of calix[4]arene C-145 on culture of endotelial cells cells was studied using 3-(4,5-Dimethylthiazol-2-yl-2,5-Diphenyltetrazolium Bromide — MTT-test. The population of proliferative pool of cells (G2/M+S was determined using flow cytometry. Aggregometry and flow cytometry showed that calix[4]arene C-145 did not activate platelets nor affect their aggregation in vitro. However intravenous injection of calix[4]arene C-145 into the bloodstream of healthy rabbits leads to strong inhibition of platelet aggregation and changes of shape and granularity of most of the platelets after 2 hours of administration. Any additional appearance of endothelial cells activation marker tPA in vivo and any inhibition of calix[4]arene C-145 on proliferation of endothelial cells in cell culture did not observe. So calix[4]arene C-145 had strong anti-platelet effect in vivo that was not a result of their direct action on platelets or endothelial cells in vitro. This allowed to assume the possibility of calix[4]arene C-145 use as an effective antithrombotic agent.

  14. Calix(4)arenes, versatile molecules for second-order nonlinear optics

    Science.gov (United States)

    Kenis, Paul Johan Andre

    This thesis deals with the preparation and characterization of second-order nonlinear optical active calix(4) arene molecules and of calix(4) arene-based materials. The theoretical background of nonlinear optics, the possible applications, and the current research efforts in this area are reviewed after a description of the historical development of nonlinear optics (NLO) and the objectives of the research described in this thesis. Secondly, the molecular second-order NLO properties of different calix (4) arenes are discussed. The second- order nonlinear optical properties of the four possible extreme conformers of tetranitrotetrapropoxy-calix (4) arene are related to their symmetries and dynamics and are compared with predicted properties based on the structures obtained from X-ray diffraction, molecular mechanics and dynamics calculations. Furthermore, calix (4) arene derivatives functionalized with highly polarizable conjugated π-systems and strongly electron-accepting groups, and resorcin (4) arenes functionalized with highly NLO-active groups are synthesized in order to obtain higher NLO activity. The third part deals with calix (4) arene-based systems with macroscopic second-order NLO activity. The calix (4) arene-based polyimides combine the desired properties of good processability, high transparency above 410 nm and, most importantly, second-harmonic generation coefficients that are stable at 80oC. This renders them suitable for frequency doubling applications from 820 to 410 nm. Annealed, unpoled thin films consisting of tetranitrotetrapropoxy-calix (4) arene only (neat films) show two optically and morphologically different domains. In scanning force microscopy (SFM) they exhibit a unique inversion of relative friction upon change of the load on the SFM tip. Furthermore, friction anisotropy was observed in one of the two domains, which originates from different orientations of the surface crystal structure. Poled neat films with second

  15. Non-covalent synthesis of calix[4]arene-capped porphyrins in polar solvents via ionic interactions

    NARCIS (Netherlands)

    Fiammengo, R.; Timmerman, P.; Huskens, Jurriaan; Versluis, Kees; Heck, Albert J.R.; Reinhoudt, David

    2002-01-01

    Non-covalent synthesis of calix[4]arene capped porphyrins can be achieved in polar solvents (up to 45% molar fraction of water) via ionic interaction. Thus tetracationic meso-tetrakis(N-alkylpyridinium-3-yl) porphyrins 1a–d and tetra anionic 25,26,27,28-tetrakis(2-ethoxyethoxy)-calix[4]arene

  16. Radiation stability of diglycolamide functionalized calix[4]arenes in ionic liquid: Solvent extraction, EPR and GC–MS studies

    NARCIS (Netherlands)

    Sengupta, A; Mohapatra, P.K.; Patil, A.B.; Kadam, R.M.; Verboom, Willem

    2016-01-01

    Ionic liquid-based solvent systems containing diglycolamide-functionalized calix[4]arenes (C4DGAs) are efficient for actinide ion extraction from nitric acid feeds. Therefore, the radiolytic stability of three C4DGAs (wide-rim, narrow-rim and both side DGA-functionalized calix[4]arenes) and TODGA

  17. Inherently chiral calix[4]arenes via oxazoline directed ortholithiation: synthesis and probe of chiral space.

    Science.gov (United States)

    Herbert, Simon A; van Laeren, Laura J; Castell, Dominic C; Arnott, Gareth E

    2014-01-01

    The diastereoselective oxazoline-directed lithiation of calix[4]arenes is reported with diastereoselective ratios of greater than 100:1 in some instances. Notably, it has been found that the opposite diastereomer can be accessed via this approach merely through the choice of an alkyllithium reagent. The inherently chiral oxazoline calix[4]arenes have also been preliminarily examined as ligands in the palladium-catalyzed Tsuji-Trost allylation reaction, returning results comparable to their planar chiral ferrocene counterparts pointing towards future application of these types of compounds.

  18. Removal of chromate and phosphate anion from aqueous solutions using calix[4]aren receptors containing proton switchable units

    Energy Technology Data Exchange (ETDEWEB)

    Ertul, Seref; Bayrakci, Mevluet [University of Selcuk, Faculty of Science, Department of Chemistry, 42031 Campus, Konya (Turkey); Yilmaz, Mustafa, E-mail: myilmaz42@yahoo.com [University of Selcuk, Faculty of Science, Department of Chemistry, 42031 Campus, Konya (Turkey)

    2010-09-15

    In the present study four new calix[4]arene amide ionophores (4-7) have been prepared by aminolysis of calix[4]arene diester (3) and investigated their extraction ability toward phosphate and dichromate anions at different pH. The {sup 1}H NMR data showed that the synthesized compounds exist in the cone conformation. Liquid-liquid extraction experiments have been performed to evaluate the dichromate and phosphate anions extraction efficiency of both calix[4]arene bearing amide-pyridinium units (4-7) and the calix[4]arene derivative bearing aminomethyl pyridinium units (8, 9). It was observed that, compounds 4-7 exhibited lower affinity toward phosphate ions than the calix[4]arene derivative bearing amine pyridinium units (8, 9). The extraction of phosphate and dichromate anions by these compounds indicates that the partially protonated pyridyl or amino groups play the major role for the formation of hydrogen bonds and electrostatic interactions.

  19. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    Energy Technology Data Exchange (ETDEWEB)

    Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)

    2009-07-01

    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  20. Visible and near-infrared light emitting calix[4]arene-based ternary lanthanide complexes

    NARCIS (Netherlands)

    Hebbink, G.A.; Klink, S.I.; Oude Alink, Patrick G.B.; van Veggel, F.C.J.M.

    2001-01-01

    In this article ternary lanthanide complexes consisting of a calix[4]arene unit and dibenzoylmethane (dbm) as the antenna are described. In the europium complex [(Eu)2]NO3 two solvent molecules are still coordinated to the ion, making substitution of them by the dbm antenna possible. In the ternary

  1. Hybrid calix[4]arenes via ionic hydrogenation and transition-metal-mediated processes.

    Science.gov (United States)

    Bew, Sean P; Brimage, Rebecca A; Hiatt-Gipson, Glyn; Sharma, Sunil V; Thurston, Sean

    2009-06-18

    We report the first application of ionic hydrogenation for the synthesis of upper-rim urea- or carbamate-derived hybrid calix[4]arenes. Subsequent metal-mediated transformations using 4-iodophenylurea calixarenes afforded structurally unique 1,3-di(biaryl)-, 1,3-di(biarylalkyne)-, or 1,3-(biaryl)(biarylalkyne)-derived hybrid calixarenes.

  2. Research on Synthesis of New Azo Calix[4]arene and its Dyeing Properties

    Directory of Open Access Journals (Sweden)

    Tang Jun

    2015-01-01

    Full Text Available With the raw materials of calix[4]arene, benzocaine, tricaine and procaine hydrochloride, three new azo calix[4]arene derivatives—6a, 6b and 6c are synthesized by diazotization–coupling reaction of an aromatic amine, with its yield of 83%, 81% and 83% respectively. The structural characterization is in a way of IR, 1H NMR and elemental analysis. This paper investigates the spectral properties of azo calix[4]arene derivatives under different solution pH conditions through the UV–visible spectroscopy, and researches the dyeing properties through the dyeing curve, color yield test and fastness test. The results show that, with the increase of pH value, the azo calix[4]arene derivatives—6a, 6b and 6c form azo–hydrazone tautomeric isomers with the maximum absorption peak redshift; the dyeing effect of the compound is good, of which the dye–uptake rate of the compound 6a is as high as 78%; the surface depth of color yield is 2.798, and the dry and wet rubbing fastness and the soaping fastness are respectively 4, which is a better disperse dye.

  3. Calix[4]arene supported clusters: a dimer of [Mn(III)Mn(II)] dimers

    DEFF Research Database (Denmark)

    Taylor, Stephanie M; McIntosh, Ruaraidh D; Beavers, Christine M

    2011-01-01

    Phosphinate ligands allow for the transformation of a calix[4]arene supported [Mn(III)(2)Mn(II)(2)] tetramer cluster motif into an unusual [Mn(III)Mn(II)](2) dimer of dimers; the clusters self-assemble in the crystal to form bi-layer arrays reminiscent of the typical packing of calixarene solvates....

  4. Noncovalent assembly of functional groups on calix[4]arene molecular boxes

    NARCIS (Netherlands)

    Timmerman, P.; Vreekamp, R.H.; Vreekamp, Remko H.; Hulst, A.J.R.L.; Verboom, Willem; Reinhoudt, David; Rissanen, Kari; Udachin, Konstatin A.; Ripmeester, John

    1997-01-01

    Calix[4]arenes diametrically substituted at the upper rim with two melamine units spontaneously form well-defined box-like assemblies in the presence of two equivalents of 5,5-diethylbarbituric acid. These assemblies, consisting of nine different components, are held together by 36 hydrogen bonds

  5. Molecular dynamics simulations of free energy and conformational transition rates of calix[4]arene in chloroform

    NARCIS (Netherlands)

    den Otter, Wouter K.; Briels, Willem J.

    1997-01-01

    In a previous article we introduced a reaction coordinate based on the unstable normal mode at the saddle point of the potential energy surface. We here calculate the free-energy distribution along this coordinate for the isomerization of calix[4]arene in vacuo and in chloroform using umbrella

  6. Silver selective electrodes based on thioether functionalized calix[4]arenes as ionophores

    NARCIS (Netherlands)

    Malinowska, Elz˙bieta; Brzozka, Zbigniew; Kasiura, Krzysztof; Egberink, Richard J.M.; Reinhoudt, David

    1994-01-01

    Silver selective electrodes based on thioether functionalized calix[4]arenes 1 and 2 as ionophores were investigated. For both ionophores the selectivity coefficients (log kAg,M) were lower than −2.2 for Hg(II) and lower than −4.6 for other cations tested. The best results were obtained with

  7. Lead selective electrodes based on thioamide functionalized calix[4]arenes as ionophores

    NARCIS (Netherlands)

    Malinowska, Elz˙bieta; Brzozka, Zbigniew; Kasiura, Krzysztof; Egberink, Richard J.M.; Reinhoudt, David

    1994-01-01

    Lead selective electrodes based on a di- and tetrathioamide functionalized calix [4] arene as ionophores were investigated. The Pb(II)-response functions exhibited almost theoretical Nernstian slopes in the activity range 10¿6¿10¿2M of lead ions. For both ionophores a preference for lead over other

  8. Calix[4]arene C-99 inhibits myosin ATPase activity and changes the organization of contractile filaments of myometrium

    Directory of Open Access Journals (Sweden)

    R. D. Labyntseva,

    2015-12-01

    Full Text Available Calix[4]arenes are cup-like macrocyclic (polyphenolic compounds, they are regarded as promising molecular “platforms” for the design of new physiologically active compounds. We have earlier found that сalix[4]arenе C-99 inhibits the ATPase activity of actomyosin and myosin subfragment-1 of pig uterus іn vitro. The aim of this study was to investigate the interaction of calix[4]arene C-99 with myosin from rat uterine myocytes. It was found that the ATPase activity of myosin prepared from pre-incubated with 100 mM of calix[4]arene C-99 myocytes was almost 50% lower than in control. Additionally, we have revealed the effect of calix[4]arene C-99 on the subcellular distribution of actin and myosin in uterus myocytes by the method of confocal microscopy. This effect can be caused by reorganization of the structure of the contractile smooth muscle cell proteins due to their interaction with calix[4]arene. The obtained results demonstrate the ability of calix[4]arene C-99 to penetrate into the uterus muscle cells and affect not only the myosin ATPase activity, but also the structure of the actin and myosin filaments in the myometrial cells. Demonstrated ability of calix[4]arene C-99 can be used for development of new pharmacological agents for efficient normalization of myometrial contractile hyperfunction.

  9. Synthesis of N,O-Type Inherently Chiral Calix[4]arenes Substituted on the Lower Rim and their Organocatalysis Properties

    OpenAIRE

    Chang, Ming-Liang; He, Yong; Zhou, Jing; Li, Shao-Yong

    2017-01-01

    This work presented the first study of organocatalytic behaviors of inherently chiral calix[4]arenes substituted at the lower rim. A pair of N, O-type enantiomers based on inherently chiral calix[4]arenes substituted at the lower rim were readily synthesized and applied to catalyze Henry reaction between aromatic aldehydes and nitromethane. Their organocatalytic reaction can afford the desired products in excellent yields (up to 99%) but poor enantioselectivities (up to 7.5% ee).

  10. The Use of a Flexible Calix[4]arene Template to Stabilize a Cyclooctatetraindiyl Samarium-Potassium Complex

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    Geoffroy Guillemot

    2013-01-01

    Full Text Available A sandwich compound of cyclooctatetraendiyl (COT2− samarium-potassium was synthesized and analyzed using a flexible calix[4]arene dianion. This compound, [p-tBu-calix[4]-(OMe2(O2]arenediyl-samarium-(η8-cyclooctatetraendiyl-potassium (tetrahydrofurane3, is constructed as a linear sequence L-Sm--K-, where L, , and are specific ligands with L = O,O-dimethyl-calix[4]arene2−, = cyclo-octatetraendiyl, and = tetrahydrofurane templates.

  11. Polyoxomolybdate-Calix[4]arene Hybrid: A Catalyst for Sulfoxidation Reactions with Hydrogen Peroxide.

    Science.gov (United States)

    Meninno, Sara; Parrella, Alessandro; Brancatelli, Giovanna; Geremia, Silvano; Gaeta, Carmine; Talotta, Carmen; Neri, Placido; Lattanzi, Alessandra

    2015-10-16

    An easily accessible polyoxomolybdate-calix[4]arene hybrid 1 has been synthesized and applied as a heterogeneous catalyst in the sulfoxidation of thioethers to sulfoxides and to sulfones under strictly stoichiometric amounts of 30% H2O2 in CH3CN as the solvent. This study represents the first promising example of successful employment of calixarenes-polyoxometalate (POM) hybrid materials in the area of catalytic oxidations.

  12. Amphiphilic Perylene-Calix[4]arene hybrids:synthesis and tunable self-assembly

    OpenAIRE

    Rodler, Fabian; Schade, Boris; Jaeger, Christof M.; Backes, Susanne; Hampel, Frank; Boettcher, Christoph; Clark, Timothy; Hirsch, Andreas

    2015-01-01

    The first highly water-soluble perylene–calix[4]arene hybrid with the calixarene scaffold acting as a structure-determining central platform is presented. In this tetrahedrally shaped amphiphilic architecture the hydrophilic and hydrophobic subunits are oriented at the opposite side of the calixarene platform. The hydrophobic part contains the two perylene diimide moieties, which enable strong π–π interactions in self-assembly processes. Two hydrophilic Newkome-type dendrons provide sufficien...

  13. Studies of morphological optical and electrical properties of the MEH-PPV/azo-calix[4]arene composite layers

    Energy Technology Data Exchange (ETDEWEB)

    Rouis, A., E-mail: rouisahlem2@yahoo.fr [Laboratoire des Interfaces et Matériaux Avancés (LIMA), Faculté des Sciences de Monastir, Avenue de l’environnement, 5000 Monastir (Tunisia); Davenas, J. [Polymer Materials Engineering Laboratory IMP, UMR CNRS 5223, Université Claude Bernard Lyon 1, 15 boulevard Latarjet, 69622 Villeurbanne (France); Bonnamour, I. [Institut de Chimie & Biochimie Moléculaires & Supramoléculaires (ICBMS), UMR CNRS 5246, 43 Boulevard du 11 Novembre 1918, Université Claude Bernard Lyon 1, 69100 Villeurbanne (France); Ben Ouada, H. [Laboratoire des Interfaces et Matériaux Avancés (LIMA), Faculté des Sciences de Monastir, Avenue de l’environnement, 5000 Monastir (Tunisia)

    2015-10-01

    Thin films of poly[2-methoxy-5-(20-ethylhexyloxy)-1,4 phenylenevinylene] (MEH-PPV), 5,17-bis(4-nitrophenylazo)-26,28-dihydroxy-25,27-di(ethoxycarbonylmethoxy) -calix[4]arene (azo-calix[4]arene) and MEH-PPV doped azo-calix[4]arene, with 30 wt% and 70 wt% doping ratios, were prepared from chloroform solution by spin coating technique on quartz and ITO substrates. Morphological and optical properties of the samples were investigated by scanning electron microscopy (SEM) and UV–visible spectrophotometry techniques, respectively. Further, the charge carrier transport properties and conduction mechanism of the composite MEH-PPV:azo-calix[4]arene thin films based junction were studied by using current–voltage (I–V) characteristics and dielectric spectroscopy technique. I–V characteristic of ITO/MEH-PPV:azo-calix[4]arene/Al devices showed that the space charge limited conduction (SCLC) dominates in the high voltage region. Moreover, frequency dependence of ac conductivity obeys Jonscher's universal power law. Finally, dielectric constant (ε′), dielectric loss (ε″) and loss tangent (tan δ) were investigated as function of amount of azo-calix[4]arene in the MEH-PPV polymer matrix.

  14. Antioxidant and DPPH (1,1-diphenyl-2-picrylhydrazyl Free Radical Scavenging Activities of Boniger Acid and Calix[4]arene Derivative

    Directory of Open Access Journals (Sweden)

    E. ERDEM

    2014-07-01

    Full Text Available Diazonium derivative of calix[4]arene has been synthesized using three different synthetic steps. Initially p-tert-butylcalix[4]arene was synthesized with the condensation reaction of p-tert-butylphenol and formaldehyde in basic conditions. Calix[4]arene was obtained after the debutylation reaction of p-tert-butylcalix[4]arene with AlCl3. Calix[4]arene reacted with diazonium salt of Böniger acid to yield the 5,17-[(Bis(azo-bis(5-hydroxy-2,7-naphthalenedisulfonicacid]-25,26,27,28-tetrahydroxy calix[4]arene which has eight free phenolic hydroxyl group. Reaction steps were shown in Fig.1.2,7-naphthalenedisulfonicacid]-25,26,27,28-tetrahydroxy calix[4]arene The antioxidant activity of the Böniger acid and calix[4]aren derivative were determined using β-karotene-linoleic acid system. Moreover, the free radical scavenging activity values were tested with DPPH free radical. The two compounds showed strong antioxidant activity. Total antioxidant activity of Böniger acid and calix[4]aren derivative was determined using β–carotenelinoleic acid model system and was found the antioxidant activity of 84.00% and 85.60 % respectively. The free radical scavenging activities were determined as 83.05% and 84.69 %. Results show that, two compounds has the antioxidant activity. The calix[4]aren derivaties has more higher activity then Boniger acid because of calix[4]aren derivative has much hydroxl groups.

  15. Development of a pH sensing membrane electrode based on a new calix[4]arene derivative.

    Science.gov (United States)

    Kormalı Ertürün, H Elif; Demirel Özel, Ayça; Sayın, Serkan; Yılmaz, Mustafa; Kılıç, Esma

    2015-01-01

    A new pH sensing poly(vinyl chloride) (PVC) membrane electrode was developed by using recently synthesized 5,17-bis(4-benzylpiperidine-1-yl)methyl-25,26,27,28-tetrahydroxy calix[4]arene as an ionophore. The effects of membrane composition, inner filling solution and conditioning solution on the potential response of the proposed pH sensing membrane electrode were investigated. An optimum membrane composition of 3% ionophore, 67% o-nitrophenyl octyl ether (o-NPOE) as plasticizer, 30% PVC was found. The electrode exhibited a near-Nernstian slope of 58.7±1.1 mV pH(-1) in the pH range 1.9-12.7 at 20±1 °C. It showed good selectivity for H(+) ions in the presence of some cations and anions and a longer lifetime of at least 12 months when compared with the other PVC membrane pH electrodes reported in the literature. Having a wide working pH range, it was not only applied as a potentiometric indicator electrode in various acid-base titrations, but also successfully employed in different real samples. It has good reproducibility and repeatability with a response time of 6-7s. Compared to traditional glass pH electrode, it exhibited excellent potentiometric response after being used in fluoride-containing media. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Protonation of calix[4]arene-(2,3-naphthylene-crown-6,crown-6): Experimental and theoretical study

    Science.gov (United States)

    Kvíčalová, Magdalena; Makrlík, Emanuel; Böhm, Stanislav; Vaňura, Petr; Asfari, Zouhair

    2017-04-01

    On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium H3O+ (aq) + 1·Na+ (nb) ⇄1·H3O+ (nb) + Na+ (aq) occurring in the two-phase water-nitrobenzene system (1 = calix[4]arene-(2,3-naphthylene-crown-6,crown-6); aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex(H3O+,1·Na+) = -0.2 ± 0.1. Further, the stability constant of the 1·H3O+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb(1·H3O+) = 5.9 ± 0.2. Finally, applying quantum chemical DFT calculations, the most probable structure of the cationic complex species 1·H3O+ was derived. In the resulting complex, the "central" cation H3O+ is bound by three strong hydrogen bonds to two phenoxy oxygen atoms and to one ethereal oxygen from the crown-6 moiety of the parent ligand 1. The interaction energy, E(int), of the considered 1·H3O+ complex was found to be -416.0 kJ/mol, confirming the formation of this cationic species as well.

  17. Formation of upper rim acylated calix[4]arenes using a sacrifici al zinc anode

    OpenAIRE

    Louati, Alain; Vataj, Rame; Gabelica, Valérie; Lejeune, Manuel; MATT, DOMINIQUE

    2005-01-01

    A straightforward electrosynthetic method is described, which allows upper rim acylation of non-p-halogenated calix[4]-arenes. For example, a solution of tetrapropoxycalix[4]arene 4 was electrolysed in the presence of ZnBr2, in an undivided cell fitted with a sacrificial zinc anode using pure acetonitrile as solvent, yielding an organozinc species, which was then treated with acetyl chloride in the presence of a palladium catalyst to afford 5,11-diacety1-25,26,27,28-tetrapropoxycalix[4]arene ...

  18. The synthesis and alkylation of p-tetrakischloro-calix[4]arene

    Directory of Open Access Journals (Sweden)

    E. A. Ivanova

    2014-11-01

    Full Text Available This work is devoted to the development of a chlorination of a calixarenes and a testing of the methods for their preparation to investigate the biological activity of the obtained compounds. New convinient undescribed in the literature methods of the chlorination using sulphuryl chloride or sodium hypochlorite were designed. By the using de-tert-butylcalix[4]arene, containing lower rin the ethoxy(hydroxycarbonyl metoxy groups, as the starting compounds in the same reactin l aed to mixture of the produts. The reaction of the calix[4]arene and the sulfuryl chloride led to the tetra-kis-chlorocalix[4]arene with good yield (95 %.

  19. Kinetics of inhibitory effect of calix[4]arene С-90 on activity of transporting plasma membrane Cа(2+,Mg(2+-ATPase of smooth muscle cells

    Directory of Open Access Journals (Sweden)

    T. O. Veklich

    2014-10-01

    Full Text Available In experiments on the suspension of myometrium cell plasma membrane, processed by 0.1% digitonin, the inhibitory action of calix[4]arene C-90 (5,11,17,23-tetra(threeftormethyl(phenilsulphonilimino-methylamino-25,26, 27,28-tetrapropoxy-calix[4]arene on the activi­ty of Ca2+,Mg2+-ATPase was investigated. The authors also examined the influence of calix[4]arene in different concentration on affinity of enzyme (Ca2+,Mg2+-ATPase for the ATP and ions of Mg and Ca, and its influence on cooperative effect and maximum velocity of ATP hydrolysis. It is shown that calix[4]arene does not influence the affinity of Ca2+,Mg2+-ATPase for the ATP, which means that these two compounds have different binding centers­. Also calix[4]arene has no influence on affinity and cooperative effect of Ca ions, if it is used in concentration lower than 50 µM. Calix[4]arene slightly increases coefficient of Ca2+,Mg2+-ATPase activation by magnesium chloride. In all three cases, where ATP, Mg and Ca ions are used to test the impact of calix[4]arene, maximum velocity of ATP hydrolysis significantly decreases. All these results clarify that calix[4]arene implements its inhibitory action through mechanism of uncompetitive inhibition of Ca2+,Mg2+-ATPase activity.

  20. Pyrazine-functionalized calix[4]arenes: synthesis by palladium-catalyzed cross-coupling with phosphorus pronucleophiles and metal ion extraction properties

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, Jurriaan; Ansari, S.A.; Mohapatra, P.K.; Verboom, Willem

    2013-01-01

    A series of pyrazine-based calix[4]arene extractants was prepared by a stepwise functionalization, comprising palladium-catalyzed exhaustive cross-coupling of di- and tetrasubstituted calix[4]arenes bearing chloropyrazine moieties. The extraction behavior of the synthesized ligands was studied on

  1. Calix[4]arene C-90 and its analogs activate ATPase of the myometrium myosin subfragment-1

    Directory of Open Access Journals (Sweden)

    R. D. Labyntseva

    2016-10-01

    Full Text Available Numerous female reproductive abnormalities are consequences of disorders in uterus smooth muscle (myometrium contractile function. In this work, we described activators of ATPase, which could be used for development of effective treatments for correcting this dysfunction. Myosin ATPase localized in the catalytic domain of myosin subfragment-1 transforms a chemical energy deposited in macroergic bonds of ATP into mechanical movement. It was shown that сalix[4]arene C-90 and its structural analogs functionalized at the upper rim of macrocycle with four or at least two N-phenylsulfonуltrifluoroacetamidine groups, are able to activate ATP hydrolysis catalyzed by myometrium myosin subfragment-1. It was shown with the method of computer modeling that N-phenylsulfonуltrifluoroacetamidine groups of calix[4]arene C-90 interact with responsible for binding, coordination and the hydrolysis of ATP amino acid residues of myosin subfragment-1. The results can be used for further research aimed at using calix[4]arene C-90 and its analogs as pharmacological compounds that can effectively normalize myometrium contractile hypofunction.

  2. Sequential FRET processes in calix[4]arene-linked orange-red-green perylene bisimide dye zigzag arrays

    NARCIS (Netherlands)

    Hippius, C.; van Stokkum, I.H.M.; Gsänger, M.; Groeneveld, M.M.; Williams, R.M.; Würthner, F.

    2008-01-01

    Perylene bisimide-calix[4]arene arrays composed of up to three different types of perylene bisimide chromophores (orange, red, and green PBIs) have been synthesized. Within these arrays, the individual chromophoric building blocks are positioned in defined spatial orientation and are easily

  3. Role of organic diluent on actinide ion extraction using a both-side diglycolamide-functionalised calix[4]arene

    NARCIS (Netherlands)

    Sengupta, A; Mohapatra, P.K.; Iqbal, M.; Huskens, Jurriaan; Verboom, Willem

    2013-01-01

    Extraction of Am3+ was done using a both-side diglycolamide-functionalised calix[4]arene with eight DGA pendent arms (Calix8DGA) in several organic diluents. The observed extraction trend was nitrobenzene>n-dodecane (with 5% isodecanol as phase modifier) > phenyltrifluoromethylsulphone (PTMS) >

  4. A bioinspired approach for controlling accessibility in calix[4]arene-bound metal cluster catalysts

    Science.gov (United States)

    de Silva, Namal; Ha, Jeong-Myeong; Solovyov, Andrew; Nigra, Michael M.; Ogino, Isao; Yeh, Sheila W.; Durkin, Kathleen A.; Katz, Alexander

    2010-12-01

    In enzymes, the electronic and steric environments of active centres, and therefore their activity in biological processes, are controlled by the surrounding amino acids. In a similar manner, organic ligands have been used for the `passivation' of metal clusters, that is, inhibition of their aggregation and control of their environment. However, the ability of enzymes to maintain large degrees of accessibility has remained difficult to mimic in synthetic systems in which little room, if any, is typically left to bind to other species. Here, using calix[4]arene macrocycles bearing phosphines as crude mimics of the rigid backbones of proteins, we demonstrate the synthesis of gold clusters and the control of their accessibility through an interplay between the sizes of the calixarene ligands and metal cores. For 0.9-nm cores, 25% of all the gold atoms within the cluster bind to the chemisorption probe 2-naphthalenethiol. This accessibility dramatically decreases with 1.1-nm and 4-nm gold cores.

  5. Synthesis of bifunctional receptor for fluoride and cadmium based on calix[4]arene with thiourea moieties

    Science.gov (United States)

    Quiroga-Campano, C.; Gómez-Machuca, H.; Moris, S.; Jara, P.; De la Fuente, J. R.; Pessoa-Mahana, H.; Jullian, C.; Saitz, C.

    2017-08-01

    A new calix[4]arene thiourea derivative bearing a benzothiazolyl moiety (L) was synthetized and characterized by single crystal X-ray, NMR and ESI-TOF. The binding ability of the bifunctional receptor towards several ions was investigated in acetonitrile by means of UV-Visible and NMR spectroscopy. The UV-Vis studies of receptor L demonstrated a stoichiometry of 1:1 for all ions studied. Also, recognize selectively F- and Cd2+ with a detection limit of 97 and 37 μM, respectively. Also, 1H NMR titration of receptor L indicated that both thiourea bridge and phenolic hydroxyl functional groups played a critical role in the binding of F- and Cd2+ ions. 1H NMR spectrum showed that receptor L has a flattened-cone conformation in solution that changes to a cone conformation in the presence of fluoride while cadmium maintained the initial conformation.

  6. Selectivity of calix[4]arene-bis(benzocrown-6) in the complexation and transport of francium ion.

    Science.gov (United States)

    Haverlock, Tamara J; Mirzadeh, Saed; Moyer, Bruce A

    2003-02-05

    It is shown for the first time that a representative member of the "cesium-selective" calix[4]arene-crown-6 family exhibits a high affinity for Fr+ ion. In the investigation, the transport of 221Fr+ and Cs+ ions by calix[4]arene-bis(benzocrown-6) from an aqueous sodium nitrate solution into the water-immiscible diluent 1,2-dichloroethane was measured and compared to address the question of selectivity of the calix-crown-6 cavity toward alkali metal ions of increasing size. Selective separation of 221Fr+ from its parent 225Ac and from the matrix Na+ ions was demonstrated. Higher distribution ratios were obtained than those for the Cs+ ion. The extraction equilibria were determined for the case of the Cs+ ion, and the same equilibria were shown to be applicable to the case of Fr+ with inclusion of additional competitive effects.

  7. Spezifische Spaltung von RNA-Dinucleotiden durch eine synthetische dreikernige Metall(II)-Phosphodiesterase auf Calix[4]aren-Basis

    NARCIS (Netherlands)

    Molenveld, P.; Engbersen, Johannes F.J.; Reinhoudt, David

    1999-01-01

    Große Geschwindigkeitssteigerung und beachtliche Spezifität für Nucleobasen in der katalytischen Umesterung von RNA-Dinucleotiden werden mit dem Calix[4]aren-Enzymmimetikum 1-Zn3 beobachtet (gezeigt ist das Computermodell des Komplexes mit dem Dinucleotid GpG). Die höhere Aktivität für GpG gegenüber

  8. The petentiometric determination of peroxide hydrogen and glucose on the glassy electrode modified by the calix[4]arene.

    Science.gov (United States)

    Jin, Gendi; Du, Shi; Hu, Xiaoya

    2009-12-15

    A new petentiometric method to determine peroxide hydrogen and glucose had been studied. This method had been applied on the petentiometric determination of peroxide hydrogen and glucose in the total ionic strength adjustment buffer (TISAB) (pH 7.5) solution with the glassy electrode modified by the calix[4]arene. The glassy carbon electrode covered with the calix[4]arene depended on the H(2)O(2) concentration in the range of log[H(2)O(2)] from -3.3 to -1.2 in the solution of TISAB (pH 7.5) with nearly Nernstian slope of about 65.6+/-3 mV and the detection limit of peroxide hydrogen was 4.0x10(-5) mol L(-1). The glassy carbon electrode covered with the calix[4]arene depended on the glucose concentration in the range of log[glucose] from -3.6 to -2.8 in the solution of TISAB (pH 7.5) with nearly Nernstian slope of about 50.2+/-2 mV and the detection limit of glucose was 2.0x10(-5) mol L(-1). The electrode had the good selectivity, sensitivity, stability and repeatability.

  9. Amphiphilic perylene-calix[4]arene hybrids: synthesis and tunable self-assembly.

    Science.gov (United States)

    Rodler, Fabian; Schade, Boris; Jäger, Christof M; Backes, Susanne; Hampel, Frank; Böttcher, Christoph; Clark, Timothy; Hirsch, Andreas

    2015-03-11

    The first highly water-soluble perylene-calix[4]arene hybrid with the calixarene scaffold acting as a structure-determining central platform is presented. In this tetrahedrally shaped amphiphilic architecture the hydrophilic and hydrophobic subunits are oriented at the opposite side of the calixarene platform. The hydrophobic part contains the two perylene diimide moieties, which enable strong π-π interactions in self-assembly processes. Two hydrophilic Newkome-type dendrons provide sufficient water solubility at slightly basic conditions. The tetrahedrally shaped amphiphile displays an unprecedented aggregation behavior down to concentrations as low as 10(-7) mol L(-1). The intriguing self-assembly process of the compound in water as well as under changed polarity conditions, achieved by addition of THF, could be monitored by the complemented use of cryogenic transmission electron microscopy (cryo-TEM), UV-vis spectroscopy, and fluorescence spectroscopy. Molecular-dynamics and molecular modeling simulations helped in understanding the interplay of supramolecular and optical behavior.

  10. Supramolecular gels with high strength by tuning of calix[4]arene-derived networks

    Science.gov (United States)

    Lee, Ji Ha; Park, Jaehyeon; Park, Jin-Woo; Ahn, Hyo-Jun; Jaworski, Justyn; Jung, Jong Hwa

    2015-03-01

    Supramolecular gels comprised of low-molecular-weight gelators are generally regarded as mechanically weak and unable to support formation of free-standing structures, hence, their practical use with applied loads has been limited. Here, we reveal a technique for in situ generation of high tensile strength supramolecular hydrogels derived from low-molecular-weight gelators. By controlling the concentration of hydrochloric acid during hydrazone formation between calix-[4]arene-based gelator precursors, we tune the mechanical and ductile properties of the resulting gel. Organogels formed without hydrochloric acid exhibit impressive tensile strengths, higher than 40 MPa, which is the strongest among self-assembled gels. Hydrogels, prepared by solvent exchange of organogels in water, show 7,000- to 10,000-fold enhanced mechanical properties because of further hydrazone formation. This method of molding also allows the gels to retain shape after processing, and furthermore, we find organogels when prepared as gel electrolytes for lithium battery applications to have good ionic conductivity.

  11. Evaluation of Factors Affecting Cesium Extraction Performance by Calix[4]Arene Derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Rumppe, J.L.; Delmau, L.

    2004-01-01

    Novel aza-crown derivatives of dioctyloxy-calix[4]arene crown-6 were examined for their cesium extraction performance at different pH levels. These studies are of interest in addressing high-level waste tank remediation and the removal of 137Cs, a major contributor to heat and radiation generation. Preliminary studies were done to assess the performance of these calixarene compounds under varying conditions. Results showed an increase of cesium extraction with pH as well as expected trends in diluent effects and anion selectivity. Poor extraction performance of some aza-crown derivatives raised questions regarding the possibility of intramolecular hydrogen-bonding. A novel methylated derivative was used to address these questions. Additional experiments were conducted to determine the extraction effect on pH. Results indicate an increase in cesium extraction with pH, as shown in preliminary studies. Mono-aza derivatives were shown to exhibit better cesium extraction performance than their di-aza counterparts. The methylated derivative showed poorer extraction performance than the non-methylated derivative, indicating that completely removing the possibility of intramolecular hydrogen-bonding has negative effects on extraction performance. This suggests that the hydrogen-bonding facilitates anion co-extraction, which would lead to better overall extraction. Mono-aza derivatives were shown to cause unexpected changes in pH. This could possibly be attributed to protonation of the calix crown.

  12. A Cr(VI) selective probe based on a quinoline-amide calix[4]arene

    Science.gov (United States)

    Ferreira, Juliane F.; Bagatin, Izilda A.

    2018-01-01

    A new quinoline-amide calix[4]arene 3-receptor for detection of hazardous anions and cations have been synthesized. The 3-receptor was examined for its sensing properties towards several different anions (Cr2O72 -, SCN-, F-, Cl-, NO3-) and metal ions (Hg2+, Cd2+, Ag+) by UV-vis and fluorescence spectroscopies. It was detected that the 3-receptor has only sensing ability for Cr2O72 - and Hg2+ ions, resulting in the association constants higher for Cr2O72 - than to the Hg2+ ions. High selectivity towards Cr2O72 - were also observed by fluorescence measurement among other ions (F-, Cl-, SCN-, Hg2+, Cd2+, Ag+) with a low limit of detection (7.36 × 10-6 mol dm-3). Proton NMR anion-binding investigations revealed a strong interaction of Cr2O72 - anion with NH and CH groups of the receptor, showing that the combination with hydrogen-bonds donor groups strengthened the anion receptor association. Furthermore, remarkable association constants for dichromate anion obtained by all techniques strongly suggest the 3-receptor as a selective Cr(VI) sensor.

  13. Fabrication of calix[4]arene derivative monolayers to control orientation of antibody immobilization.

    Science.gov (United States)

    Chen, Hongxia; Liu, Feng; Qi, Fangjie; Koh, Kwangnak; Wang, Keming

    2014-03-31

    Three calix[4]arene (Cal-4) derivatives which separately contain ethylester (1), carboxylic acid (2), and crownether (3) at the lower rim with a common reactive thiol at the upper rim were synthesized and constructed to self-assembled monolayers (SAMs) on Au films. After spectroscopic characterization of the monolayers, surface coverage and orientation of antibody immobilized on the Cal-4 derivative SAMs were studied by surface plasmon resonance (SPR) technique. Experimental results revealed that the antibody could be immobilized on the Cal-4 derivatives spontaneously. The orientation of absorbed antibody on the Cal-4 derivative SAMs is related to the SAM's dipole moment. The possible orientations of the antibody immobilized on the Cal-4 derivative 1 SAM are lying-on or side-on, while on the Cal-4 derivative 2 and Cal-4 derivative 3 head-on and end-on respectively. These experimental results demonstrate the surface dipole moment of Cal-4 derivative appears to be an important factor to antibody orientation. Cal-4 derivatives are useful in developing site direct protein chips.

  14. Hydroxyquinoline-calix[4]arene-conjugates as ligands for lanthanide complexes. Preparation, characterization, and extraction properties

    Energy Technology Data Exchange (ETDEWEB)

    Mansel, Alexander [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Reactive Transport; Jaeschke, A.; Kischel, M.; Kersting, B. [Leipzig Univ. (Germany). Inst. fuer Anorganische Chemie

    2017-06-01

    The synthesis of a calixarene-based N{sub 4}O{sub 4} donor ligand H{sub 6}L, in which two 8-hydroxyquinoline-2-carbaldehyde units are appended via hydrazone-carbonylmethoxy linkages in a 1,3-arrangement to the lower rim of tert-butyl-calix[4]arene and its coordination properties towards Eu{sup 3+} are described. Moreover, the ligand H{sub 6}L was found to extract Eu{sup 3+} and Tb{sup 3+} at pH 7-8 from aqueous solution, as established by radiotracing using the radionuclides {sup 160}Tb and {sup 152} Eu.

  15. Laser Spectroscopic and Theoretical Studies of Encapsulation Complexes of Calix[4]arene

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Shohei; Inokuchi, Yoshiya; Ebata, Takayuki; Apra, Edoardo; Xantheas, Sotiris S.

    2011-10-13

    The complexes between the host calix[4]arene (C4A) and various guest molecules such as NH3, N2, CH4, and C2H2 have been investigated via experimental and theoretical methods. The S1-S0 electronic spectra of these guest-host complexes are observed by mass-selected resonant two-photon ionization (R2PI) and laser induced fluorescence (LIF) spectroscopy. The infrared (IR) spectra of the complexes formed in molecular beams are obtained by IR-UV double resonance (IR-UV DR) and IR photodissociation (IRPD) spectroscopy. The supramolecular structures of the complexes are investigated by electronic structure methods (density functional and second order perturbation theory). The current results for the various molecular guests are put in perspective with the previously reported ones for the C4A-Rare Gas (Rg) (Phys. Chem. Chem. Phys. 2007, 126, 141101) and C4A-H2O complexes (J. Phys. Chem. A, 2010, 114, 2967). The electronic spectra of the complexes of C4A with N2, CH4 and C2H2 exhibit red-shifts of similar magnitudes with the ones observed for the C4A-Rg complexes, whereas the complexes of C4A with H2O and NH3 show much larger red-shifts. Most of the IR-UV DR spectra of the complexes, except for C4A-C2H2, show a broad hydrogen bonded OH stretching band with a peak at ~3160 cm-1. The analysis of the experimental results, in agreement with the ones resulted from the electronic structure calculations, suggest that C4A preferentially forms endo-complexes with all the guest species reported in this study. We discuss the similarities and differences of the structures, binding energies and the nature of the interaction between the C4A host and the various guest species. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy

  16. Synthesis and resolution of a multifunctional inherently chiral calix[4]arene with an ABCD substitution pattern at the wide rim: the effect of a multifunctional structure in the organocatalyst on enantioselectivity in asymmetric reactions.

    Science.gov (United States)

    Shirakawa, Seiji; Kimura, Tomohiro; Murata, Shun-ichi; Shimizu, Shoichi

    2009-02-06

    An efficient synthetic route to inherently chiral calix[4]arenes with an ABCD substitution pattern at the wide rim in the cone conformation was developed for the first time. For the synthesis of inherently chiral ABCD-type calix[4]arenes, first 5,11-dibromo-17-(3,5-dimethylphenyl)-25,26,27,28-tetrapropoxycalix[4]arene (9) was prepared as a key intermediate. Then, functionalization of the calix[4]arene 9 was examined, and highly regioselective monofunctionalization was achieved via selective monolithiation of bromo groups. Various multifunctionalized inherently chiral ABCD-type calix[4]arenes can be synthesized by using this method; thus, the synthesis of inherently chiral phosphine and carboxylic acid derivatives of ABCD-type calix[4]arene was demonstrated. In addition, the aminophenol derivative 1b of an ABCD-type calix[4]arene with a 3,5-dimethylphenyl group at the wide rim was synthesized and resolved into optically pure enantiomers. The chiral calix[4]arene 1b was used as an organocatalyst in asymmetric Michael addition reactions of thiophenols. The effect of the 3,5-dimethylphenyl group at the wide rim of calix[4]arene 1b on enantioselectivity was examined, and a positive effect of the 3,5-dimethylphenyl group was observed.

  17. Calix[4]arene-click-cyclodextrin and supramolecular structures with watersoluble NIPAAM-copolymers bearing adamantyl units: “Rings on ring on chain”

    Directory of Open Access Journals (Sweden)

    Bernd Garska

    2010-08-01

    Full Text Available We describe the calixarene-cyclodextrin-coupling via click reaction starting from 5,11,17,23-tetra-tert-butyl-25,27-dipropargylether-26,28-hydroxy-calix[4]arene (calix[4]arene-dipropargylether (2 onto 6I-azido-6I-deoxycyclomaltoheptaose (3 under microwave assisted conditions. The coupling was proven by MALDI-TOF mass spectrometry, 1H NMR and IR-spectroscopy. The pH dependent supramolecular complex formation with poly(NIPAAM bearing attached adamantyl units was investigated by dynamic light scattering (DLS and turbidity measurements.

  18. Diglycolamide-functionalized calix[4]arene for Am(III) recovery from radioactive wastes: liquid membrane studies using a hollow fiber contactor

    NARCIS (Netherlands)

    Ansari, S.A.; Mohapatra, P.K.; Kandwal, P.; Verboom, Willem

    2016-01-01

    The transport of Am(III) from nitric acid feeds was investigated using hollow fiber supported liquid membrane (HFSLM) containing a diglycolamide-functionalized calix[4]arene (C4DGA) as the carrier extractant. The effect of feed acidity and Nd(III) concentration (used to represent Am(III)) in the

  19. Dinuclear and trinuclear Zn(II) calix[4]arene complexes as models for hydrolytic metallo-enzymes. Synthesis and catalytic activity in phosphate diester transesterification

    NARCIS (Netherlands)

    Molenveld, P.; Stikvoort, Wendy M.G.; Kooijman, Huub; Spek, Anthony L.; Engbersen, Johannes F.J.; Reinhoudt, David

    1999-01-01

    Calix[4]arenes modified with two or three Zn(II)-2,6-bis(aminomethyl)pyridyl groups, 3-[Zn]2 and 5-[Zn]3, respectively, were investigated as models for dinuclear and trinuclear metallo-enzymes that catalyze the cleavage of phosphate diesters. Under neutral conditions, 0.48 mM of 3-[Zn]2 causes a

  20. Diglycolamide-functionalized calix[4]arenes showing unusual complexation of actinide ions in room temperature ionic liquids: role of ligand structure, raiolytic stability, emission spectroscopy, and thermodynamic studies

    NARCIS (Netherlands)

    Mohapatra, Prasanta K.; Sengupta, A.; Iqbal, M.; Huskens, Jurriaan; Verboom, Willem

    2013-01-01

    Diglycolamide-functionalized calix[4]arenes (C4DGAs) with varying structural modifications were evaluated for actinide complexation from their extraction behavior toward actinide ions such as UO22+, Pu4+, PuO22+, and Am3+ in the room temperature ionic liquid (RTIL) 1-n-octyl-3-methylimidazolium

  1. Inclusion complex formation of ternary system: Fluoroscein-p-sulfonato calix[4]arene-Cu(2+) by cooperative binding.

    Science.gov (United States)

    Gawhale, Sharadchandra; Jadhav, Ankita; Rathod, Nilesh; Malkhede, Dipalee; Chaudhari, Gajanan

    2015-09-05

    The aqueous solution of fluorescein-para sulfonato calix[4]arene-metal ion complex has been studied based on absorption, fluorescence, (1)H NMR and FTIR spectroscopic results. It was found that the fluorescence intensity quenched regularly upon addition of pSCX4 and metal ion. The quenching constants and binding constants were determined for pSCX4-FL and pSCX4-FL-Cu(2+) systems. 1:1 stoichiometry is obtained for pSCX4-Cu(2+) system by continuous variation method. The NMR and IR results indicates the interaction among FL, pSCX4 and Cu(2+). The combined results demonstrate the cooperative binding to design the complex for ternary system. The life time for binary and ternary system has been studied. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Spectrofluorometric study on the inclusion behavior of p-( p-carboxyl benzeneazo) calix[4]arene with norfloxacin

    Science.gov (United States)

    Zhou, Yunyou; Xu, Hongwei; Yu, Huapeng; Chun, Liu; Lu, Qin; Wang, Lun

    2008-07-01

    Spectrofluorometric titrations have been performed to investigate the inclusion behavior of p-( p-carboxyl benzeneazo) calix[4]arene (CBC4A) with norfloxacin (NFLX) in NaAc-HAc buffer solution (pH = 5.0). It was found that the fluorescence intensity of NFLX quenched regularly upon the addition of CBC4A. The results indicated 1:1 complex stoichiometry and an association constant of 8.21 × 10 5 L mol -1 at 20.0 °C were calculated by applying a deduced equation. Job's plot also verified the existence of 1:1 inclusion complex. The proposed interaction mechanism indicates that NFLX goes into (or partially goes into) the cavity of CBC4A with the help of hydrogen bonding and other forces. The various factors (pH value, ionic strength, and surfactants) affecting the inclusion process were examined in details.

  3. Qualitative Analysis of the Helical Electronic Energy of Inherently Chiral Calix[4]arenes: An Approach to Effectively Assign Their Absolute Configuration

    Directory of Open Access Journals (Sweden)

    Shuang Zheng

    2014-06-01

    Full Text Available For all microhelices on aromatic rings of inherently chiral calix[4]arene, an expression was derived from one approximation and one hypothesis on the basis of the electron-on-a-helix model of Tinoco and Woody as follows: 1/E = μ (H − K Δα2 , where μ = 1 for the right-handed microhelix and μ = −1 for the left-handed microhelix; and H and K are constant and greater than zero. The expression correlates microhelical electronic energy (E with the atom polarizability difference (Δα on both microhelix ends, which intuitively and clearly shows the impact of helical substituent polarizability on helical electronic energy. The case analysis almost entirely proves that the qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes with the expression is scientific and can be used to effectively assign their absolute configuration

  4. A new ion selective electrode for cesium (I) based on calix[4]arene-crown-6 compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ramanjaneyulu, P.S. [Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400094 (India); Kumar, Abha Naveen [Bio-Organic Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400094 (India); Sayi, Y.S. [Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400094 (India); Ramakumar, K.L., E-mail: klram@barc.gov.in [Radiochemistry and Isotope Group, Bhabha Atomic Research Centre, Trombay, Mumbai 400094 (India); Nayak, S.K.; Chattopadhyay, S. [Bio-Organic Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400094 (India)

    2012-02-29

    Highlights: Black-Right-Pointing-Pointer First report on Cs(I)-ISE employing 25,27-bis(1-octyloxy)calix[4]arene-crown-6. Black-Right-Pointing-Pointer Higher sensitivity and selectivity achieved by minimizing trans-membrane fluxes. Black-Right-Pointing-Pointer 10 months life time is longest reported so far for membrane based Cs-ISE. Black-Right-Pointing-Pointer Cesium is chemically toxic displaces potassium from muscles and red blood cells. Black-Right-Pointing-Pointer Its monitoring in environment is essential. - Abstract: A polyvinylchloride (PVC) based liquid membrane ion selective electrode (ISE) for cesium has been developed. 25,27-Dihydroxycalix[4]arene-crown-6 (L1), 5,11,17,23-tetra-tert-butyl-25,27-dimethoxycalix[4]arene-crown-6 (L2) and 25,27-bis(1-octyloxy)calix[4]arene-crown-6 (L3) were investigated for their use as ionophores. The cation exchange resin DOWEX-50W was used to maintain low activity Cs{sup +} in inner filling solution to improve the performance. The best response for cesium was observed with L3 along with optimized membrane constituents and composition. Excellent Nernstian response (56.6 mV/decade of Cs(I)) over the concentration range 10{sup -7} to 10{sup -2} M of Cs(I) was obtained with a fast response time of less than 10 s. Detection limit for Cs(I) using the present ISE is 8.48 Multiplication-Sign 10{sup -8} M Cs(I). Separate solution method (SSM) was applied to ascertain the selectivity for Cs(I) over alkali, alkaline earth and transition metal ions. The response of ISE for Cs(I) was fairly constant over the pH range of 4-11. The lifetime of the electrode is 10 months which is the highest life for any membrane based Cs-ISE so far developed. The concentration of cesium ion in two simulated high level active waste streams was determined and results agreed well with those obtained independently employing AAS.

  5. New water soluble Hg2 + selective fluorescent calix[4]arenes: Synthesis and application in living cells imaging

    Science.gov (United States)

    Oguz, Mehmet; Bhatti, Asif Ali; Karakurt, Serdar; Aktas, Mehmet; Yilmaz, Mustafa

    2017-01-01

    The present study demonstrates the synthesis of water-soluble fluorescent calix[4]arenes (6 and 7) and its application in living cell imaging for Hg2 + detection at a low level. The synthesized fluorescent ligands 6 and 7 were characterized by 1H NMR technique. The fluorescent study showed both water soluble ligands were Hg2 + selective and follow photo-induced electron transfer (PET) process. From the fluorimeter titration experiment detection limit was calculated as 1.14 × 10- 5 and 3.42 × 10- 5 for ligand 6 and 7, respectively. From the Benesi-Hildebrand plot binding constant values were evaluated as 666.7 and 733.3 M- 1 for 6 and 7, respectively. The interactions between ligands 6 and 7 and Hg2 + were also demonstrated in living cells, SW-620, using Fluorescent Cell Imager. While ligands 6 and 7 alone show fluorescent properties, they loss their action with the presence of Hg2 + in SW-620 cells.

  6. Interaction of the cesium cation with calix[4]arene-bis(t-octylbenzo-18-crown-6): Extraction and DFT study

    Science.gov (United States)

    Makrlík, Emanuel; Toman, Petr; Vaňura, Petr; Moyer, Bruce A.

    2013-02-01

    From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I- (aq) + 1 (org) ⇔ 1ṡCs+ (org) + I- (org) taking place in the two-phase water-phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as log Kex (1ṡCs+, I-) = 2.1 ± 0.1. Further, the stability constant of the 1ṡCs+ complex in FS 13 saturated with water was calculated for a temperature of 25 °C: log βorg (1ṡCs+) = 9.9 ± 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1ṡCs+ was derived. In the resulting 1ṡCs+ complex, the "central" cation Cs+ is bound by eight bond interactions to six oxygen atoms of the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent ligand 1 via cation-π interaction.

  7. Complexation study of a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand with uranium(VI) in non-aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Anne; Schmeide, Katja [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The actinide uranium, well known from nuclear power cycle, plays also a role in rare earth production as it is an undesired constituent of the respective ores. To facilitate the production of rare earth elements, uranium has to be removed. Due to their modifiable selectivity and solubility calix[n]arenes are interesting compounds for the extraction of actinides and lanthanides. The mechanism of uranium(VI) interaction with a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand (L1) was studied by TRLFS, UV-vis spectroscopy and isothermal calorimetry.

  8. Easy and selective method for the synthesis of various mono-O-functionalized calix[4]arenes: de-O-functionalization using TiCl4.

    Science.gov (United States)

    Bois, Joackim; Espinas, Jeff; Darbost, Ulrich; Felix, Caroline; Duchamp, Christian; Bouchu, Denis; Taoufik, Mostafa; Bonnamour, Isabelle

    2010-11-19

    An efficient and selective method for the monofunctionalization of p-tert-butylcalix[4]arene is described. A mono-de-O-functionalization of disubstituted p-tert-butylcalix[4]arenes using titanium tetrachloride was developed to synthesize a series of monosubstituted p-tert-butylcalix[4]arenes with the pendant functions being ethoxycarbonylmethyloxy, 3-ethoxycarbonylpropyloxy, cyanomethyloxy, 3-cyanopropyloxy, 4-bromobutyloxy, 3-hydroxypropyloxy, propyloxy, 2-methylpropyloxy, 3-butynyloxy, and 3-cyanopropyloxy groups. The reaction mechanism of the formation of 5,11,17,23-tetra-tert-butyl-26,27,28-trihydroxy-25-(3-ethoxycarbonylpropyloxy) calix[4]arene was studied by (1)H NMR and GC/mass spectroscopy monitoring. Reaction of TiCl4 with the disubstituted p-tert-butylcalix[4]arene produced the corresponding dioxocalix[4]arene titanium dichloride complex, which undergoes elimination of ethyl 4-chlorobutyrate, leading to a trioxocalix[4]arene titanium dichloride complex and to monosubstituted calix[4]arene after hydrolysis. These two complexes were also synthesized, isolated, and fully characterized.

  9. Antioxidant and DPPH (1,1-diphenyl-2-picrylhydrazyl Free Radical Scavenging Activities of New the Calix[4]arene-bodipy Derivative

    Directory of Open Access Journals (Sweden)

    E. ERDEM

    2014-07-01

    Full Text Available p-tert-butylcalix[4]arene was synthesized with the condesation reaction of p-tert-butylphenol and formaldehyde in basic conditions and then has derivatized from the both of two hydroxyl position with chloride which is containing donor oxygen atoms. BODIPY compound (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene was synthesized with appropriate pyrrole and aldehyde compounds and then was bonded p-tert-butylcalix[4]arene derivative via lower rim hydroxyl groups.The antioxidant activity of the calix[4]arene-BODIPY compound were determined using β-karotene-linoleic acid system. Moreover, the free radical scavenging activity values were tested with DPPH free radical. The compound showed strong antioxidant activity.Total antioxidant activity of the compound was determined using β–carotenelinoleic acid model system and was found the antioxidant activity of 72,50%. The free radical scavenging activities were determined as 75.19%. Results show that, calix[4]arene-BODIPY compound has the antioxidant activity. 

  10. The inhibitory influence of calix[4]arene of C-90 on the activity of Ca(2+,Mg(2+-ATPases in plasma membrane and sarcoplasmic reticulum in myometrium сells

    Directory of Open Access Journals (Sweden)

    T. O. Veklich

    2016-04-01

    Full Text Available Our study on the plasma membrane vesicles and myometrium cells treated with 0.1% digitonin showed that inhibitory effect of calix[4]arene C-90 (5,11,17,23-tetra(trifluoromethyl(phenylsulphonylimino-methylamino-25,26,27,28-tetrapropoxy-calix[4]arene on the plasma membrane Ca2+,Mg2+-ATPase was more significant than on the Ca2+,Mg2+-ATPase in sarcoplasmic reticulum (the inhibition coefficient I0.5 values were 20.2 ± 0.5 µM and 57.0 ± 1.4 µM for the plasma membrane Ca2+,Mg2+-ATPase and Ca2+,Mg2+-ATPase in sarcoplasmic reticulum, respectively (n = 5. Inhibition kinetics of calix[4]arene C-90 effect on the Ca2+,Mg2+-ATPase activities in plasma membrane and sarcoplasmic reticulum were studied. This substance inhibited both pumps as complete noncompetitive inhibitor. Calix[4]arene C-90 caused the increase of intracellular Ca2+ concentration and decrease of hydrodynamic diameter in smooth muscle cells similar to the action of uterotonic drug oxytocin.

  11. Lithium-ion induced conformational change of 5,17-bis(9-fluorenyl)-25,26,27,28-tetrapropoxy calix[4]arene resulting in an egg-shaped dimeric clathrate

    DEFF Research Database (Denmark)

    Faldt, A.; Krebs, Frederik C; Jørgensen, Mikkel

    2000-01-01

    Synthesis and structural investigation of a 5,17-bis(9-fluorenyl)-25,26,27,28-tetrapropoxy calix[4]arene and its lithium complex salt that forms a dimeric clathrate with a molecule of solvent inside a cavity. At least three different interactions were identified as being responsible for the forma...

  12. A comparative evaluation of the liquid-liquid extraction and pertraction efficiency of a both-side diglycolamide-functionalized calix[4]arene with analogous upper and lower-rim calixarenes for actinide separations

    NARCIS (Netherlands)

    Mohapatra, P.K.; Rout, D.R.; Iqbal, M.; Huskens, Jurriaan; Verboom, Willem

    2013-01-01

    A lower-rim (L-I), an upper-rim (L-II), and a both-side (L-III) diglycolamide-functionalized calix[4]arene were evaluated for the extraction of actinide ions such as UO22+, Pu4+, and Am3+ and fission product element ions such as Eu3+, Cs+, and Sr2+ from dilute nitric acid feed solutions. Conditions

  13. A New Cone Shaped Asymmetrically Substituted Calix[4]arene as an ExcellentIonophore in Construction of Ag(I) ion-Selective Membrane Electrode

    Energy Technology Data Exchange (ETDEWEB)

    Ganjali, Mohammad Reza; Babaei, Leila Hajiagha [Tehran University, Tehran (Iran, Islamic Republic of); Ganjali, Saeed Taghvaei; Modjallal, Atoosa [Azad University, Tehran (Iran, Islamic Republic of); Shamsipur, Mojtaba [Kermanshah University, Kermanshah (Iran, Islamic Republic of); Hosseini, Morteza [Tarbiat Modarres University, Tehran (Iran, Islamic Republic of); Javanbakht, Mehran [Payamenoor University, Delijan (Iran, Islamic Republic of)

    2004-02-15

    A PVC membrane electrode for silver ion based on a new cone shaped calix[4]arene (CASCA) as membrane carrier was prepared. The electrode exhibits a Nernstian response for Ag+ over a wide concentration range (1.0 x 10{sup -1}-8.0 x 10{sup -6} M) with a slope of 58.2 {+-} 0.5 mV per decade. The limit of detection of the sensor is 5.0 x 10{sup -6} M. The sensor has a very fast response time ({approx}5 s) in the concentration range of {<=} = 1.0 x 10{sup -3} M, and a useful working pH range of 4.0-9.5. The proposed sensor displays excellent discriminating ability toward Ag{sup +} ion with respect to common alkali, alkaline earth, transition and heavy metal ions. It was used as an indicator electrode in potentiometric titration of Ag{sup +} with EDTA and in direct determination of silver ion in wastewater of silver electroplating

  14. Structural and spectroscopic investigation of new luminescent hybrid materials based on calix[4]arene-tetracarboxylate and Ln3+ ions (Ln = Gd, Tb or Eu)

    Science.gov (United States)

    Viana, R. S.; Oliveira, C. A. F.; Chojnacki, J.; Barros, B. S.; Alves-Jr, S.; Kulesza, J.

    2017-07-01

    Lanthanide-calixarene hybrid materials are of particular interest due to the combination of the interesting properties of the ligand cavity-like structure and the luminescent features of lanthanides. The aim of this study was to synthesize and investigate the photophysical properties of Eu3+, Tb3+ and Gd3+ hybrids based on calix[4]arene-tetracarboxylate. The preparation of two structurally different Tb3+ compounds (calix-TA-SC-Tb and calix-TA-Tb) was dictated by the ligand to metal molar ratio and the synthesis time. Analysis of calix-TA-SC-Tb monocrystals revealed the formation of a mononuclear complex of C2 symmetry containing Tb3+ coordinated by four calixarene ionized groups and formate anion encapsulated within the upper cavity. Syntheses of other hybrids failed in producing high-quality crystals and the structures could not be solved. The solid-state luminescent properties of hybrids were evaluated, and the structure/property relationship was investigated. Based on the emission and excitation spectra, the energy diagrams for calix-TA-Eu, calix-TA-Tb and calix-TA-Gd were proposed.

  15. Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT of calix[4]arene: A TDDFT study

    Directory of Open Access Journals (Sweden)

    Wang Se

    2016-01-01

    Full Text Available The time-dependent density functional theory (TDDFT method was performed to investigate the excited-state intramolecular double proton transfer (ESIDPT reaction of calix[4]arene (C4A and the role of the intramolecular hydrogen bonds in the ESIDPT process. The geometries of C4A in the ground state and excited states (S1, S2 and T1 were optimized. Four intramolecular hydrogen bonds formed in the C4A are strengthened or weakened in the S2 and T1 states compared to those in the ground state. Interestingly, upon excitation to the S1 state of C4A, two protons H1 and H2 transfer along the two intramolecular hydrogen bonds O1-H1···O2 and O2-H2···O3, while the other two protons do not transfer. The ESIDPT reaction breaks the primary symmetry of C4A in the ground state. The potential energy curves of proton transfer demonstrate that the ESIDPT process follows the stepwise mechanism but not the concerted mechanism. Findings indicate that intramolecular hydrogen bonding is critical to the ESIDPT reactions in intramolecular hydrogen-bonded systems.

  16. Interaction of the thallium cation with 1,3-alternate-25,27-bis(1-octyloxy)calix[4]arene-crown-6: Experimental and theoretical study

    Science.gov (United States)

    Makrlík, Emanuel; Dybal, Jiří; Vaňura, Petr

    2013-06-01

    From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Tl+ (aq) + 1·Cs+ (nb) ⇔ 1·Tl+ (nb) + Cs+ (aq) taking place in the two-phase water-nitrobenzene system (1 = 1,3-alternate-25,27-bis(1-octyloxy)calix[4]arene-crown-6; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log Kex (Tl+, 1·Cs+) = -2.1 ± 0.1. Further, the stability constant of the 1·Tl+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb(1·Tl+) = 11.6 ± 0.2. Finally, by using quantum mechanical DFT calculations, the most probable structures A and B of the cationic complex species 1·Tl+, which are obviously in a dynamic equilibrium, were indicated. In both of these structures of the resulting 1·Tl+ complex, the "central" cation Tl+ is bound by eight strong bond interactions to six oxygen atoms from the 18-crown-6 moiety and to two carbons of the respective two benzene rings of the parent ligand 1 via cation-π interaction.

  17. Calix[4]arene-(2,3-naphthylene-crown-6,crown-6) as an extraordinarily efficient macrocyclic receptor for the univalent thallium cation

    Science.gov (United States)

    Makrlík, Emanuel; Böhm, Stanislav; Kvíčalová, Magdalena; Vaňura, Petr; Asfari, Zouhair

    2015-11-01

    On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Tl+ (aq) + 1.Cs+ (nb) ? 1.Tl+ (nb) + Cs+ (aq) taking place in the two-phase water-nitrobenzene system (1 = calix[4]arene-(2,3-naphthylene-crown-6,crown-6); aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex(Tl+,1.Cs+) = 0.3 ± 0.1. Further, the extremely high stability constant of the 1.Tl+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb(1.Tl+) = 10.0 ± 0.2. Finally, applying quantum mechanical calculations, the most probable structure of the cationic complex species 1.Tl+ was derived. In the resulting complex, the 'central' cation Tl+ is bound by eight strong bonds to six oxygen atoms of the crown-6 moiety and to two carbons from the respective two benzene rings of the parent ligand 1 via cation-π interaction. The interaction energy, E(int), of the considered 1.Tl+ complex was found to be -305.7 kJ/mol, also confirming the formation of this cationic species.

  18. Bis-phosphites and bis-phosphinites based on distally-functionalised calix[4]arenes: coordination chemistry and use in rhodium-catalysed, low-pressure olefin hydroformylation.

    Science.gov (United States)

    Steyer, Stephane; Jeunesse, Catherine; Harrowfield, Jack; Matt, Dominique

    2005-04-07

    Six calix[4]arenes each bearing two non-cyclic PR2 units attached at distal phenolic oxygen atoms, p-Bu t-calix[4]arene-25,27-(OPR2)2-26,28-(OR')2(R = OPh; R'= Prn, L1; R = OPh; R'= CH2CO2Et, L2; R= OPh; R'= CO2 cholesteryl, L3; R = Ph; R'= Prn, 4; R = Ph; R'= CH2CO2Et, L5; R = Ph; R'= CO2cholesteryl, L6) have been synthesized and their coordinative properties investigated. The diphosphites L1-L3, where the P centres are separated by 12 bonds, readily form chelate complexes provided the complexation reaction is achieved either by using a starting complex that possesses good leaving groups or by operating under high dilution in order to avoid oligomer formation. Thus, the cationic complexes [Rh(COD)L1]BF4 and [Rh(COD)L3]BF4 were both formed in high yield by reacting the appropriate diphosphite with either [Rh(COD)(THF)2]BF4 or [Rh(COD)2]BF4. At high dilution, reaction of L3 with the neutral complex [PdCl2(COD)] afforded the chelate complex [PdCl2L3] in 90% yield. The reaction of one equiv. of L1 with [Rh(acac)(CO)2] resulted in the formation of [Rh(acac)L1] without requiring high dilution conditions. When the latter reaction was carried out with 0.5 equiv. of L1, the bimetallic complex [{Rh(acac)(CO)}2(eta]1-P,eta1-P'-L1)] was formed instead. Reaction at high dilution of with the cyclometallated complex [Pd(o-C6H4CH2NMe2)(THF)2]BF4 gave the expected chelate complex [Pd(o-C6H4CH2NMe2)]BF4. The latter slowly converts in solution to an oligomer in which the ligand behaves as a (eta1-P,eta1-P') bridging ligand, thus leading to a less strained structure. All six ligands, when mixed with [Rh(acac)CO2], effectively catalyse the hydroformylation of octene and styrene. In the hydroformylation of octene, the linear aldehyde selectivities observed with L2 and L3 are significantly higher (linear : branched =ca. 10) than those obtained with the other 4 ligands of this study and also with respect to PPh3. Molecular modelling shows that the lower rim substituents of and form

  19. Comparative Study of Tributyltin Adsorption onto Mesoporous Silica Functionalized with Calix[4]arene, p-tert-Butylcalix[4]arene and p-Sulfonatocalix[4]arene

    Directory of Open Access Journals (Sweden)

    Sana Alahmadi

    2014-04-01

    Full Text Available The adsorption of tributyltin (TBT, onto three mesoporous silica adsorbents functionalized with calix[4]arene, p-tert-butylcalix[4]arene and p-sulfonatocalix[4]arene (MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively has been compared. Batch adsorption experiments were carried out and the effect of contact time, initial TBT concentration, pH and temperature were studied. The Koble–Corrigan isotherm was the most suitable for data fitting. Based on a Langmuir isotherm model, the maximum adsorption capacities were 12.1212, 16.4204 and 7.5757 mg/g for MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively. The larger uptake and stronger affinity of MCM-TDI-PC4 than MCM-TDI-C4 and MCM-TDI-C4S probably results from van der Waals interactions and the pore size distribution of MCM-TDI-PC4. Gibbs free energies for the three adsorption processes of TBT presented a negative value, reflecting that TBT/surface interactions are thermodynamic favorable and spontaneous. The interaction processes were accompanied by an increase of entropy value for MCM-TDI-C4 and MCM-TDI-C4S (43.7192 and 120.7609 J/mol K, respectively and a decrease for MCM-TDI-PC4 (−37.4704 J/mol K. It is obviously observed that MCM-TDI-PC4 spontaneously adsorbs TBT driven mainly by enthalpy change, while MCM-TDI-C4 and MCM-TDI-C4S do so driven mainly by entropy changes.

  20. CMPO-calix[4]arenes with spacer containing intramolecular hydrogen bonding: effect of local rigidification on solvent extraction toward f-block elements.

    Science.gov (United States)

    Chu, Hongzhu; He, Lutao; Jiang, Qian; Fang, Yuyu; Jia, Yiming; Yuan, Xiangyang; Zou, Shuliang; Li, Xianghui; Feng, Wen; Yang, Yuanyou; Liu, Ning; Luo, Shunzhong; Yang, Yanqiu; Yang, Liang; Yuan, Lihua

    2014-01-15

    To understand intramolecular hydrogen bonding in effecting liquid-liquid extraction behavior of CMPO-calixarenes, three CMPO-modified calix[4]arenes (CMPO-CA) 5a-5c with hydrogen-bonded spacer were designed and synthesized. The impact of spacer rotation that is hindered by introduction of intramolecular hydrogen bonding upon extraction of La(3+), Eu(3+), Yb(3+), Th(4+), and UO2(2+) has been examined. The results show that 5b and 5c containing only one hydrogen bond with a less hindered rotation spacer extract La(3+) more efficiently than 5a containing two hydrogen bonds with a more hindered rotation spacer, demonstrating the importance of local rigidification of spacer in the design of extractants in influencing the coordination environment. The large difference in extractability between La(3+) and Yb(3+) (or Eu(3+)) by 5b (or 5c), and the small difference by 5a, suggests intramolecular hydrogen bonding do exert pronounced influence upon selective extraction of light and heavy lanthanides. Log-log plot analysis indicates a 1:1, 2:1 and 1:1 stoichiometry (ligand/metal) for the extracted complex formed between 5b and La(3+), Th(4+), UO2(2+), respectively. Additionally, their corresponding acyclic analogs 7a-7c exhibit negligible extraction toward these metal ions. These results reveal the possibility of selective extraction via tuning local chelating surroundings of CMPO-CA by aid of intramolecular hydrogen bonding. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Diglycolamide-functionalized calix[4]arenes showing unusual complexation of actinide ions in room temperature ionic liquids: role of ligand structure, radiolytic stability, emission spectroscopy, and thermodynamic studies.

    Science.gov (United States)

    Mohapatra, Prasanta K; Sengupta, Arijit; Iqbal, Mudassir; Huskens, Jurriaan; Verboom, Willem

    2013-03-04

    Diglycolamide-functionalized calix[4]arenes (C4DGAs) with varying structural modifications were evaluated for actinide complexation from their extraction behavior toward actinide ions such as UO2(2+), Pu(4+), PuO2(2+), and Am(3+) in the room temperature ionic liquid (RTIL) 1-n-octyl-3-methylimidazolium bis(trifluoromethane)sulfonamide (C8mimNTf2). The formation constants were calculated for Am(3+) which showed a significant role of ligand structure, nature of substituents, and spacer length. Although the alkyl substituents on the amidic nitrogen increase the extraction efficiency of americium at lower acidity because of the inductive effect of the alkyl groups, at higher acidity the steric crowding around the ligating site determines the extraction efficiency. All C4DGAs formed 1:1 complexes with Am(3+) while for the analogous Eu(3+) complexes no inner sphere water molecules were detected and the asymmetry of the metal ligand complex differed from one another as proved by time-resolved laser induced fluorescence spectroscopy (TRLIFS). Thermodynamic studies indicated that the extraction process, predominant by the Am(3+)-C4DGA complexation reaction, is exothermic. The unique role of the medium on Am(3+) complexation with the C4DGA molecules with varying spacer length, L-IV and L-V, was noticed for the first time with a reversal in the trend observed in the RTIL compared to that seen in a nonpolar molecular diluent like n-dodecane. Various factors leading to a more preorganized structure were responsible for favorable metal ion complexation. The solvent systems show promise to be employed for nuclear waste remediation, and sustainability options were evaluated from radiolytic stability as well as stripping studies.

  2. Chromatographic behavior of a new hybrid type RP material containing silica bonded 1,3-alternate 25,27-bis-[cyanopropyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene.

    Science.gov (United States)

    Sliwka-Kaszyńska, Magdalena; Łępicka, Kamila; Slebioda, Marek

    2010-10-01

    A novel 1,3-alternate 25,27-bis-[cyanopropyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase (CalixPrCN) was prepared and its structure was confirmed by ATR-FTIR spectroscopy and elemental analysis. The CalixPrCN phase was characterized in terms of its surface coverage, hydrophobic selectivity, aromatic selectivity, shape selectivity, hydrogen bonding capacity, residue metal content, and silanol activity based on Tanaka, Lindner, and SMR 870 test protocols. The effect of the acetonitrile content on the retention and selectivity of the selected neutral, basic, and acidic solutes was studied. The neutral and acidic analytes exhibited classical RP behavior, in which retention time decreases with increasing acetonitrile content. In contrast, basic analytes showed an increase in retention at low and high percentages of acetonitrile, forming "U-shaped" retention profiles. The new calixarene phase was compared with previously reported 1,3-alternate 25,27-bis-[propyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene stationary phase and commercial cyanopropyl column. The results indicate that the CalixPrCN stationary phase behaves like RP packing; however, inclusion complex formation, dipole-dipole, and π-π interactions seem to be involved in the separation process. The selectivity of this phase was demonstrated in separation of polynuclear aromatic hydrocarbons, non-steroidal anti-inflammatory drugs, and sulfonamides as analytes.

  3. Multiple sensor array of Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ complexes of a triazole linked imino-phenol based calix[4]arene conjugate for the selective recognition of Asp, Glu, Cys, and His.

    Science.gov (United States)

    Pathak, Rakesh K; Dessingou, Jayaraman; Rao, Chebrolu P

    2012-10-02

    The triazole linked o-imino phenol appended calix[4]arene conjugate (L) has been synthesized and characterized. The structure of L has been established based on single crystal XRD. The binding and recognition behavior of conjugate, L toward the transition metal ions, such as Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+), has been demonstrated using fluorescence, absorption and ESI-MS techniques. The in situ prepared complexes of these metal ions, namely, [Mn(2)L], [Fe(2)L], [Co(2)L], [Ni(2)L], [Cu(2)L], and [Zn(2)L] have shown recognition toward Glu, Asp, His and Cys. Hence L provides a multiple sensing molecular tool where the response for the recognition of biologically active amino acids of metalloproteins is elicited by the presence of specific metal ion.

  4. The Nature of Aqueous Solutions of a Cationic Calix[4]arene: A Comparative Study of Dye–Calixarene and Dye–Surfactant Interactions

    Directory of Open Access Journals (Sweden)

    V. I. Kalchenko

    2006-08-01

    Full Text Available Among different types of calixarenes, the water–soluble ones are of especial interestbecause of their possible applications in biochemical research. In order to elucidate the natureof aqueous solutions of a cationic amphiphilic calixarene, substituted tetrapropoxycalix[4]arene bearing hydrophilic choline groups at the upper rim, we studied vis–spectroscopically the influence of the above system on the acid–base behavior of threeindicator dyes, namely, 2,4-dinitrophenol, bromophenol blue, and N,N/-dioctadecylrhodamine,at constant ionic strength of 0.05 M, maintained with NaCl addition. Simultaneously,‘apparent’ ionization constants, Kaa , of the same dyes were determined in the presence ofcommon cationic surfactant micelles. Within the concentration range from 1.0×10–5 to 0.01 M,the aforementioned water–soluble calixarene displays effects similar to those of micelles ofcetyltrimethylammonium bromide (or chloride. The shifts of the absorption and emissionbands in the visible region, as well as the alterations of the Kaa values against the ‘aqueous’ones appeared to be very similar in aqueous solutions of both calix[4]arene and cationicsurfactant. A conclusion can be made about aggregation (or association, i.e., micelleformation of the cationic calix[4]arene under study.

  5. Calix[4]arenes with one and two N-linked imidazolium units as precursors of N-heterocyclic carbene complexes. Coordination chemistry and use in Suzuki-Miyaura cross-coupling.

    Science.gov (United States)

    Brenner, Eric; Matt, Dominique; Henrion, Mickaël; Teci, Matthieu; Toupet, Loïc

    2011-10-14

    The calix[4]arene-imidazolium salts 5-(3-butyl-1-imidazolylium)-25,26,27,28-tetrabenzyloxy-calix[4]arene bromide (cone) (2), and 5,11-bis(3-alkyl-1-imidazolylium)-25,26,27,28-tetrabenzyloxycalix[4]arene diiodide (cone) (R = methyl, 3a; R = n-butyl, 3b) have been synthesised. Reaction of 2 in dioxane with PdCl(2) in the presence of CsCO(3) and KBr (80 °C, 24 h) gives the carbene complex trans-[PdBr(2)(calix-monocarbene)(2)] (14), containing two N-heterocyclic carbene ligands derived from 2 (yield: 63%). Repeating the reaction in pyridine instead of dioxane gives the mixed pyridine-carbene complex trans-[PdBr(2)(calix-carbene)(pyridine)] (15) in 75% yield. Treatment of the bis-imidazolium salt 3a with [Pd(OAc)(2)] affords a chelate complex, trans-[PdI(2){calix-bis(carbene)}] (16), in which a metallo-(bis-carbene) fragment caps the upper rim of the calixarene basket. Complex 16, as well as its analogue 17, obtained from 3b, display apparent C(s)-symmetry in solution. This is not the case in the solid state, a single X-ray diffraction study carried out for 16 revealing a pinced cone structure for the calixarene skeleton, which reduces the symmetry to C(1). The chelate complex 17 shows poor activity in Suzuki-Miyaura cross-coupling of phenyl boronic acid and p-tolyl halides, an observation that suggests the presence of a strained metallocyclic unit preventing easy stereochemical rearrangement to an active species. Unlike 17, complexes 14 and 15 show good activities in cross-coupling. A comparative study using the carbene precursor 1-butyl-3-(2,6-diisopropylphenyl)imidazolium bromide (18), which is devoid of the receptor fragment, strongly suggests that the carbene ligands of 14 and 15 operate typically as bulky NHC-ligands.

  6. Enhanced free energy of extraction of Eu(3+) and Am(3+) ions towards diglycolamide appended calix[4]arene: insights from DFT-D3 and COSMO-RS solvation models.

    Science.gov (United States)

    Ali, Sk Musharaf

    2017-08-22

    Density functional theory in conjunction with COSMO and COSMO-RS solvation models employing dispersion correction (DFT-D3) has been applied to gain an insight into the complexation of Eu(3+)/Am(3+) with diglycolamide (DGA) and calix[4]arene appended diglycolamide (CAL4DGA) in ionic liquids by studying structures, energetics, thermodynamics and population analysis. The calculated Gibbs free energy for both Eu(3+) and Am(3+) ions with DGA was found to be smaller than that with CAL4DGA. The entropy of complexation was also found to be reduced to a large extent with DGA compared to complexation with CAL4DGA. The solution phase free energy was found to be negative and was higher for Eu(3+) ion. The entropy of complexation was not only found to be further reduced but also became negative in the case of DGA alone. Though the entropy was found to be negative it could not outweigh the high negative enthalpic contribution. The same trend was observed in the solution where the free energy of extraction, ΔG, for Eu(3+) ions was shown to be higher than that for Am(3+) ions towards free DGA. But the values of ΔG and ΔΔG(= ΔGEu-ΔGAm) were found to be much higher with CAL4DGA (-12.58 kcal mol(-1)) in the presence of nitrate ions compared to DGA (-1.69 kcal mol(-1)) due to enhanced electronic interaction and positive entropic contribution. Furthermore, both the COSMO and COSMO-RS models predict very close values of ΔΔΔG (= ΔΔGCAL4DGA - ΔΔGnDGA), indicating that both solvation models could be applied for evaluating the metal ion selectivity. The value of the reaction free energy was found to be higher after dispersion correction. The charge on the Eu and Am atoms for the complexes with DGA and CAL4DGA indicates the charge-dipole type interaction leading to strong binding energy. The present theoretical results support the experimental findings and thus might be of importance in the design of functionalized ligands.

  7. Rational Design of Cesium-Selective Ionophores and Chemosensors: Dihydrocalix[4]arene Crown-6 Ethers

    Energy Technology Data Exchange (ETDEWEB)

    Sachleben, Richard A.; Bryan, Jeffrey C.; Brown, Gilbert M.; Engle, Nancy L.; Haverlock, Tamara J.; Hay, Benjamin P.; Urvoas, Agathe; Moyer, Bruce A.

    2003-12-15

    Molecular mechanics calculations performed on calix[4]arene crown-6 ethers predict that the 1,3-dihydro derivatives will exhibit greater complementarity for potassium and cesium ions than the parent 1,3-dialkoxy calix crowns. The X-ray crystal structures of 1,3-alt bis-octyloxycalix[4]arene benzocrown-6 ether, dihydrocalix[4]arene benzocrown-6 ether, and the cesium nitrate complex of dihydrocalix[4]arene benzocrown-6 ether were determined. The cesium complex structure corresponds closely to the structure predicted by molecular mechanics. The dihydrocalix[4]arene crown-6 ethers exhibit enhanced cesium selectivity in the extraction of alkali metal salts and provide a platform for a highly sensitive and selective cesium chemosensor.

  8. Calix[4]arenes as Molecular Platforms in Magnetic Resonance Imaging

    NARCIS (Netherlands)

    Schühle, D.T.

    2009-01-01

    Magnetic resonance imaging (MRI) is an important tool in medical diagnosis. It uses non-ionizing radio-frequency radiation and produces images with excellent resolution. To increase the contrast, Gd(III)-containing compounds are applied leading to a brightening of the area of interest. The

  9. Hybrid liposomal PEGylated calix[4]arene systems as drug delivery platforms for curcumin

    OpenAIRE

    Drakalska, Elena; Momekova, Denitsa; Manolova, Yana; Budurova, Desislava; Momekov, Georgi; Genova, Margarita; Antonov, Liudmil; Lambov, Nikolay; Rangelov, Stanislav

    2014-01-01

    The tremendous therapeutic potential of curcumin as a chemopreventive, antineoplastic and chemosensitizing agent has failed to progress towards clinical development and commercialization due to its unfavorable physicochemical properties, low aqueous solubility, chemical instability, and pharmacokinetics. The present contribution is focused on the feasibility of using PEGylated calixarene, in particular polyoxyethylene-derivatized tert-butylcalix[4]arene, to prepare various platforms for deliv...

  10. Hybrid liposomal PEGylated calix[4]arene systems as drug delivery platforms for curcumin.

    Science.gov (United States)

    Drakalska, Elena; Momekova, Denitsa; Manolova, Yana; Budurova, Dessislava; Momekov, Georgi; Genova, Margarita; Antonov, Liudmil; Lambov, Nikolay; Rangelov, Stanislav

    2014-09-10

    The tremendous therapeutic potential of curcumin as a chemopreventive, antineoplastic and chemosensitizing agent has failed to progress towards clinical development and commercialization due to its unfavorable physicochemical properties, low aqueous solubility, chemical instability, and pharmacokinetics. The present contribution is focused on the feasibility of using PEGylated calixarene, in particular polyoxyethylene-derivatized tert-butylcalix[4]arene, to prepare various platforms for delivery of curcumin such as inclusion complex, supramolecular aggregates, and hybrid liposomal systems. The inclusion complex is characterized by UV-vis and FT-IR spectroscopy as well as thermal gravimetrical analysis and differential scanning calorimetry. At concentrations exceeding the critical micellization concentration of PEGylated calixarene, the tremendous solubility enhancement of curcumin is attributed to additional solubilization and hydrophobic non-covalent interactions of the drug with supramolecular aggregates. A hybrid liposomal system is created via encapsulation of the inclusion complex in dipalmitoylphosphatidylcholine:cholesterol liposomes. Bare and liposomal curcumin:BEC-X inclusion complexes, as well as free curcumin were additionally investigated for cytotoxicity and apoptogenic activity against human tumor cell lines. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Colorimetric detection of Cu 2 and Pb 2 ions using calix [4] arene ...

    Indian Academy of Sciences (India)

    Calixarene functionalized gold nanoparticles (CFAuNPs) have been prepared and characterized by spectroscopic and microscopic (TEM) techniques. To use this material as potential colorimetric sensor, the binding property of this new material has been investigated with a large number of metal ions. It exhibited sharp ...

  12. Electrochemical Studies for Cation Recognition with Diazo-Coupled Calix[4]arenes

    Directory of Open Access Journals (Sweden)

    Bongsu Kim

    2015-01-01

    Full Text Available The electrochemical properties of diazophenylcalix[4]arenes bearing ortho-carboxyl group (o-CAC and ortho-ester group (o-EAC, respectively, in the presence of various metal ions were investigated by voltammetry in CH3CN. o-CAC and o-EAC showed voltammetric changes toward divalent metal ions and no significant changes with monovalent alkali metal ions. However, o-CAC preferentially binds with alkaline earth and transition metal ions, whereas no significant changes in voltammetric signals are observed in o-EAC with alkaline earth metal ions. o-EAC only binds with other transition metal ions. This can be explained on metal ion complexation-induced release of proton from the azophenol to the quinone-hydrazone tautomer followed by internal complexation of the metal ion with aid of nitrogen atoms and ortho-carbonyl groups in the diazophenylazocalix[4]arenes.

  13. Hydrophobic concave surfaces and cavities by combination of calix[4]arenes and resorcin[4]arenes

    NARCIS (Netherlands)

    Timmerman, P.; Nierop, Klaas G.A.; Brinks, Erik A.; Verboom, Willem; van Veggel, F.C.J.M.; van Hoorn, Willem P.; van Hoorn, W.P.; Reinhoudt, David

    1995-01-01

    A general approach to the family of completely spirocyclopropanated macrocyclic polydiacetylenes, that is, cyclic dehydrooligomers of 1,1-diethynylcyclopropane 4, is reported. The characterized examples of these 'exploding' [n]rotanes are for n = 5, 6, 7, 8, 9, 10, and 12. X-ray crystal structure

  14. Role of electronic polarization on the liquid phase affinity of calixarene crown-ethers towards alkali cations: a QM/MM molecular dynamics simulation

    Science.gov (United States)

    Golebiowski, Jérôme; Lamare, Véronique; Martins-Costa, Marilia T. C.; Millot, Claude; Ruiz-López, Manuel F.

    2001-10-01

    We report molecular dynamics simulations of calixarene-crown-ether complexes with alkali cations in water using hybrid quantum mechanics/molecular mechanics (QM/MM) potentials. The approach allows us, for the first time in this kind of systems, to make a detailed discussion on the role of electronic polarization. Such an effect had been omitted in previous studies of calixarene-alkali cation complexes, although it is known to be important in many host-guest systems. The macrocycle, calix[4]arene-bis-crown6 (BC6), is treated at the semiempirical AM1 level whereas solvent water molecules are treated using the TIP3P model. The alkali metal cations (Na + and Cs +) are described as classical point charges with a set of Lennard-Jones parameters developed in this work. The interaction energy is analysed in terms of strain, electrostatic, polarization and van der Waals contributions. The polarization component is shown to be substantial and may represent 20% of the total electrostatic energy. We show that instantaneous fluctuation of the net atomic charge on O atoms and aromatic rings are quite large. The structural results predicted by the AM1/TIP3P model are shown to agree reasonably well with X-ray data. Comparison with previous MM simulations using effective pairwise additive potentials is made. Some differences found in the case of the BC6/Na + system, namely for the solvation number, are discussed.

  15. Recyclable calix[4]arene-lanthanoid luminescent hybrid materials with color-tuning and color-switching properties.

    Science.gov (United States)

    Ennis, Brendan W; Muzzioli, Sara; Reid, Brodie L; D'Alessio, Daniel M; Stagni, Stefano; Brown, David H; Ogden, Mark I; Massi, Massimiliano

    2013-05-21

    Inorganic-organic hybrid materials combine the properties of both components providing functionality with a wide range of potential applications. Phase segregation of the inorganic and organic components is a common challenge in these systems, which is overcome here by copolymerizing a metal-free calixarene ionophore and methyl methacrylate. A lanthanoid ion is then added using a swelling-deswelling procedure. The resulting luminescent hybrid materials can be made to emit any required color, including white light, by loading with an appropriate mixture of lanthanoids. The gradation of the emitted color can also be finely adjusted by changing the excitation wavelength. The polymer monolith can be recycled to emit a different color by swelling with a solution containing a different lanthanoid ion. This methodology is flexible and has the potential to be extended to many different ionophores and polymer matrices.

  16. Diphosphines with expandable bite angles: highly active ethylene dimerisation catalysts based on upper rim, distally diphosphinated calix[4]arenes.

    Science.gov (United States)

    Lejeune, Manuel; Sémeril, David; Jeunesse, Catherine; Matt, Dominique; Peruch, Frédéric; Lutz, Pierre J; Ricard, Louis

    2004-10-25

    The binding properties of two large diphosphines, cone-5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene (1) and cone-5,17-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene (2) toward Ni(II) centres have been investigated. Whatever the starting complex, NiBr2 or [NiCp]BF4, quantitative formation of a chelate complex was observed, illustrating the preorganisation of the ligands. An X-ray structure determination was carried out for [NiCp1]BF4 which revealed that the nickel atom is positioned to one side of the calixarene axis, the PNiP plane being roughly parallel to the calixarene reference plane. The molecule has C(1) symmetry in the solid state, a feature which is also observed in solution at low temperature. As shown by variable-temperature 1H and 31P NMR studies, the complex undergoes two distinct motions: 1) a fan-like swinging of the coordination plane which displaces the metal from one side of the calixarene axis to the other, a motion during which the PNiP angle is likely to undergo a significant enlargement; 2) a rapid oscillation of each PPh2 unit about the corresponding Ni--P bond. In the latter dynamics the two endo-oriented PPh rings alternately occupy the calixarene entry. The two flexible ligands were assessed in ethylene oligomerisation. Activation with methylaluminoxane of the paramagnetic complexes [NiBr2.(1 or 2)] afforded highly active ethylene dimerisation catalysts, with turnover frequencies up to 10(6) (mol C2H4) (mol Ni)(-1) h(-1). The selective formation of 1-butene can be rationally controlled by using low catalyst concentrations.

  17. Calix[4]arene-phosphine dimers: precursors of flexible metallo-capsules and self-compacting molecules.

    Science.gov (United States)

    Sameni, Soheila; Jeunesse, Catherine; Matt, Dominique; Toupet, Loïc

    2009-10-12

    The first diphosphines based on a double calixarene, namely 1,4 (or 1,3)-bis-(5-diphenylphosphino-25,26,27,28-tetrapropoxycalix[4]aren-17-yl)benzene (L(2), L(3)) were each prepared in four steps starting from 5,17-dibromo-25,26,27,28-tetrapropoxycalix[4]arene. Upon reaction of L(2) with [Au(tht)(thf)]BF(4), (tht = C(4)H(8)S) a rigid metallo-capsule was quantitatively formed, which adopts an oblique form owing to the distinct nature of the spacers linking the two calixarene half-spheres. In the solid state, the 1,4-substituted phenylene linker is turned towards the gold ion, suggesting the existence of weak bonding interactions between two aromatic CH protons of this ring and the metal centre (AuH =2.67 A). In contrast to this gold complex, the related silver complex shows dynamic behaviour in solution, the exchange between two enantiomeric oblique forms being facilitated by the greater stereochemical flexibility of Ag(I) vs. Au(I). A heteronuclear (109)Ag{(1)H} HMQC experiment established strong correlations between the CH protons of the phenylene linker and the (109)Ag ion. Dynamic behaviour similar to that observed for the silver complex was further observed in trans-[PtCl(2)L(2)], a chelate complex that could be obtained quantitatively from L(2) and [PtCl(2)(PhCN)(2)]. The intended formation of a chelate complex leading to a capsule with an endo-oriented metal centre was achieved by reacting L(3) with [Pd(allyl)(thf)(2)]BF(4). The complex thus formed constitutes the first organometallic transition metal complex embedded in a cavity with large portals. Binding of [RuCl(2)(p-cymene)] to L(2) and L(3) resulted in self-compacting bimetallic complexes in which each calixarene basket entraps a Ru(p-cymene) unit, thereby forming molecules occupying a minimal volume.

  18. First synthesis of a '1,2-diquinone-calix[4]arene'. Interaction of its reduced form with Ag+

    OpenAIRE

    Vataj, Rame; Ridaoui, Hassan; Louati, Alain; Gabelica, Valérie; Steyer, Stéphane; MATT, DOMINIQUE

    2002-01-01

    Electrochemical oxidation of 5,11,17,23-tetra-tert-butyl-25,26-bis(diphenylphosphinoylmethoxy)-27,28-dihydroxycalix[4]arene (3), a calixarene with two phosphoryl units appended on proximal positions, affords the corresponding '1,2-diquinonecalix[4]arene' (4). The formation of 4 results from nucleophilic attack of residual water on anodically generated diphenoxylium. cations. Preliminary voltammetric experiments in CH3CN on a platinum electrode showed that 4 is suitable for electrochemical det...

  19. Three-dimensional tetranuclear Cd(II) coordination network based on a 1,3-alternate calix[4]arene derivative

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Eun Ji; Ju, Hui Yeong; Park, Ki Min [Dept. of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju (Korea, Republic of); Moon, ASuk Hee [Dept. of Food and Nutrition, Kyungnam College of Inform ation and Technology, Busan (Korea, Republic of); Kang, Young Jin [Div. of cience Education, Kangwon National University, Chuncheon (Korea, Republic of)

    2015-08-15

    Polynuclear coordination polymers can exhibit more intriguing network topologies and better functionalities than those of common complexes because they have metal-cluster nodes for the construction of multidimensional frameworks and the potential applications induced by collaborative activities between metal ions. New tetranuclear Cd(II) coordination polymer 1 based on 1,3-alternate calix arene derivative (H{sub 4} CTA) with four carboxyl pendant arms has been synthesized by the solvo thermal reaction at 110 .deg. C for 2 days. Compound 1 shows a 3-D framework consisting of tetranuclear Cd(II) cluster core as a metal-cluster node and 1,3-alternate H{sub 4}CTA as a multidentate linker. The coordination polymer 1 displays intense blue emission, implying that this tetranuclear Cd(II) coordination polymer could be a suitable material in the area of luminescence research.

  20. Rare earth (Eu 3+ , Tb 3+ ) mesoporous hybrids with calix[4]arene derivative covalently linking MCM-41: Physical characterization and photoluminescence property

    Science.gov (United States)

    Li, Ya-Juan; Yan, Bing; Wang, Li

    2011-09-01

    MCM-41 mesoporous silica has been functionalized with two kinds of macrocylic calixarene derivatives Calix[4] and Calix[4]Br (Calix[4]=P- tert-butylcalix[4]arene, Calix[4]Br=5.11,17.23-tetra- tert-butyl-25.27-bihydroxy-26.28-bibromopropoxycalix[4]arene) through condensation approach of tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as a template. Novel organic-inorganic mesoporous luminescent hybrid containing RE3+ (Eu 3+, Tb 3+) complexes covalently attached to the functionalized ordered mesoporous MCM-41, which are designated as RE-Calix[4]-MCM-41 and RE-Calix[4]Br-MCM-41, respectively, are obtained by sol-gel process. It is found that they all have high surface area, uniform in the mesostructure and good crystallinity. Measurement of the photoluminescence properties show the mesoporous material covalently bonded Tb 3+ complexes (Tb-Calix[4]-MCM-41 and Tb-Calix[4]Br-MCM-41) exhibit the stronger characteristic emission of Tb 3+ and longer lifetime than the corresponding Eu-containing materials Eu-Calix[4]-MCM-41 and Eu-Calix[4]Br-MCM-41 due to the triplet state energy of modified organic ligands Calix[4]-Si and Calix[4]Br-Si match with the emissive energy level of Tb 3+ very well.

  1. A "plug-and-play" approach to the preparation of transparent luminescent hybrid materials based on poly(methyl methacrylate), a calix[4]arene cross-linking agent, and terbium ions.

    Science.gov (United States)

    Driscoll, Christopher R; Reid, Brodie L; McIldowie, Matthew J; Muzzioli, Sara; Nealon, Gareth L; Skelton, Brian W; Stagni, Stefano; Brown, David H; Massi, Massimiliano; Ogden, Mark I

    2011-04-07

    A novel methodology to prepare transparent luminescent hybrid materials is reported. Using a calixarene ionophore as a PMMA cross-linker avoids problems, such as phase segregation, and produces a polymer monolith that can be loaded with the metal ion required for luminescence post-synthesis. This approach is versatile and will simplify the production of such materials.

  2. Extractant composition including crown ether and calixarene extractants

    Science.gov (United States)

    Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.

    2009-04-28

    An extractant composition comprising a mixed extractant solvent consisting of calix[4] arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The DtBu18C6 may be present at from approximately 0.01M to approximately 0.4M, such as at from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present at from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The extractant composition further comprises an aqueous phase. The mixed extractant solvent may be used to remove cesium and strontium from the aqueous phase.

  3. Ethyleneglycol ethers (ethyleneglycol monomethyl ether, ethyleneglycol monomethyl ether acetate, diethyleneglycol monomethyl ether, diethyleneglycol monoethyl ether and diethyleneglycol monobutyl ether).

    NARCIS (Netherlands)

    Maclaine Pont, M.A.

    1996-01-01

    The committee recommends the following exposure limits as concentrations in air averaged over 8 hours (8 h TWA): - ethyleneglycol monomethyl ether: 1 mg/m3 (0.3 ppm) - ethyleneglycol monomethyl ether acetate: 1.5 mg/3 (0.3 ppm) - diethyleneglycol monomethyl ether: 45 mg/m3 (9 ppm) - diethyleneglycol

  4. Ether: a forgotten addiction.

    Science.gov (United States)

    Krenz, Sonia; Zimmermann, Grégoire; Kolly, Stéphane; Zullino, Daniele Fabio

    2003-08-01

    Among abused inhalants, ether has recently received little attention. The case of a patient suffering from ether dependence is reported. Whereas several features of DSM-IV dependence were fulfilled, no physical withdrawal signs were observed.

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

    African Journals Online (AJOL)

    Proton-conducting membranes of organic–inorganic (sulfonated poly (ether ether ketone)/phosphated zirconia nanoparticles) composite were prepared by incorporating various ratios of phosphated zirconia nanoparticles (ZP) in sulfonated poly (ether ether ketone) (SPEEK). SPEEK/ZP showed an improvement of ...

  6. Ether formulations of relativity

    Energy Technology Data Exchange (ETDEWEB)

    Duffy, M.C.

    1980-12-01

    Contemporary ether theories are surveyed and criticized, especially those formally identical to orthodox Relativity. The historical development of Relativity, Special and General, in terms of an ether, is briefly indicated. Classical interpretations of Generalized Relativity using ether are compared to Euclidean formulations using a background space. The history of a sub-group of theories, formulating a 'new' Relativity involving modified transforms, is outlined. According to the theory with which they agree, recent supposed detections of drift are classified and criticized. Cosmological evidence suggesting an ether is mentioned. Only ether theories formally identical to Relativity have been published in depth. They stand criticized as being contrary to the positivist spirit. The history of mechanical analogues is traced, from Hartley's representing gravitating matter as spherical standing waves, to recent suggestions that vortex-sponge might model electromagnetic, quantum, uncertainty and faster-than-light phenomena. Contemporary theories are particular physical theories, themselves 'second interpretations' of a primary mathematical model. Mechanical analogues are auxiliary, not necessary, to other theory, disclosing relationships between classical and non-classical descriptions of assemblies charging state. The ether-relativity polemic, part of a broader dispute about relativity, is founded on mistaken conceptions of the roles of mathematical and physical models, mechanical analogues; and a distored view of history, which indicates that ether theories have become relativistic. 103 references.

  7. Synthesis & Characterization of New bis-Symmetrical Adipoyl ...

    African Journals Online (AJOL)

    Full Title: Synthesis and Characterization of New bis-Symmetrical Adipoyl, Terepthaloyl, Chiral Diimido-di-L-alanine Diesters and Chiral Phthaloyl-L-alanine Ester of Tripropoxy p-tert-Butyl Calix[4]arene and Study of Their Hosting Ability for Alanine and Na+. Bis-symmetrical tripropoxy p-tert-butyl calix[4]arene esters were ...

  8. Cobalt bis(dicarbollides)(1-) covalently attached to the calyx[4]arene platform: the first combination of organic bowl-shaped matrices and inorganic metallaborane cluster anions

    NARCIS (Netherlands)

    Grüner, Bohumír; Mikulasek, Libor; Baca, Jirí; Cisarova, Ivana; Böhmer, Volker; Danila, Crenguta; Reinoso garcia, M.M.; Verboom, Willem; Reinhoudt, David; Casnati, Alessandro; Ungaro, Rocco

    2005-01-01

    Various calix[4]arene and resorc[4]arene ionic compounds substituted by cobalt bis(dicarbollide) anions (1) have been prepared for the first time. From tBu-calix[4]arene (A) the complete series of mono-, di-, tri- and tetrasubstituted derivatives bearing one to four cluster anions on the lower rim

  9. Cation permeable membranes from blends of sulfonated poly(ether ether ketone) and poly (ether sulfone)

    NARCIS (Netherlands)

    Wilhelm, F.G.; Punt, Ineke G.M.; van der Vegt, N.F.A.; Strathmann, H.; Wessling, Matthias

    2002-01-01

    Sulfonated poly(aryl ether ether ketone), S-PEEK, is blended with non-sulfonated poly(ether sulfone) (PES) to adjust the properties of ion permeable and ion selective membranes. In this study, membranes are prepared from blends with (i) a S-PEEK content between 10 and 100 wt.% using one S-PEEK batch

  10. Ether space-time & cosmology

    CERN Document Server

    Levy, Joseph

    2008-01-01

    The aim of this first volume of papers is to examine the different paths by which the modern ether concept has been developed and to highlight the part it plays in major departments of 21st century physics. The evidence for its existence is reviewed, and it is hoped, widespread misconceptions concerning ether are corrected. It is anticipated that the emerging modern concept of ether will play a fundamental part in the development of 21st century physical science.

  11. Exogenous ether lipids predominantly target mitochondria

    DEFF Research Database (Denmark)

    Kuerschner, Lars; Richter, Doris; Hannibal-Bach, Hans Kristian

    2012-01-01

    Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high...... amounts of ether-phosphatidylcholine and ether-phosphatidylethanolamine. Both lipids were specifically labeled using the corresponding lyso-ether lipids, which we established as supreme precursors for lipid tagging. Polyfosine, a fluorescent analogue of the anti-neoplastic ether lipid edelfosine...... in ether lipid metabolism and intracellular ether lipid trafficking....

  12. Structural assessment and catalytic consequences of the oxygen coordination environment in grafted Ti-calixarenes.

    Science.gov (United States)

    Notestein, Justin M; Andrini, Leandro R; Kalchenko, Vitaly I; Requejo, Felix G; Katz, Alexander; Iglesia, Enrique

    2007-02-07

    Calixarene-Ti complexes were grafted onto SiO2 (0.18-0.24 Ti nm-2) to form isolated and accessible Ti centers persistently coordinated to multidentate calixarene ligands. Grafted Ti-tert-butylcalix[4]arenes gave Ti K-edge absorption spectra with pre-edge features at 4968.6-4968.9 eV, independently of Ti surface density and of their use in epoxidation catalysis. The structure and reactivity of grafted Ti-calix[4]arenes were weakly dependent on thermal treatment below 573 K, and the relative epoxidation rates of trans- and cis-alkenes showed that calixarene ligands did not restrict access to Ti centers more than corresponding calcined Ti-SiO2 materials. For all materials, 13C NMR and UV-visible spectroscopies confirmed the presence of Ti-O-Si connectivity and identical ligand-to-metal transitions. Grafted Ti-homooxacalix[3]arene complexes, however, gave weaker pre-edge features at higher energies ( approximately 4969.5 eV), consistent with greater Ti 3d occupancy and coordination numbers greater than four, and 20-fold lower cyclohexene epoxidation rate constants (per Ti) than on calix[4]arene-based materials. These different rates and near-edge spectra result from aldehyde formation caused by unimolecular cleavage of ether linkages in homooxacalix[3]arene ligands during grafting, leading to higher coordination and electron density at Ti centers. Materials based on tert-butylcalix[4]arene and homooxacalix[3]arenes led to similar epoxidation rates and near-edge spectra after calcination, consistent with the conversion of both materials to isolated Ti centers with identical structure. These materials provide a systematic approach for relating oxidation reactivity to Ti 3d occupancy, a descriptor of Lewis acid strength, and Ti coordination, because they provide Ti centers with varying electron density and coordination, but maintain accessible active centers with uniform structure and unrestricted access to reactants.

  13. Biodegradation of gasoline ether oxygenates.

    Science.gov (United States)

    Hyman, Michael

    2013-06-01

    Ether oxygenates such as methyl tertiary butyl ether (MTBE) are added to gasoline to improve fuel combustion and decrease exhaust emissions. Ether oxygenates and their tertiary alcohol metabolites are now an important group of groundwater pollutants. This review highlights recent advances in our understanding of the microorganisms, enzymes and pathways involved in both the aerobic and anaerobic biodegradation of these compounds. This review also aims to illustrate how these microbiological and biochemical studies have guided, and have helped refine, molecular and stable isotope-based analytical approaches that are increasingly being used to detect and quantify biodegradation of these compounds in contaminated environments. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. 21 CFR 868.5420 - Ether hook.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ether hook. 868.5420 Section 868.5420 Food and... ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a device that fits inside a patient's mouth and that is intended to deliver vaporized ether. (b) Classification...

  15. Ether the nothing that connects everything

    CERN Document Server

    Milutis, Joe

    2006-01-01

    In Ether, the histories of the unseen merge with discussions of the technology of electromagnetism. Navigating more than three hundred years of the ether''s cultural and artistic history, Joe Milutis reveals its continuous reinvention and tangible impact without ever losing sight of its ephemeral, elusive nature. The true meaning of ether, Milutis suggests, may be that it can never be fully grasped.

  16. Rearrangements of Cycloalkenyl Aryl Ethers

    Directory of Open Access Journals (Sweden)

    Mercedesz Törincsi

    2016-04-01

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

  17. Recent Advances of Poly(ether-ether) and Poly(ether-ester) Block Copolymers in Biomedical Applications.

    Science.gov (United States)

    He, Zhi-Yao; Shi, Kun; Wei, Yu-Quan; Qian, Zhi-Yong

    2016-01-01

    Poly(ether-ether) and poly(ether-ester) block copolymers have been widely applied in biomedical fields over two decades due to their good safety and biocompatibility. Poly(ethylene glycol), poly(ethylene glycol)-poly(propylene glycol) and poly(lactic-co-glycolic acid) have been approved as excipients by Food and Drug Administration. Because of the broad perspective in biomedical fields, many novel poly(etherether) and poly(ether-ester) block copolymers have been developed for drug delivery, gene therapy and tissue engineering in recent years. This review focuses on active targeting theranostic systems, gene delivery systems and tissue engineering based on poly(ether-ether) and poly(ether-ester) block copolymers. We perform a structured search of bibliographic databases for peer-reviewed scientific reports using a focused review question and inclusion/exclusion criteria. The literatures related to the topics of this review are cataloged according to the developed copolymers or their applications such as active targeting theranostic systems, gene delivery systems and tissue engineering. Some important advances and new trends are summarized in this review. Some commercial poly(ether-ether) copolymers have been used as excipients for drug research and development. Amphiphilic and biodegradable poly(ether-ester) diblock copolymers are capable of formulating biomedical nanoparticulate theranostic systems, and targeting moiety-functionalized poly(ether-ester) diblock copolymers will be further developed and applied in biomedical nanotechnology fields in the near future. Meanwhile, triblock or multiblock poly(ether-ether) and poly(ether-ester) copolymers with environmentsensitive properties are suitable for gene delivery and tissue engineering. Poly(ether-ether) and poly(ether-ester) copolymers are being extensively applied in active targeting theranostic systems, gene delivery systems and tissue engineering. Biodegradable, environment-sensitive and targeting moiety

  18. Exogenous ether lipids predominantly target mitochondria.

    Directory of Open Access Journals (Sweden)

    Lars Kuerschner

    Full Text Available Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high amounts of ether-phosphatidylcholine and ether-phosphatidylethanolamine. Both lipids were specifically labeled using the corresponding lyso-ether lipids, which we established as supreme precursors for lipid tagging. Polyfosine, a fluorescent analogue of the anti-neoplastic ether lipid edelfosine, accumulated to mitochondria and induced morphological changes and cellular apoptosis. These data indicate that edelfosine could exert its pro-apoptotic power by targeting and damaging mitochondria and thereby inducing cellular apoptosis. In general, this study implies an important role of mitochondria in ether lipid metabolism and intracellular ether lipid trafficking.

  19. Monovalent cation selective crown ether containing poly(arylene ether ketone)/SPEEK blend membranes

    NARCIS (Netherlands)

    Tas, Sinem; Zoetebier, Bram; Hempenius, Mark A.; Vancso, Gyula J.; Nijmeijer, Dorothea C.

    2016-01-01

    Blend membranes of sulfonated poly(ether ether ketone) (SPEEK) and poly(arylene ether ketone) (PAEK) derivatives containing crown ether units in the main chain (CPAEK) were prepared and characterized in terms of water swelling and ion exchange capacity (IEC). The miscibility of the polymers was

  20. 40 CFR 721.3437 - Dialkyl ether.

    Science.gov (United States)

    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 section...

  1. 40 CFR 721.3374 - Alkylenediolalkyl ether.

    Science.gov (United States)

    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 to...

  2. 40 CFR 721.3380 - Anilino ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 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 for...

  3. 40 CFR 721.3364 - Aliphatic ether.

    Science.gov (United States)

    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 this...

  4. Synthesis and photophysics of light-converting lanthanide complexes

    NARCIS (Netherlands)

    Klink, S.I.

    2000-01-01

    The work described in this thesis deals with the synthesis, characterization, and photophysical studies of luminescent lanthanide complexes that are based on m-terphenyl and calix[4]arene building blocks.

  5. Hydrogen storage by functionalised Poly(ether ether ketone)

    Energy Technology Data Exchange (ETDEWEB)

    Pedicini, R.; Giacoppo, G.; Carbone, A.; Passalacqua, E. [CNR-ITAE, Messina (Italy). Inst. for Advanced Energy Technologies

    2010-07-01

    In this work a functionalised polymer was studied as potential material for hydrogen storage in solid state. A Poly(ether ether ketone) (PEEK) matrix was modified by a manganese oxide in situ formation. Here we report the functionalisation process and the preliminary results on hydrogen storage capability of the synthesised polymer. The polymer was characterized by Scanning Electron Microscopy, X-ray diffraction, Transmission Electron Microscopy and Gravimetric Hydrogen Adsorption measurements. In the functionalised PEEK, morphological changes occur as a function of oxide precursor concentration and reaction time. Promising results by gravimetric measurements were obtained with a hydrogen sorption of 0.24%wt/wt at 50 C and 60 bar, moreover, reversibility hydrogen adsorption and desorption in a wide range of both temperature and pressure was confirmed. (orig.)

  6. High-efficiency pyrene-based blue light emitting diodes: Aggregation suppression using a calixarene 3D-scaffold

    KAUST Repository

    Chan, Khaileok

    2012-01-01

    An efficient blue light emitting diode based on solution processable pyrene-1,3-alt-calix[4]arene is demonstrated, providing a record current efficiency of 10.5 cd A -1 in a simple non-doped OLED configuration. Complete suppression of pyrene aggregation in the solid state is achieved by controlling chromophore dispersion using the 1,3-alt-calix[4]arene scaffold. © 2012 The Royal Society of Chemistry.

  7. Élaboration de matériaux moléculaires à partir d'unités calixaréniques

    OpenAIRE

    Ben Maamar, Sami

    2008-01-01

    During this work of thesis, new calixarenes complexing selectively metal ions have been synthesized. After a bibliographic presentation, a calix[4]arene containing organosiloxane group has been synthesized and grafted on a periodically mesoporous SBA-15. The multiple characterization techniques, such as XRD, nitrogen adsorption, TEM, FT-IR and solid state 29Si NMR, as well as TG indicate that the calix[4]arene derivative has been well-anchored on the surface of SBA-15 generating a new class o...

  8. Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketones and Linear Poly(ether ketones

    Directory of Open Access Journals (Sweden)

    Atsushi Morikawa

    2016-02-01

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

  9. Conformational Study of Dibenzyl Ether

    Science.gov (United States)

    Hernandez-Castillo, Alicia O.; Abeysekera, Chamara; Hewett, Daniel M.; Zwier, Timothy S.

    2017-06-01

    Understanding the initial stages of polycyclic aromatic hydrocarbon (PAH) aggregation, the onset of soot formation, is an important goal on the pathway to cleaner combustion processes. PAHs with short alkyl chains, present in fuel-rich combustion environments, can undergo reactions that will chemically link aromatic rings together. One such example of a linked diaryl compound is dibenzyl ether, C_{6}H_{5}-CH_{2}-O-CH_{2}-C_{6}H_{5}. The -CH_{2}-O-CH_{2}- linkage has a length and flexibility well-suited to forming a π-stacked conformation between the two phenyl rings. In this talk, we will explore the single-conformation spectroscopy of dibenzyl ether under jet-cooled conditions in the gas phase. Laser-induced fluorescence, chirped pulse Fourier transform microwave (8-18 GHz region), and single-conformation infrared spectroscopy in the alkyl CH stretch region were all carried out on the molecule, thereby interrogating its full array of electronic, vibrational and rotational degrees of freedom. This work is the first step in a broader study to determine the extent of π-stacking in linked aryl compounds as a function of linkage and PAH size.

  10. 27 CFR 21.108 - Ethyl ether.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Ethyl ether. 21.108 Section 21.108 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT....108 Ethyl ether. (a) Odor. Characteristic odor. (b) Specific gravity at 15.56 °/15.56 °C. Not more...

  11. The synthesis of cholesteryl alkyl ethers.

    Science.gov (United States)

    Halperin, G; Gatt, S

    1980-01-01

    Seventeen cholesteryl alkyl ethers were synthesized through alcoholysis of cholesterol p-toluenesulfonate. This method was found superior to the etherification of sodium or potassium cholesterylate with alkyl halides or methanesulfonates, especially for the preparation of long-chain unsaturated aklyl ethers of [7(m)-3H]cholesterol of high specific activity.

  12. Atmospheric lifetimes of selected fluorinated ether compounds

    DEFF Research Database (Denmark)

    Heathfield, A.E.; Anastasi, C.; Pagsberg, Palle Bjørn

    1998-01-01

    Atmospheric lifetimes have been estimated for a selection of ethers, the latter representing a class of compounds being considered as replacements for chlorofluorocarbons. The estimates are based on laboratory measurements of rate constants for the reaction of the OH radical with the ethers......, and a comparison with the behaviour of methyl chloroform in the atmosphere. The lifetimes for the ethers ranged from a few hours to half a year, significantly lower than those of chlorofluorocarbons and other replacements being considered. (C) 1998 Elsevier Science Ltd. All rights reserved....

  13. Clinical comparison of ethyl acetate and diethyl ether in the formalin-ether sedimentation technique.

    OpenAIRE

    Erdman, D D

    1981-01-01

    A substitute for the volatile solvent diethyl ether has been actively sought for the Formalin-ether sedimentation technique. Ethyl acetate has recently been shown to be a comparable substitute. In an effort to verify these findings and evaluate ethyl acetate under clinical conditions, comparison studies with 62 fresh human stool specimens were performed. Parallel concentrates with diethyl ether and ethyl acetate were prepared for each specimen, and the quantity and appearance of recovered par...

  14. Activity relationships for aromatic crown ethers

    CERN Document Server

    Wilson, M J

    1998-01-01

    This thesis involves an investigation of aromatic crown ethers and a study of their binding constants for alkali metals. The study was motivated by the current needs of the semiconductor industry to improve the scavenging of mobile ions from fabricated circuits. A number of aromatic crown ethers have been sulphonated in an attempt to improve their water solubility and cation binding activity. These materials have been extensively studied and their binding activity determined. In collaboration with a molecular modelling study, the effect of ionisable sulphonate groups on the macrocycles' behaviour has been investigated. The broader issue of the effect of substituents in aromatic crown ethers has also been studied with the preparation of a wide range of substituted crown ethers. The cation binding activity of these materials has been found to bear a simple relationship to the electron withdrawing nature of the aromatic substituents. This relationship can be accurately monitored using electronic charge densities...

  15. Isomerization of allyl ethers initiated by lithium diisopropylamide.

    Science.gov (United States)

    Su, Chicheung; Williard, Paul G

    2010-12-03

    Lithium diisopropylamide (LDA) promotes virtually quantitative conversion of allylic ethers to (Z)-propenyl ethers. It was discovered that allylic ethers can be isomerized efficiently with very high stereoselectivity to (Z)-propenyl ethers by LDA in THF at room temperature. The reaction time for the conversion increases with more sterically hindered allylic ethers. Different amides were also compared with LDA for their ability to effect this isomerization.

  16. Final report on the safety assessment of PPG-2 methyl ether, PPG-3 methyl ether, and PPG-2 methyl ether acetate.

    Science.gov (United States)

    Robinson, Valerie; Bergfeld, Wilma F; Belsito, Donald V; Klaassen, Curtis D; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2009-01-01

    PPG-2 methyl ether, PPG-3 methyl ether, and PPG-2 methyl ether acetate are used in cosmetics as fragrance ingredients and/or solvents at concentrations of 0.4% to 2%. Propylene glycol ethers are rapidly absorbed and distributed throughout the body when introduced by inhalation or oral exposure, but the inhalation toxicity of PPG-2 methyl ether vapor, for example, is low. Aerosols, such as found with hair sprays, produce particle sizes that are not respirable. Because these ingredients are highly water-soluble, they are likely to be absorbed through the human skin only at slow rates, resulting in low blood concentrations and rapid removal by the kidney. These ingredients are not genotoxic and are not reproductive or developmental toxicants. Overall the data are sufficient to conclude that PPG-2 methyl ether, PPG-3 methyl ether, and PPG-2 methyl ether acetate are safe as used in cosmetics.

  17. Sulfonated poly(ether ether ketone) based composite membranes for nanofiltration of acidic and alkaline media

    NARCIS (Netherlands)

    Dalwani, M.R.; Bargeman, Gerrald; Hosseiny, Seyed Schwan; Schwan Hosseiny, Seyed; Boerrigter, M.E.; Wessling, Matthias; Benes, Nieck Edwin

    2011-01-01

    Several thin film composite nanofiltration membranes have been prepared by spin coating a sulfonated poly(ether ether ketone) solution on a polyethersulfone support, followed by thermal treatment. The most optimal developed nanofiltration membrane shows a clean water permeance of ∼4.5 L m−2 h−1

  18. Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells.

    Science.gov (United States)

    Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam

    2011-07-14

    Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

  19. Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

    Science.gov (United States)

    Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

    2017-08-01

    Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (k OH ) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of k OH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τ OH ) assuming k OH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σ λ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10 -7 s -1 , implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τ OH , the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Inhalation anaesthesia: from diethyl ether to xenon.

    Science.gov (United States)

    Bovill, J G

    2008-01-01

    Modern anaesthesia is said to have began with the successful demonstration of ether anaesthesia by William Morton in October 1846, even though anaesthesia with nitrous oxide had been used in dentistry 2 years before. Anaesthesia with ether, nitrous oxide and chloroform (introduced in 1847) rapidly became commonplace for surgery. Of these, only nitrous oxide remains in use today. All modern volatile anaesthetics, with the exception of halothane (a fluorinated alkane), are halogenated methyl ethyl ethers. Methyl ethyl ethers are more potent, stable and better anaesthetics than diethyl ethers. They all cause myocardial depression, most markedly halothane, while isoflurane and sevoflurane cause minimal cardiovascular depression. The halogenated ethers also depress the normal respiratory response to carbon dioxide and to hypoxia. Other adverse effects include hepatic and renal damage. Hepatitis occurs most frequently with halothane, although rare cases have been reported with the other agents. Liver damage is not caused by the anaesthetics themselves, but by reactive metabolites. Type I hepatitis occurs fairly commonly and takes the form of a minor disturbance of liver enzymes, which usually resolves without treatment. Type II, thought to be immune-mediated, is rare, unpredictable and results in a severe fulminant hepatitis with a high mortality. Renal damage is rare, and was most often associated with methoxyflurane because of excessive plasma fluoride concentrations resulting from its metabolism. Methoxyflurane was withdrawn from the market because of the high incidence of nephrotoxicity. Among the contemporary anaesthetics, the highest fluoride concentrations have been reported with sevoflurane, but there are no reports of renal dysfunction associated with its use. Recently there has been a renewed interest in xenon, one of the noble gases. Xenon has many of the properties of an ideal anaesthetic. The major factor limiting its more widespread is the high cost, about

  1. A technique to anesthetize turtles with ether.

    Science.gov (United States)

    Belló, A A; Belló-Klein, A

    1991-10-01

    A technique to anesthetize turtles with ether is presented, in which a plastic cannula is passed through the glottis into the trachea. This procedure avoids apnea and allows ether vapours obtained from a chamber to be introduced, by the animal respiratory movements or by means of a pump, into the animal lungs. The anesthesia is rapidly obtained and lasts from 45-90 minutes. The time of recovery from anesthesia ranged from 60-90 minutes. With this technique no deaths were observed and the same animal could be anesthetized repeatedly.

  2. Synthesis of alkynyl ethers and low-temperature sigmatropic rearrangement of allyl and benzyl alkynyl ethers.

    Science.gov (United States)

    Sosa, Juan R; Tudjarian, Armen A; Minehan, Thomas G

    2008-11-06

    Alpha-alkoxy ketones 3 can be transformed into 1-alkynyl ethers 5 by a two-step procedure involving formation of the enol triflate or phosphate and base-induced elimination. Performing the same reaction sequence with allylic alcohols (R2OH, R2 = allyl) furnishes instead gamma,delta-unsaturated carboxylic acid derivatives 6, derived from [3,3]-sigmatropic rearrangement of the intermediate allyl alkynyl ethers at -78 degrees C and trapping of the subsequently formed ketene with nucleophiles (Nu-H). Benzyl alkynyl ether 5 (R2 = benzyl) rearranges to indanone 7 upon heating to 60 degrees C.

  3. Synthesis of Alkynyl Ethers and Low Temperature Sigmatropic Rearrangement of Allyl and Benzyl Alkynyl Ethers

    Science.gov (United States)

    Sosa, Juan R.; Tudjarian, Armen A.; Minehan, Thomas G.

    2009-01-01

    α–Alkoxy ketones 3 can be transformed into 1-alkynyl ethers 5 by a two-step procedure involving formation of the enol triflate or phosphate and base-induced elimination. Performing the same reaction sequence with allylic alcohols (R2OH, R2 = allyl) furnishes instead γ,δ-unsaturated carboxylic acid derivatives 6, derived from [3,3]-sigmatropic rearrangement of the intermediate allyl alkynyl ethers at −78 °C and trapping of the subsequently formed ketene with nucleophiles (Nu-H). Benzyl alkynyl ether 5 (R2 = benzyl) rearranges to indanone 7 upon heating to 60 °C. PMID:18847213

  4. Syntheses of Diazadithiacrown Ethers Containing Two 8-Hydroxyquinoline Side Arms

    National Research Council Canada - National Science Library

    Song, H

    2001-01-01

    Ten new diazadithiacrown ethers containing two 8-hydroxyquinoline (HQ) sidearms attached through the HQ 7-positions and four new diazadithiacrown ethers containing two HQ sidearms attached through the HQ 2-positions have been prepared...

  5. IRIS Toxicological Review of Decabromodiphenyl Ether (Final Report)

    Science.gov (United States)

    EPA announced the release of the final report, Toxicological Review of Decabromodiphenyl Ether: in support of the Integrated Risk Information System (IRIS). The updated Summary for Decabromodiphenyl Ether and accompanying toxicological review have been added to the IRIS Da...

  6. 40 CFR 721.3486 - Polyglycerin mono(4-nonylphenyl) ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polyglycerin mono(4-nonylphenyl) ether... Substances § 721.3486 Polyglycerin mono(4-nonylphenyl) ether. (a) Chemical substance and significant new uses...-nonylphenyl) ether (PMN P-94-2230) is subject to reporting under this section for the significant new uses...

  7. 40 CFR 721.3500 - Perhalo alkoxy ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Perhalo alkoxy ether. 721.3500 Section... Substances § 721.3500 Perhalo alkoxy ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as perhalo alkoxy ether (PMN P-83-1227) is...

  8. 46 CFR 151.50-42 - Ethyl ether.

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Ethyl ether. 151.50-42 Section 151.50-42 Shipping COAST... LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-42 Ethyl ether. (a)(1) Gravity tanks... liquid. (g) Precautions shall be taken to prevent the contamination of ethyl ether by strong oxidizing...

  9. 40 CFR 721.3435 - Butoxy-substituted ether alkane.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butoxy-substituted ether alkane. 721... Substances § 721.3435 Butoxy-substituted ether alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as butoxy-substituted ether alkane...

  10. 40 CFR 799.4440 - Triethylene glycol monomethyl ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 31 2010-07-01 2010-07-01 true Triethylene glycol monomethyl ether... REQUIREMENTS Specific Chemical Test Rules § 799.4440 Triethylene glycol monomethyl ether. (a) Identification of test substance. (1) Triethylene glycol monomethyl ether (TGME, CAS No. 112-35-6) shall be tested in...

  11. 40 CFR 721.3485 - Hydrofluorocarbon alkyl ether.

    Science.gov (United States)

    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 ether...

  12. 40 CFR 721.3550 - Dipropylene glycol dimethyl ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Dipropylene glycol dimethyl ether. 721... Substances § 721.3550 Dipropylene glycol dimethyl ether. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as dipropylene glycol dimethyl ether (PMN P-93...

  13. 40 CFR 721.3420 - Brominated arylalkyl ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Brominated arylalkyl ether. 721.3420... Substances § 721.3420 Brominated arylalkyl ether. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as brominated arylalkyl ether (P-83-906) is...

  14. 40 CFR 721.10069 - Ether amine phosphonate (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ether amine phosphonate (generic). 721... Substances § 721.10069 Ether amine phosphonate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as ether amine phosphonate (PMN P...

  15. 40 CFR 721.3465 - Stilbene diglycidyl ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Stilbene diglycidyl ether. 721.3465... Substances § 721.3465 Stilbene diglycidyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as stilbene diglycidyl ether (PMN P-96-1427) is subject to...

  16. 40 CFR 721.3438 - Chlorohydroxyalkyl butyl ether (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Chlorohydroxyalkyl butyl ether... Specific Chemical Substances § 721.3438 Chlorohydroxyalkyl butyl ether (generic). (a) Chemical substance... chlorohydroxyalkyl butyl ether (PMN P-99-1295) is subject to reporting under this section for the significant new use...

  17. 21 CFR 520.1846 - Polyoxyethylene (23) lauryl ether blocks.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Polyoxyethylene (23) lauryl ether blocks. 520.1846... Polyoxyethylene (23) lauryl ether blocks. (a) Specifications. Each molasses-based block contains 2.2 percent polyoxyethylene (23) lauryl ether. (b) Sponsor. See No. 067949 in § 510.600(c) of this chapter. (c) Conditions of...

  18. 40 CFR 721.3520 - Aliphatic polyglycidyl ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic polyglycidyl ether. 721.3520... Substances § 721.3520 Aliphatic polyglycidyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aliphatic polyglycidyl ether (PMN P-89-1036) is subject to...

  19. 40 CFR 721.3430 - 4-Bromophenyl phenyl ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 4-Bromophenyl phenyl ether. 721.3430... Substances § 721.3430 4-Bromophenyl phenyl ether. (a) Chemical substance and significant new use subject to reporting. (1) The chemical substance 4-bromophenyl phenyl ether (CAS No. 101-55-3) is subject to reporting...

  20. Biosynthesis of archaeal membrane ether lipids

    NARCIS (Netherlands)

    Jain, Samta; Caforio, Antonella; Driessen, Arnold J. M.

    2014-01-01

    A vital function of the cell membrane in all living organism is to maintain the membrane permeability barrier and fluidity. The composition of the phospholipid bilayer is distinct in archaea when compared to bacteria and eukarya. In archaea, isoprenoid hydrocarbon side chains are linked via an ether

  1. Children's exposure to polybrominated diphenyl ethers

    NARCIS (Netherlands)

    Zuurbier, M.; Leijs, M.; Schoeters, G.; Tusscher, G. Ten; Koppe, J.G.

    2006-01-01

    Background: Polybrominated biphenyl ethers (PBDEs), a class of brominated flame retardants, are frequently used in consumer products. PBDEs levels in environmental and human samples have increased in recent decades. Children are exposed to PBDEs through diet, mainly through fish, meat and milk.

  2. The Lubrication Qualities of Dimethyl Ether (DME)

    DEFF Research Database (Denmark)

    Sivebæk, Ion Marius; Sorenson, Spencer C; Jakobsen, J.

    2002-01-01

    Dimethyl Ether (DME) has been recognised as a clean alternative for diesel oil for some years now. Fuelling diesel engines with DME solves their two most significant problems: The emission of particulate matter is virtually eliminated and the level of NOx can be reduced considerably by exhaust gas......, as the clean emission advantage obtained when using DME will be lost....

  3. Miniature sodium-selective ion-exchange optode with fluorescent pH chromoionophores and tunable dynamic range.

    Science.gov (United States)

    Shortreed, M; Bakker, E; Kopelman, R

    1996-08-01

    An extension into the fluorescence mode of ion-exchange optodes is described, allowing miniaturization and its concomitant benefits. A micrometer-size, fluorescent fiber-optic sodium sensor is described, based on a highly sodium-selective, crown ether-capped calix[4]arene ionophore, capable of ratiometric operation. Three sensor configurations are given, employing different lipophilic, fluorescent pH chromoionophores (Nile Blue derivatives), demonstrating the ability to improve the detection limit and tune the dynamic range to the desired region of interest. Two of the sensors are of special interest in that their working ranges lie within those desired for measuring intracellular cytosolic or blood levels of sodium at the respective physiological pH. These optodes have excellent sodium selectivity, with other physiologically relevant cations (e.g., potassium, calcium, and magnesium) being highly discriminated. Three simple mathematical relationships are given for the three experimentally used fluorescent signal mechanisms (intensity, intensity ratios, and inner-filter or energy transfer effects), permitting visualization on a single graph and enabling direct comparison of the different sensors' optical responses on a common platform. Finally, these optodes measure the sample's sodium activity, rather than the concentration, provided that the sample's pH is measured simultaneously by another sensor, such as a glass electrode.

  4. Ion-Selective Ionic Polymer Metal Composite (IPMC) Actuator Based on Crown Ether Containing Sulfonated Poly(Arylene Ether Ketone)

    NARCIS (Netherlands)

    Tas, Sinem; Zoetebier, Bram; Sardan Sukas, Ö.; Bayraktar, Muharrem; Hempenius, Mark A.; Vancso, Gyula J.; Nijmeijer, Dorothea C.

    This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane

  5. Preparation and characterization of monovalent ion selective cation exchange membranes based on sulphonated poly(ether ether ketone)

    NARCIS (Netherlands)

    Balster, J.H.; Krupenko, O.; Krupenko, O.; Punt, Ineke G.M.; Stamatialis, Dimitrios; Wessling, Matthias

    2005-01-01

    This paper analyses the separation properties of various commercial cation exchange membranes (CEMs) and tailor made membranes based on sulphonated poly(ether ether ketone) and poly(ether sulphone) for binary electrolyte solutions containing protons and calcium ions. All membranes are thoroughly

  6. Inclusion Complexes of a New Family of Non-Ionic Amphiphilic Dendrocalix[4]arene and Poorly Water-Soluble Drugs Naproxen and Ibuprofen

    Directory of Open Access Journals (Sweden)

    Khalid Khan

    2017-05-01

    Full Text Available The inclusion complexes of a new family of nonionic amphiphilic calix[4]arenes with the anti-inflammatory hydrophobic drugs naproxen (NAP and ibuprofen (IBP were investigated. The effects of the alkyl chain’s length and the inner core of calix[4]arenes on the interaction of the two drugs with the calix[4]arenes were explored. The inclusion complexes of Amphiphiles 1a–c with NAP and IBP increased the solubility of these drugs in aqueous media. The interaction of 1a–c with the drugs in aqueous media was investigated through fluorescence, molecular modeling, and 1H-NMR analysis. TEM studies further supported the formation of inclusion complexes. The length of lipophilic alkyl chains and the intrinsic cyclic nature of cailx[4]arene derivatives 1a–c were found to have a significant impact on the solubility of NAP and IBP in pure water.

  7. Ether bridge formation in loline alkaloid biosynthesis

    Science.gov (United States)

    Pan, Juan; Bhardwaj, Minakshi; Faulkner, Jerome R.; Nagabhyru, Padmaja; Charlton, Nikki D.; Higashi, Richard M.; Miller, Anne-Frances; Young, Carolyn A.; Grossman, Robert B.; Schardl, Christopher L.

    2014-01-01

    Lolines are potent insecticidal agents produced by endophytic fungi of cool-season grasses. These alkaloids are composed of a pyrrolizidine ring system and an uncommon ether bridge linking carbons 2 and 7. Previous results indicated that 1-aminopyrrolizidine was a pathway intermediate. We used RNA interference to knock down expression of lolO, resulting in the accumulation of a novel alkaloid identified as exo-1-acetamidopyrrolizidine based on high-resolution MS and NMR. Genomes of endophytes differing in alkaloid profiles were sequenced, revealing that those with mutated lolO accumulated exo-1-acetamidopyrrolizidine but no lolines. Heterologous expression of wild-type lolO complemented a lolO mutant, resulting in the production of N-acetylnorloline. These results indicated that the non-heme iron oxygenase, LolO, is required for ether bridge formation, probably through oxidation of exo-1-acetamidopyrrolizidine. PMID:24374065

  8. Synthesis of New Liquid Crystalline Diglycidyl Ethers

    Directory of Open Access Journals (Sweden)

    Issam Ahmed Mohammed

    2012-01-01

    Full Text Available The phenolic Schiff bases I–VI were synthesized by condensation reactions between various diamines, namely o-dianisidine, o-tolidine and ethylenediamine with vanillin or p-hydroxybenzaldehyde and subsequent reactions between these phenolic Schiff bases and epichlorohydrin to produce new diglycidyl ethers Ia–VIa. The structures of these compounds were confirmed by CHN, FT-IR, 1H-NMR, and 13C-NMR spectroscopy. Their thermotropic liquid crystalline behavior was studied using differential scanning calorimetry (DSC and polarizing optical microscopy (POM. All the diglycidyl ethers prepared exhibit nematic mesophases, except for Va and VIa, which did not show any transition mesophases, but simply flow to liquids.

  9. Model for Photodegradation of Polybrominated Diphenyl Ethers

    Czech Academy of Sciences Publication Activity Database

    Veselý, M.; Vajglová, Zuzana; Kotas, Petr; Křišťál, Jiří; Ponec, Robert; Jiřičný, Vladimír

    2015-01-01

    Roč. 22, č. 7 (2015), s. 4949-4963 ISSN 0944-1344 R&D Projects: GA ČR GA104/09/0880; GA ČR(CZ) GAP105/12/0664 Institutional support: RVO:67985858 ; RVO:67179843 Keywords : polybrominated diphenyl ethers * photodegradation model * quantum chemical calculation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.760, year: 2015

  10. Alkyl aryl ethers in lignite solubilization

    Energy Technology Data Exchange (ETDEWEB)

    Mustral, A.M.; Cebolla, V.L.; Gavilan, J.M.

    1985-03-01

    The FT-I.R. and /sup 1/H N.M.R. spectroscopic analyses of oils or maltenes from a Spanish lignite (Utrillas, Teruel), are reported. These oils were obtained by depolymerization with alkyl aromatic ethers (anisole, 3-methyl anisole and 1,3-dimethoxybenzene) catalyzed by Lewis acids ZnCl/sub 2/, AlCl/sub 3/, SbCl/sub 3/ and BF/sub 3/ (as boron trifluoride etherate), at atmospheric pressure and temperatures <220/sup 0/C. Bands due to aromatic ethers in the I.R. and N.M.R. spectra of the oils obtained by depolymerization indicate solvent incorporation. Oils obtained by direct lignite extraction showed 25% aromatic H and some H /sub i/ (approx. = 3%) without OH groups. These appeared in some oils obtained by depolymerization with AlCl/sub 3/ and were due to secondary reactions with the aromatic extract. Oils derived from processes with good yields showed increases in aromaticity. The extent of substitution of aromatic rings in oils obtained by depolymerization was less than for oils directly extracted. All the oils studied show a low degree of condensation.

  11. Nikola Tesla, the Ether and his Telautomaton

    Science.gov (United States)

    Milar, Kendall

    2014-03-01

    In the nineteenth century physicists' understanding of the ether changed dramatically. New developments in thermodynamics, energy physics, and electricity and magnetism dictated new properties of the ether. These have traditionally been examined from the perspective of the scientists re-conceptualizing the ether. However Nikola Tesla, a prolific inventor and writer, presents a different picture of nineteenth century physics. Alongside the displays that showcased his inventions he presented alternative interpretations of physical, physiological and even psychical research. This is particularly evident in his telautomaton, a radio remote controlled boat. This invention and Tesla's descriptions of it showcase some of his novel interpretations of physical theories. He offered a perspective on nineteenth century physics that focused on practical application instead of experiment. Sometimes the understanding of physical theories that Tesla reached was counterproductive to his own inventive work; other times he offered new insights. Tesla's utilitarian interpretation of physical theories suggests a more scientifically curious and invested inventor than previously described and a connection between the scientific and inventive communities.

  12. From ether theory to ether theology: Oliver Lodge and the physics of immortality.

    Science.gov (United States)

    Raia, Courtenay Grean

    2007-01-01

    This article follows the development of physicist Oliver Lodge's religio-scientific worldview, beginning with his reticent attraction to metaphysics in the early 1880s to the full formulation of his "ether theology" in the late 1890s. Lodge undertook the study of psychical phenomena such as telepathy, telekinesis, and "ectoplasm" to further his scientific investigations of the ether, speculating that electrical and psychical manifestations were linked phenomena that described the deeper underlying structures of the universe, beneath and beyond matter. For Lodge, to fully understand the ether was to force from the universe an ultimate Revelation, and psychical research, as the most modern and probatory science, was poised to replace religion as the means of that disclosure. (c) 2007 Wiley Periodicals, Inc.

  13. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and P...

  14. Upper rim appended hybrid calixarenes via click chemistry.

    Science.gov (United States)

    Bew, Sean P; Brimage, Rebecca A; L'Hermite, Nathalie; Sharma, Sunil V

    2007-09-13

    We report the application of "click" chemistry for the synthesis of hybrid calixarenes appended on the upper rim with carbohydrate and N,C-protected alpha-amino acids. The chemoselective N- or C-deprotection of the alpha-amino acids and their subsequent transformation into dipeptides is described. The first example of a chemo-enzymatic synthesis on upper rim derived calix[4]arenes using trans-sialidase affords sialylated lactose calix[4]arenes. Our innovative chemo-enzymatic process paves the way for further applications.

  15. Silane Cross-Linked Sulfonted Poly(Ether Ketone/Ether Benzimidazoles for Fuel Cell Applications

    Directory of Open Access Journals (Sweden)

    Zilu Yao

    2017-11-01

    Full Text Available γ-(2,3-epoxypropoxy propyltrimethoxysilane (KH-560 was incorporated in various proportions into side-chain-type sulfonated poly(ether ketone/ether benzimidazole (SPEKEBI as a crosslinker, to make membranes with high ion exchange capacities and excellent performance for direct methanol fuel cells (DMFCs. Systematical measurements including Fourier transform infrared (FT-IR, scanning electron microscopy-energy-dispersive and X-ray photoelectron spectroscopy (XPS proved the complete disappearance of epoxy groups in KH-560 and the existence of Si in the membranes. The resulting membranes showed increased mechanical strength and thermal stability compared to the unmodified sulfonated poly(ether ketone/ether benzimidazole membrane in appropriate doping amount. Meanwhile, the methanol permeability has decreased, leading to the increase of relative selectivities of SPEKEBI-x-SiO2 membranes. Furthermore, the H2/O2 cell performance of SPEKEBI-2.5-SiO2 membrane showed a much higher peak power density compared with the pure SPEKEBI memrbrane.

  16. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Chiu, K.-F.; Su, S.-H., E-mail: minimono42@gmail.com

    2013-10-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO{sub 4} were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO{sub 4}, the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance.

  17. Synthesis and Antiplasmodial Activity of EG-Artemisinin Ethers and ...

    African Journals Online (AJOL)

    The aim of this study was to synthesize a series of ethylene glycol (EG) ethers and quinoline hybrids of the antimalarial drug artemisinin and to evaluate their antimalarial activity in vitro against Plasmodium falciparum strains. The ethers were synthesized in a one-step process by coupling ethylene glycol (EG) moieties of ...

  18. 40 CFR 721.825 - Certain aromatic ether diamines.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Certain aromatic ether diamines. 721.825 Section 721.825 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.825 Certain aromatic ether diamines. (a) Chemical substances and significant new uses...

  19. Synthesis and bioactivity of rotenone oxime O -ether derivatives ...

    African Journals Online (AJOL)

    A series of rotenone oxime O-ether derivatives were synthesized and characterized. All compounds were tested for their insecticidal, miticidal and fungicidal activities against the selected pests and compared with those of rotenone. The results of biological tests show that the rotenone oxime O-ether derivatives have ...

  20. 29 CFR 1915.1008 - bis-Chloromethyl ether.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 7 2010-07-01 2010-07-01 false bis-Chloromethyl ether. 1915.1008 Section 1915.1008 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1008 bis-Chloromethyl ether. Note: The requirements applicable to shipyard employment under this...

  1. 29 CFR 1915.1006 - Methyl chloromethyl ether.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 7 2010-07-01 2010-07-01 false Methyl chloromethyl ether. 1915.1006 Section 1915.1006 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION... Hazardous Substances § 1915.1006 Methyl chloromethyl ether. Note: The requirements applicable to shipyard...

  2. 29 CFR 1926.1108 - bis-Chloromethyl ether.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 8 2010-07-01 2010-07-01 false bis-Chloromethyl ether. 1926.1108 Section 1926.1108 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR...-Chloromethyl ether. Note: The requirements applicable to construction work under this section are identical to...

  3. 29 CFR 1910.1008 - bis-Chloromethyl ether.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 6 2010-07-01 2010-07-01 false bis-Chloromethyl ether. 1910.1008 Section 1910.1008 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... bis-Chloromethyl ether. See § 1910.1003, 13 carcinogens. ...

  4. 29 CFR 1910.1006 - Methyl chloromethyl ether.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 6 2010-07-01 2010-07-01 false Methyl chloromethyl ether. 1910.1006 Section 1910.1006 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION... Substances § 1910.1006 Methyl chloromethyl ether. See § 1910.1003, 13 carcinogens. ...

  5. 29 CFR 1926.1106 - Methyl chloromethyl ether.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 8 2010-07-01 2010-07-01 false Methyl chloromethyl ether. 1926.1106 Section 1926.1106 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION... § 1926.1106 Methyl chloromethyl ether. Note: The requirements applicable to construction work under this...

  6. Synthesis and Biophysical Characterization of Chlorambucil Anticancer Ether Lipid Prodrugs

    DEFF Research Database (Denmark)

    Pedersen, Palle Jacob; Christensen, Mikkel Stochkendahl; Ruysschaert, Tristan

    2009-01-01

    The synthesis and biophysical characterization of four prodrug ether phospholipid conjugates are described. The lipids are prepared from the anticancer drug chlorambucil and have C16 and C18 ether chains with phosphatidylcholine or phosphatidylglycerol headgroups. All four prodrugs have the ability...

  7. Congenital malformations and maternal occupational exposure to glycol ethers

    NARCIS (Netherlands)

    Cordier, S; Bergeret, A; Goujard, J; Ha, MC; Ayme, S; Calzolari, E; DeWalle, HEK; KnillJones, R; Candela, S; Dale, [No Value; Dananche, B; deVigan, C; Fevotte, J; Kiel, G; Mandereau, L

    Glycol ethers are found in a wide range of domestic and industrial products, many of which are used in women's work environments. Motivated by concern about their potential reproductive toxicity, we have evaluated the risk of congenital malformations related to glycol ether exposure during preg

  8. Formation and Structural Analysis of Novel Dibornyl Ethers

    African Journals Online (AJOL)

    PROF P.T. KAYE

    stereochemistry of novel dibornyl ethers, obtained by acid-catalysed condensation of camphor-derived α-hydroxybornanones. Keywords Dibornyl ethers; structure analysis; camphor derivatives. The results of some of our previous studies on the use of camphor-derived chiral auxiliaries in asymmetric synthesis1,2 indicated ...

  9. Ether in the developing world: rethinking an abandoned agent.

    Science.gov (United States)

    Chang, Connie Y; Goldstein, Elisabeth; Agarwal, Nitin; Swan, Kenneth G

    2015-10-16

    The first true demonstration of ether as an inhalation anesthetic was on October 16, 1846 by William T.G. Morton, a Boston dentist. Ether has been replaced completely by newer inhalation agents and open drop delivery systems have been exchanged for complicated vaporizers and monitoring systems. Anesthesia in the developing world, however, where lack of financial stability has halted the development of the field, still closely resembles primitive anesthetics. In areas where resources are scarce, patients are often not given supplemental intraoperative analgesia. While halothane provides little analgesia, ether provides excellent intra-operative pain control that can extend for several hours into the postoperative period. An important barrier to the widespread use of ether is availability. With decreasing demand, production of the inexpensive inhalation agent has fallen. Ether is inexpensive to manufacture, and encouraging increased production at a local level would help developing nations to cut costs and become more self-sufficient.

  10. Synthesis of poly(arylene ether ketone)s bearing skeletal crown ether units for cation exchange membranes

    NARCIS (Netherlands)

    Zoetebier, Bram; Tas, Sinem; Vancso, Gyula J.; Nijmeijer, Dorothea C.; Hempenius, Mark A.

    2015-01-01

    Poly(arylene ether ketone)s (PAEKs) are the most commonly known high-performance materials used for ion exchange and fuel cell membranes. Described here is the design of novel sulfonated PAEKs (SPAEKs) and nonsulfonated PAEKs containing crown ether units in the main chain, which can be used in

  11. Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Tewatia, Arya; Hendrix, Justin [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Dong, Zhizhong [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Taghon, Meredith [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Tse, Stephen [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Lynch, Jennifer, E-mail: jklynch@rci.rutgers.edu [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States)

    2017-02-15

    Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

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

    Science.gov (United States)

    Chen, Yan; Pan, Yusong

    2014-12-01

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

  13. Modification of Poly(ether ether ketone Polymer for Fuel Cell Application

    Directory of Open Access Journals (Sweden)

    Devesh Shukla

    2013-01-01

    Full Text Available Polyelectrolyte membrane (PEM is an important part of PEM fuel cell. Nafion is a commercially known membrane which gives the satisfactory result in PEM fuel cell operating at low temperature. Present research paper includes functionalization of Poly(ether ether ketone (PEEK polymer with phosphonic acid group. The functionalization was done with the help of nickel-based catalyst. Further, the polymer was characterized by the FTIR, EDAX, DSC, TGA, and 1H NMR, and it was found that PEEK polymer was functionalized with phosphonic acid group with good thermal stability in comparison to virgin PEEK. Finally, the thin films of functionalized polymer were prepared by solution casting method, and proton conductivity of film samples was measured by impedance spectra whose value was found satisfactory with good thermal stability in comparison to commercially available Nafion membrane.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-02-15

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

  15. Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Silva, V.S.; Boaventura, M.; Mendes, A.M.; Madeira, L.M. [LEPAE, Chemical Engineering Department, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Ruffmann, B.; Vetter, S.; Nunes, S.P. [GKSS Research Centre, Max-Planck Str., 21502 Geesthacht (Germany)

    2006-05-05

    Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion{sup (R)} 112 was used as reference material. DMFC tests were also performed at 50{sup o}C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion{sup (R)} 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD=71% showed to have similar performance, or even better, as that of Nafion{sup (R)} 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD=52%. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. Vapor intrusion risk of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME) and ethyl tert-butyl ether (ETBE): A modeling study.

    Science.gov (United States)

    Ma, Jie; Xiong, Desen; Li, Haiyan; Ding, Yi; Xia, Xiangcheng; Yang, Yongqi

    2017-06-15

    Vapor intrusion of synthetic fuel additives represents a critical yet still neglected problem at sites contaminated by petroleum fuel releases. This study used an advanced numerical model to investigate the vapor intrusion potential of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), and ethyl tert-butyl ether (ETBE). Simulated indoor air concentration of these compounds can exceed USEPA indoor air screening level for MTBE (110μg/m 3 ). Our results also reveal that MTBE has much higher chance to cause vapor intrusion problems than TAME and ETBE. This study supports the statements made by USEPA in the Petroleum Vapor Intrusion (PVI) Guidance that the vertical screening criteria for petroleum hydrocarbons may not provide sufficient protectiveness for fuel additives, and ether oxygenates in particular. In addition to adverse impacts on human health, ether oxygenate vapor intrusion may also cause aesthetic problems (i.e., odour and flavour). Overall, this study points out that ether oxygenates can cause vapor intrusion problems. We recommend that USEPA consider including the field measurement data of synthetic fuel additives in the existing PVI database and possibly revising the PVI Guidance as necessary. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Characterization of Microsolvated Crown Ethers from Broadband Rotational Spectroscopy

    Science.gov (United States)

    Perez, Cristobal; Schnell, Melanie; Blanco, Susana; Lopez, Juan Carlos

    2016-06-01

    Since they were first synthetized, crown ethers have been extensively used in organometallic chemistry due to their unparalleled binding selectivity with alkali metal cations. From a structural point of view, crown ethers are heterocycles containing oxygen and/or other heteroatoms, although the most common ones are formed from ethylene oxide unit. Crown ethers are conventionally seen as being hydrophilic inside and hydrophobic outside when the structures found for the metal cation complexes are considered. However, crown ethers are extremely flexible and in isolation may present a variety of stable conformations so that their structure may be easily adapted in presence of a strong ligand as an alkali metal cation minimize the energy of the resulting complex. Water can be considered a soft ligand which interacts with crown ethers through moderate hydrogen bonds. It is thus interesting to investigate which conformers are selected by water to form complexes, the preferred interaction sites and the possible conformational changes due to the presence of one or more water molecules. Previous studies identified microsolvated crown ethers but in all cases with a chromophore group attached to the structure. Here we present a broadband rotational spectroscopy study of microsolvated crown ethers produced in a pulsed molecular jet expansion. Several 1:1 and 1:2 crown ether:water aggregates are presented for 12-crown-4, 15-crown-5 and 18-crown-6. Unambiguous identification of the structures has been achieved using isotopic substitution within the water unit. The subtle changes induced in the structures of the crown ether monomer upon complexation and the hydrogen-bonding network that hold them together will be also discussed. F. Gámez, B. Martínez-Haya, S. Blanco,J. C. López and J. L. Alonso, Phys. Chem. Chem. Phys. 2014, 14 12912-12918 V. A. Shubert, C.W. Müller and T. Zwier, J. Phys. Chem. A 2009, 113 8067-8079

  19. Enzymatic network for production of ether amines from alcohols

    DEFF Research Database (Denmark)

    Palacio, Cyntia M.; Crismaru, Ciprian G.; Bartsch, Sebastian

    2016-01-01

    We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production...... of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed...

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

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-lauryl vinyl ether copolymers. 177...-lauryl vinyl ether copolymers. The vinyl chloride-lauryl vinyl ether copolymers identified in paragraph... section vinyl chloride-lauryl vinyl ether copolymers consist of basic copolymers produced by the...

  1. Evaluation of crystallization kinetics of poly (ether-ketone-ketone and poly (ether-ether-ketone by DSC

    Directory of Open Access Journals (Sweden)

    Gibran da Cunha Vasconcelos

    2010-08-01

    Full Text Available The poly (aryl ether ketones are used as matrices in advanced composites with high performance due to its high thermal stability, excellent environmental performance and superior mechanical properties. Most of the physical, mechanical and thermodynamic properties of semi-crystalline polymers depend on the degree of crystallinity and morphology of the crystalline regions. Thus, a study on the crystallization process promotes a good prediction of how the manufacturing parameters affect the developed structure, and the properties of the final product. The objective of this work was to evaluate the thermoplastics polymers PEKK e PEEK by DSC, aiming to obtain the relationship between kinetics, content, nucleation and geometry of the crystalline phases, according to the parameters of the Avrami and Kissinger models. The analysis of the Avrami exponents obtained for the studied polymers indicates that both showed the formation of crystalline phases with heterogeneous nucleation and growth geometry of the type sticks or discs, depending on the cooling conditions. It was also found that the PEEK has a higher crystallinity than PEKK.

  2. The zeolite mediated isomerization of allyl phenyl ether

    Science.gov (United States)

    Pebriana, R.; Mujahidin, D.; Syah, Y. M.

    2017-04-01

    Allyl phenyl ether is an important starting material in organic synthesis that has several applications in agrochemical industry. The green transformation of allyl phenyl ether assisted by heterogeneous catalyst is an attractive topic for an industrial process. In this report, we investigated the isomerization of allyl phenyl ether by heating it in zeolite H-ZSM-5 and Na-ZSM-5. The conversion of allyl phenyl ether (neat) in H-ZSM-5 was 67% which produced 40% of 2-allylphenol, 17% of 2-methyldihydrobenzofuran, and other product (4:1.7:1), while in Na-ZSM-5 produced exclusively 2-allylphenol with 52% conversion. These results showed that zeolite properties can be tuned to give a selective transformation by substitution of metal ion into the zeolite interior.

  3. Formation and Structural Analysis of Novel Dibornyl Ethers

    African Journals Online (AJOL)

    PROF P.T. KAYE

    . SHORT COMMUNICATION. Formation and Structural Analysis of Novel Dibornyl Ethers. Perry T. Kaye*, Andrew R. Duggan, Joseph M. Matjila, Warner E. Molema, and. Swarnam S. Ravindran. Department of Chemistry, Rhodes University, Grahamstown, ...

  4. Fluorinated Alkyl Ether Epoxy Resin Compositions and Applications Thereof

    Science.gov (United States)

    Wohl, Christopher J. (Inventor); Connell, John W. (Inventor); Smith, Joseph G. (Inventor); Siochi, Emilie J. (Inventor); Gardner, John M. (Inventor); Palmieri, Frank M. (Inventor)

    2017-01-01

    Epoxy resin compositions prepared using amino terminated fluoro alkyl ethers. The epoxy resin compositions exhibit low surface adhesion properties making them useful as coatings, paints, moldings, adhesives, and fiber reinforced composites.

  5. Aquatic Life Criteria - Methyl Tertiary-Butyl Ether (MTBE)

    Science.gov (United States)

    Information pertaining to the 1999 Acute and Chronic Ambient Aquatic Life Water Quality Criteria for Methyl Tertiary-Butyl Ether (MTBE) for freshwater and salt water. Information includes the safe levels of MTBE that should protect the majority of species.

  6. Catalytic rearrangement of the chloroallyl ethers of p-cresol

    Energy Technology Data Exchange (ETDEWEB)

    Andreev, N.A.; Bunina-Krivorukova, L.I.; Levashova, V.I.

    1986-07-20

    The rearrangement of a series of p-cresol ethers (..beta..- and ..gamma..-chloro-, ..beta gamma..- and ..beta gamma..,..gamma..-trichloroallyl), catalyzed by boron trifluoride etherate, was studied. Increase in the number of chlorine atoms in the allyl unit of the ether hinders the rearrangement, and its mechanism changes in the investigated series of ethers from intramolecular (3,3)-sigmatropic (with inversion of the allyl unit) to intermolecular, which corresponds to electrophilic substitution in the aromatic ring (without inversion). The presence of the chlorine atom at the ..beta.. position of the allyl unit promotes rearrangement by a concerted intramolecular mechanism, while a chlorine atom at the ..gamma.. position promotes rearrangement by an intermolecular stage mechanism. Two chlorine atoms at the ..gamma.. position give rise mainly to the intermolecular rearrangement path.

  7. Spatial trends of polybrominated diphenyl ether (PBDE) congeners

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Spatial trends of polybrominated diphenyl ether (PBDE) congeners were analyzed in young of the year bluefish collected along the U.S. Atlantic coastline from...

  8. Evaluation of polybrominated diphenyl ethers in sediment of Lagos ...

    African Journals Online (AJOL)

    user

    Polybrominated diphenyl ethers (PBDEs) are additive flame retardants that are present in many commercial ... recent monitoring study conducted by United States Fish and Wildlife Service, Division of Environmental .... building materials, electronic products manufacturing factories) Oworonsoki and Agboyin stations were.

  9. POLYBROMINATED DIPHENYL ETHERS IN HOUSE DUST AND CLOTHES DRYER LINT

    Science.gov (United States)

    Polybrominated diphenyl ether (PBDE) flame retardants are now considered ubiquitous and persistent pollutants. Few studies have examined the concentrations of these chemicals in the home and here we report measurements of PBDEs in house dust samples collected from the Washington...

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

    Directory of Open Access Journals (Sweden)

    V. Gaina

    2013-07-01

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

  11. Nickel-catalyzed direct synthesis of dialkoxymethane ethers

    Indian Academy of Sciences (India)

    catalyzed direct synthesis of dialkoxymethane ethers. MURUGAN SUBARAMANIAN ABHIJIT BERA BHAGAVATULA L V PRASAD EKAMBARAM BALARAMAN. RAPID COMMUNICATION Volume 129 Issue 8 August 2017 pp 1153-1159 ...

  12. Synthesis and Antiplasmodial Activity of EG-Artemisinin Ethers and ...

    African Journals Online (AJOL)

    NICO

    capillary temperature of 180 °C and discharge Current at 10 uA. 2.2. Synthetic Procedures. 2.2.1. Synthesis of EG Ethers of Artemisinin 3–8. The synthesis of EG ethers of artemisinin (Scheme 1) was achieved by using with slight modifications the general method reported by Li et al.18, and described as follows: to a solution.

  13. Impaired neurotransmission in ether lipid-deficient nerve terminals

    OpenAIRE

    Brodde, Alexander; Teigler, Andre; Brugger, Britta; Lehmann, Wolf D.; Wieland, Felix; Berger, Johannes; Just, Wilhelm W.

    2012-01-01

    Isolated defects of ether lipid (EL) biosynthesis in humans cause rhizomelic chondrodysplasia punctata type 2 and type 3, serious peroxisomal disorders. Using a previously described mouse model [Rodemer, C., Thai, T.P., Brugger, B., Kaercher, T., Werner, H., Nave, K.A., Wieland, F., Gorgas, K., and Just, W.W. (2003) Inactivation of ether lipid biosynthesis causes male infertility, defects in eye development and optic nerve hypoplasia in mice. Hum. Mol. Genet., 12, 1881–1895], we investigated ...

  14. Accelerated Expansion as Predicted by an Ether Theory of Gravitation

    OpenAIRE

    Arminjon, Mayeul

    1999-01-01

    Cosmology is investigated within a new, scalar theory of gravitation, which is a preferred-frame bimetric theory with flat background metric. Before coming to cosmology, the motivation for an " ether theory " is exposed at length; the investigated concept of ether is presented: it is a compressible fluid, and gravity is seen as Archimedes' thrust due to the pressure gradient in that fluid. The construction of the theory is explained and the current status of the experimental confrontation is ...

  15. Marine Sponge Dysidea herbacea revisited: Another Brominated Diphenyl Ether

    Directory of Open Access Journals (Sweden)

    Bruce F. Bowden

    2005-03-01

    Full Text Available Abstract: A pentabrominated phenolic diphenyl ether (1 that has not previously been reported from marine sources has been isolated from Dysidea herbacea collected at Pelorus Island, Great Barrier Reef, Australia. The structure was determined by comparison of NMR data with those of known structurally-related metabolites. NMR spectral assignments for (1 are discussed in context with those of three previously reported isomeric pentabrominated phenolic diphenyl ethers.

  16. Effects of the ether phospholipid AMG-PC on mast cells are similar to that of the ether lipid AMG but different from that of the analogue hexadecylphosphocholine

    DEFF Research Database (Denmark)

    Grosman, Nina

    1991-01-01

    Farmakologi, ether phospholipid, hexacylphosphocholine, miltefosine, protein kinase C, AMG-PC(alkyl-methyl-glycero-phosphocholine), Histamine release, mast cell......Farmakologi, ether phospholipid, hexacylphosphocholine, miltefosine, protein kinase C, AMG-PC(alkyl-methyl-glycero-phosphocholine), Histamine release, mast cell...

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

    Energy Technology Data Exchange (ETDEWEB)

    Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang, E-mail: zhangpolyu@aliyun.com

    2016-06-10

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

  18. Review on Modification of Sulfonated Poly (-ether-ether-ketone Membranes Used as Proton Exchange Membranes

    Directory of Open Access Journals (Sweden)

    Xiaomin GAO

    2015-11-01

    Full Text Available The proton exchange membrane fuel cell (PEMFC is a type of modern power, but the traditional proton exchange membranes (PEM of PEMFC are limited by high methanol permeability and water uptake. Poly-ether-ether-ketone (PEEK is a widely used thermoplastic with good cost-effective property. Sulfonated poly (-ether-ether-ketone (SPEEK has high electric conductivity and low methanol permeability, as well as comprehensive property, which is expected to be used as PEMs. However, the proton exchange ability, methanol resistance, mechanical property and thermal stability of SPEEK are closely related to the degree of sulfonation (DS of SPEEK membranes. Additionally, the proton conductivity, methanol permeability, and stability of SPEEK membranes applied in various conditions need to be further improved. In this paper, the research into modification of SPEEK membranes made by SPEEK and other polymers, inorganic materials are introduced. The properties and modification situation of the SPEEK and the composite membranes, as well as the advantages and disadvantages of membranes prepared by different materials are summarized. From the results we know that, the methanol permeability of SPEEK/PES-C membranes is within the order of magnitude, 10-7cm2/s. The proton conductivity of the SPPESK/SPEEK blend membrane reaches 0.212 S cm-1 at 80 °C. The cross-linked SPEEK membranes have raised thermal and dimensional stability. The non-solvent caused aggregation of the SPEEK ionomers. The proton conductivity of SPEEK/50%BMIMPF6/4.6PA membrane maintains stable as 2.0 x 10-2S cm-1 after 600 h at 160 °C. Incorporation of aligned CNT into SPEEK increases the proton conductivity and reduces the methanol permeability of the composite membranes. The PANI improves the hydrothermal stability. More proton transfer sites lead to a more compact structure in the composite membranes. According to the results, the proton exchange capacity, water uptake, and conductivity of

  19. Nonlinear dielectric effect in supercritical diethyl ether.

    Science.gov (United States)

    Drozd-Rzoska, Aleksandra; Rzoska, Sylwester J; Martinez-Garcia, Julio Cesar

    2014-09-07

    Nonlinear dielectric effect (NDE) describes changes of dielectric permittivity induced by a strong electric field in a liquid dielectric. The most classical finding related to this magnitude is the negative sign of NDE in liquid diethyl ether (DEE), recalled by Peter Debye in his Nobel Prize lecture. This article shows that the positive sign of NDE in DEE is also possible, in the supercritical domain. Moreover, NDE on approaching the gas-liquid critical point exhibits a unique critical effect described by the critical exponent ψ ≈ 0.4 close to critical temperature (T(C)) and ψ ≈ 0.6 remote from T(C). This can be linked to the emergence of the mean-field behavior in the immediate vicinity of T(C), contrary to the typical pattern observed for critical phenomena. The multi-frequency mode of NDE measurements made it possible to estimate the evolution of lifetime of critical fluctuations. The new way of data analysis made it possible to describe the critical effect without a knowledge of the non-critical background contribution in prior.

  20. Emergent gravity and ether-drift experiments

    Science.gov (United States)

    Consoli, M.; Pappalardo, L.

    2010-11-01

    According to several authors, gravity might be a long-wavelength phenomenon emerging in some ‘hydrodynamic limit’ from the same physical, flat-space vacuum viewed as a form of superfluid medium. In this framework, light might propagate in an effective acoustic geometry and exhibit a tiny anisotropy that could be measurable in the present ether-drift experiments. By accepting this view of the vacuum, one should also consider the possibility of sizeable random fluctuations of the signal that reflect the stochastic nature of the underlying ‘quantum ether’ and could be erroneously interpreted as instrumental noise. To test the present interpretation, we have extracted the mean amplitude of the signal from various experiments with different systematics, operating both at room temperature and in the cryogenic regime. They all give the same consistent value {< A rangle ={mathcal O}(10^{-15})} which is precisely the magnitude expected in an emergent-gravity approach, for an apparatus placed on the Earth’s surface. Since physical implications could be substantial, it would be important to obtain more direct checks from the instantaneous raw data and, possibly, with new experimental set-ups operating in gravity-free environments.

  1. Dimethyl ether (DME) as an alternative fuel

    Science.gov (United States)

    Semelsberger, Troy A.; Borup, Rodney L.; Greene, Howard L.

    With ever growing concerns on environmental pollution, energy security, and future oil supplies, the global community is seeking non-petroleum based alternative fuels, along with more advanced energy technologies (e.g., fuel cells) to increase the efficiency of energy use. The most promising alternative fuel will be the fuel that has the greatest impact on society. The major impact areas include well-to-wheel greenhouse gas emissions, non-petroleum feed stocks, well-to-wheel efficiencies, fuel versatility, infrastructure, availability, economics, and safety. Compared to some of the other leading alternative fuel candidates (i.e., methane, methanol, ethanol, and Fischer-Tropsch fuels), dimethyl ether appears to have the largest potential impact on society, and should be considered as the fuel of choice for eliminating the dependency on petroleum. DME can be used as a clean high-efficiency compression ignition fuel with reduced NO x, SO x, and particulate matter, it can be efficiently reformed to hydrogen at low temperatures, and does not have large issues with toxicity, production, infrastructure, and transportation as do various other fuels. The literature relevant to DME use is reviewed and summarized to demonstrate the viability of DME as an alternative fuel.

  2. Keeping ether "en-vogue": the role of Nathan Cooley Keep in the history of ether anesthesia.

    Science.gov (United States)

    Guralnick, Walter C; Kaban, Leonard B

    2011-07-01

    In this report, we explore the little known role of Dr Nathan Cooley Keep in the dissemination of ether anesthesia in Boston. Keep was a prominent Boston dentist who, for a short time, taught and employed both William Morton and Horace Wells. He used ether anesthesia for a variety of dental and other surgical procedures requiring pain control. Keep administered ether to anesthetize Henry Wadsworth Longfellow's wife during the delivery of their daughter. This was the first use of ether for obstetric anesthesia. Dr Keep was also the first Dean of the Harvard Dental School and convinced the Massachusetts General Hospital to appoint a dentist to the staff of the hospital for the first time. Copyright © 2011 American Association of Oral and Maxillofacial Surgeons. Published by Elsevier Inc. All rights reserved.

  3. Biscalix[4]arene derivative as a very efficient phase selective gelator for oil spill recovery.

    Science.gov (United States)

    Tsai, Chia-Chen; Cheng, Ying-Tsai; Shen, Li-Ching; Chang, Kai-Chi; Ho, I-Ting; Chu, Jean-Ho; Chung, Wen-Sheng

    2013-11-15

    A biscalixarene framework, without long alkyl chains, has been readily synthesized in three steps starting from the parent calix[4]arene. The biscalix[4]arene 1 was able to form organogels in various alcoholic solvents; furthermore, it exhibited an excellent phase selective gelation property that is potentially useful in oil spill recovery.

  4. Linked supramolecular building blocks for enhanced cluster formation

    DEFF Research Database (Denmark)

    McLellan, Ross; Palacios, Maria A.; Beavers, Christine M.

    2015-01-01

    (Figure Presented). Methylene-bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the com...

  5. Noncovalent assembly of a fifteen-component hydrogen-bonded nanostructure

    NARCIS (Netherlands)

    Jolliffe, K.A.; Timmerman, P.; Reinhoudt, David

    1999-01-01

    A total of 72 hydrogen bonds are formed in the spontaneous association of calix[4]arene tetramelamine and barbituric acid derivatives to give nanosized assemblies of the type represented in the picture. These consist of 15 components that assemble in a completely diastereoselective sense: of the

  6. Heme-Protein Active Site Models via Self-Assembly in Water

    NARCIS (Netherlands)

    Fiammengo, R.; Wojciechowski, Kamil; Crego Calama, Mercedes; Figoli, A.; Wessling, Matthias; Reinhoudt, David; Timmerman, P.

    2003-01-01

    Water-soluble models of heme-protein active sites are obtained via the self-assembly of cationic porphyrins 1 and tetrasulfonato calix[4]arene 2 (K1·2 = 105 M-1). Selective binding of ligands either outside or inside the cavity of assemblies 1·2 via coordination to the zinc center has been observed.

  7. Selective self-organization of guest molecules in self-assembled molecular boxes

    NARCIS (Netherlands)

    Kerckhoffs, J.M.C.A.; ten Cate, M.G.J.; Mateos timoneda, Miguel; van Leeuwen, F.W.B.; Ruel, Bianca H.M.; Spek, Anthony L.; Kooijman, Huub; Crego Calama, Mercedes; Reinhoudt, David

    2005-01-01

    This article describes the synthesis and binding properties of highly selective noncovalent molecular receptors 13·(DEB)6 and 33·(DEB)6 for different hydroxyl functionalized anthraquinones 2. These receptors are formed by the self-assembly of three calix[4]arene dimelamine derivative molecules (1 or

  8. Synthesis, characterization and ion recognition studies of lower rim ...

    Indian Academy of Sciences (India)

    An amido-linked rhodamine conjugate of calix[4]arene, L has been synthesized and characterized. Metal ion recognition properties of L have been studied by emission and absorption techniques with 14 different metal ions including the transition ones. Results show that, L exhibits ratiometric emission intensity towards ...

  9. Influence of alkali and alkaline earth ions on the -alkylation of the ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 120; Issue 2. Influence of alkali and alkaline earth ions on the -alkylation of the lower rim phenolic-OH groups of -tert-butyl-calix[4]arene to result in amide-pendants: Template action of K+ and the structure of K+ bound tetra-amide derivative crystallized with a ...

  10. Diastereoselective noncovalent synthesis of hydrogen-bonded double-rosette assemblies

    NARCIS (Netherlands)

    Prins, L.J.; Hulst, A.J.R.L.; Timmerman, P.; Reinhoudt, David

    2002-01-01

    Chiral centers present either in the dimelamine components of calix[4]arene 1 or in the cyanurate components CA quantitatively induce one handedness (P or M) in the corresponding hydrogen-bonded assemblies 13(CA)6 (de>98 %). The high degree of chiral induction results from the presence of six chiral

  11. Kinetics of carrier-mediated alkali cation transport through supported liquid membranes: Effect of membrane solvent, co-transported anion, and support

    NARCIS (Netherlands)

    Visser, H.C.; Visser, Herman C.; de Jong, Feike; Reinhoudt, David

    1995-01-01

    The rate-limiting step in the transport of alkali cations through supported liquid membranes mediated by calix [4] arene carriers can be the diffusion of the carrier cation complex through the membrane and/or the kinetics of cation release from the complex. The effects of membrane solvent,

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

    Science.gov (United States)

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

    2016-02-01

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

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

    Science.gov (United States)

    Li, Hongtao; Zhang, Gang; Wu, Jing; Zhao, Chengji; Zhang, Yang; Shao, Ke; Han, Miaomiao; Lin, Haidan; Zhu, Jing; Na, Hui

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

  14. Copoly(arlene ether)s containing pendant sulfonic acid groups as proton exchange membrane

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu Seung [Los Alamos National Laboratory; Kim, Dae Sik [CANADA NRC; Robertson, Gilles [CANADA NRC; Guiver, Michael [CANADA NRC

    2008-01-01

    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The P AE and PAEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2-phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. The sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sP AE and sP AEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (DS) of 1.0 had high ion exchange capacities (IEC{sub v}(wet) (volume-based, wet state)) of 1.77 and 2.55 meq./cm{sup 3}, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5-51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the area of outstanding properties in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based). Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  15. The Effects of Sulfonated Poly(ether ether ketone Ion Exchange Preparation Conditions on Membrane Properties

    Directory of Open Access Journals (Sweden)

    Rebecca S. L. Yee

    2013-08-01

    Full Text Available A low cost cation exchange membrane to be used in a specific bioelectrochemical system has been developed using poly(ether ether ketone (PEEK. This material is presented as an alternative to current commercial ion exchange membranes that have been primarily designed for fuel cell applications. To increase the hydrophilicity and ion transport of the PEEK material, charged groups are introduced through sulfonation. The effect of sulfonation and casting conditions on membrane performance has been systematically determined by producing a series of membranes synthesized over an array of reaction and casting conditions. Optimal reaction and casting conditions for producing SPEEK ion exchange membranes with appropriate performance characteristics have been established by this uniquely systematic experimental series. Membrane materials were characterized by ion exchange capacity, water uptake, swelling, potential difference and NMR analysis. Testing this extensive membranes series established that the most appropriate sulfonation conditions were 60 °C for 6 h. For mechanical stability and ease of handling, SPEEK membranes cast from solvent casting concentrations of 15%–25% with a resulting thickness of 30–50 µm were also found to be most suitable from the series of tested casting conditions. Drying conditions did not have any apparent impact on the measured parameters in this study. The conductivity of SPEEK membranes was found to be in the range of 10−3 S cm−1, which is suitable for use as a low cost membrane in the intended bioelectrochemical systems.

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

    Science.gov (United States)

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

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

  17. Evaluation of workers exposed to ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate.

    Science.gov (United States)

    Park, Jiyoung; Yoon, Chungsik; Byun, Hyaejeong; Kim, Yangho; Park, Donguk; Ha, Kwonchul; Lee, Sang man; Park, Sungki; Chung, Eunkyo

    2012-01-01

    Ethylene glycol monomethyl ether (EGME) and ethylene glycol monomethyl ether acetate (EGMEA) are widely used in industries as solvents for coatings, paint and ink, but exposure data are limited because they are minor components out of mixed solvents, as well as because of inconsistency in desorption solvent use. The objective of this study was to investigate the worker exposure profile of EGME and EGMEA. Our study investigated 27 workplaces from June to September 2008 and detected EGME and EGMEA in 20 and 13, respectively. Both personal and area sampling were conducted using a charcoal tube to collect EGME and EGMEA. Gas chromatography with a flame ionization detector was used to analyze these compounds after desorption using a mixture of methylene chloride and methanol. The arithmetic mean concentrations of EGME and EGMEA during periods of full work shifts were 2.59 ppm and 0.33 ppm, respectively. The exposure levels were lower than the Korean Ministry of Labor (MOL) OEL (5 ppm) but higher than the ACGIH TLV (0.1 ppm). In general, the working environments were poor and required much improvement, including the use of personal protective equipment. Only 50% of the workplaces had local exhaust ventilation systems in operation. The average capture velocity of the operating local exhaust ventilation systems was 0.27 m/s, which did not meet the legal requirement of 0.5 m/s. Educating workers to clearly understand the handling and use of hazardous chemicals and improving working conditions are strongly suggested.

  18. Rheological, mechanical and tribological properties of carbon-nanofibre reinforced poly (ether ether ketone composites

    Directory of Open Access Journals (Sweden)

    Volker Altstaedt

    2003-12-01

    Full Text Available Poly(ether ether ketone nanocomposites containing vapour-grown carbon nanofibres (CNF were produced using standard polymer processing techniques. At high shear rates no significant increase in resin viscosity was observed. Nevertheless, the addition of the CNFs results in a higher melt strength at 360°C. Electron microscopy confirmed the homogeneous dispersion and alignment of nanofibres in the polymer matrix. Evaluation of the mechanical composite properties revealed a linear increase in tensile stiffness and strength with nanofibre loading fractions up to 15 wt% whilst matrix ductility was maintained up to 10 wt%. An interpretation of the composite performance by short-fibre theory resulted in rather low intrinsic stiffness properties of the vapour-grown CNF. Differential scanning calorimetry was used to investigate crystallization kinetics and degree of crystallinity. The CNFs were found not to act as nucleating sites. Furthermore, unidirectional sliding tests against two different counterpart materials (100Cr6 martensitic bearing steel, X5CrNi18-10 austenitic stainless steel were performed. The carbon nanofibres were found to reduce the wear rate of PEEK significantly.

  19. Microwave-assisted extraction for the simultaneous determination of Novolac glycidyl ethers, bisphenol A diglycidyl ether, and its derivatives in canned food using HPLC with fluorescence detection.

    Science.gov (United States)

    Zhang, Hong; Xue, Ming; Lu, Yanbin; Dai, Zhiyuan; Wang, Honghai

    2010-02-01

    A microwave-assisted extraction (MAE) protocol and an efficient HPLC analysis method were first developed for the fast extraction and simultaneous determination of bisphenol F diglycidyl ether (Novolac glycidyl ether 2-Ring), Novolac glycidyl ether 3-Ring, Novolac glycidyl ether 4-Ring, Novolac glycidyl ether 5-Ring, Novolac glycidyl ether 6-Ring, bisphenol A diglycidyl ether, bisphenol A (2,3-dihydroxypropyl) glycidyl ether, bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol A bis(3-chloro-2-hydroxypropyl) ether, bisphenol A (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) ether in canned fish and meat. After being optimized in terms of solvents, microwave power and irradiation time, MAE was selected to carry out the extraction of ten target compounds. Analytes were purified by poly(styrene-co-divinylbenzene) SPE columns and determined by HPLC-fluorescence detection. LOD varied from 0.79 to 3.77 ng/g for different target compounds based on S/N=3; LOQ were from 2.75 to 10.92 ng/g; the RSD for repeatability were <8.64%. The analytical recoveries ranged from 70.46 to 103.44%. This proposed method was successfully applied to 16 canned fish and meat, and the results acquired were in good accordance with the studies reported. Compared with the conventional liquid-liquid extraction and ultrasonic extraction, the optimized MAE approach gained the higher extraction efficiency (20-50% improved).

  20. Next Generation Extractants for Cesium Separation from High-Level Waste

    Energy Technology Data Exchange (ETDEWEB)

    Moyer, Bruce A [ORNL; Bazelaire, Eve [ORNL; Bonnesen, Peter V [ORNL; Custelcean, Radu [ORNL; Delmau, Laetitia Helene [ORNL; Ditto, Mary E [ORNL; Engle, Nancy L [ORNL; Gorbunova, Maryna [ORNL; Haverlock, Tamara [ORNL; Levitskaia, Tatiana G. [Pacific Northwest National Laboratory (PNNL); Bartsch, Richard A. [Texas Tech University, Lubbock; Surowiec, Malgorzata A. [Texas Tech University, Lubbock; Marquez, Manuel [University of Texas; Zhou, Hui [Texas Tech University, Lubbock

    2006-01-01

    This project seeks a fundamental understanding and major improvement in cesium separation from high-level waste by cesium-selective calixcrown extractants. Systems of particular interest involve novel solvent-extraction systems containing specific members of the calix[4]arene-crown-6 family, alcohol solvating agents, and alkylamines. Questions being addressed bear upon cesium binding strength, extraction selectivity, cesium stripping, and extractant solubility. Enhanced properties in this regard will specifically benefit applied projects funded by the USDOE Office of Environmental Management to clean up sites such as the Savannah River Site (SRS), Hanford, and the Idaho National Environmental and Engineering Laboratory. The most direct beneficiary will be the SRS Salt Processing Project, which has recently identified the Caustic-Side Solvent Extraction (CSSX) process employing a calixcrown as its preferred technology for cesium removal from SRS high-level tank waste. Disposal of high-level waste is horrendously expensive, in large part because the actual radioactive matter in underground waste tanks at various USDOE sites has been diluted over 1000-fold by ordinary inorganic chemicals. To vitrify the entire mass of the high-level waste would be prohibitively expensive. Accordingly, an urgent need has arisen for technologies to remove radionuclides such as {sup 137}Cs from the high-level waste so that the bulk of it may be diverted to cheaper low-level waste forms and cheaper storage. To address this need in part, chemical research at Oak Ridge National Laboratory (ORNL) has focused on calixcrown extractants, molecules that combine a crown ether with a calixarene. This hybrid possesses a cavity that is highly complementary for the Cs{sup +} ion vs. the Na+ ion, making it possible to cleanly separate cesium from wastes that contain 10,000- to 1,000,000-fold higher concentrations of sodium. Previous EMSP results in Project 55087 elucidated the underlying extraction

  1. 40 CFR 721.6181 - Fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

    Science.gov (United States)

    2010-07-01

    ... substituted oxirane, formaldehyde-phenol polymer glycidyl ether, substituted proplyamine and...-phenol polymer glycidyl ether, substituted proplyamine and polyethylenepolyamines (generic). (a) Chemical... as fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

  2. Copoly(arylene ether)s containing pendant sulfonic acid groups as proton exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Dae Sik, Kim [Los Alamos National Laboratory; Yu Seung, Kim [Los Alamos National Laboratory; Gilles, Robertson [CANADA-NRC; Guiver, Michael D [CANADA-NRC

    2009-01-01

    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The PAE and P AEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sPAE and sPAEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (OS) of 1.0 had high ion exchange capacities (IEC{sub v})(wet) (volume-based, wet state) of 1.77 and 2.55 meq./cm3, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5 -51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the upper left-hand corner in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based), i.e., high proton conductivity and low water uptake. Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

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

    Science.gov (United States)

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

    2017-09-22

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

  4. Fuel cell performance of pendent methylphenyl sulfonated poly(ether ether ketone ketone)s

    Science.gov (United States)

    Zhang, Hanyu; Stanis, Ronald J.; Song, Yang; Hu, Wei; Cornelius, Chris J.; Shi, Qiang; Liu, Baijun; Guiver, Michael D.

    2017-11-01

    Meta- and para-linked homopolymers bearing 3-methylphenyl (Me) pendent groups were postsulfonated to create sulfonated poly(ether ether ketone ketone) (SPEEKK) backbone isomers, which are referred to as Me-p-SPEEKK and Me-m-SPEEKK. Their thermal and oxidative stability, mechanical properties, dimensional stability, methanol permeability, and proton conductivity are characterized. Me-p-SPEEKK and Me-m-SPEEKK proton conductivities at 100 °C are 116 and 173 mS cm-1, respectively. Their methanol permeabilities are 3.3-3.9 × 10-7 cm2 s-1, and dimensional swelling at 100 °C is 16.4-17.5%. Me-p-SPEEKK and Me-m-SPEEKK were fabricated into membrane electrode assemblies (MEAs), and electrochemical properties were evaluated within a direct methanol fuel cell (DMFC) and proton-exchange membrane fuel cell (PEMFC). When O2 is used as the oxidant at 80 °C and 100% RH, the maximum power density of Me-m-SPEEKK reaches 657 mW cm-2, which is higher than those of Nafion 115 (552 mW cm-2). DMFC performance is 85 mW cm-2 at 80 °C with 2.0 M methanol using Me-p-SPEEKK due to its low MeOH crossover. In general, these electrochemical results are comparable to Nafion. These ionomer properties, combined with a potentially less expensive and scalable polymer manufacturing process, may broaden their potential for many practical applications.

  5. Thermolysis of phenethyl phenyl ether: a model for ether linkages in lignin and low rank coal

    Energy Technology Data Exchange (ETDEWEB)

    Britt, P.F.; Buchanan, A.C.; Malcolm, E.A. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Division of Chemistry and Analytical Science

    1995-10-06

    The thermolysis of phenethyl phenyl ether (PPE) was studied at 330-425{degree}C to resolve the discrepancies in the reported mechanisms of this important model of the beta-ether linkage found in lignin and low rank coal. Cracking of PPE proceeded by two competitive pathways that produced styrene plus phenol and two previously undetected products, benzaldehyde plus toluene. The ratio of these pathways, defined as the alpha/beta selectivity, was 3.1 +/- 0.3 at 375{degree}C and independent of the PPE concentration. Thermolysis of PPE in tetralin, a model hydrogen donor solvent, increased the alpha/beta selectivity to 7 and accelerated the formation of secondary products. All the data were consistent with a free-radical chain mechanism for the decomposition of PPE. Styrene and phenol are produced by hydrogen abstraction at the alpha-carbon, beta-scission to form styrene and the phenoxy radical, followed by hydrogen abstraction. Benzaldehyde and toluene are formed by hydrogen abstraction at the beta-carbon, 1,2-phenyl migration from oxygen to carbon, beta-scission to form benzaldehyde, and the benzyl radical followed by hydrogen abstraction. Thermochemical kinetic estimates indicate that product formation is controlled by the relative rate of hydrogen abstraction at the alpha- and beta-carbons by the phenoxy radical (dominant) and benzyl radical (minor) since beta-scission and 1,2-phenyl migration are fast relative to hydrogen abstraction. Thermolysis of PhCD{sub 2}CH{sub 2}OPh and PhCH{sub 2}CD{sub 2}OPh was consistent with the previous results, indicating that there was no significant contribution of a concerted retro-ene pathway to the thermolysis of PPE.

  6. Enzymatic network for production of ether amines from alcohols.

    Science.gov (United States)

    Palacio, Cyntia M; Crismaru, Ciprian G; Bartsch, Sebastian; Navickas, Vaidotas; Ditrich, Klaus; Breuer, Michael; Abu, Rohana; Woodley, John M; Baldenius, Kai; Wu, Bian; Janssen, Dick B

    2016-09-01

    We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed for reactions containing 10 mM alcohol and up to 280 mM ammonia corresponded well to predicted conversions. The results indicate that efficient amination can be driven by high concentrations of ammonia and may require improving enzyme robustness for scale-up. Biotechnol. Bioeng. 2016;113: 1853-1861. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  7. Kinetics and mechanism of thermolysis of dibenzyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Korobov, V.Yu.; Grigorieva, E.N.; Senko, O.V.; Kalechitz, I.V.

    1988-10-01

    The kinetics of thermolysis of dibenzyl ether in tetralin have been studied at 350-410 degrees C in a hydrogen atmosphere at 8.5 MPa pressure. A kinetic model has been proposed that satisfactorily describes the process and takes into account both the known transformation of ethers into toluene and benzaldehyde and the direct destruction of ether to benzene and toluene with elimination of CO and secondary conversions of benzaldehyde. It has been shown that at lower temperatures the first reaction prevails whereas at higher temperatures both reactions become competitive. The kinetic parameters support an intramolecular rearrangement as a pathway of the first reaction and a radical mechanism as a pathway of the second. 16 refs., 4 figs., 1 tab.

  8. Coal liquefaction model studies: free radical chain decomposition of diphenylpropane, dibenzyl ether, and phenyl ether via. beta. -scission reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gillert, K.E. (Indiana Univ., Bloomington); Gojewski, J.J.

    1982-12-03

    The thermal decompositions to 1,3-diphenylpropane (1), dibenzyl ether (2), and phenethyl phenyl ether (3) have been found to proceed by free radical chain processes. 1 gave toluene and styrene with a reaction order of 1.55, E/sub A/ = 51.4 kcal/mol, and log A = 12.5. The reaction could be initiated by benzyl phenyl ether but not by 1,2-diphenylethane. 2 gave toluene and benzaldehyde with a reaction order of 1.43,E/sub A/ = 48 kcal/mol, and log A = 12.6. The reaction could be initiated with benzyl phenyl ether. 3 gave phenol and styrene with a reaction order of 1.21, E/sub A/ = 50.3 kcal/mol, and log A =12.3. The reaction could be initiated by benzyl phenyl ether. All of the data are consistent with free radical processes with the reaction order determined by the termination reaction. No evidence for concerted reactions has been found.

  9. A local-ether model of propagation of electromagnetic wave

    Energy Technology Data Exchange (ETDEWEB)

    Su, C.C. [Dept. of Electrical Engineering, National Tsinghua University, Hsinchu (Taiwan)

    2001-07-01

    It is pointed out that the classical propagation model can be in accord with the Sagnac effect due to earth's rotational and orbital motions in the high-precision GPS (global positioning system) and interplanetary radar, if the reference frame of the classical propagation medium is endowed with a switchability according to the location of the wave. Accordingly, it is postulated that, as in the obsolete theory, electromagnetic waves propagate via a medium like the ether. However, the ether is not universal. It is proposed that in the region under sufficient influence of the gravity due to the earth, the sun, or another celestial body, there forms a local ether, which in turn is stationary with respect to the gravitational potential of the respective body. For earthbound and interplanetary propagation, the medium is stationary in a geocentric and a heliocentric inertial frame, respectively. An electromagnetic wave propagates at a constant speed with respect to the associated local ether, independent of the motions of source and receiver. Based on this local-ether model of wave propagation, a wide variety of earthbound, interplanetary, and interstellar propagation phenomena are accounted for. Strong evidence of this new classical model is its consistent account of the Sagnac effect due to earth's motions among GPS, the intercontinental microwave link, and the interplanetary radar. Moreover, as examined within the present precision, this model is still in accord with the Michelson-Morley experiment. To test the local-ether propagation model, a one-way-link rotor experiment is proposed. (orig.)

  10. [Effect of ether and fluorothane on higher nervous activity].

    Science.gov (United States)

    Batrak, G E; Zakopka, V M

    1978-01-01

    Tests conducted with dogs by using Pavlov's method of conditioned reflexes (salivation procedure) showed fluothane to act on the central nervous system 3 times as strong as does ether. This is confirmed by a longer time necessary for the higher nervous system to normalize. Thus, awakening of the animals after the ether anesthesia, the re-establishment of the conditioned reflex activity supervened by the 7th day on the average, whereas, after the fluothane anesthesia, this occurred only on the 24th day.

  11. A crown ether appended super gelator with multiple stimulus responsiveness.

    Science.gov (United States)

    Dong, Shengyi; Zheng, Bo; Xu, Donghua; Yan, Xuzhou; Zhang, Mingming; Huang, Feihe

    2012-06-26

    A crown ether appended super gelator is designed and synthesized. It can gel a variety of organic solvents and shows excellent gelation properties with both low critical gelation concentration and short gelation time. Due to the introduction of the crown ether moiety and a secondary ammonium unit, the supramolecular gels show reversible gel-sol transitions. The supramolecular gels can also be molded into shape-persistent and free-standing objects. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Molecular engineering and fluorescence for the detection of toxic cations; Ingenierie moleculaire et fluorescence pour la reconnaissance de cations toxiques

    Energy Technology Data Exchange (ETDEWEB)

    Souchon, V

    2007-11-15

    This work is a part of the 'Toxicologie Nucleaire Environnementale' program which aims at studying the effects on the living of heavy metals or radionuclides involved in nuclear industry. Most particularly, it deals with the design of new fluorescent sensors for the selective detection of Pb{sup 2+}, Cd{sup 2+} and Cs{sup +} in biological media. Several fluorescent calixarenes possessing nitrogen atoms were synthesized and their properties as potential lead sensors were investigated. One of them could be used in experimental conditions close to biological media and new target compounds with amide functional groups were proposed. Many approaches were considered for the design of selective fluorescent sensors for cadmium. On the basis of literature results, many chelating compounds incorporating sulfur atoms were synthesized but showed no significant affinity towards cadmium. On the opposite, compounds functionalized with several pyridine-2'-yl-1,2,3-triazol fluorescent moieties linked to a {beta}-cyclodextrin or a calix[4]arene showed good affinity for cadmium in methanol, but the selectivity was found to be insufficient. In contrast, very satisfying results in terms of both selectivity and sensitivity could be obtained with the commercial calcium sensor Rhod-5N in an aqueous medium at neutral pH. Lastly, micromolar detection limits for the selective detection of caesium were reached in an aqueous medium at neutral pH thanks to a new sulfonated fluorescent calixarene with two appended crown-ethers. An original complexation mechanism was proposed and validated by molecular modelling (DFT). (author)

  13. Simulation of cesium nitrate extraction by a calixarene. Application to supported liquid membranes transport; Modelisation de l`extraction du nitrate de cesium par un calixarene. Application a la modelisation du transport a travers des membranes liquides supportees

    Energy Technology Data Exchange (ETDEWEB)

    Sorel, C.

    1996-12-12

    This work fits into the general pattern of the CEA studies on the decontamination of liquid effluents containing long-lived radioactive isotopes. Some calixarenes have proved to be very effective to selectively extract the cesium of aqueous solutions whose composition simulates those of the effluents to be reprocessed. On account of the difficulty of the studied extraction mechanisms, a physical and chemical simulation has been necessary. The system takes into account: 1)a concentrated nitric acid aqueous phase and/or sodium nitrate 2)an organic phase constituted by the diluent 1,2-nitro-phenyl-octyl-ether and 1,3-diisopropoxy-calix(4)arene-couronne-6. The use of concentrated aqueous solutions requires to take into account variations to ideality by the mean of activity coefficients reckoning. The different theories on the reckoning of variations to ideality in aqueous or organic phases are described in the first part. The determination of cesium and sodium nitrates activity coefficients in very concentrated matrices has required an important theoretical and experimental study which is given in the second part. The aim of this study was indeed to complete the thermodynamic data of cesium and sodium nitrates aqueous solutions. The computerized tools required for the modeling are reviewed. The stoichiometry of the extracted species in the organic phase has been determined in the third part. The supported membrane technique is an original method of separation by liquid-liquid extraction. A membrane transport model has been developed and is given in the last part of this work. (O.M.). 128 refs.

  14. Study of the simultaneous complexation of a cation and of an anion using functionalized calixarenes; Etude de la complexation simultanee d'un cation et d'un anion par des calixarenes fonctionnalises

    Energy Technology Data Exchange (ETDEWEB)

    Moli, Ch. [CEA Cadarache, Dept. d' Etudes des Dechets, DED, 13 - Saint Paul lez Durance (France)]|[Universite Louis Pasteur, 67 - Strasbourg (France)

    2002-03-01

    The chemical reprocessing of irradiated nuclear fuels leads to the production of high-level radioactive liquid wastes which contain long-lived toxic radioelements. In the framework of the long-term management of these wastes, important research work is carried out for the separation of these radioelements for their further transmutation or immobilization inside specific matrices. These radioelements are present in acid solutions of fission products in the form of cations (cesium), anions (technetium, selenium) and molecules (iodine). Crown calixarenes have been successfully used for the extraction of cesium thanks to their exceptional selectivities. This work is mainly based on the use of the chelating properties of calixarenes for the extraction of anionic radioelements. Calixarenes functionalized by amino-carbon chains have been selected. The synthesis of amine calix[4]arenes and calix[6]arenes is described and their extractive and ionophoretic properties with respect to radioelements are shown using aqueous selective separation techniques like the liquid-liquid extraction and the supported liquid membrane transport. Technetium and selenium are extracted by amine calixarenes from a 10{sup -2} M aqueous solution of nitric acid. At this acidity, no selenium transport is observed, while technetium transport is efficient: the solution is quasi-totally decontaminated in 6 hours. Molecular iodine is efficiently extracted with a simple organic diluent, the 1,2-nitro-phenyl-hexyl-ether, from a strongly concentrated aqueous solution of nitric acid (HNO{sub 3} = 3 M). The transport of iodine becomes faster and more efficient when its concentration in the solution is higher. (J.S.)

  15. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Science.gov (United States)

    2010-10-01

    ... bisulfide) and ethyl ether. 151.50-40 Section 151.50-40 Shipping COAST GUARD, DEPARTMENT OF HOMELAND... ether. (a) The provisions of this section are applicable if specifically referenced in the Special... disulfide (carbon bisulfide) and § 151.50-42 for ethyl ether shall also be observed. ...

  16. 76 FR 69659 - Methacrylic Acid-Methyl Methacrylate-Polyethylene Glycol Monomethyl Ether Methacrylate Graft...

    Science.gov (United States)

    2011-11-09

    ... AGENCY 40 CFR Part 180 Methacrylic Acid-Methyl Methacrylate-Polyethylene Glycol Monomethyl Ether... residues of methacrylic acid-methyl methacrylate- polyethylene glycol monomethyl ether methacrylate graft... permissible level for residues of methacrylic acid-methyl methacrylate-polyethylene glycol monomethyl ether...

  17. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Science.gov (United States)

    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 this...

  18. 40 CFR 721.10017 - Amine terminated bisphenol A diglycidyl ether polymer (generic).

    Science.gov (United States)

    2010-07-01

    ... diglycidyl ether polymer (generic). 721.10017 Section 721.10017 Protection of Environment ENVIRONMENTAL... ether polymer (generic). (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substances identified generically as amine terminated bisphenol A diglycidyl ether polymer (PMNs P...

  19. 40 CFR 721.9952 - Alkoxylated aliphatic diisocyanate allyl ether (generic).

    Science.gov (United States)

    2010-07-01

    ... allyl ether (generic). 721.9952 Section 721.9952 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.9952 Alkoxylated aliphatic diisocyanate allyl ether... identified generically as alkoxylated aliphatic diisocyanate allyl ether (PMN P-00-0353) is subject to...

  20. 75 FR 4288 - Oxirane, 2-Methyl-, Polymer with Oxirane, Dimethyl Ether; Tolerance Exemption

    Science.gov (United States)

    2010-01-27

    ... AGENCY 40 CFR Part 180 Oxirane, 2-Methyl-, Polymer with Oxirane, Dimethyl Ether; Tolerance Exemption... oxirane, dimethyl ether (CAS Reg. No. 61419-46-3); minimum number average molecular weight (in AMW) 2,800... oxirane, dimethyl ether (CAS Reg. No. 61419-46-3) on food or feed commodities. DATES: This regulation is...

  1. Ionic crosslinking of imidazolium functionalized poly(aryl ether ketone) by sulfonated poly(ether ether ketone) for anion exchange membranes.

    Science.gov (United States)

    Xu, Yixin; Ye, Niya; Zhang, Dengji; Yang, Jingshuai; He, Ronghuan

    2017-07-01

    Two N3-substituted imidazoles 1,2-dimethylimidazole and 1-butyl-2-methylimidazole were chosen to functionalize poly(aryl ether ketone), respectively. The generated imidazolium cations could electrostatically react with sulfonate ions of the sulfonated poly(ether ether ketone) forming the ionic crosslinking structure of the membranes. The changes in crosslinking degree and the alkyl chain-length on N3 site of the imidazoliums could highly affect the properties of the anion exchange membranes (AEMs). The AEMs functionalized by 1-butyl-2-methylimidazole exhibited superior properties compared to those functionalized by 1,2-dimethylimidazole according to the tolerance tests of the AEMs towards hot alkaline solutions. After exposed to 1M KOH at 80°C for 200h, the 1-butyl-2-methylimidazole modified AEMs maintained the ion exchange capacity of above 85%, the conductivity of about 70%, and the tensile stress at break of around 80%, respectively. The hydrophile-lipophile balance of the polymer membranes was calculated and proposed to better understand the correlation between structures and properties of the AEMs. The degradation of the imidazolium functional groups of the AEMs under the attack of hydroxide ions was evidenced by FT-IR analysis. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Evaluation of polybrominated diphenyl ethers in sediment of Lagos ...

    African Journals Online (AJOL)

    user

    Certain pollutants, particularly synthetic organic compounds have given rise to important environmental concerns. New organic pollutants especially polybrominated diphenyl ether (PBDEs) employed in electronic equipment and in some household items as flame retardants are now finding their way into the aquatic ...

  3. Formation and Structural Analysis of Novel Dibornyl Ethers | Kaye ...

    African Journals Online (AJOL)

    One- and two-dimensional NMR spectroscopy has been used to establish the regio- and stereochemistry of novel dibornyl ethers, obtained by acid-catalysed condensation of camphor-derived a-hydroxybornanones. South African Journal of Chemistry Vol.55 2002: 111-118 ...

  4. Infrared Spectroscopy of Divalent Zinc and Cadmium Crown Ether Systems

    NARCIS (Netherlands)

    Cooper, T. E.; Carl, D. R.; Oomens, J.; Steill, J. D.; Armentrout, P. B.

    2011-01-01

    The gas-phase structures of transition-metal dication (Zn2+ and Cd2+) complexes with varying sized crown ethers, 12-crown-4 (12c4), 15-crown-5 (15c5), and 18-crown-6 (18c6), are investigated using infrared multiple photon dissociation (IRMPD) spectroscopy and quantum mechanical calculations. The

  5. Ether lipids of planktonic archae in the marine water column

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Hoefs, M.J.L.; Schouten, S.; King, L.L.; Wakeham, S.G.; Leeuw, J.W. de

    1997-01-01

    Acyclic and cyclic biphytanes derived from the membrane ether lipids of archaea were found in water column particulate and sedimentary organic matter from several oxic and anoxic marine environments. Compound-specific isotope analyses of the carbon skeletons suggest that planktonic archaea utilize

  6. Photodegradation of poly(ether sulphone). Part 2

    DEFF Research Database (Denmark)

    Norrman, K.; Krebs, Frederik C

    2004-01-01

    The photodegradation of poly(ether sulphone) (PES) was investigated systematically by time-of-flight SIMS (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS). The effect of varying the irradiation dose, wavelength and the atmosphere was studied along with mechanistic photooxidation studies using...

  7. Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

    NARCIS (Netherlands)

    Heeres, A.; Spoelma, F.F.; Doren, H.A. van; Gotlieb, K.F.; Bleeker, I.P.; Kellogg, R.M.

    2000-01-01

    Several 2-nitroalkyl polysaccharide ethers (from pullulan (1), guar (2), agarose (3), inulin (4), cellulose (5), Na-α-polyglucuronate (6) and hydroxyethyl cellulose (7)) were synthesized by reaction with 2-nitro-1-alkenes (2-nitro-1-propene and 2-nitro-1-butene) formed in situ from 2-nitroalkyl

  8. Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

    NARCIS (Netherlands)

    Heeres, A; Spoelma, FF; van Doren, HA; Gotlieb, KF; Bleeker, IP; Kellogg, RM

    Several 2-nitroalkyl polysaccharide ethers (from pullulan (1), guar (2), agarose (3), inulin (4), cellulose (5), Na-alpha-polyglucuronate (6) and hydroxyethyl cellulose (7)) were synthesized by reaction with 2-nitro-1-alkenes (2-nitro-1-propene and 2-nitro-1-butene) formed in situ from 2-nitroalkyl

  9. Comparative evaluation of direct stool smear and Formol-ether ...

    African Journals Online (AJOL)

    Cryptosporidium is a common cause of diarrhoea in patients with Human Immunodeficiency Virus (HIV)/Acquired Immunodeficiency Syndrome (AIDS). Unfortunately this pathogen is not often checked for in Microbiology laboratories because the formol-ether stool concentration method for identification of Cryptosporidium is ...

  10. Binary mixtures of carbon dioxide and dimethyl ether as alternative ...

    African Journals Online (AJOL)

    Vapor-liquid equilibrium (VLE) data were predicted for the binary mixture of carbon dioxide (CO2) and dimethyl ether (DME) at ten temperatures ranging from 273.15 to 386.56 K and pressure upto 7.9 MPa to observe this mixture's potential of COP enhancement and capacity modulation as a working fluid in a refrigeration ...

  11. Acute toxicities of diethyl ether and ethanol extracted Nerium ...

    African Journals Online (AJOL)

    A four-day static renewal acute toxicity test was performed to determine the LC50 value of ethanol and diethyl ether extracted Nerium indicum leaf for the freshwater fish, Heteropneustes fossilis. The LC50 values, their upper and lower confidence limits and slope functions were calculated. The LC50 values for ethanol ...

  12. Evaluation of polybrominated diphenyl ethers in sediment of Lagos ...

    African Journals Online (AJOL)

    user

    environmental concerns. New organic pollutants especially polybrominated diphenyl ether (PBDEs) employed in electronic equipment and in some household items as flame retardants are now finding their way into the aquatic environment as components of waste discharge into the water body. These highly hazardous ...

  13. Lithium air batteries having ether-based electrolytes

    Science.gov (United States)

    Amine, Khalil; Curtiss, Larry A.; Lu, Jun; Lau, Kah Chun; Zhang, Zhengcheng; Sun, Yang-Kook

    2016-10-25

    A lithium-air battery includes a cathode including a porous active carbon material, a separator, an anode including lithium, and an electrolyte including a lithium salt and polyalkylene glycol ether, where the porous active carbon material is free of a metal-based catalyst.

  14. Li-air batteries having ether-based electrolytes

    Science.gov (United States)

    Amine, Khalil; Curtiss, Larry A; Lu, Jun; Lau, Kah Chun; Zhang, Zhengcheng; Sun, Yang-Kook

    2015-03-03

    A lithium-air battery includes a cathode including a porous active carbon material, a separator, an anode including lithium, and an electrolyte including a lithium salt and polyalkylene glycol ether, where the porous active carbon material is free of a metal-based catalyst.

  15. Synthesis of Hydroxytyrosyl Alkyl Ethers from Olive Oil Waste Waters

    Directory of Open Access Journals (Sweden)

    Juan Fernández-Bolaños

    2009-05-01

    Full Text Available The preparation of a new type of derivatives of the naturally occurring antioxidant hydroxytyrosol is reported. Hydroxytyrosyl alkyl ethers were obtained in high yield by a three-step procedure starting from hydroxytyrosol isolated from olive oil waste waters. Preliminary results obtained by the Rancimat method have shown that these derivatives retain the high protective capacity of free hydroxytyrosol.

  16. Dimethyl ether in diesel engines - progress and perspectives

    DEFF Research Database (Denmark)

    Sorenson, Spencer C

    2001-01-01

    A review of recent developments related to the use of dimethyl ether (DME) in engines is presented Research work discussed is in the areas of engine performance and emissions, fuel injection systems, spray and ignition delay, and detailed chemical kinetic modeling. DME's properties and safety...

  17. Bio-inspired ion selective crown-ether polymer membranes

    NARCIS (Netherlands)

    Tas, Sinem

    2016-01-01

    Development of unctional membranes that are capable of selectively recognizing and transporting ions have key importance for the recovery and separation of specific icons (e.d. K+, Li+, Na+) from multicomponent mixtures. In this thesis, new membrane materials based on crown ether-metal ion

  18. Preparation and Characterization of Water-Soluble Xylan Ethers

    Directory of Open Access Journals (Sweden)

    Kay Hettrich

    2017-03-01

    Full Text Available Xylan is a predominant hemicellulose component that is found in plants and in some algae. This polysaccharide is made from units of xylose (a pentose sugar. One promising source of xylan is oat spelt. This feedstock was used for the synthesis of two xylan ethers. To achieve water soluble products, we prepared dihydroxypropyl xylan as a non-ionic ether on the one hand, and carboxymethyl xylan as an ionic derivative on the other hand. Different preparation methods like heterogeneous, pseudo-homogeneous, and homogeneous syntheses were compared. In the case of dihydroxypropyl xylan, the synthesis method did not significantly affect the degree of substitution (DS. In contrast, in the case of carboxymethyl xylan, clear differences of the DS values were found in dependence on the synthesis method. Xylan ethers with DS values of >1 could be obtained, which mostly show good water solubility. The synthesized ionic, as well as non-ionic, xylan ethers were soluble in water, even though the aqueous solutions showed slight turbidity. Nevertheless, stable, transparent, and stainable films could be prepared from aqueous solutions from carboxymethyl xylans.

  19. Why do crown ethers activate enzymes in organic solvents?

    NARCIS (Netherlands)

    van Unen, D.J.; Engbersen, Johannes F.J.; Reinhoudt, David

    2002-01-01

    One of the major drawbacks of enzymes in nonaqueous solvents is that their activity is often dramatically low compared to that in water. This limitation can be largely overcome by crown ether treatment of enzymes. In this paper, we describe a number of carefully designed new experiments that have

  20. Binding of ether and carbonyl oxygens to lithium ion

    Energy Technology Data Exchange (ETDEWEB)

    Blint, R.J. [Physical Chemistry Dept., Warren, MI (United States)

    1994-12-31

    The electrolyte for a lithium battery is a lithium salt (e.g. lithium Perchlorate) dissolved in an organic solvent or a mixture of organic solvents. The conductivity in these electrolytes is ionic and needs to be as high as possible to efficiently remove energy from the battery. The diffusion coefficient of the solvated ion in liquid electrolytes is inversely dependent on the radius of the salvation sphere. Consequently conductivity will increase with a decrease in the size of the salvation shell. The size of the salvation shell is determined by the size and coordination number of the solvent molecules. The types of organic solvents in electrolytes used in lithium battery applications are usually differentiated based on their perceived solvation properties. These solvents are often small, oxygen containing organic molecules which move with the Li{sup +} ions. This paper calculates the binding energies of some of these solvents to Li{sup +} using molecular quantum mechanics (MQM) techniques. The binding energies of the various solvents to Li{sup +} may determine which solvents will be preferentially bound to the ion. In liquid organic electrolytes, then, it will be the identity of the solvent and the coordination number which most affect the conductivity; the binding energies determine both of these properties. Carbonyl oxygens which occur in formaldehyde, acetaldehyde, acetone, ethylene carbonate and propylene carbonate have different Li{sup +} bonding properties than do the ether oxygens which occur in water, dimethyl ether and diethyl ether. Polymer solvents for the lithium salts such as the polyethers have chains which are too long to move with the binding energies then serve as the basis for a different Li{sup +} transport. Dimethyl ether and diethyl ether serve both as solvents and models for the polyethers.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ayyaru, Sivasankaran; Dharmalingam, Sangeetha, E-mail: sangeetha@annauniv.edu

    2014-03-01

    Graphical abstract: - Highlights: • Sulfonated poly ether ether ketone (SPEEK) membrane in SCMFC used to determine the BOD. • The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm. • This sensing range was 62.5% higher than that of Nafion{sup ®}. • SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}. • Nafion{sup ®} shows high anodic internal resistance (67 Ω) than the SPEEK (39 Ω). - Abstract: The present study is focused on the development of single chamber microbial fuel cell (SCMFC) using sulfonated poly ether ether ketone (SPEEK) membrane to determine the biochemical oxygen demand (BOD) matter present in artificial wastewater (AW). The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm when using artificial wastewater. This sensing range was 62.5% higher than that of Nafion{sup ®}. The most serious problem in using MFC as a BOD sensor is the oxygen diffusion into the anode compartment, which consumes electrons in the anode compartment, thereby reducing the coulomb yield and reducing the electrical signal from the MFC. SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}, resulting in low internal resistance and substrate loss, thus improving the sensing range of BOD. The system was further improved by making a double membrane electrode assembly (MEA) with an increased electrode surface area which provide high surface area for electrically active bacteria.

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

    Science.gov (United States)

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

    2017-09-01

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

  3. A mild and efficient procedure for the synthesis of ethers from various alkyl halides

    Directory of Open Access Journals (Sweden)

    Mosstafa Kazemi

    2013-10-01

    Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

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

    Energy Technology Data Exchange (ETDEWEB)

    Fayolle-Guichard, F.

    2005-04-01

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

  5. Coal liquefaction model studies: free radical chain decomposition of diphenylpropane, dibenzyl ether, and phenyl ether via. beta. -scission reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gilbert, K.E.; Gajewski, J.J.

    1982-01-01

    The thermal decompositions of 1,3-diphenylpropane (1), dibenzyl ether (2), and phenethyl phenyl ether (3) have been found to proceed by free radical chain processes. 1 gave toluene and styrene with a reaction order of 1.55, E/sub A/ = 51.4 kcal/mol, and log A = 12.5. The reaction could be initiated by benzyl phenyl ether but not by 1,2-diphenylethane. 2 gave toluene and benzaldehyde with a reaction order of 1.43, E/sub A/ = 48 kcal/mol, and log A = 12.6. The reaction could be initiated with benzyl phenyl ether. 3 gave phenol and styrene with a reaction order of 1.21, E/sub A/ = 50.3 kcal/mol, and log A = 12.3. The reaction could be initiated by benzyl phenyl ether. All of the data are consistent with free radical chain processes with the reaction order determined by the termination reaction. No evidence for concerted reactions has been found. The thermal chemistry of three-atom links is best described by free radical chain processes. The products are consistent with a free radical chain process involving a ..beta..-scission reaction, and the reaction orders range between first and three-halves order depending upon the nature of the chain termination reaction. Activation parameters are readily estimated from thermochemical kinetic data on the individual reactions with log A approx. = 12 and E/sub A/approx. = 50 kcal/mol. Unlike the one- and two-atom linkages, reactions of the three-atom linkages are promoted by free radical initiators. The potential for inhibition of free radical chains also exists and is currently being studied. 4 tables.

  6. 40 CFR 721.6980 - Dimer acids, polymer with polyalkylene glycol, bisphenol A-diglycidyl ether, and alky-lenepolyols...

    Science.gov (United States)

    2010-07-01

    ... glycol, bisphenol A-diglycidyl ether, and alky-lenepolyols polyglycidyl ethers (generic name). 721.6980... Substances § 721.6980 Dimer acids, polymer with polyalkylene glycol, bisphenol A-diglycidyl ether, and alky-lenepolyols polyglycidyl ethers (generic name). (a) Chemical substance and significant new uses subject to...

  7. [Ethylene glycol and propylene glycol ethers - Reproductive and developmental toxicity].

    Science.gov (United States)

    Starek-Świechowicz, Beata; Starek, Andrzej

    2015-01-01

    Both ethylene and propylene glycol alkyl ethers (EGAEs and PGAEs, respectively) are widely used, mainly as solvents, in industrial and household products. Some EGAEs demonstrate gonadotoxic, embriotoxic, fetotoxic and teratogenic effects in both humans and experimental animals. Due to the noxious impact of these ethers on reproduction and development of organisms EGAEs are replaced for considerably less toxic PGAEs. The data on the mechanisms of testicular, embriotoxic, fetotoxic and teratogenic effects of EGAEs are presented in this paper. Our particular attention was focused on the metabolism of some EGAEs and their organ-specific toxicities, apoptosis of spermatocytes associated with changes in the expression of various genes that code for oxidative stress factors, protein kinases and nuclear hormone receptors. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

  8. SYNTHESIS OF ALLYL PHENYL ETHER AND CLAISEN REARRANGEMENT

    Directory of Open Access Journals (Sweden)

    Gagik Torosyan

    2011-12-01

    Full Text Available It has been established the possibility for phenol allylation on natural zeolites and them analogs. Here is demonstrated the synthesis of allyl phenol, which has wide industrial applications. The offered method in comparison with the traditional methods has more advantages – higher selectivity, smaller material and power resources consumption. It has been obtained the mixture of allylating phenols (30% in general with allyl phenyl ether (1 with 80% yields. At 600 K is obtained allylphenyl ether, at 700 K beginning the formation of allyl phenols, which is the result of direct C-allylation of the aromatic ring. It has been investigated the possibility of Claisen rearrangement in the same conditions. All of that are established by gas-liquid chromatography and liquid chromatography data.

  9. Ether and ester derivatives of the perborate icosahedron

    Science.gov (United States)

    Hawthorne, M. Frederick; Peymann, Toralf; Maderna, Andreas

    2003-12-16

    New boron icosahedral ethers and esters formed from Cs.sub.2 [closo-B.sub.12 (OH).sub.12 ],; Cs[closo-1-H-1-CB.sub.11 (OH).sub.11 ]; and closo-1,12-H.sub.2 -1,12-C.sub.2 B.sub.10 (OH).sub.10 are disclosed. Also set forth are their preparation by reacting the icosahedral boranes [closo-B.sub.12 H.sub.12 ].sup.2-, [closo-1-CB.sub.11 H.sub.12 ].sup.- and closo-1,12-(CH.sub.2 OH).sub.2 -1,12-C.sub.2 B.sub.10 H.sub.10 with an acid anhdride or acid chloride to form the ester or an alkylating agent to form the ether.

  10. SYNTHESIS OF ALLYL PHENYL ETHER AND CLAISEN REARRANGEMENT

    OpenAIRE

    Gagik Torosyan; Dezy Hovhannisyan

    2011-01-01

    It has been established the possibility for phenol allylation on natural zeolites and them analogs. Here is demonstrated the synthesis of allyl phenol, which has wide industrial applications. The offered method in comparison with the traditional methods has more advantages – higher selectivity, smaller material and power resources consumption. It has been obtained the mixture of allylating phenols (30%) in general with allyl phenyl ether (1) with 80% yields. At 600 K is obtained allylphenyl e...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1987-08-01

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

  12. Patch test with ether extracts in salicaceae allergy

    Directory of Open Access Journals (Sweden)

    Sawhney M

    2002-01-01

    Full Text Available A total of 23 cases suggestive of airborne contact dermatitis were patch tested with ether extracts of flowers and leaves of populus sp. and salix sp. in a study conducted in Ladakh at an altitude of 3445 meters above sea level. Overall positivity was found in 12 (52.17%, with populus sp. alone in 7 (30. 43%, salix sp. alone in 4 17.39% and to both in one (8.33%.

  13. Homogeneous Charge Compression Ignition Combustion of Dimethyl Ether

    OpenAIRE

    Pedersen, Troels Dyhr; Schramm, Jesper

    2011-01-01

    This thesis is based on experimental and numerical studies on the use of dimethyl ether (DME) in the homogeneous charge compression ignition (HCCI) combustion process. The first paper in this thesis was published in 2007 and describes HCCI combustion of pure DME in a small diesel engine. The tests were designed to investigate the effect of engine speed, compression ratio and equivalence ratio on the combustion timing and the engine performance. It was found that the required compression ratio...

  14. Numerical investigation on the effect of injection pressure on the internal flow characteristics for diethyl ether, dimethyl ether and diesel fuel injectors using CFD

    Directory of Open Access Journals (Sweden)

    Vijayakumar Thulasi

    2011-01-01

    Full Text Available The spray characteristics of the diesel fuel are greatly affected by the cavitation formed inside the injector due to the high pressure differential across the nozzle. Many researchers across the globe are exploring the potential of using diethyl ether and dimethyl ether as an alternate for diesel fuel to meet the strict emission norms. Due to the variation in the fuel properties the internal flow characteristics in injectors for ether fuels are expected to be different from that of the diesel fuel. In this paper computational technique is used to study and compare the internal flow characteristics of diethyl ether, dimethyl ether and diesel fuel. The two phase flow model considering the fuel as a mixture of liquid and vapor is adopted for the simulation study. The injection pressure is varied from 100 to 400 bar and the flow characteristics of all three fuels are simulated and compared. Results indicate that all three fuels have distinct cavitating patterns owing to different property values. The dimethyl ether is found to be more cavitating than diesel and diethyl ether fuels as expected. The mass of fuel injected are found to be decreasing for the ether fuels when compared with diesel fuel at all injection pressures.

  15. Diethyl Ether Production Process with Various Catalyst Type

    Directory of Open Access Journals (Sweden)

    Widayat

    2013-01-01

    Full Text Available Several H-zeolite and HZSM-5 catalysts was preparated and their characters have also been investigated. H-zeolit Catalyst was preparated from Natural Zeolite that obtained from Malang District and Gunung Kidul District. Diethyl ether was produced by Ethanol with concentration of 95%. This research use fixed bed reactor that 1 gram of catalyst as bed catalyst, atmospheric pressure and temperature 140oC as the operating condition. Ethanol vapor from vaporization tank was driven by 200 ml/min Nitrogen stream. The responds in this research is liquid product concentration; diethyl ether, ethanol, methanol and water concentration. The results showed that the largest ethanol conversion was produced by the use of 56.44% HZSM-5 and the largest yield of diethyl ether diethyl was produced by the use of alumina and H-zeolite catalyst. The larger ratio between natural zeolite with HCl solvent will produce the larger surface area of catalyst and ethanol conversion. The largest ethanol conversion was produced at reactan ratio 1:20.

  16. Selective cytotoxic activity of new lipophilic hydroxytyrosol alkyl ether derivatives.

    Science.gov (United States)

    Calderón-Montaño, José Manuel; Madrona, Andrés; Burgos-Morón, Estefanía; Orta, Manuel Luis; Mateos, Santiago; Espartero, José Luis; López-Lázaro, Miguel

    2013-05-29

    Recent data suggest that hydroxytyrosol, a phenolic compound of virgin olive oils, has anticancer activity. This communication reports the synthesis of decyl and hexadecyl hydroxytyrosyl ethers, as well as the cytotoxic activity of hydroxytyrosol and a series of seven hydroxytyrosol alkyl ether derivatives against A549 lung cancer cells and MRC5 non-malignant lung fibroblasts. Hydroxytyrosyl dodecyl ether (HTDE) showed the highest selective cytotoxicity, and possible mechanisms of action were investigated; results suggest that HTDE can moderately inhibit glycolysis, induce oxidative stress, and cause DNA damage in A549 cells. The combination of HTDE with the anticancer drug 5-fluorouracil induced a synergistic cytotoxicity in A549 cancer cells but not in non-malignant MRC5 cells. HTDE also displayed selective cytotoxicity against MCF7 breast cancer cells versus MCF10 normal breast epithelial cells in the 1-30 μM range. These results suggest that the cytotoxicity of HTDE is more potent and selective than that of parent compound hydroxytyrosol.

  17. Quantum mechanistic insights on aryl propargyl ether Claisen rearrangement.

    Science.gov (United States)

    Srinivasadesikan, Venkatesan; Dai, Jiun-Kuang; Lee, Shyi-Long

    2014-06-28

    The mechanism of aryl propargyl ether Claisen rearrangement in gas and solvent phase was investigated using DFT methods. Solvent phase calculations are carried out using N,N-diethylaniline as a solvent in the PCM model. The most favorable pathways involve a [3,3]-sigmatropic reaction followed by proton transfer in the first two steps and then deprotonation or [1,5]-sigmatropic reaction. Finally, cyclization yields benzopyran or benzofuran derivatives. The [3,3]-sigmatropic reaction is the rate-determining step for benzopyran and benzofuran with ΔG(‡) value of 38.4 and 37.9 kcal mol(-1) at M06/6-31+G**//B3LYP/6-31+G* level in gas and solvent phase, respectively. The computed results are in good agreement with the experimental results. Moreover, it is found that the derivatives of aryl propargyl ether proceeded Claisen rearrangement and the rate-determining step may be shifted from the [3,3]-sigmatropic reaction to the tautomerization step. The NBO analysis revealed that substitution of the methyl groups on the aliphatic segment has decreased the stabilization energy E(2) and favors the aryl propargyl ether Claisen rearrangement.

  18. Poly (ether ether ketone) membranes for fuel cells; Membranas de poli (eter eter cetona) sulfonado para celulas a combustivel

    Energy Technology Data Exchange (ETDEWEB)

    Marrero, Jacqueline C.; Gomes, Ailton de S.; Filho, Jose C.D., E-mail: jacquecosta@gmail.com [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil); Hui, Wang S. [Universidade de Sao Paulo (USP), Sao Paulo, SP (Brazil); Oliveira, Vivianna S. de [Escola Tecnica Rezende-Rammel, Rio de Janeiro, RJ (Brazil)

    2015-07-01

    Polymeric membranes were developed using a SPEEK polymer matrix (sulphonated poly (ether ether ketone)), containing hygroscopic particles of zirconia (Zr) (incorporated by sol-gel method), for use as electrolyte membranes in fuel cells. SPEEK with different sulfonation degrees were used: 63 and 86%. The thermal analysis (TGA and DSC) was carried out to characterize the membranes and electrochemical impedance spectroscopy (EIS) was carried out to evaluating the proton conductivity of the membranes. Additional analysis were underway in order to characterize these membranes, which include: X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to evaluate the influence of zirconia and sulfonation degree on the properties of the membranes. (author)

  19. Thermochemical properties and bond dissociation enthalpies of 3- to 5-member ring cyclic ether hydroperoxides, alcohols, and peroxy radicals: cyclic ether radical + (3)O(2) reaction thermochemistry.

    Science.gov (United States)

    Auzmendi-Murua, Itsaso; Bozzelli, Joseph W

    2014-05-01

    The formation of cyclic ethers is a major product in the oxidation of hydrocarbons, and the oxidation of biomass derived alcohols. Cyclic ethers are formed in the initial reactions of alkyl radicals with dioxygen in combustion and precombustion processes that occur at moderate temperatures. They represent a significant part of the oxygenated pollutants found in the exhaust gases of engines. Cyclic ethers can also be formed from atmospheric reactions of olefins. Additionally, cyclic ethers have been linked to the formation of the secondary organic aerosol (SOA) in the atmosphere. In combustion and thermal oxidation processes these cyclic ethers will form radicals that react with (3)O2 to form peroxy radicals. Density functional theory and higher level ab initio calculations are used to calculate thermochemical properties and bond dissociation enthalpies of 3 to 5 member ring cyclic ethers (oxirane, yC2O, oxetane, yC3O, and oxolane, yC4O), corresponding hydroperoxides, alcohols, hydroperoxy alkyl, and alkyl radicals which are formed in these oxidation reaction systems. Trends in carbon-hydrogen bond dissociation energies for the ring and hydroperoxide group relative to ring size and to distance from the ether group are determined. Bond dissociation energies are calculated for use in understanding effects of the ether oxygen in the cyclic ethers, their stability, and kinetic properties. Geometries, vibration frequencies, and enthalpies of formation, ΔH°f,298, are calculated at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), the composite CBS-QB3, and G3MP2B3 methods. Entropy and heat capacities, S°(T) and Cp°(T) (5 K ≤ T ≤ 5000), are determined using geometric parameters and frequencies from the B3LYP/6-31G(d,p) calculations. The strong effects of ring strain on the bond dissociation energies in these peroxy systems are also of fundamental interest. Oxetane and oxolane exhibit a significant stabilization, 10 kcal mol(-1), lower ΔfH°298 when an oxygen group is on

  20. Correspondence by Charles T. Jackson containing the earliest known illustrations of a Morton ether inhaler.

    Science.gov (United States)

    Haridas, Rajesh P; Bause, George S

    2013-11-01

    A letter, dated December 1, 1846, from Charles T. Jackson, MD, to Josiah D. Whitney contains a previously unreported description of a Morton ether inhaler and the only known contemporaneous hand-drawn illustrations of this type of ether inhaler. This letter and 2 other known letters on ether anesthesia were probably carried from Boston, MA, to Liverpool, United Kingdom, on the same paddle steamer (Acadia) that carried the well-known letter from Jacob Bigelow, MD, to Francis Boott, MD.

  1. Evaluation of alternariol and alternariol methyl ether for mutagenic activity in Salmonella typhimurium

    Energy Technology Data Exchange (ETDEWEB)

    Davis, V.M.; Stack, M.E. (Food and Drug Administration, Washington, DC (United States))

    1994-10-01

    Alternariol and alternariol methyl ether were tested in the Ames Salmonella typhimurium assay, and both were shown, with and without metabolic activation, to be nonmutagenic to strains TA98 and TA100. The finding of other investigators that alternariol methyl ether is weakly mutagenic to Ta98 without metabolic activation could have resulted from the presence of a small amount of one of the highly mutagenic altertoxins in the alternariol methyl ether originally tested. 9 refs., 3 figs., 1 tab.

  2. Polyaza crown ether as non-nucleosidic building blocks in DNA-conjugates

    DEFF Research Database (Denmark)

    Jakobsen, Ulla; Rohr, Katja; Madsen, Rasmus K

    2007-01-01

    The synthesis of amphiphilic polyaza crown ether monomers X (palmityl-substituted), Y (cholesteryl-substituted) and Z (dipalmityl-subtituted) and their incorporation into oligonucleotides are described. Their effects on thermal duplex stability were investigated by UV melting curve analysis....... Thermal denaturation experiments showed remarkable stabilization of dsDNA by polyaza crown ether monomers when incorporated in opposite positions. The series of polyaza crown ether monomers (X, Y, and Z) with different lipophilicity showed a trend of increased stability of the corresponding ds......DNA with increasing lipophilicity of the polyaza crown ether monomer....

  3. N–H•••O hydrogen bonding. An FT-IR, NIR study of N-methylformamide–ether systems

    Directory of Open Access Journals (Sweden)

    BRANISLAV JOVIĆ

    2010-02-01

    Full Text Available This paper reports the results of an FT-IR and NIR study of N-methylformamide in carbon tetrachloride solution in presence of ethers as the O--electron donors, i.e., diethyl ether (DEE, diisopropyl ether (DiPE, methyl t--butyl ether (MtBE, dibutyl ether (DBE, dipentyl ether (DPE, tetrahydro-furan (THF and tetrahydropyran (THP. The spectroscopic characteristics of the N–H•••O hydrogen bonded complexes are given. In addition, the equilibrium constants for 1:1 complex formation were determined at 25 °C using Mid-IR and NIR measurements.

  4. On the radiation stability of crown ethers in ionic liquids.

    Energy Technology Data Exchange (ETDEWEB)

    Shkrob, I.; Marin, T.; Dietz, M. (Chemical Sciences and Engineering Division); (Benedictine Univ.); (Univ. of Wisconsin at Milwaukee)

    2011-04-14

    Crown ethers (CEs) are macrocyclic ionophores used for the separation of strontium-90 from acidic nuclear waste streams. Room temperature ionic liquids (ILs) are presently being considered as replacements for traditional molecular solvents employed in such separations. It is desirable that the extraction efficacy obtained with such solvents should not deteriorate in the strong radiation fields generated by decaying radionuclides. This deterioration will depend on the extent of radiation damage to both the IL solvent and the CE solute. While radiation damage to ILs has been extensively studied, the issue of the radiation stability of crown ethers, particularly in an IL matrix, has not been adequately addressed. With this in mind, we have employed electron paramagnetic resonance (EPR) spectroscopy to study the formation of CE-related radicals in the radiolysis of selected CEs in ILs incorporating aromatic (imidazolium and pyridinium) cations. The crown ethers have been found to yield primarily hydrogen loss radicals, H atoms, and the formyl radical. In the low-dose regime, the relative yield of these radicals increases linearly with the mole fraction of the solute, suggesting negligible transfer of the excitation energy from the solvent to the solute; that is, the solvent has a 'radioprotective' effect. The damage to the CE in the loading region of practical interest is relatively low. Under such conditions, the main chemical pathway leading to decreased extraction performance is protonation of the macrocycle. At high radiation doses, sufficient to increase the acidity of the IL solvent significantly, such proton complexes compete with the solvent cations as electron traps. In this regime, the CEs will rapidly degrade as the result of H abstraction from the CE ring by the released H atoms. Thus, the radiation dose to which a CE/IL system is exposed must be maintained at a level sufficiently low to avoid this regime.

  5. Electrochemical Study of Diphenyl Ether Derivatives Used as Herbicides

    Directory of Open Access Journals (Sweden)

    Amira Zaouak

    2011-01-01

    Full Text Available The electrochemical behaviour of five nitro diphenyl ethers used as herbicides is investigated in acetonitrile. A detailed study by cyclic voltammetry and exhaustive electrolysis is carried out for the anodic oxidation of 2-Chloro-6-nitro-3-phenoxyaniline (aclonifen and shows that the major oxidation product is a dimeric compound. A mechanistic scheme involving a coupling process is postulated for the electrochemical oxidation of this compound. Furthermore, the use of differential pulse voltammetry on a glassy carbon electrode permits the selective determination of aclonifen. The limit of detection is 0.6 μg/mL.

  6. Density measurements of compressed-liquid dimethyl ether + pentane mixtures.

    Science.gov (United States)

    Outcalt, Stephanie L; Lemmon, Eric W

    2016-01-01

    Compressed-liquid densities of three compositions of the binary mixture dimethyl ether (CAS No. 115-10-6) + pentane (CAS No. 109-66-0) have been measured with a vibrating U-tube densimeter. Measurements were made at temperatures from 270 K to 390 K with pressures from 1.0 MPa to 50 MPa. The overall combined uncertainty (k=2) of the density data is 0.81 kg·m-3. Data presented here have been used to improve a previously formulated Helmholtz energy based mixture model. The newly derived parameters are given.

  7. Dimethyl ether production from methanol and/or syngas

    Science.gov (United States)

    Dagle, Robert A; Wang, Yong; Baker, Eddie G; Hu, Jianli

    2015-02-17

    Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production. The disclosed processes generally function at higher temperatures with lower contact times and at lower pressures than conventional processes so as to produce higher DME yields than do conventional processes. Certain embodiments of the processes are carried out in reactors providing greater surface to volume ratios than the presently used DME reactors. Certain embodiments of the processes are carried out in systems comprising multiple microchannel reactors.

  8. A new diphenyl ether from Phoma sp. strain, SHZK-2.

    Science.gov (United States)

    Fang, M J; Fang, H; Li, W J; Huang, D M; Wu, Z; Zhao, Y F

    2012-01-01

    A new diphenyl ether methyl 2-(2-formyl-3-hydroxy-5-methylphenoxy)-5-hydroxy-3-methoxybenzoate (3), together with four known compounds, asterric acid (1), methyl asterrate (2), 9(Z),12(Z)-nonadecadienoic acid (4) and orsellinic acid (5), were isolated from the Phoma sp. strain SHZK-2, which was isolated from a polluted environment in southern China. The structures of these compounds were determined by spectroscopic methods. Cytotoxicities of compounds against HEPG2 cell and Raji cell lines were preliminarily evaluated by the MTT method.

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

    Science.gov (United States)

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

    1990-01-01

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

  10. Synthesis of hydroxy thio-ether derivatives of vegetable oil.

    Science.gov (United States)

    Sharma, Brajendra K; Adhvaryu, A; Erhan, S Z

    2006-12-27

    Bio-based additives are desirable commodities due to their eco-friendly nature. These additives can demonstrate physical and chemical properties comparable to those of conventional mineral oil-based products. Sulfur incorporated triacylglycerol can function as an antiwear/antifriction additive for lubricants. The synthesis of four useful hydroxy thio-ether derivatives of vegetable oils, from commercially available epoxidized soybean oil and common organic thiols, is reported in this paper. The common thiols used herein were 1-butanethiol, 1-decanethiol, 1-octadecanethiol, and cyclohexyl mercaptan. Currently, there is no reported literature describing the synthesis of hydroxy thio-ether derivatives of vegetable oil. The reaction was monitored, and products were confirmed by NMR and FTIR spectroscopies. Experimental conditions involving various thiols, solvent, catalyst amount, time, and temperature were optimized for research quantity and laboratory scale-up. The synthetic process retains the vegetable oil structure, eliminates polyunsaturation in the molecule, and adds polar functional groups on triacylglycerol. These products can be used as agriculturally-based antiwear additives for lubricant applications.

  11. Direct dimethyl ether high temperature polymer electrolyte membrane fuel cells

    DEFF Research Database (Denmark)

    Vassiliev, Anton; Jensen, Jens Oluf; Li, Qingfeng

    A high temperature polybenzimidazole (PBI) polymer fuel cell was fed with dimethyl ether (DME) and water vapour mixture on the anode at ambient pressure with air as oxidant. A peak power density of 79 mW/cm2 was achieved at 200°C. A conventional polymer based direct DME fuel cell is liquid fed an......V higher than that of methanol, indicating less fuel crossover.......A high temperature polybenzimidazole (PBI) polymer fuel cell was fed with dimethyl ether (DME) and water vapour mixture on the anode at ambient pressure with air as oxidant. A peak power density of 79 mW/cm2 was achieved at 200°C. A conventional polymer based direct DME fuel cell is liquid fed...... and suffers from low DME solubility in water. When the DME - water mixture is fed as vapour miscibility is no longer a problem. The increased temperature is more beneficial for the kinetics of the direct oxidation of DME than of methanol. The Open Circuit Voltage (OCV) with DME operation was 50 to 100 m...

  12. Ether-Bond-Containing Ionic Liquids as Supercapacitor Electrolytes.

    Science.gov (United States)

    Rennie, Anthony J R; Sanchez-Ramirez, Nédher; Torresi, Roberto M; Hall, Peter J

    2013-09-05

    Electrochemical capacitors (ECs) are electrical energy storage devices that have the potential to be very useful in a wide range of applications, especially where there is a large disparity between peak and average power demands. The use of ionic liquids (ILs) as electrolytes in ECs can increase the energy density of devices; however, the viscosity and conductivity of ILs adversely influence the power density of the device. We present experimental results where several ILs containing different cations have been employed as the electrolyte in cells containing mesoporous carbon electrodes. Specifically, the behavior of ILs containing an ether bond in an alkyl side chain are compared with those of a similar structure and size but containing purely alkyl side chains. Using electrochemical impedance spectroscopy and constant current cycling, we show that the presence of the ether bond can dramatically increase the specific capacitance and reduce device resistance. These results have the important implication that such ILs can be used to tailor the physical properties and electrochemical performance of IL-based electrolytes.

  13. Molecular dynamics simulations of ether- and ester-linked phospholipids.

    Science.gov (United States)

    Kruczek, James; Saunders, Matthew; Khosla, Meghna; Tu, Yicheng; Pandit, Sagar A

    2017-12-01

    Dissimilarities in the bulk structure of bilayers composed of ether- vs ester-linked lipids are well-established; however, the atomistic interactions responsible for these differences are not well known. These differences are important in understanding of why archaea have a different bilayer composition than the other domains of life and why humans have larger concentrations of plasmalogens in specialized membranes? In this paper, we simulate two lipid bilayers, the ester linked dipalmitoylphosphatidylcholine (DPPC) and the ether lined dihexadecylphosphatidylcholine (DHPC), to study these variations. The structural analysis of the bilayers reveals that DPPC is more compressible than DHPC. A closer examination of dipole potential shows DHPC, despite having a smaller dipole potential of the bilayer, has a higher potential barrier than DPPC at the surface. Analysis of water order and dynamics suggests DHPC has a more ordered, less mobile layer of water in the headgroup. These results seem to resolve the issue as to whether the decrease in permeability of DHPC is due to of differences in minimum area per lipid (A0) or diffusion coefficient of water in the headgroup region (Dhead) (Guler et al., 2009) since we have shown significant changes in the order and mobility of water in that region. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. a Physical Random Signal in Ether-Drift Experiments

    Science.gov (United States)

    Consoli, M.; Pluchino, A.

    2015-01-01

    In ether-drift experiments, one usually assumes that the oscopic Earth's motion should be detectable in the laboratory from the time dependence of the data. Therefore a stochastic signal, which does not exhibit the smooth modulations expected from the Earth's rotation, tends to be considered as a spurious instrumental effect. The real situation, however, might be more subtle if the hypothetical ether (i.e. the physical vacuum) resembles a turbulent fluid where large-scale and small-scale motions are only indirectly related. In this case, the data might contain a genuine stochastic component. To test this scenario, a numerical simulation was performed to estimate the signal by assuming i) an `emergent-gravity' picture and ii) a simple model of statistically isotropic and homogeneous turbulence. In this framework, the present data become consistent with velocity fluctuations whose absolute scale is determined by the Earth's cosmic motion with respect to the CMB (projected in the plane of the interferometer at the latitude of the laboratory). Therefore the Earth's motion, although undetectable from the naive time dependence of the data, could nevertheless show up in their statistical distributions. In particular, the predicted non-gaussian nature of the instantaneous data could be tested with the forthcoming generation of precise cryogenic experiments, with potentially important implications for our understanding of both gravity and relativity.

  15. Synthesis of Novel Bibrachial Lariat Ethers (BiBLEs) Containing [1,2 ...

    African Journals Online (AJOL)

    NICO

    Introduction. The first synthetic crown ether was discovered by Pederson.1. Since then, various structural changes have been made to the basic crown ether skeleton in an attempt to enhance the selectivity of these rings and the capacity of complexation with metal ions. When hard and soft donor atoms were added into the ...

  16. The kinetics of 1,4-butanediol diglycidyl ether crosslinking of dermal sheep collagen

    NARCIS (Netherlands)

    Zeeman, R.; Dijkstra, Pieter J.; van Wachem, Pauline B.; van Luyn, Marja J.A.; Hendriks, Marc; Cahalan, Patrick T.; Feijen, Jan

    2000-01-01

    Dermal sheep collagen was crosslinked with 1,4-butanediol diglycidyl ether (BDDGE) or modified with glycidyl isopropyl ether (PGE). The reduction in amine groups as a function of time was followed to study the overall reaction kinetics of collagen with either BDDGE or PGE. Linearization of the

  17. The kinetics of 1,4-butanediol diglycidyl ether crosslinking of dermal sheep collagen

    NARCIS (Netherlands)

    Zeeman, R; Dijkstra, PJ; van Wachem, PB; van Luyn, MJA; Hendriks, M; Cahalan, PT; Feijen, J

    2000-01-01

    Dermal sheep collagen was crosslinked with 1,4-butanediol diglycidyl ether (BDDGE) or modified with glycidyl isopropyl ether (PGE). The reduction in amine groups as a function of time was followed to study the overall reaction kinetics of collagen with either BDDGE or PGE;. Linearization of the

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

    Science.gov (United States)

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

  19. Inhibition of dimethyl ether and methane oxidation in Methylococcus capsulatus and Methylosinus trichosporium.

    Science.gov (United States)

    Patel, R; Hou, C T; Felix, A

    1976-01-01

    Metal-chelating or -binding agents inhibited the oxidation of dimethyl ether and methane, but not methanol, by cell suspensions of Methylococcus capsulatus and Methylosinus trichosporium. Evidence suggests that the involvement of metal-containing enzymatic systems in the initial step of oxidation of dimethyl ether and methane. PMID:4428

  20. Mild Ti-mediated transformation of t-butyl thio-ethers into thio-acetates.

    Science.gov (United States)

    Pijper, Thomas C; Robertus, Jort; Browne, Wesley R; Feringa, Ben L

    2015-01-07

    We report a straightforward method for the rapid conversion of thio-ethers to thio-acetates using TiCl4, in good to excellent yields. The reaction conditions tolerate a variety of functional groups, including halide, nitro, ether, thiophene and acetylene functionalities. A catalytic variant of this reaction is also described.

  1. The antifungal activity of methanol and ether extracts of the leaves of ...

    African Journals Online (AJOL)

    user

    extracts from the leaves of Leonotis nepetafolia showed that they contain quinones, saponosides, flavonoids and tannins. The high amount of quinones was remarked in both methanol and ether extracts while saponins were more well extracted by methanol compared to ether. Tannins and flavonoids found in methanol ...

  2. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Science.gov (United States)

    2010-07-01

    ... ether, and ethylene oxide. 721.7000 Section 721.7000 Protection of Environment ENVIRONMENTAL PROTECTION... ethylene oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polymer of disodium maleate, allyl ether, and ethylene oxide (P-91...

  3. Development and validation of a congener-specific photodegradation model for polybrominated diphenyl ethers

    NARCIS (Netherlands)

    Zeng, X.; Simonich, S.L.M.; Robrock, K.R.; Korytar, P.; Alvarez-Cohen, L.; Barofsky, D.F.

    2008-01-01

    With the phaseout of the manufacture of some polybrominated diphenyl ether ( PBDE) formulations, namely penta-brominated diphenyl ether (BDE) and octa-BDE, and the continued use of the deca-BDE formulation, it is important to be able to predict the photodegradation of the more highly brominated

  4. 77 FR 39236 - Nanomaterial Case Study: A Comparison of Multiwalled Carbon Nanotubes and Decabromodiphenyl Ether...

    Science.gov (United States)

    2012-07-02

    ... AGENCY Nanomaterial Case Study: A Comparison of Multiwalled Carbon Nanotubes and Decabromodiphenyl Ether... ``Nanomaterial Case Study: A Comparison of Multiwalled Carbon Nanotubes and Decabromodiphenyl Ether Flame... nanomaterial case study and the workshop process that the draft document will be used in for identifying and...

  5. Interactions between ether phospholipids and cholesterol as determined by scattering and molecular dynamics simulations.

    Science.gov (United States)

    Pan, Jianjun; Cheng, Xiaolin; Heberle, Frederick A; Mostofian, Barmak; Kučerka, Norbert; Drazba, Paul; Katsaras, John

    2012-12-27

    Cholesterol and ether lipids are ubiquitous in mammalian cell membranes, and their interactions are crucial in ether lipid mediated cholesterol trafficking. We report on cholesterol's molecular interactions with ether lipids as determined using a combination of small-angle neutron and X-ray scattering, and all-atom molecular dynamics (MD) simulations. A scattering density profile model for an ether lipid bilayer was developed using MD simulations, which was then used to simultaneously fit the different experimental scattering data. From analysis of the data the various bilayer structural parameters were obtained. Surface area constrained MD simulations were also performed to reproduce the experimental data. This iterative analysis approach resulted in good agreement between the experimental and simulated form factors. The molecular interactions taking place between cholesterol and ether lipids were then determined from the validated MD simulations. We found that in ether membranes cholesterol primarily hydrogen bonds with the lipid headgroup phosphate oxygen, while in their ester membrane counterparts cholesterol hydrogen bonds with the backbone ester carbonyls. This different mode of interaction between ether lipids and cholesterol induces cholesterol to reside closer to the bilayer surface, dehydrating the headgroup's phosphate moiety. Moreover, the three-dimensional lipid chain spatial density distribution around cholesterol indicates anisotropic chain packing, causing cholesterol to tilt. These insights lend a better understanding of ether lipid-mediated cholesterol trafficking and the roles that the different lipid species have in determining the structural and dynamical properties of membrane associated biomolecules.

  6. Interactions between Ether Phospholipids and Cholesterol as Determined by Scattering and Molecular Dynamics Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Jianjun [ORNL; Cheng, Xiaolin [ORNL; Heberle, Frederick A [ORNL; Mostofian, Barmak [ORNL; Kucerka, Norbert [Canadian Neutron Beam Centre and Comelius University (Slovakia); Drazba, Paul [ORNL; Katsaras, John [ORNL

    2012-01-01

    Cholesterol and ether lipids are ubiquitous in mammalian cell membranes, and their interactions are crucial in ether lipid mediated cholesterol trafficking. We report on cholesterol s molecular interactions with ether lipids as determined using a combination of small-angle neutron and Xray scattering, and all-atom molecular dynamics (MD) simulations. A scattering density profile model for an ether lipid bilayer was developed using MD simulations, which was then used to simultaneously fit the different experimental scattering data. From analysis of the data the various bilayer structural parameters were obtained. Surface area constrained MD simulations were also performed to reproduce the experimental data. This iterative analysis approach resulted in good agreement between the experimental and simulated form factors. The molecular interactions taking place between cholesterol and ether lipids were then determined from the validated MD simulations. We found that in ether membranes cholesterol primarily hydrogen bonds with the lipid headgroup phosphate oxygen, while in their ester membrane counterparts cholesterol hydrogen bonds with the backbone ester carbonyls. This different mode of interaction between ether lipids and cholesterol induces cholesterol to reside closer to the bilayer surface, dehydrating the headgroup s phosphate moiety. Moreover, the three-dimensional lipid chain spatial density distribution around cholesterol indicates anisotropic chain packing, causing cholesterol to tilt. These insights lend a better understanding of ether lipid-mediated cholesterol trafficking and the roles that the different lipid species have in determining the structural and dynamical properties of membrane associated biomolecules.

  7. Crown ether activation of cross-linked subtilisin Carlsberg crystals in organic solvents

    NARCIS (Netherlands)

    van Unen, D.J.; Sakodinskaya, I.K.; Sakodinskaya, Inna K.; Engbersen, Johannes F.J.; Reinhoudt, David

    1998-01-01

    The activity of cross-linked subtilisin Carlsberg crystals in the catalysis of peptide bond formation can be significantly enhanced by pretreatment of the enzyme crystals with crown ethers. Soaking of the enzyme crystals in a solution of crown ether in acetonitrile followed by evaporation of the

  8. The antifungal activity of methanol and ether extracts of the leaves of ...

    African Journals Online (AJOL)

    The antifungal test of the crude methanol and the crude ether extracts was realized and revealed that crude methanol extract was more active than crude ether extract on Candida albicans and Malassezia fulfur growth. The minimum inhibitor concentration (MIC) of the crude methanol extract were 4.12 mg/ml and 2.38 mg/ml ...

  9. Sulfonated poly(ether ether ketone), an ion conducting polymer, as alternative polymeric membrane for the construction of anion-selective electrodes

    OpenAIRE

    González Bellavista, Anna; Macanás de Benito, Jorge; Muñoz Tapia, Maria; Fàbregas Martínez, Esteve

    2007-01-01

    A novel arrangement for polymeric membranes used in anion-selective electrodes is presented. Sulfonated poly(ether ether ketone) (SPEEK), an ion conducting polymer has been used as a polymeric matrix to build an anion-selective electrode (ISE). A NO3--ISE has been chosen as a model electrode to study the efficiency of the polymeric membrane. The effect of membrane composition and polymer compatibility with the electro-active components was investigated. The polymer matrix showed good mechanic...

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

    Science.gov (United States)

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

    2016-01-01

    Long-chain bases (LCBs) are the precursors to ceramide and sphingolipids in eukaryotic cells. They are formed by the action of serine palmitoyl-CoA transferase (SPT), a complex of integral membrane proteins located in the endoplasmic reticulum. SPT activity is negatively regulated by Orm proteins to prevent the toxic overaccumulation of LCBs. Here we show that overaccumulation of LCBs in yeast results in their conversion to a hitherto undescribed LCB derivative, an LCB vinyl ether. The LCB vinyl ether is predominantly formed from phytosphingosine (PHS) as revealed by conversion of odd chain length tracers C17-dihydrosphingosine and C17-PHS into the corresponding LCB vinyl ether derivative. PHS vinyl ether formation depends on ongoing acetyl-CoA synthesis, and its levels are elevated when the LCB degradative pathway is blocked by deletion of the major LCB kinase, LCB4, or the LCB phosphate lyase, DPL1. PHS vinyl ether formation thus appears to constitute a shunt for the LCB phosphate- and lyase-dependent degradation of LCBs. Consistent with a role of PHS vinyl ether formation in LCB detoxification, the lipid is efficiently exported from the cells. PMID:27561298

  11. Degradation of Perfluorinated Ether Lubricants on Pure Aluminum Surfaces: Semiempirical Quantum Chemical Modeling

    Science.gov (United States)

    Slaby, Scott M.; Ewing, David W.; Zehe, Michael J.

    1997-01-01

    The AM1 semiempirical quantum chemical method was used to model the interaction of perfluoroethers with aluminum surfaces. Perfluorodimethoxymethane and perfluorodimethyl ether were studied interacting with aluminum surfaces, which were modeled by a five-atom cluster and a nine-atom cluster. Interactions were studied for edge (high index) sites and top (low index) sites of the clusters. Both dissociative binding and nondissociative binding were found, with dissociative binding being stronger. The two different ethers bound and dissociated on the clusters in different ways: perfluorodimethoxymethane through its oxygen atoms, but perfluorodimethyl ether through its fluorine atoms. The acetal linkage of perfluorodimeth-oxymethane was the key structural feature of this molecule in its binding and dissociation on the aluminum surface models. The high-index sites of the clusters caused the dissociation of both ethers. These results are consistent with the experimental observation that perfluorinated ethers decompose in contact with sputtered aluminum surfaces.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1973-05-22

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

  13. Identification of oxygenated ions in premixed flames of dimethyl ether and oxygen

    DEFF Research Database (Denmark)

    Frøsig Østergaard, L.; Egsgaard, H.; Hammerum, S.

    2003-01-01

    The structure of characteristic flame-ions in premixed flames of dimethyl ether and oxygen was studied by ion-molecule reactions with ammonia and collision activation with argon. The results obtained show that the flame-ions m/z 45 and m/z 47 are the methoxymethyl cation, CH3OCH2+, and protonated...... dimethyl ether, (CH3)(2)OH+. The flame-ion m/z 61 is a mixture of the trimethyloxonium ion, (CH3)(3)O+ and lesser amounts of protonated methyl formate and/or protonated ethyl methyl ether. The viability of an ionic mechanism to soot formation for dimethyl ether-oxygen flames is discussed on the background...... of ions present in the dimethyl ether flames and the reactivity of the ions....

  14. Effect of surface finishing on friction and wear of Poly-Ether-Ether-Ketone (PEEK under oil lubrication

    Directory of Open Access Journals (Sweden)

    Thiago Fontoura de Andrade

    Full Text Available Abstract The tribological properties of poly-ether-ether-ketone (PEEK containing 30% of carbon fiber were studied in an oil-lubricated environment and different surface finishing of the metallic counterbody. Four different finishing processes, commonly used in the automotive industry, were chosen for this study: turning, grinding, honing and polishing. The test system used was tri-pin on disc with pins made of PEEK and counterbody made of steel; they were fully immersed in ATF Dexron VI oil. Some test parameters were held constant, such as the apparent pressure of 2 MPa, linear velocity of 2 m/s, oil temperature at 85 °C, and the time - 120 minutes. The lubrication regime for the apparent pressure of 1 MPa to 7 MPa range was also studied at different sliding speeds. A direct correlation was found between the wear rate, friction coefficient and the lubrication regime, wherein wear under hydrodynamic lubrication was, on average, approximately 5 times lower, and the friction coefficient 3 times lower than under boundary lubrication.

  15. 3'-O-(5-fluoro-2,4-dinitrophenyl)ADP ether and ATP ether. Affinity reagents for labeling ATPases.

    Science.gov (United States)

    Chuan, H; Wang, J H

    1988-09-15

    The affinity reagents 3'-O-(5-fluoro-2,4-dinitrophenyl)ADP ether (FDNP-ADP) and 3'-O-(5-fluoro-2,4-dinitrophenyl)ATP ether (FDNP-ATP) were synthesized and characterized. FDNP[14C]ADP was found to label the active site of mitochondrial F1-ATPase slowly at room temperature but with high specificity. F1 was effectively protected from the labeling reagent by ATP or ADP. An average number of 1.3 covalent label per F1 is sufficient for 100% inhibition of the ATPase. About 73% of the radioactive label was found covalently attached to beta subunits, 9% on alpha, practically none on gamma, delta, and epsilon. Cleavage of the labeled enzyme by pepsin and sequencing of the major radioactive peptide showed that the labeled amino acid residue in beta subunit was Lys beta 162. These results show that Lys beta 162 is indeed at the active site of F1 as assumed in the recently proposed models (Fry, D. C., Kuby, S. A., and Mildvan, A. S. (1986) Proc. Natl. Acad. Sci. U. S. A. 83, 907-911; Duncan, I. M., Parsonage, D., and Senior, A. E. (1986) FEBS Lett. 208, 1-6).

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

    Science.gov (United States)

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

    2017-05-01

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

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

    Directory of Open Access Journals (Sweden)

    Iole Venditti

    2017-03-01

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

  18. Novel proton exchange membranes based on structure-optimized poly(ether ether ketone ketone)s and nanocrystalline cellulose

    Science.gov (United States)

    Ni, Chuangjiang; Wei, Yingcong; Zhao, Qi; Liu, Baijun; Sun, Zhaoyan; Gu, Yan; Zhang, Mingyao; Hu, Wei

    2018-03-01

    Two sulfonated fluorenyl-containing poly(ether ether ketone ketone)s (SFPEEKKs) were synthesized as the matrix of composite proton exchange membranes by directly sulfonating copolymer precursors comprising non-sulfonatable fluorinated segments and sulfonatable fluorenyl-containing segments. Surface-modified nanocrystalline cellulose (NCC) was produced as the "performance-enhancing" filler by treating the microcrystalline cellulose with acid. Two families of SFPEEKK/NCC nanocomposite membranes with various NCC contents were prepared via a solution-casting procedure. Results revealed that the insertion of NCC at a suitable ratio could greatly enhance the proton conductivity of the pristine membranes. For example, the proton conductivity of SFPEEKK-60/NCC-4 (SFPEEKK with 60% fluorenyl segments in the repeating unit, and inserted with 4% NCC) composite membrane was as high as 0.245 S cm-1 at 90 °C, which was 61.2% higher than that of the corresponding pure SFPEEKK-60 membrane. This effect could be attributed to the formation of hydrogen bond networks and proton conduction paths through the interaction between -SO3H/-OH groups on the surface of NCC particles and -SO3H groups on the SFPEEKK backbones. Furthermore, the chemically modified NCC filler and the optimized chemical structure of the SFPEEKK matrix also provided good dimensional stability and mechanical properties of the obtained nanocomposites. In conclusion, these novel nanocomposites can be promising proton exchange membranes for fuel cells at moderate temperatures.

  19. SYNTHESIS OF C-METHYL-4,10,16,22-TETRAMETHOXYCALIX[4]ARENE FROM PHENOL USING BF3-METHANOL AS THE CATALYST

    Directory of Open Access Journals (Sweden)

    Jumina Jumina

    2010-06-01

    Full Text Available C-Methyl 4,10,16,22-tetramethoxycalix[4]arene has been synthesized from phenol. The reaction performed consisted of methylation of phenol, acetylation of methyl phenyl ether, reduction of p-methoxyacetophenone, and cyclization of p-methoxy-(1-hydroxyethylbenzene to form C-methyl-4,10,16,22-tetramethoxycalix[4]-arene using BF3-methanol as the acid catalyst.  Methylation of phenol was done by reacting phenol with solution of NaOH to generate sodium phenoxide salt. This mixture was strirred at  reflux for 0.5 hours. Dimethyl sulphate was added and the reflux was continued for 2,5 hours. The product obtained was methyl phenyl ether, which was found as  a colorless liquid in 99.0% yield. Acetylation of methyl phenyl ether was carried out in chloroform using acetic anhydride as the acetylating agent and anhydrous aluminium chloride as the catalyst. The addition of acetic anhydride and anhydrous aluminium chloride was done in two portions. The first portion was 0.967 g of acetic anhydride and 1.4 g of anhydrous aluminium chloride. The second portion was 0.54 g of acetic anhydride and 0.6 g of anhydrous aluminium chloride. The product obtained was found as a reddish yellow liquid in 69.6% yield. Reduction of p-methoxyacetophenone as the acetylation product  was  done using NaBH4 in ethanol at reflux for 2.5 hours. From this reaction, p-methoxy-(1-hydroxyethylbenzene was obtained as a brown viscous liquid in 44.9% yield. Cyclization of p-methoxy(1-hydroxyethylbenzene was done using BF3-methanol as the acid catalyst for two days at room temperature. The product obtained from this cyclization was found as a brown very viscous liquid in 87.3% yield. Identification of reaction products were carried out using Infra Red (IR Spectrophotometer, Proton Nuclear Magnetic Resonance (1H NMR spectrometer and Gas Chromatography-Mass spectroscopy (GC-MS.       Keywords: synthesis, calix[4]arene, cyclization, and catalyst.

  20. 40 CFR 721.7260 - Polymer of poly-ethylene-polyamine and alkanediol di-gly-cidyl ether.

    Science.gov (United States)

    2010-07-01

    ... alkanediol di-gly-cidyl ether. 721.7260 Section 721.7260 Protection of Environment ENVIRONMENTAL PROTECTION... di-gly-cidyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The... ether (PMN P-89-810) is subject to reporting under this section for the significant new uses described...

  1. 40 CFR 721.522 - Oxirane, methyl-, polymer with oxirane, mono(3,5,5,-trimethylhexyl) ether.

    Science.gov (United States)

    2010-07-01

    ..., mono(3,5,5,-trimethylhexyl) ether. 721.522 Section 721.522 Protection of Environment ENVIRONMENTAL...,5,5,-trimethylhexyl) ether. (a) Chemical substance and significant new uses subject to reporting. (1...,-trimethylhexyl) ether (PMN P-99-0669; CAS No. 204336-40-3) is subject to reporting under this section for the...

  2. Computational study of small molecule binding for both tethered and free conditions.

    Science.gov (United States)

    Ytreberg, F Marty

    2010-04-29

    Using a calix[4]arene-benzene complex as a test system, we compare the potential of mean force for when the calix[4]arene is tethered versus free. When the complex is in vacuum, our results show that the difference between tethered and free is primarily due to the entropic contribution to the potential of mean force resulting in a significant binding free energy difference of 6.6 kJ/mol. By contrast, when the complex is in water, our results suggest that there is no appreciable difference between tethered and free. This study elucidates the roles of entropy and enthalpy for this small molecule system and emphasizes the point that tethering the receptor has the potential to dramatically impact the binding properties. These findings should be taken into consideration when using calixarene molecules in nanosensor design.

  3. Polar self-assembled thin films for non-linear optical materials

    Science.gov (United States)

    Yang, XiaoGuang; Swanson, Basil I.; Li, DeQuan

    2000-01-01

    The design and synthesis of a family of calix[4]arene-based nonlinear optical (NLO) chromophores are discussed. The calixarene chromophores are macrocyclic compounds consisting of four simple D-.pi.-A units bridged by methylene groups. These molecules were synthesized such that four D-.pi.-A units of the calix[4]arene were aligned along the same direction with the calixarene in a cone conformation. These nonlinear optical super-chromophores were subsequently fabricated into covalently bound self-assembled monolayers on the surfaces of fused silica and silicon. Spectroscopic second harmonic generation (SHG) measurements were carried out to determine the absolute value of the dominant element of the second-order nonlinear susceptibility, d.sub.33, and the average molecular alignment, .PSI.. A value of d.sub.33 =60 pm/V at a fundamental wavelength of 890 nm, and .PSI..about.36.degree. was found with respect to the surface normal.

  4. Binding of calixarene-based Langmuir monolayers to mercury chloride is dependent on the amphiphile structure

    Energy Technology Data Exchange (ETDEWEB)

    Tulli, Ludovico G.; Wang, Wenjie; Rullaud, Vanessa; Lindemann, William R.; Kuzmenko, Ivan; Vaknin, David; Shahgaldian, Patrick

    2016-01-01

    Two amphiphilic calix[4]arenes bearing four dodecyl chains at the lower rim and two amino functions (vicinal and distal) at the para-phenolic positions have been synthesized. Surface-pressure versus molecular-area isotherms reveal that Langmuir monolayers of the two regioisomers show considerably distinct self-assembly behaviors at the air–water interface. Compression isotherms, Brewster angle microscopy and synchrotron-based X-ray near-total-reflection fluorescence, X-ray reflectivity and grazing incidence X-ray diffraction reveal that the monolayers of the two diamino calix[4]arene derivatives and those of their structural analogues bearing four amino moieties in para positions exhibit significant differences in their binding properties towards HgCl2 despite the structural and functional similarity among the macrocycles.

  5. A BODIPY-derived fluorescent probe for cellular pH measurements.

    Science.gov (United States)

    Han, Fangfei; Xu, Yanmei; Jiang, Dechen; Qin, Yu; Chen, Hongyuan

    2013-04-15

    In this study, BODIPY-appended calix[4]arene was chosen as a fluorescent probe for intracellular pH. The compound with cell permeability can monitor the minor pH change near neutrality inside the cell and is the first BODIPY-derived probe reported for cytosolic pH. Owing to a high level of cell retention and minor cytotoxicity of the probe, stable fluorescence is provided in the cells for 24h, facilitating the precise observation of intracellular pH. A model of cell apoptosis was designed by exposure of the cells to a low concentration of hydrogen peroxide. An increase in the fluorescence of the cells confirmed that BODIPY-appended calix[4]arene sensed the fluctuation of the cellular pH during early cell apoptosis. The developed fluorescent pH probe will be useful for the study of cell apoptosis. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. Poly (ether imide sulfone) membranes from solutions in ionic liquids

    KAUST Repository

    Kim, Dooli

    2017-11-20

    A membrane manufacture method based on non-volatile solvents and a high performance polymer, poly (ether imide sulfone) (EXTEM™), is proposed, as greener alternative to currently industrial process. We dissolved EXTEM™ in pure ionic liquids: 1-ethyl-3-methylimidalzolium thiocyanate ([EMIM]SCN), 1-butyl-3-methylimidalzolium thiocyanate ([BMIM]SCN), and 1-ethyl-3-methylimidalzolium acetate ([EMIM]OAc). The following polymer solution parameters were evaluated to optimize the manufacture: Gibbs free energy of mixing (G), intrinsic viscosity ([]) and hydrodynamic diameter. Membranes with sponge-like structure and narrow pore size distribution were obtained from solutions in [EMIM]SCN. They were tested for separation of proteins and deoxyribonucleic acids (DNA). Due to the polymer stability, we foresee that applications in more demanding chemical separations would be possible. [EMIM]SCN was 96 % purified and recovered after the membrane fabrication, contributing to the sustainability of the whole manufacturing process.

  7. Probing supramolecular complexation of cetylpyridinium chloride with crown ethers

    Science.gov (United States)

    Saha, Subhadeep; Roy, Mahendra Nath

    2017-11-01

    Supramolecular complexations of cetylpyridinium chloride with three comparable cavity dimension based crown ethers, namely, dibenzo-18-crown-6, 18-crown-6 and dicyclohexano-18-crown-6 have been explored and adequately compared in acetonitrile with the help of conductivity in a series of temperatures to reveal the stoichiometry of the three host-guest complexes. Programme based mathematical treatment of the conductivity data affords association constants for complexations from which the thermodynamic parameters were derived for better comprehension about the process. The interactions at molecular level have been explained and decisively discussed by means of FT-IR and 1H NMR spectroscopic studies that demonstrate H-bond type interactions as the primarily force of attraction for the investigated supramolecular complexations.

  8. Removal of methyl tert-butyl ether (MTBE) with Nafion.

    Science.gov (United States)

    Lien, Hsing-Lung; Zhang, Wei-Xian

    2007-06-01

    A solid organic polymer, Nafion, is tested for the removal of methyl tert-butyl ether (MTBE) in water. Nafion with perfluorosulfonic acid backbone and terminal sulfonic acid groups has a surface acidity similar to 100% sulfuric acid, and has been commonly used as a strong-acid catalyst in many organic reactions. Sorption and subsequent transformation of MTBE were observed in batch experiments. The transformation of MTBE by porous nanocomposite Nafion SAC-13 to tert-butyl alcohol (TBA), acetone, isobutene and probably methanol was found. Subsequent transformation of TBA to acetone was also observed. Results suggest that transformational pathways may include hydrolysis, dehydrogenation and oxidation. Dissolved oxygen is needed for the oxidation of isobutene to acetone. As Nafion is insoluble in water, chemically stable, and regenerable, its use in packed-bed reactors for MTBE removal looks promising.

  9. Homogeneous Charge Compression Ignition Combustion of Dimethyl Ether

    DEFF Research Database (Denmark)

    Pedersen, Troels Dyhr

    an increase in engine power. The use of methanol for combustion phasing control was tested successfully in a large diesel engine with common rail, in which the piston bowls were widened to give a compression ratio of 14.5. This compression ratio still allows DI CI operation with DME, but requires...... in the combustion chamber and hence the noise emitted from the engine. The study showed that minimum exposure of the cylinder liner is critical in reducing the transmitted noise. The effect of splitting the chamber into smaller volumes was tested, by shaping piston crowns with cavities. It was found that piston......This thesis is based on experimental and numerical studies on the use of dimethyl ether (DME) in the homogeneous charge compression ignition (HCCI) combustion process. The first paper in this thesis was published in 2007 and describes HCCI combustion of pure DME in a small diesel engine. The tests...

  10. Polybrominated diphenyl ethers in Mississippi River suspended sediment

    Energy Technology Data Exchange (ETDEWEB)

    Raff, J.; Hites, R. [Indiana Univ., Bloomington, IN (United States)

    2004-09-15

    The Mississippi River Basin drains water from 41% of the conterminous U.S. and is a valuable resource that supplies food, transportation, and irrigation to more than 95 million people of the region. Discharge and runoff from industry, agriculture, and population centers have increased the loads of anthropogenic organic compounds in the river. There has been growing concern over the rising levels of polybrominated diphenyl ethers (PBDEs) in air, sediment, biota, and humans, but there have been no studies to measure the concentrations of these chemicals in North America's largest river system. The goal of this study was to investigate the occurrence of PBDEs (15 congeners including BDE-209) and to identify possible sources within the Mississippi River Basin. We found PBDEs to be widespread throughout the region, rivaling PCBs in their extent and magnitude of contamination. We have also calculated the total amount of PBDEs released to the Gulf of Mexico in 2002.

  11. (R,R-Disynephrine ether bis(hydrogen sulfate

    Directory of Open Access Journals (Sweden)

    William Arbuckle

    2009-08-01

    Full Text Available The asymmetric unit of the title compound [systematic name: (R,R-2,4-bis(4-hydroxyphenyl-N,N′-dimethyl-3-oxapentane-1,5-diammonium bis(hydrogen sulfate], C18H26N2O32+·2HSO4−, contains one half-cation and one hydrogen sulfate anion. The cation has crystallographically imposed twofold symmetry with the rotation axis passing through the central ether O atom. Hydrogen bonds between the hydroxy group and amine H atoms of the cation to two hydrogen sulfate anions link the three ions in a ring motif. A three-dimensional network is accomplished by additional O—H...O hydrogen bonds between the anions and by N—H...O hydrogen bonds between the cations. Disorder with equally occupied sites affects the H-atom position in the anion.

  12. Poly(phenylene ether Based Amphiphilic Block Copolymers

    Directory of Open Access Journals (Sweden)

    Edward N. Peters

    2017-09-01

    Full Text Available Polyphenylene ether (PPE telechelic macromonomers are unique hydrophobic polyols which have been used to prepare amphiphilic block copolymers. Various polymer compositions have been synthesized with hydrophilic blocks. Their macromolecular nature affords a range of structures including random, alternating, and di- and triblock copolymers. New macromolecular architectures can offer tailored property profiles for optimum performance. Besides reducing moisture uptake and making the polymer surface more hydrophobic, the PPE hydrophobic segment has good compatibility with polystyrene (polystyrene-philic. In general, the PPE contributes to the toughness, strength, and thermal performance. Hydrophilic segments go beyond their affinity for water. Improvements in the interfacial adhesion between polymers and polar substrates via hydrogen bonding and good compatibility with polyesters (polyester-philic have been exhibited. The heterogeneity of domains in these PPE based block copolymer offers important contributions to diverse applications.

  13. Biosynthetic Origin of the Ether Ring in Platensimycin.

    Science.gov (United States)

    Rudolf, Jeffrey D; Dong, Liao-Bin; Manoogian, Karina; Shen, Ben

    2016-12-28

    Platensimycin (PTM) and platencin (PTN) are highly functionalized bacterial diterpenoid natural products that target bacterial and mammalian fatty acid synthases. PTM and PTN feature varying diterpene-derived ketolides that are linked to the same 3-amino-2,4-dihydroxybenzoic acid moiety. As a result, PTM is a selective inhibitor for FabF/FabB, while PTN is a dual inhibitor of FabF/FabB and FabH. We previously determined that the PTM cassette, consisting of five genes found in the ptm, but not ptn, gene cluster, partitions the biosynthesis of the PTM and PTN diterpene-derived ketolides. We now report investigation of the PTM cassette through the construction of diterpene production systems in E. coli and genetic manipulation in the PTM-PTN dual overproducer Streptomyces platensis SB12029, revealing two genes, ptmT3 and ptmO5, that are responsible for the biosynthetic divergence between the PTM and PTN diterpene-derived ketolides. PtmT3, a type I diterpene synthase, was determined to be a (16R)-ent-kauran-16-ol synthase, the first of its kind found in bacteria. PtmO5, a cytochrome P450 monooxygenase, is proposed to catalyze the formation of the characteristic 11S,16S-ether ring found in PTM. Inactivation of ptmO5 in SB12029 afforded the ΔptmO5 mutant SB12036 that accumulated nine PTM and PTN congeners, seven of which were new, including seven 11-deoxy-16R-hydroxy-PTM congeners. The two fully processed PTM analogues showed antibacterial activities, albeit lower than that of PTM, indicating that the ether ring, or minimally the stereochemistry of the hydroxyl group at C-16, is crucial for the activity of PTM.

  14. The ether lipid precursor hexadecylglycerol protects against Shiga toxins.

    Science.gov (United States)

    Bergan, Jonas; Skotland, Tore; Lingelem, Anne Berit Dyve; Simm, Roger; Spilsberg, Bjørn; Lindbäck, Toril; Sylvänne, Tuulia; Simolin, Helena; Ekroos, Kim; Sandvig, Kirsten

    2014-11-01

    Shiga toxin-producing Escherichia coli bacteria cause hemorrhagic colitis and hemolytic uremic syndrome in humans. Currently, only supportive treatment is available for diagnosed patients. We show here that 24-h pretreatment with an ether lipid precursor, the alkylglycerol sn-1-O-hexadecylglycerol (HG), protects HEp-2 cells against Shiga toxin and Shiga toxin 2. Also the endothelial cell lines HMEC-1 and HBMEC are protected against Shiga toxins after HG pretreatment. In contrast, the corresponding acylglycerol, DL-α-palmitin, has no effect on Shiga toxicity. Although HG treatment provides a strong protection (~30 times higher IC₅₀) against Shiga toxin, only a moderate reduction in toxin binding was observed, suggesting that retrograde transport of the toxin from the plasma membrane to the cytosol is perturbed. Furthermore, endocytosis of Shiga toxin and retrograde sorting from endosomes to the Golgi apparatus remain intact, but transport from the Golgi to the endoplasmic reticulum is inhibited by HG treatment. As previously described, HG reduces the total level of all quantified glycosphingolipids to 50-70% of control, including the Shiga toxin receptor globotriaosylceramide (Gb3), in HEp-2 cells. In accordance with this, we find that interfering with Gb3 biosynthesis by siRNA-mediated knockdown of Gb3 synthase for 24 h causes a similar cytotoxic protection and only a moderate reduction in toxin binding (to 70% of control cells). Alkylglycerols, including HG, have been administered to humans for investigation of therapeutic roles in disorders where ether lipid biosynthesis is deficient, as well as in cancer therapy. Further studies may reveal if HG can also have a therapeutic potential in Shiga toxin-producing E. coli infections.

  15. Impaired neurotransmission in ether lipid-deficient nerve terminals.

    Science.gov (United States)

    Brodde, Alexander; Teigler, Andre; Brugger, Britta; Lehmann, Wolf D; Wieland, Felix; Berger, Johannes; Just, Wilhelm W

    2012-06-15

    Isolated defects of ether lipid (EL) biosynthesis in humans cause rhizomelic chondrodysplasia punctata type 2 and type 3, serious peroxisomal disorders. Using a previously described mouse model [Rodemer, C., Thai, T.P., Brugger, B., Kaercher, T., Werner, H., Nave, K.A., Wieland, F., Gorgas, K., and Just, W.W. (2003) Inactivation of ether lipid biosynthesis causes male infertility, defects in eye development and optic nerve hypoplasia in mice. Hum. Mol. Genet., 12, 1881-1895], we investigated the effect of EL deficiency in isolated murine nerve terminals (synaptosomes) on the pre-synaptic release of the neurotransmitters (NTs) glutamate and acetylcholine. Both Ca(2+)-dependent exocytosis and Ca(2+)-independent efflux of the transmitters were affected. EL-deficient synaptosomes respire at a reduced rate and exhibit a lowered adenosin-5'-triphosphate/adenosine diphosphate (ATP/ADP) ratio. Consequently, ATP-driven processes, such as synaptic vesicle cycling and maintenance of Na(+), K(+) and Ca(2+) homeostasis, might be disturbed. Analyzing reactive oxygen species in EL-deficient neural and non-neural tissues revealed that plasmalogens (PLs), the most abundant EL species in mammalian central nervous system, considerably contribute to the generation of the lipid peroxidation product malondialdehyde. Although EL-deficient tissue contains less lipid peroxidation products, fibroblasts lacking ELs are more susceptible to induced oxidative stress. In summary, these results suggest that due to the reduced energy state of EL-deficient tissue, the Ca(2+)-independent efflux of NTs increases while the Ca(2+)-dependent release declines. Furthermore, lack of PLs is mainly compensated for by an increase in the concentration of phosphatidylethanolamine and results in a significantly lowered level of lipid peroxidation products in the brain cortex and cerebellum.

  16. Evaluating the swelling, erosion, and compaction properties of cellulose ethers.

    Science.gov (United States)

    Ghori, Muhammad U; Grover, Liam M; Asare-Addo, Kofi; Smith, Alan M; Conway, Barbara R

    2018-02-01

    Swelling, erosion, deformation, and consolidation properties can affect the performance of cellulose ethers, the most commonly used matrix former in hydrophilic sustained tablet formulations. The present study was designed to comparatively evaluate the swelling, erosion, compression, compaction, and relaxation properties of the cellulose ethers in a comprehensive study using standardised conditions. The interrelationship between various compressional models and the inherent deformation and consolidation properties of the polymers on the derived swelling and erosion parameters are consolidated. The impact of swelling (K w ) on erosion rates (K E ) and the inter-relationship between Heckel and Kawakita plasticity constants was also investigated. It is evident from the findings that the increases in both substitution and polymer chain length led to higher K w , but a lower K E ; this was also true for all particle size fractions regardless of polymer grade. Smaller particle size and high substitution levels tend to increase the relative density of the matrix but reduce porosity, yield pressure (P y ), Kawakita plasticity parameter (b -1 ) and elastic relaxation. Both K W versus K E (R 2  = 0.949-0.980) and P y versus. b -1 correlations (R 2  = 0.820-0.934) were reasonably linear with regards to increasing hydroxypropyl substitution and molecular size. Hence, it can be concluded that the combined knowledge of swelling and erosion kinetics in tandem with the in- and out-of-die compression findings can be used to select a specific polymer grade and further to develop and optimize formulations for oral controlled drug delivery applications.

  17. Calixcyclitols: a new class of polar hybrid hosts obtained by oxygenation of calixarene phenol rings.

    Science.gov (United States)

    Troisi, Francesco; Mogavero, Luca; Gaeta, Carmine; Gavuzzo, Enrico; Neri, Placido

    2007-03-01

    [structure: see text] The first examples of hybrid calixarene hosts containing cyclitol moieties (calixcyclitols) have been obtained by treatment with LiAlH4 of diepoxydiol and tetraepoxytetrol calix[4]arene derivatives. A 6-oxabicyclo[3:1:1]heptanetriol or a cyclohexanetetrol ring was obtained depending on the stereochemical features of the diepoxydiol moiety. Preliminary binding studies toward anionic guests showed a discrete selectivity of calixcyclitol 9 vs H2PO4-.

  18. Polycaps: Reversibly formed polymeric capsules

    Science.gov (United States)

    Castellano, Ronald K.; Rudkevich, Dmitry M.; Rebek, Julius

    1997-01-01

    Described are assemblies consisting of polymeric capsules, “polycaps,” formed from two calix[4]arene tetraureas covalently connected at their lower rims. In these structures self-assembly leads to reversibly formed capsule sites along a chain, reminiscent of beads on a string. Their dynamic behavior is characterized by 1H NMR spectroscopy through encapsulation of guest species, reversible polymerization, and the formation of sharply defined hybrid capsules. PMID:11038556

  19. Synthesis, Structure and Fluorescence Properties of 5,17-Distyryl-25,26,27,28-tetraproproxycalix[4]arenes in the Cone Conformation

    DEFF Research Database (Denmark)

    Larsen, Mogens; Krebs, Frederik C; Jørgensen, Mikkel

    1998-01-01

    The HWE (Horner-Wadsworth-Emmons) reaction performed on the easily obtainable 5,17-diformyl- calix[4]arenes (cone) with arylmethyl phosphorus ylides yielded 5,17-distyryl-25,26,27, 28-tetrapropoxycalix[4]arenes (cone) in high yield and purely in the E/E configuration. Compounds 2-5 were prepared ...... and fluorescence spectroscopy and compared to the monomeric fluorophore, 3,5-dimethyl-4-propoxy-(E)-stilbene (10)....

  20. Supramolecular stabilization of N(2)H(7)(+).

    Science.gov (United States)

    Atwood, Jerry L; Barbour, Leonard J; Jerga, Agoston

    2002-03-13

    The cation N(2)H(7)(+) has been stabilized in a largely hydrophobic supramolecular environment and characterized in the solid state. The cation is situated in the bowl-shaped cavity of calix[4]arene. All of the hydrogen atoms are clearly discernible owing to high-quality X-ray data as well as lack of disorder and symmetry-imposed ambiguity. It appears that electrostatic interactions play a critical role in stabilizing the structure.

  1. EXPOSURE TO ETHYLENE GLYCOL MONOBUTYL ETHER AND RELATED WORKERS HABITS IN AN INK FACTORY

    Directory of Open Access Journals (Sweden)

    W. C. Lin, H. Y. Chang, F. H. Chang

    2008-01-01

    Full Text Available Forty six workers from an ink factory were included in this study, in which, passive badge sampler and questionnaire interview were used to assess the concentrations of airborne exposure to ethylene glycol monobutyl ether during work shifts and to understand the subjects' working habits. The geometric mean value (95% confidence interval of the airborne ethylene glycol monobutyl ether concentrations was 0.12(0.08-0.19ppm, with a range of <0.02-1.82ppm. The exposure group was exposed to statistically significantly higher ethylene glycol monobutyl ether concentrations than the control group (geometric mean value: 0.14vs. 0.03ppm; P=0.017. Some chromatograms showed that subjects were co-exposed to m-xylene, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether acetate. According to the completed questionnaires, subjects might also be exposed to 1,2,4,5-tetramethylbenzene, propylene glycol ethers, ethanol, 1,2,4-trimethylbenzene, methanol and diisononyl phthalate. This study also suggests that, the Taiwan occupational time-weighted average level of ethylene glycol monobutyl ether be reconsidered with a view to being lowered.

  2. Alternariol 9-methyl ether from the endophytic fungus Alternaria sp. Samif01 and its bioactivities.

    Science.gov (United States)

    Lou, Jingfeng; Yu, Ruiting; Wang, Xiaohan; Mao, Ziling; Fu, Linyun; Liu, Yang; Zhou, Ligang

    2016-01-01

    One bioactive compound, identified as alternariol 9-methyl ether, was isolated from the crude extract of the endophytic fungus Alternaria sp. Samif01 residing in the roots of Salvia miltiorrhiza Bunge. Alternariol 9-methyl ether was active against bacteria with minimum inhibitory concentration values ranging from 25 to 75μg/mL and median inhibitory concentration (IC50) values ranging from 16.00 to 38.27μg/mL. The IC50 value of alternariol 9-methyl ether against spore germination of Magnaporthe oryzae was 87.18μg/mL. Alternariol 9-methyl ether also showed antinematodal activity against Bursaphelenchus xylophilus and Caenorhabditis elegans with IC50 values of 98.17μg/mL and 74.62μg/mL, respectively. This work is the first report on alternariol 9-methyl ether and its biological activities from the endophytic fungus Alternaria sp. Samif01 derived from S. miltiorrhiza Bunge. The results indicate the potential of Alternaria sp. Samif01 as a source of alternariol 9-methyl ether and also support that alternariol 9-methyl ether is a natural compound with high potential bioactivity against microorganisms. Copyright © 2015 Sociedade Brasileira de Microbiologia. Published by Elsevier Editora Ltda. All rights reserved.

  3. The Preparation and Intramolecular Radical Cyclisation Reactions of Chiral Oxime Ethers

    Directory of Open Access Journals (Sweden)

    Booth Susan E.

    1998-01-01

    Full Text Available Chiral oxime ether 2 and Oxime ester 4 have been prepared by alkylation and esterification of the oxime 1. Racemic hydroxylamine 6 and chiral hydroxylamine 10 have been synthesised from N-hydroxysuccinimide and the corresponding alcohol in the presence of diethylazodicarboxylate, the two products were converted into the oxime ethers 7 and 11 respectively. The intramolecular radical cyclisation reactions of these oxime ethers and esters has been studied, successful reaction was observed to produce alkyl hydroxylamines 3, 8 and 12.

  4. FT-IR and NIR spectroscopic investigation of hydrogen bonding in indole-ether systems

    Science.gov (United States)

    Kordić, B.; Kovačević, M.; Sloboda, T.; Vidović, A.; Jović, B.

    2017-09-01

    This paper reports FTIR and NIR spectroscopic study of hydrogen bonding between indole and different ethers in carbon tetrachloride. With increase in ether concentration increase in intensity of red-shifted band, and decrease of intensity of monomer band has been observed. The FTIR and NIR spectroscopic characteristics for N-H⋯O hydrogen bonded complexes and also the equilibrium constants for 1:1 complex formation are given. Influence of structural differences of ethers on hydrogen bonding was investigated using Taft equation. Good correlation has been obtained.

  5. Amination of ethers using chloramine-T hydrate and a copper(I) catalyst.

    Science.gov (United States)

    Albone, David P; Challenger, Stephen; Derrick, Andrew M; Fillery, Shaun M; Irwin, Jacob L; Parsons, Christopher M; Takada, Hiroya; Taylor, Paul C; Wilson, D James

    2005-01-07

    Amination of C-H bonds activated by ether oxygen atoms is facile with chloramine-T as nitrene source and copper(I) chloride in acetonitrile as catalyst. For cyclic ethers the hemiaminal products are generally stable and can be isolated pure. For acyclic ethers, the hemiaminal products, as expected, fragment with elimination of alcohol to yield imines. When activation of benzylic positions is remote through a conjugated system, stable benzylamine derivatives are isolated. Mechanistic studies are consistent with concerted insertion of an electrophilic nitrenoid into the C-H bond in the rate-determining step, though in an asynchronous manner with a more activated substrate.

  6. State of the water in crosslinked sulfonated poly(ether ether ketone). Two-dimensional differential scanning calorimetry correlation mapping

    Energy Technology Data Exchange (ETDEWEB)

    Al Lafi, Abdul G. [Department of Chemistry, Atomic Energy Commission, Damascus, P.O. Box 6091 (Syrian Arab Republic); Hay, James N., E-mail: cscientific9@aec.org.sy [The School of Metallurgy and Materials, College of Physical Sciences and Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

    2015-07-20

    Highlights: • 2D-DSC mapping was applied to analyze the heat flow responses of hydrated crosslinked sPEEK. • Two types of loosely bond water were observed. • The first was bond to the sulfonic acid groups and increased with ion exchange capacity. • The second was attributed to the polar groups introduced by ions irradiation and increased with crosslinking degree. • DSC combined with 2D mapping provides a powerful tool for polymer structural determination. - Abstract: This paper reports the first application of two-dimensional differential scanning calorimetry correlation mapping, 2D-DSC-CM to analyze the heat flow responses of sulphonated poly(ether ether ketone), sPEEK, films having different ion exchange capacity and degrees of crosslinks. With the help of high resolution and high sensitivity of 2D-DSC-CM, it was possible to locate two types of loosely bound water within the structure of crosslinked sPEEK. The first was bound to the sulfonic acid groups and dependent on the ion exchange capacity of the sPEEK. The second was bound to other polar groups, either introduced by irradiation with ions and dependent on the crosslinking degree or present in the polymer such as the carbonyl groups or terminal units. The results suggest that the ability of the sulfonic acid groups in the crosslinked sPEEK membranes to adsorb water molecules is increased by crosslinking, probably due to the better close packing efficiency of the crosslinked samples. DSC combined with 2D correlation mapping provides a fast and powerful tool for polymer structural determination.

  7. Dihydrogenimidazole modified silica-sulfonated poly(ether ether ketone) hybrid materials as electrolyte membranes for direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Roelofs, Kimball S.; Hirth, Thomas [Fraunhofer Institute for Interfacial Engineering and Biotechnology, Nobelstr. 12, 70569 Stuttgart (Germany); Schiestel, Thomas, E-mail: Thomas.Schiestel@igb.fraunhofer.de [Fraunhofer Institute for Interfacial Engineering and Biotechnology, Nobelstr. 12, 70569 Stuttgart (Germany)

    2011-05-25

    The present study reports on dihydrogenimidazole modified inorganic-organic mixed matrix membranes for possible application as a proton exchange membrane in direct ethanol fuel cells. The polymeric phase consisted mainly of sulfonated poly(ether ether ketone) (sPEEK) with a sulfonation degree of 55%. The inorganic phase was built up from hydrophilic fumed silica particles interconnected with partially hydrolyzed and condensed tetraethoxysilane with a total inorganic loading of 27.3%. This inorganic phase was further modified with N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole (DHIM), which consists of an hydrolyzable inorganic part and a functional organic group. The influence of the modifier on the mixed matrix system was studied by means of various modifier concentrations in various aqueous-ethanolic systems (water, 2 M and 4 M ethanol). Modifier concentration and ethanol concentration of the ethanol-water mixture exhibited significant but opposite effects on the liquid uptake of the mixed matrix membranes. The proton conductivity as well as the proton diffusion coefficient as a function of modifier content showed a linear decrease. The proton conductivity as a function of temperature showed Arrhenius behavior and the activation energy of the mixed matrix membranes was 43.9 {+-} 2.6 kJ mol{sup -1}. High selectivity of proton diffusion coefficient to ethanol permeability coefficient was obtained with high modifier concentrations. At low modifier concentrations, this selectivity was dominated by ethanol permeation and at high modifier concentrations by proton diffusion. The main electrolyte properties can be optimized by setting the DHIM content in mixed matrix membrane. With this approach, tailor-made membranes can be prepared for possible application in direct ethanol fuel cells.

  8. Ether-bond-containing ionic liquids and the relevance of the ether bond position to transport properties.

    Science.gov (United States)

    Monteiro, Marcelo J; Camilo, Fernanda F; Ribeiro, Mauro C C; Torresi, Roberto M

    2010-10-07

    The ionic liquids (ILs) 1-ethoxyethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [EtO(CH(2))(2)MMI][Tf(2)N], and N-(ethoxyethyl)-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [EtO(CH(2))(2)MMor][Tf(2)N] were synthesized, and relevant properties, such as thermal stability, density, viscosity, electrochemical behavior, ionic conductivity, and self-diffusion coefficients for both ionic species, were measured and compared with those of their alkyl counterparts, 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [BMMI][Tf(2)N], and N-n-butyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide, [BMP][Tf(2)N] and N-n-butyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide [BMMor][Tf(2)N]. This comparison was done to evaluate the effects caused by the presence of the ether bond in either the side chain or in the organic cation ring. The salt, LiTf(2)N, was added to the systems to estimate IL behavior with regard to lithium cation transport. Pure [EtO(CH(2))(2)MMI][Tf(2)N] and their LiTf(2)N solutions showed low viscosity and the highest conductivity among the ILs studied. The H(R) (AC conductivity/NMR calculated conductivity ratio) values showed that, after addition of LiTf(2)N, ILs containing the ether bond seemed to have a greater number of charged species. Structural reasons could explain these high observed H(R) values for [EtO(CH(2))(2)MMor][Tf(2)N].

  9. Evaluation of calix-crown ionophores for selective separation of radio-cesium from acidic nuclear waste solution

    Energy Technology Data Exchange (ETDEWEB)

    Mohapatra, P.K. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Ansari, S.A. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Sarkar, A. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Bhattacharyya, A. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Manchanda, V.K. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)]. E-mail: vkm@magnum.barc.ernet.in

    2006-07-07

    Extraction of Cs-137 from nitric acid was carried out using nitrobenzene solutions of calix-crowns such as calix[4]arene-bis(crown-6) (CC-A), calix[4]arene-bis(benzo crown-6) (CC-B) and calix[4]arene-bis(napthocrown-6) (CC-C). CC-C was found to be superior extractant for Cs(I) as compared to the other two calix-crown ligands used in the present study. The effect of diluent on the extraction of Cs(I) indicated the trend: nitrobenzene > dichloroethane > chloroform > decanol >> carbon tetrachloride {approx} n-hexane {approx} toluene. Subsequently, the studies were carried out with nitrobenzene solutions of the calix-crown ligands (mainly CC-C) on the effects of (a) aqueous phase acidity (b) ligand concentration, and (c) cesium concentration on Cs extraction from nitric acid media. Conditions for quantitative extraction and stripping were optimized and the extracted species conformed to {l_brace}[CsL]{sup +}.[NO{sub 3}]{sup -}.nH{sub 2}O{r_brace}. Selectivity studies were carried out using an irradiated natural U target involving tracer amount of fission products activities. Extraction of Cs(I) from a synthetic high level waste solution was also carried out. The promising results obtained in the present studies indicate possible use of the calix-crown ligand for Cs(I) recovery from the acidic high level waste.

  10. Flourimetric and prototropic studies on the inclusion complexation of 2-amino and 4-aminodiphenyl ethers with {beta}-cyclodextrin: Unusual behavior of 4-aminodiphenyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Enoch, Israel V. Muthu Vijayan [Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamil Nadu (India); Swaminathan, Meenakshisundaram [Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamil Nadu (India)], E-mail: chemsam@yahoo.com

    2007-12-15

    The fluorescence characteristics of diphenyl ether (DPE), 2-aminodiphenyl ether (2ADPE) and 4-aminodiphenyl ether (4ADPE) and prototropic behavior of 2ADPE and 4ADPE on inclusion complexation with {beta}-cyclodextrin have been investigated. DPE forms 1:1 complex whereas 2ADPE and 4ADPE form 1:2 complex with {beta}-CDx. The fluorimetric and prototropic behaviors of 4ADPE in {beta}-CDx are different from those in aqueous solution. The dual fluorescence of 4ADPE in {beta}-CDx is found to be due to twisted intramolecular charge transfer (TICT) character induced by inclusion complexation. The two equilibria viz. monocation{r_reversible}monocation solvent exciplex{r_reversible}neutral reported for 4ADPE in aqueous solution are not observed in presence of {beta}-CDx. The ground and excited state pK{sub a} values for monocation-neutral equilibrium of 2ADPE and 4ADPE have been reported.

  11. ETHER: HISTORICAL IMPORTANCE IN SCIENCE AND APPROACH THE TEXTBOOK OF SECONDARY EDUCATION

    National Research Council Canada - National Science Library

    J. C. B. Soares; E. P. Soares; J. A. Pereira

    2016-01-01

    This article aimed to conduct a brief rereading as the importance of the ether, from its earliest conception to the present within a historical context to the current scientific knowledge development...

  12. Fluorinated 5- and 7-membered carbacycle motifs by reaction of difluorocarbene with acetylene ethers.

    Science.gov (United States)

    Chia, Poh Wai; Bello, Davide; Slawin, Alexandra M Z; O'Hagan, David

    2013-03-18

    The reaction of acetylene ethers with difluorocarbene (CF(2)), generated from the Ruppert-Prakash reagent, unexpectedly gave rise to co-produced fluorinated bicyclic [2.1.1]-hex-2-ene and cyclohepta-1,4-diene ring products.

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

    Science.gov (United States)

    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. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

  14. Oxime Ethers of (E)-11-Isonitrosostrychnine as Highly Potent Glycine Receptor Antagonists

    DEFF Research Database (Denmark)

    Mohsen, Amal M Y; Mandour, Yasmine M; Sarukhanyan, Edita

    2016-01-01

    A series of (E)-11-isonitrosostrychnine oxime ethers, 2-aminostrychnine, (strychnine-2-yl)propionamide, 18-oxostrychnine, and N-propylstrychnine bromide were synthesized and evaluated pharmacologically at human α1 and α1β glycine receptors in a functional fluorescence-based and a whole-cell patch......-clamp assay and in [(3)H]strychnine binding studies. 2-Aminostrychnine and the methyl, allyl, and propargyl oxime ethers were the most potent α1 and α1β antagonists in the series, displaying IC50 values similar to those of strychnine at the two receptors. Docking experiments to the strychnine binding site...... of the crystal structure of the α3 glycine receptor indicated the same orientation of the strychnine core for all analogues. For the most potent oxime ethers, the ether substituent was accommodated in a lipophilic receptor binding pocket. The findings identify the oxime hydroxy group as a suitable attachment...

  15. Elton Romeo Smilie, the not-quite discoverer of ether anesthesia.

    Science.gov (United States)

    Stone, Martha E; Meyer, Marlene R; Alston, Theodore A

    2010-01-01

    Like William T.G. Morton, Elton Romeo Smilie (1819-1889) was raised in Massachusetts, attended medical school in New England, practiced dentistry there, strove for clinical invention, and moved to Boston. In October 1846, both announced that inhaled ethereal preparations achieved reversible insensibility in surgical patients. Smilie published a report in the Boston Med Surg J 3 wk before Bigelow used that forum to broadcast Morton's Ether Day. Smilie's preparation was an ethereal tincture of opium, and, as he mistakenly believed the opium to be volatile and important, he ceded priority to Morton for ether anesthesia. The two authors collaborated on chloroform, but Smilie soon headed off in the Gold Rush to California. It is tempting to speculate that Charles T. Jackson and Morton were indebted in part to Smilie.

  16. IRIS Toxicological Review of Ethylene Glycol Mono-Butyl Ether (Egbe) (External Review Draft)

    Science.gov (United States)

    EPA has conducted a peer review of the scientific basis supporting the human health hazard and dose-response assessment of ethylene glycol monobutyl ether that will appear on the Integrated Risk Information System (IRIS) database.

  17. Santonic acid: Zn-HCl-ether reduction and ceric ammonium nitrate oxidation.

    Science.gov (United States)

    Fondekar, Kamlesh Pai; Malik, Bhiwa; Paknikar, Shashikumar Keshav

    2014-01-01

    Reduction of santonic acid using Zn-HCl-ether yielded succinic anhydride derivatives via pinacolisation followed by rearrangement, whereas oxidation of santonic acid using ceric ammonium nitrate afforded five oxidative decarboxylation products. Dedicated to Prof. TBH McMurry.

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

    DEFF Research Database (Denmark)

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

    2006-01-01

    Several chemical and clinical observations have suggested the presence of at least one more allergen in addition to primin in Primula obconica. The aim of this study was to investigate the allergenicity of the primin precursor miconidin and the related miconidin methyl ether, both isolated from P....... obconica. 12 primin-positive persons were patch tested with miconidin 0.01% petrolatum (pet.), miconidin in 96% ethanol incorporated into 0.01% pet., and miconidin methyl ether 1.0% pet. All persons were positive to miconidin 0.01% pet., with the strength of reactions very similar to those...... of the individual primin reactions, and remained inexplicably negative while testing with miconidin in 96% ethanol and pet., while miconidin methyl ether elicited 7 positive reactions. Although both miconidin and miconidin methyl ether may be allergenic only due to their conversion to primin in the skin...

  19. Concentrations of organochlorine pesticides, polybrominated diphenyl ethers and perfluorinated compounds in the atmosphere of North Greenland

    DEFF Research Database (Denmark)

    Bossi, Rossana; Vorkamp, Katrin; Skov, Henrik

    2016-01-01

    Atmospheric concentrations of organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs) and neutral per- and polyfluoroalkyl substances (PFAS) have been measured at Villum Research Station, Station Nord (North Greenland) in the period 2008–2013. Atmospheric concentrations of OCPs...

  20. Ethereal C–O Bond Cleavage Mediated by Ni(0)-Ate Complex: A DFT Study

    National Research Council Canada - National Science Library

    Kojima, Kumiko; Yang, Ze-Kun; Wang, Chao; Uchiyama, Masanobu

    2017-01-01

    Density functional theory calculations were performed to explore the mechanism of Ni-catalyzed cross-coupling reactions involving organo-lithium and -zinc reagents through ethereal C–O bond cleavage...

  1. Exposure of German residents to ethylene and propylene glycol ethers in general and after cleaning scenarios.

    Science.gov (United States)

    Fromme, H; Nitschke, L; Boehmer, S; Kiranoglu, M; Göen, T

    2013-03-01

    Glycol ethers are a class of semi-volatile substances used as solvents in a variety of consumer products like cleaning agents, paints, cosmetics as well as chemical intermediates. We determined 11 metabolites of ethylene and propylene glycol ethers in 44 urine samples of German residents (background level study) and in urine samples of individuals after exposure to glycol ethers during cleaning activities (exposure study). In the study on the background exposure, methoxyacetic acid and phenoxyacetic acid (PhAA) could be detected in each urine sample with median (95th percentile) values of 0.11 mgL(-1) (0.30 mgL(-1)) and 0.80 mgL(-1) (23.6 mgL(-1)), respectively. The other metabolites were found in a limited number of samples or in none. In the exposure study, 5-8 rooms were cleaned with a cleaner containing ethylene glycol monobutyl ether (EGBE), propylene glycol monobutyl ether (PGBE), or ethylene glycol monopropyl ether (EGPE). During cleaning the mean levels in the indoor air were 7.5 mgm(-3) (EGBE), 3.0 mgm(-3) (PGBE), and 3.3 mgm(-3) (EGPE), respectively. The related metabolite levels analysed in the urine of the residents of the rooms at the day of cleaning were 2.4 mgL(-1) for butoxyacetic acid, 0.06 mgL(-1) for 2-butoxypropionic acid, and 2.3 mgL(-1) for n-propoxyacetic acid. Overall, our study indicates that the exposure of the population to glycol ethers is generally low, with the exception of PhAA. Moreover, the results of the cleaning scenarios demonstrate that the use of indoor cleaning agents containing glycol ethers can lead to a detectable internal exposure of residents. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. Carbamate-directed benzylic lithiation for the diastereo- and enantioselective synthesis of diaryl ether atropisomers

    Directory of Open Access Journals (Sweden)

    Abigail Page

    2011-09-01

    Full Text Available Diaryl ethers carrying carbamoyloxymethyl groups may be desymmetrised enantio- and diastereoselectively by the use of the sec-BuLi–(−-sparteine complex in diethyl ether. Enantioselective deprotonation of one of the two benzylic positions leads to atropisomeric products with ca. 80:20 e.r.; an electrophilic quench typically provides functionalised atropisomeric diastereoisomers in up to 97:3 d.r.

  3. Water-Filled Telescopes and the Pre-History of Fresnel's Ether Dragging

    DEFF Research Database (Denmark)

    Pedersen, Kurt Møller

    2000-01-01

    The idea of measuring stellar aberration with a water-filled telescope was entertained from the middle of the 18th century by Thomas Melvill, Patrick Wilson, Roger Joseph Boscovich, and John Robison. I shall discuss their ideas as well as those discussed by Thomas Young, Francois Arago, and Augus...... for the ether dragging, the ether being the very subtle medium through which light propagates....

  4. Metal ion complexation by ionizable crown ethers. Final report, January 1, 1988--June 30, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, R.A.

    1994-12-31

    During the report period a variety of new lipophilic ionizable crown ethers with pendent proton-ionizable groups has been synthesized. The ligands possess one or more ionizable group (carboxylic acid, phosphonic acid monoethyl ester, para-nitrophenol, phosphonic acid) attached to crown ether, monoazacrown ether or diazacrown ether frameworks. These novel chelating agents have either pendent or inward-facing proton-ionizable groups. Such lipophilic proton-ionizable crown ethers are designed for use in multiphase metal ion separations (solvent extraction, liquid membrane transport). In addition a series of proton-ionizable crown ethers without lipophilic groups was prepared to study how structural variations within the ligand influence metal ion complexation in homogeneous media as assessed by NMR spectroscopy or titration calorimetry. A third class of new metal ion-complexing agents is a series of lipophilic acyclic polyether dicarboxylic acids. Competitive solvent extractions of alkali metal and alkaline earth cations and of the mixed species have been conducted to reveal the influence of ring size, nature and attachment site of the lipophilic group, sidearm length, and proton-ionizable group identity and location upon the selectivity and efficiency of metal ion complexation. In addition to such studies of structural variation within the lipophilic proton-ionizable crown ether, the effect of changing the organic solvent and variation of the stripping conditions have been assessed. The influence of structural variations within lipophilic acyclic polyether dicarboxylic acids upon competitive solvent extraction of alkaline earth cations has been probed. Also a new chromogenic, di-ionizable crown ether with extremely high selectivity for Hg{sup 2+} has been discovered.

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

    Science.gov (United States)

    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. © The Author(s) 2016.

  6. Determination of fuel ethers in water by membrane extraction ion mobility spectrometry.

    Science.gov (United States)

    Holopainen, Sanna; Nousiainen, Marjaana; Sillanpää, Mika

    2013-03-15

    Fuel oxygenates are environmentally detrimental compounds due to their rapid migration to groundwater. Fuel oxygenates have been reported to cause taste and odour problems in drinking water, and they also have long-term health effects. Feasible analytical methods are required to observe the presence of fuel oxygenates in drinking and natural water. The authors studied ion mobility spectrometry (IMS) to determinate isomeric fuel ether oxygenates; ethyl tert-butyl ether (ETBE), diisopropyl ether (DIPE), and tert-amyl methyl ether (TAME), separated from aqueous matrices with a pervaporation membrane module. Methyl tert-butyl ether (MTBE) was also membrane extracted and detected with IMS. The authors demonstrated that fuel ethers (MTBE, ETBE, DIPE, and TAME) can be quantified at μg/L level with membrane extraction IMS. A membrane extraction module coupled to IMS is a time and cost effective analysis method because sampling can be performed in a single procedure and from different natural water matrices within a few minutes. Consequently, IMS combined with membrane extraction is suitable not only for waterworks and other online applications but also in the field monitoring the quality of drinking and natural water. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Rotational Spectra of Halogenated Ethers Used as Volatile Anaesthetics

    Science.gov (United States)

    Vega-Toribio, Alicia; Lesarri, Alberto; Suenram, Richard D.; Grabow, Jens-Uwe

    2009-06-01

    Following previous microwave investigations by Suenram et al., we will report on the rotational spectrum of several halogenated ethers used as volatile anaesthetics, including sevoflurane ((CF_3)_2CH-O-CH_2F), isoflurane (CF_3CHCl-O-CHF_2), enflurane (CHFClCF_2-O-CHF_2) and methoxyflurane (CHCl_2CF_2-O-CH_3). This study has been conducted in the 6-18 GHz centimetre-wave region using Balle-Flygare-type FT-microwave spectroscopy. The results will include the analysis of the rotational spectra of minor species in natural abundance (^{13}C and ^{18}O in some cases), structural calculations and auxiliary ab initio modelling. The conformational and structural conclusions will be compared with previous gas-phase electron diffraction and solid-state X-ray diffraction analysis. R. D. Suenram, D. J. Brugh, F. J. Lovas and C. Chu, 51st OSU Int. Symp. On Mol. Spectrosc., Columbus, OH, 1999, RB07

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

    Directory of Open Access Journals (Sweden)

    Kiković Dragan D.

    2012-01-01

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

  9. Maternal-infant transfer of polybrominated diphenyl ethers

    Energy Technology Data Exchange (ETDEWEB)

    Hirai, T.; Fujimine, Y.; Watanabe, S. [Otsuka Pharmaceutical Co., Ltd., Tokushima (Japan); Nakamura, Y. [SRL Nishinihon, Fukuoka (Japan); Shimomura, H. [Shimomura OBGY Clinic, Fukuoka (Japan); Nagayama, J. [Kyushu Univ., Fukuoka (Japan)

    2004-09-15

    Polybrominated diphenyl ethers (PBDEs) are widely used brominated flame retardants (BFRs) in plastics of automobiles, textile industry, television, personal computer, electronic appliances etc. The amount of production world-wide has reached 40,000 tons in 1992. In 1992 world-wide production of PBDEs reached 40,000 tons raising serious concern over the dangers of environmental pollution by BFRs. The toxicity of PBDEs was reported to be an antagonist of thyroid-hormone (T4) and inhibition to aryl hydrocarbon (Ah) receptor. Since PBDEs are structurally similar to PCBs and therefore they work as an antagonist. Polychlorinated biphenyl (PCBs) demonstrate biological stability and high lipophilicity. As a result, PCBs used in the past and released into the environment, have been transmitted through the food chain and accumlated in the human body over time. In Japan, approximately 58,000 tons of PCBs were produced with the grade name of Kanechlor in between 1954 and 1971. In this study, all PCB congeners and 25 PBDE congeners (17, 25, 28, 30, 32, 33, 35, 37, 47, 49, 66, 71, 75, 77, 85, 99, 100, 116, 119, 126, 138, 153, 154, 155, 166) were analyzed by the method that combines high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). The purpose of this study was to investigate whether congener-specific PCBs and PBDEs were transferred from pregnant women to their infants.

  10. Phthalates and polybrominated diphenyl ethers in retail stores

    Science.gov (United States)

    Xu, Ying; Liang, Yirui; Urquidi, Jorge R.; Siegel, Jeffrey A.

    2014-04-01

    Retail stores contain a wide range of products that can emit a variety of indoor pollutants. Among these chemicals, phthalate esters and polybrominated diphenyl ethers (PBDEs) are two important categories, because they are extensively used as additives in consumer products and associated with serious health concerns. This study measured six phthalate and 14 PBDE compounds inside of 12 retail stores in Texas and Pennsylvania, U.S. Phthalates and PBDEs were widely found in the retail environment, indicating that they are ubiquitous indoor air pollutants. DEP, DnBP, and DEHP were the most abundant phthalates, with DnBP showing the highest concentration (0.23 ± 0.36 μg m-3). PBDEs were dominated by BDE-28, -99, and -209, having concentrations as high as 0.85 ± 1.99 ng m-3 (BDE-99). The levels of phthalates and PBDEs measured in this study are comparable to concentrations found in previous investigations of residential buildings, with phthalates showing lower concentrations and PBDEs exhibiting higher concentrations in retail stores. The potential co-occurrence of phthalates was not as strong as that of PBDEs, suggesting that phthalates might have more diverse sources. Whole building emission rates were calculated and showed similar patterns of variations as indoor air concentrations, suggestion the diversity of indoor sources of phthalates and PBDEs in retail environments.

  11. The effect of ether anesthesia on fin-clipping rate

    Science.gov (United States)

    Eschmeyer, Paul H.

    1953-01-01

    As part of an experimental program to learn the effects of stocking lake trout (Salvelinus namaycush) in Lake Superior, 141, 392 fingerlings were marked at the Charlevoix (Michigan) Station of the U.S. Fish and Wildlife Service in October 1952. The adipose fin was removed from all fish, the right pelvic from the remainder. A random sample of 2, 417 of the fish showed an average total length of 4.0 inches (range, 2.7 to 5.4). The mean weight of all fish marked was slightly less than one-third ounce (49 fish per pound). The local women, none of whom had previous experience in the work, were employed to mark the fish. Bone-cutting forceps were used for excision of the fins, and each worker wore a bobbinet glove to facilitate handling of the fish. On alternate days the fish were anesthetized with ether before marking, to determine the effect of its use on the fin-clipping rate.

  12. Theoretical investigations on direct photolysis mechanisms of polychlorinated diphenyl ethers.

    Science.gov (United States)

    Wang, Se; Hao, Ce; Gao, Zhanxian; Chen, Jingwen; Qiu, Jieshan

    2014-09-01

    Polychlorinated diphenyl ethers (PCDEs) are a focus of current environmental concern as a group of ubiquitous potential persistent organic pollutants. There are still significant gaps in our knowledge concerning the photolysis mechanisms of PCDEs. In this study, the direct photolysis mechanisms of PCDEs were investigated by density functional theory. The direct photolysis of PCDEs has three potential reaction pathways including photodechlorination, C-O bond photodissociation, and PCDFs formation. Taking a representative PCDE (i.e., CDE8) for example, we found that C-Cl bond dissociation is the rate-determining step for the photodechlorination. Chlorobenzene is predicted to be photoproduct of CDE8 through the photodissociation of the C-O bond. Furthermore, the calculated mean bond dissociation energies of both C-Cl and C-O bonds of 20 PCDEs decrease with the increased degree of chlorination. It is also found that the photoactivity of PCDEs increases with an increase of chlorination degree by evaluating the average charge of Cl atoms and mean bond dissociation energies of C-Cl and C-O bonds from reaction thermodynamics. Our findings provided a new insight into the mechanisms of direct photolysis of PCDEs, which may be useful in the future in utilizing quantum chemistry calculation in investigating the behavior and fate of organic pollutants in the environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Isolation of Ether-Resistant Enteroviruses from Sewage: Methodology

    Science.gov (United States)

    Duff, Michael F.

    1970-01-01

    Experiments were conducted to determine whether polio type 1 (Mahoney and coxsackie A8 viruses adsorb onto cotton fibers of sewer swabs. Negative results were obtained. It has been shown that viruses may exist in sewage as free virus particles or as bound (adsorbed) virus particles. The sewer-swab method of sampling is superior because it filters out the bound virus over several days; when collected, it represents a catch (grab) sample at that particular time which may or may not contain free virus. A simple method for the preparation of sewage inocula for virus isolations is described which samples the bound virus fraction. Only ether-resistant viruses can be isolated, and an ultracentrifuge is not required. By this method, an isolation rate between 60 and 80% of positive sewer swabs can be achieved. Corresponding figures of 84 and 96% were achieved by concentration of sewer-swab eluates with an ultracentrifuge. Quantitative studies showed that the virus concentration in raw sewage can be as high as one infectious particle per 0.5 ml. PMID:4313310

  14. Preparation and evaluation of some amide ether carboxylate surfactants

    Directory of Open Access Journals (Sweden)

    M.M.A. El-Sukkary

    2012-06-01

    Full Text Available A homologous series of new mild surfactants, namely: Alkyl amide ether carboxylates surfactants (AEC RCO–NHCH2CH2O (CH2CH2O6CH2COONa, were synthesized by esterification, amidation, ethoxylation and carboxymethylation reaction steps of fatty acids (Lauric, Myristic, palmitic, stearic, oleic or linoleic. The chemical structures of the prepared compounds were confirmed using different spectroscopic techniques, FTIR spectroscopy, mass spectra and HNMR. The surface properties including surface and interfacial tensions, foaming height, emulsification power, calcium ion stability, stability to hydrolysis and critical micelle concentration (cmc were determined. The study of their surface properties showed their stability in hard water and in acidic and alkaline media. These compounds have high calcium ion stability. The low foaming power could have an application in the dyeing auxiliary industry. The lower values of the interfacial tension values indicate the ability of using these surfactants in several applications as corrosion inhibitors and biocides. The data revealed various advantages and potentials as a main surfactant as well as co- surfactants.

  15. Crown ethers and phase transfer catalysis in polymer science

    CERN Document Server

    Carraher, Charles

    1984-01-01

    Phase transfer catalysis or interfacial catalysis is a syn­ thetic technique involving transport of an organic or inorganic salt from a solid or aqueous phase into an organic liquid where reaction with an organic-soluble substrate takes place. Over the past 15 years there has been an enormous amount of effort invested in the development of this technique in organic synthe­ sis. Several books and numerous review articles have appeared summarizing applications in which low molecular weight catalysts are employed. These generally include either crown ethers or onium salts of various kinds. While the term phase transfer catalysis is relatively new, the concept of using a phasetrans­ fer agent (PTA) is much older~ Both Schnell and Morgan employed such catalysts in synthesis of polymeric species in the early 1950's. Present developments are really extensions of these early applications. It has only been within the last several years that the use of phase transfer processes have been employed in polymer synthesis...

  16. Effect of decabromodiphenyl ether (BDE 209) and dibromodiphenyl ether (BDE 15) on soil microbial activity and bacterial community composition

    Energy Technology Data Exchange (ETDEWEB)

    Liu Lu, E-mail: liulu519@gmail.com [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046 (China); Zhu Wei [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046 (China); Xiao Lin, E-mail: xiaolin@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046 (China); Yang Liuyan, E-mail: yangly@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046 (China)

    2011-02-15

    There is now increasing concern regarding the effect of polybrominated diphenyl ethers (PBDEs) on the environment. These compounds are widely used as fire retardants and by the electronic industry. Our study examined the effects of adding different doses of BDE 15 and BDE 209 on the soil microbial activities and function by using denaturing gradient gel electrophoresis (DGGE), fluorescence in situ hybridization (FISH) and soil enzymatic activity analyses. Soils were spiked with 1, 10, and 100 mg kg{sup -1} BDE 209 and BDE 15, respectively, and incubated for up to 180 days. No degradation of BDE 209 was observed; however, about 40% of the added BDE 15 underwent declining extractable concentration. Bacterial counts were significantly higher in the microcosms amended with BDE 15, while the suppression effect increased as the BDE 209 concentration increased. Pseudomonas, Bacillus and uncultured bacteria dominated the bacterial communities in all soil treatments, and PCA analysis showed that high doses of BDE 209 and BDE 15 altered the soil microbial community structure. This study provides new information on the effect of higher and lower PBDEs on the soil microbial community in an aerobic environment.

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

    Science.gov (United States)

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

    2015-08-01

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

  18. Block copolymers of poly(vinyl ethers) and poly(ethylene glycol) by means of the living cationic polymerization of vinyl ethers

    NARCIS (Netherlands)

    Loontjens, Ton; Derks, Frank; Kleuskens, Engelien

    1992-01-01

    If living poly(vinyl ethers) are terminated with a large excess of methanol, containing aqueous ammonia, well-defined products are obtained. If only a slight excess of methanol is used, aldehydes and coupling products are formed. However, termination with an excess of a hydroxy terminated polymer is

  19. Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

    Directory of Open Access Journals (Sweden)

    Jungho Jun

    2013-08-01

    Full Text Available Gold-catalyzed intermolecular couplings of sulfonylacetylenes with allyl ethers are reported. A cooperative polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3]-rearrangement products through the formation of a tight ion–dipole pair.

  20. Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements.

    Science.gov (United States)

    Jun, Jungho; Yeom, Hyu-Suk; An, Jun-Hyun; Shin, Seunghoon

    2013-01-01

    Gold-catalyzed intermolecular couplings of sulfonylacetylenes with allyl ethers are reported. A cooperative polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3]-rearrangement products through the formation of a tight ion-dipole pair.

  1. Effects of ethylene glycol ethers on diesel fuel properties and emissions in a diesel engine

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Cuenca, F.; Gomez-Marin, M. [Compania Logistica de Hidrocarburos (CLH), Central Laboratory, Mendez Alvaro 44, 28045 Madrid (Spain); Folgueras-Diaz, M.B., E-mail: belenfd@uniovi.es [Department of Energy, University of Oviedo, Independencia 13, 33004 Oviedo (Spain)

    2011-08-15

    Highlights: {yields} Effect of ethylene glycol ethers on diesel fuel properties. {yields} Effect of ethylene glycol ethers on diesel engine specific consumption and emissions. {yields} Blends with {<=}4 wt.% of oxygen do not change substantially diesel fuel quality. {yields} Blends with 1 and 2.5 wt.% of oxygen reduce CO and HC emissions, but not smoke. - Abstract: The effect of ethylene glycol ethers on both the diesel fuel characteristics and the exhaust emissions (CO, NO{sub x}, smoke and hydrocarbons) from a diesel engine was studied. The ethers used were monoethylene glycol ethyl ether (EGEE), monoethylene glycol butyl ether (EGBE), diethylene glycol ethyl ether (DEGEE). The above effect was studied in two forms: first by determining the modification of base diesel fuel properties by using blends with oxygen concentration around 4 wt.%, and second by determining the emission reductions for blends with low oxygen content (1 wt.%) and with 2.5 wt.% of oxygen content. The addition of DEGEE enhances base diesel fuel cetane number, but EGEE and EGBE decrease it. For concentrations of {>=}4 wt.% of oxygen, EGEE and diesel fuel can show immiscibility problems at low temperatures ({<=}0 {sup o}C). Also, every oxygenated compound, according to its boiling point, modifies the distillation curve at low temperatures and the distillate percentage increases. These compounds have a positive effect on diesel fuel lubricity, and slightly decrease its viscosity. Blends with 1 and 2.5 wt.% oxygen concentrations were used in order to determine their influence on emissions at both full and medium loads and different engine speeds. Generally, all compounds help to reduce CO, and hydrocarbon emissions, but not smoke. The best results were obtained for blends with 2.5 wt.% of oxygen. At this concentration, the additive efficiency in decreasing order was EGEE > DEGEE > EGBE for CO emissions and DGEE > EGEE > EGBE for hydrocarbon emissions. For NO{sub x}, both its behaviour and the

  2. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. Their strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis (FMEA, referred to by Air Products as a ''HAZOP'' analysis) with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operational in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation Institute's test track facility near the University Park airport. After modification and optimization of the system on

  3. Polybrominated diphenyl ether flame retardants in the North American environment.

    Science.gov (United States)

    Hale, Robert C; Alaee, Mehran; Manchester-Neesvig, Jon B; Stapleton, Heather M; Ikonomou, Michael G

    2003-09-01

    North America consumes over half of the world's production of polybrominated diphenyl ether (PBDE) flame retardants. About 98% of global demand for the Penta-BDE mixture, the constituents of which are the most bioaccumulative and environmentally widespread, resides here. However, research on the environmental distribution of PBDEs in North America has lagged behind that in Northern Europe. Examination of available governmentally maintained release data suggests that Deca-BDE use in the US substantially exceeds that in Canada. Penta-BDE use probably follows a similar pattern. PBDE demand in Mexico is uncertain, but is assumed to be comparatively modest. Recent research examining air, water, sediment, sewage sludge and aquatic biota suggests that Penta-BDE constituents are present in geographically disparate locations in the US and Canada. The less brominated congeners have been observed in areas distant from their known use or production, e.g. the Arctic. PBDEs have been detected in low concentrations in North American air, water and sediment, but much higher levels in aquatic biota. Increased burdens as a function of position in the food web have been noted. PBDE concentrations in US and Canadian sewage sludges appear to be at least 10-fold greater than European levels and may be a useful barometer of release. In general, PBDE concentrations in environmental media reported in North America are comparable or exceed those observed elsewhere in the world. In contrast to Europe, environmental burdens are increasing over time here, consistent with the greater consumption of the commercial mixtures. However, data remain relatively scarce. Deca-BDE in the North American environment appears largely restricted to points of release, e.g. urban areas and those where PBDE-containing sewage sludges have been applied. This lack of redistribution is likely due to its extremely low volatility and water solubility. Penta-BDE and Deca-BDE products are used in different applications

  4. Synthesis and physicochemical properties of polyhydroxylated diphenyl ethers

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fu; Zhang, Xuesheng; Qu, Ruijuan; Shi, Jiaqi; Wang, Zunyao, E-mail: wangzun315cn@163.com

    2013-09-20

    Highlights: • The experimental pK{sub a1} values of five synthesized PHODEs were determined. • The hydrogen bonds existed in PHODEs were investigated. • There exist close relationships between the thermodynamic properties and N{sub PHOS}. • The relative stability order of PHODE congeners was theoretically proposed. - Abstract: Five polyhydroxylated diphenyl ethers (PHODEs) were synthesized. The first ionization constants (pK{sub a1}) of the synthesized compounds and seven phenolic compounds were determined using potentiometric titration experiments, together with the software ACD/Labs pK{sub a} DB program (version 6.0). The compared results showed that the software could be used to predict the pK{sub a1} of all 209 PHODEs. The thermodynamic properties of 209 PHODEs were calculated using density functional theory (DFT) at the B3LYP/6-311G** level with Gaussian 09 program. The standard enthalpy of formation (Δ{sub f}H{sup θ}) and the standard Gibbs energy of formation (Δ{sub f}G{sup θ}) were obtained. Two types of hydrogen bond were found to exist in the PHODEs’ molecules. The intramolecular hydrogen bond energies were discussed. The relative stability of PHODEs isomers was proposed theoretically with the relative standard Gibbs energy of formation (Δ{sub f}G{sub R}{sup θ}). The relationships of S{sup θ}, Δ{sub f}H{sup θ} and Δ{sub f}G{sup θ} to the number and position of the hydroxyl substitution (N{sub PHOS}) were studied.

  5. Phospholipid ether analogs for the detection of colorectal tumors.

    Directory of Open Access Journals (Sweden)

    Dustin A Deming

    Full Text Available The treatment of localized colorectal cancer (CRC depends on resection of the primary tumor with adequate margins and sufficient lymph node sampling. A novel imaging agent that accumulates in CRCs and the associated lymph nodes is needed. Cellectar Biosciences has developed a phospholipid ether analog platform that is both diagnostic and therapeutic. CLR1502 is a near-infrared fluorescent molecule, whereas 124/131I-CLR1404 is under clinical investigation as a PET tracer/therapeutic agent imaged by SPECT. We investigated the use of CLR1502 for the detection of intestinal cancers in a murine model and 131I-CLR1404 in a patient with metastatic CRC. Mice that develop multiple intestinal tumors ranging from adenomas to locally advanced adenocarcinomas were utilized. After 96 hours post CLR1502 injection, the intestinal tumors were analyzed using a Spectrum IVIS (Perkin Elmer and a Fluobeam (Fluoptics. The intensity of the fluorescent signal was correlated with the histological characteristics for each tumor. Colon adenocarcinomas demonstrated increased accumulation of CLR1502 compared to non-invasive lesions (total radiant efficiency: 1.76×10(10 vs 3.27×10(9 respectively, p = 0.006. Metastatic mesenteric tumors and uninvolved lymph nodes were detected with CLR1502. In addition, SPECT imaging with 131I-CLR1404 was performed as part of a clinical trial in patients with advanced solid tumors. 131I-CLR1404 was shown to accumulate in metastatic tumors in a patient with colorectal adenocarcinoma. Together, these compounds might enhance our ability to properly resect CRCs through better localization of the primary tumor and improved lymph node identification as well as detect distant disease.

  6. Depositional characteristics of atmospheric polybrominated diphenyl ethers on tree barks

    Directory of Open Access Journals (Sweden)

    Man Young Chun

    2014-07-01

    Full Text Available Objectives This study was conducted to determine the depositional characteristics of several tree barks, including Ginkgo (Ginkgo biloba, Pine (Pinus densiflora, Platanus (Platanus, and Metasequoia (Metasequoia glyptostroboides. These were used as passive air sampler (PAS of atmospheric polybrominated diphenyl ethers (PBDEs. Methods Tree barks were sampled from the same site. PBDEs were analyzed by highresolution gas chromatography/high-resolution mass spectrometer, and the lipid content was measured using the gravimetric method by n-hexane extraction. Results Gingko contained the highest lipid content (7.82 mg/g dry, whereas pine (4.85 mg/g dry, Platanus (3.61 mg/g dry, and Metasequoia (0.97 mg/g dry had relatively lower content. The highest total PBDEs concentration was observed in Metasequoia (83,159.0 pg/g dry, followed by Ginkgo (53,538.4 pg/g dry, Pine (20,266.4 pg/g dry, and Platanus (12,572.0 pg/g dry. There were poor correlations between lipid content and total PBDE concentrations in tree barks (R2=0.1011, p =0.682. Among the PBDE congeners, BDE 206, 207 and 209 were highly brominated PBDEs that are sorbed to particulates in ambient air, which accounted for 90.5% (84.3-95.6% of the concentration and were therefore identified as the main PBDE congener. The concentrations of particulate PBDEs deposited on tree barks were dependent on morphological characteristics such as surface area or roughness of barks. Conclusions Therefore, when using the tree barks as the PAS of the atmospheric PBDEs, samples belonging to same tree species should be collected to reduce errors and to obtain reliable data.

  7. CCQM-K102: polybrominated diphenyl ethers in sediment

    Science.gov (United States)

    Ricci, Marina; Shegunova, Penka; Conneely, Patrick; Becker, Roland; Maldonado Torres, Mauricio; Arce Osuna, Mariana; On, Tang Po; Man, Lee Ho; Baek, Song-Yee; Kim, Byungjoo; Hopley, Christopher; Liscio, Camilla; Warren, John; Le Diouron, Véronique; Lardy-Fontan, Sophie; Lalere, Béatrice; Mingwu, Shao; Kucklick, John; Vamathevan, Veronica; Matsuyama, Shigetomo; Numata, Masahiko; Brits, Martin; Quinn, Laura; Fernandes-Whaley, Maria; Ceyhan Gören, Ahmet; Binici, Burcu; Konopelko, Leonid; Krylov, Anatoli; Mikheeva, Alena

    2017-01-01

    The key comparison CCQM-K102: Polybrominated diphenyl ethers in sediment was coordinated by the JRC, Directorate F - Health, Consumers & Reference Materials, Geel (Belgium) under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM). Thirteen National Metrology institutes or Designated Institutes and the JRC participated. Participants were requested to report the mass fraction (on a dry mass basis) of BDE 47, 99 and 153 in the freshwater sediment study material. The sediment originated from a river in Belgium and contained PBDEs (and other pollutants) at levels commonly found in environmental samples. The comparison was designed to demonstrate participants' capability of analysing non-polar organic molecules in abiotic dried matrices (approximate range of molecular weights: 100 to 800 g/mol, polarity corresponding to pKow influence the accurate quantification of the PBDEs, if the analytical methodology applied is not appropriately adapted and optimised. This comparison shows that quantification of PBDEs at the μg/kg low-middle range in a challenging environmental abiotic dried matrix can be achieved with relative expanded uncertainties below 15 % (more than 70 % of participating laboratories), well in line with the best measurement performances in the environmental analysis field. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

  8. Oxidation mechanism of aliphatic ethers: theoretical insights on the main reaction channels.

    Science.gov (United States)

    Di Tommaso, Stefania; Rotureau, Patricia; Adamo, Carlo

    2012-09-13

    This paper presents a quantum chemical study on oxidation process of a series of aliphatic ethers. On the basis of a detailed theoretical work on diethyl ether oxidation, the mechanism has been reduced at three competing reactions: the β-scission of the alkyl radical (R(I)OR(II)(•)) issued from the initiation step, the isomerization of the peroxy radical (R(I)OR(II)OO(•)) produced by reaction of the alkyl radical with molecular oxygen, and the hydroperoxide production, a bimolecular reaction between the peroxy radical and an ether molecule that also regenerates a R(I)OR(II)(•) radical. Results obtained from DFT calculations, including thermochemistry and rate constant evaluations, have been reported and discussed. The influence of the presence of the oxygen atom in the ether skeleton has been evaluated by making a comparison between some ethers and parent hydrocarbons. In particular, it has been found that oxygen increases the reactivity of vicinal sites by lowering activation barriers and favors the stabilization of radicals. Direct proportionality relationships have been searched between activation and reaction enthalpies of each class of competing reactions, but one has been found only for the isomerization reaction.

  9. [Determination of residual glycol ethers in leather and leather products by gas chromatography/mass spectrometry].

    Science.gov (United States)

    Wang, Ghengyun; Zhang, Weiya; Li, Lixia; Shen, Yalei; Lin, Junfeng; Xie, Tangtang; Chu, Naiqing

    2014-08-01

    An effective method was established for the simultaneous determination of residual glycol ethers in leather and leather products by gas chromatography/mass spectrometry. Glycol ethers in leather and leather products were ultrasonically extracted at 45 °C, using ethyl acetate as the extraction solvent. The extracts were purified by solid phase extraction (SPE) columns, and then analyzed by gas chromatography/mass spectrometry in selected ion monitoring mode. The content of each analyte was calibrated by external standard method. The limit of detection of ethylene glycol ethyl ether (EGEE) was 0. 10 mg/kg under the condition of signal to noise (S/N) of 3 and the limits of the other 11 glycol ethers were all less than 0.05 mg/kg. The spiked recoveries varied from 81. 2% to 95. 5% at three different spiked levels with the relative standard deviations (RSDs) ranged from 1.4% to 6. 6%. The proposed method is simple, rapid and accurate, with the limits of detection much less than the requirements of the Regulation Concerning Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) of European Union. It is applicable to the determination of residual glycol ethers in leather and leather products, and provides a reference for the relevant testing standards.

  10. Another case of diethyl ether intoxication?: a case report focusing on toxicological analysis.

    Science.gov (United States)

    Monticelli, Fabio; Kemmerling, Ralf; Schulz, Katja; Keller, Thomas

    2011-09-01

    Diethyl ether was widely used as an anesthetic agent in many countries in the second half of the 19th century and the first half of the 20th century. For this reason the majority of lethal cases involving diethyl ether reported during this period were associated with anesthesia. We present a case of asphyxial death by plastic-bag suffocation with additional detection of diethyl ether in autopsy specimens. Autopsy initially failed to reveal the cause of death. Macroscopic and microscopic findings as well as subsequent toxicological examination procedures and results are pointed out in the present case report. Headspace gas chromatography with flame ionization detection (HS-GC-FID) coupled with gas chromatography/mass spectrometry (GC-MS) proved to be the method of choice for fast and reliable analysis of unknown highly volatile substances (other than blood alcohol). In this case the detection of diethyl ether in autopsy specimens led to further investigations by the police at the death scene. During these investigations a bottle bearing a diethyl ether label was found and confiscated, which proved the insufficiency of prior death scene investigation. In order to evaluate the case from every possible angle, in such cases, especially when plastic-bag suffocation is suspected, we strongly recommend the collection of postmortem specimens in gas-tight vessels as well as the presence of a forensic expert at the death scene. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  11. A theoretical investigation of the interaction between fluorinated dimethyl ethers and molecular chlorine

    Science.gov (United States)

    Sutradhar, Dipankar; Chandra, Asit K.; Zeegers-Huyskens, Therese

    2014-11-01

    Halogen bonds have received a great deal of attention in recent years. In this work, the interaction between fluorinated dimethyl ethers (nF = 0-4) and molecular chlorine has been investigated by the theoretical methods. The two molecules are bonded together by an O...Cl‒Cl halogen bond and the interaction energies calculated at the MP2/aug-cc-pVDZ level range between -15.5 (nF = 0) and -6.1 (nF = 4) kJ mol-1. The correlations between interaction energies and proton affinity or ionisation potential of the ethers are discussed. The interaction between the molecules results in a small contraction of the CH bond of ethers and an elongation of the Cl‒Cl bond. The data are analysed by a natural bond orbital analysis carried out at the wB97XD/6-311++G(d,p) level. The charge transfer from the ethers to Cl2 is weak, ranges between 0.044 and 0.008 e and occurs mainly to the external Cl atom. The elongation of the Cl‒Cl bond is related to the occupation of the σ*(Cl‒Cl) orbital and to the intermolecular hyperconjugation interaction between LP(O) and σ*(Cl‒Cl) orbitals. The interaction between the ethers and chlorine induces an enhancement of the infrared intensity and Raman scattering activity of the ν(Cl‒Cl) vibration.

  12. Broadband Microwave Spectroscopy as a Tool to Study Intermolecular Interactions in the Diphenyl Ether - Water System

    Science.gov (United States)

    Fatima, Mariyam; Perez, Cristobal; Schnell, Melanie

    2017-06-01

    Many biological processes, such as chemical recognition and protein folding, are mainly controlled by the interplay of hydrogen bonds and dispersive forces. This interplay also occurs between organic molecules and solvent water molecules. Broadband rotational spectroscopy studies of weakly bound complexes are able to accurately reveal the structures and internal dynamics of molecular clusters isolated in the gas phase. Amongst them, water clusters with organic molecules are of particular interest. In this work, we investigate the interplay between different types of weak intermolecular interactions and how it controls the preferred interaction sites of aromatic ethers, where dispersive interactions may play a significant role. We present our results on diphenyl ether (C_{12}H_{10}O, 1,1'-Oxydibenzene) complexed with up to three molecules of water. Diphenyl ether is a flexible molecule, and it offers two competing binding sites for water: the ether oxygen and the aromatic π system. In order to determine the structure of the diphenyl ether-water complexes, we targeted transitions in the 2-8 GHz range using broadband rotational spectroscopy. We identify two isomers with one water, one with two water, and one with three water molecules. Further analysis from isotopic substitution measurements provided accurate structural information. The preferred interactions, as well as the observed structural changes induced upon complexation, will be presented and discussed.

  13. {sup 13}C solution NMR spectra of poly(ether)urethanes. Technical memorandum

    Energy Technology Data Exchange (ETDEWEB)

    Hiltz, J.A

    2002-11-15

    The {sup 13}C solution nuclear magnetic resonance (NMR) spectra of the 15 poly(ether)urethanes are presented. The poly(urethane)s were prepared using one of two diisocyanates, either methylene diphenyl diisocyanate (MDI) or hexamethylene diisocyanate (HDI), one of five poly(ether glycol)s, poly(tetramethylene ether glycol) of molecular weight 650, 1000, or 1400, or poly(ethylene glycol) of molecular weight 600 or 1000, and one of three chain extenders, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, or diethylene glycol. These polymers were prepared as part of a modelling study to determine if Group Contribution Theory and Group Interaction Modelling could be used to predict dynamic mechanical properties of poly(ether)urethanes on the basis of the structural fragments in the polymers. The chemical shifts of the unique carbons in each of the poly(urethane)s are assigned. They can be used to unambiguously identify the diisocyanate/diol/poly(ether glycol) used to prepare the various polyurethanes. For some compounds the spectra show resonances for terminal hydroxyl substituted carbons. These could provide a method, under the right experimental conditions, to compare molecular weights of batches of the same polymer. (author)

  14. Calixarene methylene bisphosphonic acids as promising effectors of biochemical processes

    Directory of Open Access Journals (Sweden)

    S. V. Komisarenko

    2013-12-01

    Full Text Available This interdisciplinary study, performed with participation of research workers of Palladin Institute of Biochemistry and Institute of Organic Chemist­ry of NAS of Ukraine, is devoted to analysis of biochemical effects of some calixarene methylene bisphosphonic acids (cyclic phenol oligomers on two well-known biological phenomenons – Mg2+-dependent ATP hydrolysis (myosin subfragment-1 of myometrium smooth muscle was used as an example and fibrin polymerization. Calix[4]arene С-97 (calix[4]arene methylene bisphosphonic acids is a macrocyclic substance, which contains intramolecular highly ordered lipophilic cavity formed by four aromatic rings, one of which is functionalized at the upper rim with methylene bisphosphonic group. At concentration of 100 µM, this substance was shown to effectively inhibit ATPase activity of pig myometrium myosin subfragment-1 (inhibition coefficient І0.5 = 83 ± 7 µM. At the same time, this calix[4]arene causes significant (vs. control increase of myosin subfragment-1 hydrodynamic diameter, which may indicate formation of an intermolecular complex between calixa­rene and myosin head. Computer simulation methods (docking and molecular dynamics with addition of grid technologies enabled to elucidate the grounds of intermolecular interactions between calix[4]arene С-97 and myometrium myosin subfragment-1, that involve hydrophobic, electrostatic and π-π-stacking interactions, some of which are close to the ATPase active centre. In view of the ability of calixarenes to penetrate into the cell and their low toxicity, the results obtained may be used as a basis for further development of a new generation of supramolecular effectors (starting from the above mentioned substances, in particular calix[4]arene С-97 for regulation of smooth muscle contractile activity at the level of ATP dependent actin-myosin interaction. Calix[4]arenes bearing two or four methylenebisphosphonic acid groups at the macrocyclic upper

  15. Effects of Buffer Gas Composition on Autoignition of Dimethyl Ether

    Directory of Open Access Journals (Sweden)

    Zhicheng Shi

    2015-09-01

    Full Text Available Experimental and numerical studies are conducted on the thermal, chemical and dilution effects of buffer gas composition on autoignition of dimethyl ether (DME. The buffer gases considered are nitrogen (N2, a mixture of N2 and argon (Ar at a mole ratio of 50%/50% and a mixture of Ar and carbon dioxide (CO2 at a mole ratio of 61.2%/38.8%. Experiments are performed using a rapid compression machine (RCM at compressed pressure of 10 bar, equivalence ratio (φ of 1, and compressed temperature from 670 K to 795 K. The N2 dilution ratio considered ranges from 36.31% to 55.04%. The experimental results show that buffer gas composition has little impact on the first-stage ignition delay. However, significant differences in the total ignition delay as a function of buffer gas composition are observed in the negative temperature coefficient (NTC region. Compared to N2, N2/Ar (50%/50% mixture decreases the total ignition delay by 31%. The chemical effects of buffer gas composition on the first-stage and total ignition delays are negligible. With increasing N2 dilution ratio, the first-stage ignition delay slightly increases, while a significant increase in the total ignition delay is observed. Moreover, the NTC behavior of total ignition delay is noted to become more pronounced at high N2 dilution ratio. The heat release during the first-stage ignition decreases as N2 dilution ratio increases. Results of numerical simulations with the Zhao DME mechanism over a wider range of temperature show good agreement with that of experiments. Further numerical simulations are conducted using pure N2, Ar and CO2 as buffer gases. Results indicate that the thermal effects are the dominant factor in low temperature and NTC regions. The chemical effects become pronounced in the NTC region, and the chemical effect of CO2 exceeds the thermal effect at the compressed temperature higher than 880 K.

  16. Reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, B.

    2017-01-01

    concentrations in CO between 0.2 and 2.0%, and at a temperature of 438 K. The theoretical study showed that the reaction of CO with surface methyl groups, the rate-limiting step, is faster in the eight-membered side pockets than in the twelve-membered main channel of the zeolite; the subsequent reaction......The reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite was studied theoretically with periodic density functional theory calculations including dispersion forces and experimentally in a fixed bed flow reactor at pressures between 10 and 100 bar, dimethyl ether...... of dimethyl ether with surface acetyl to form methyl acetate was demonstrated to occur with low energy barriers in both the side pockets and in the main channel. The present analysis has thus identified a path, where the entire reaction occurs favourably on a single site within the side pocket, in good...

  17. Interaction of Polybrominated Diphenyl Ethers and Aerobic Granular Sludge: Biosorption and Microbial Degradation

    Directory of Open Access Journals (Sweden)

    Shou-Qing Ni

    2014-01-01

    Full Text Available As a new category of persistent organic pollutants, polybrominated diphenyl ethers (PBDEs have become ubiquitous global environmental contaminants. No literature is available on the aerobic biotransformation of decabromodiphenyl ether (BDE-209. Herein, we investigated the interaction of PBDEs with aerobic granular sludge. The results show that the removal of BDE-209 from wastewater is mainly via biosorption onto aerobic granular sludge. The uptake capacity increased when temperature, contact time, and sludge dosage increased or solution pH dropped. Ionic strength had a negative influence on BDE-209 adsorption. The modified pseudo first-order kinetic model was appropriate to describe the adsorption kinetics. Microbial debromination of BDE-209 did not occur during the first 30 days of operation. Further study found that aerobic microbial degradation of 4,4′-dibromodiphenyl ether happened with the production of lower BDE congeners.

  18. [Ether Day--no laughing matter. The birth of modern anaesthesia].

    Science.gov (United States)

    Goerig, Michael; Wulf, Hinnerk

    2013-10-01

    Since centuries the first public demonstration of the anaesthetic properties of ether by William Thomas Green Morton at the Massachusetts General Hospital in Boston on October 16th 1846 is celebrated as "Ether Day" world-wide. The news of the beneficial effects, primarily disposed as a "Yankee Invention", spread over all continents quickly. This was the result of an article, published in the Boston Medical and Surgical Journal on November 18th, 1846. It is mentioning worth that this article was written when Morton had disclosed that the used "preparation", later named as "Nostrum" or "Letheon", was sulphuric ether. The important discovery later became a patent case and was overshadowed by a long lasting priority claim. Nevertheless the readers of the New England Journal of Medicine voted in a survey that this article was the most important publication in the 200 years journals history ever. © Georg Thieme Verlag Stuttgart · New York.

  19. [Questions on the first operation with ethyl ether as anaesthetic by Dr. Peter Parker].

    Science.gov (United States)

    Chen, Q

    2017-01-28

    Ethyl ether was the first accepted effective general anaesthetic. It was introduced into China by an America missionary, Dr. Peter Parker. This was one of the historical events of medical communication between China and the West. In the records of the first operation with ether, however, Dr. Parker unusually omitted the patient's medical record number and the date of the operation, while those of other operations with ether anesthetics were all available. This was very unusual for a doctor like Peter Parker who always recorded every important case in detail in the hospital reports. It seems that he deliberately rather than carelessly omitted the information for some reasons. Based on the analysis of Parker's reports, a conclusion is made that the anesthetic effect of the case was actually ineffective. Furthermore, possible answers to this are outlined and question by discussion based on the situation that Parker faced in the late Qing era.

  20. The hydrolysis of geminal ethers: a kinetic appraisal of orthoesters and ketals

    Directory of Open Access Journals (Sweden)

    Sonia L. Repetto

    2016-07-01

    Full Text Available A novel approach to protecting jet fuel against the effects of water contamination is predicated upon the coupling of the rapid hydrolysis reactions of lipophilic cyclic geminal ethers, with the concomitant production of a hydrophilic acyclic hydroxyester with de-icing properties (Fuel Dehydrating Icing Inhibitors - FDII. To this end, a kinetic appraisal of the hydrolysis reactions of representative geminal ethers was undertaken using a convenient surrogate for the fuel–water interface (D2O/CD3CN 1:4. We present here a library of acyclic and five/six-membered cyclic geminal ethers arranged according to their hydroxonium catalytic coefficients for hydrolysis, providing for the first time a framework for the development of FDII. A combination of 1H NMR, labelling and computational studies was used to assess the effects that may govern the observed relative rates of hydrolyses.

  1. Arginine-responsive terbium luminescent hybrid sensors triggered by two crown ether carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Lasheng [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Tang, Ke; Ding, Xiaoping [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Wang, Qianming, E-mail: qmwang@scnu.edu.cn [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Zhou, Zhan; Xiao, Rui [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China)

    2013-12-01

    Crown ether carboxylic acids constitute main building blocks for the synthesis of terbium containing covalent cross-linked luminescent materials. Both the complexes and the hybrid nanomaterials could exhibit remarkable green emissions in pure water. More importantly, they were found to have a profound effect on the luminescence responses to arginine compared with glutamic acid, histidine, tryptophan, threonine, tyrosine and phenylalanine in aqueous environment. The present study provided the possibility of using a host–guest mechanism as a way of signal transduction based on lanthanide supramolecular hybrid materials. - Highlights: • Crown ether carboxylic acids were found to sensitize terbium ions among a group of ethers. • The complexes and silica hybrid materials were both prepared and characterized. • They could exhibit remarkable green emissions in pure water.

  2. Oil-in-water emulsions stabilised by cellulose ethers: stability, structure and in vitro digestion.

    Science.gov (United States)

    Borreani, Jennifer; Espert, María; Salvador, Ana; Sanz, Teresa; Quiles, Amparo; Hernando, Isabel

    2017-04-19

    The effect of cellulose ethers in oil-in-water emulsions on stability during storage and on texture, microstructure and lipid digestibility during in vitro gastrointestinal digestion was investigated. All the cellulose ether emulsions showed good physical and oxidative stability during storage. In particular, the methylcellulose with high methoxyl substituents (HMC) made it possible to obtain emulsions with high consistency which remained almost unchanged during gastric digestion, and thus could enhance fullness and satiety perceptions at gastric level. Moreover, the HMC emulsion slowed down lipid digestion to a greater extent than a conventional protein emulsion or the emulsions stabilised by the other cellulose ethers. Therefore, HMC emulsions could be used in weight management to increase satiation capacity and decrease lipid digestion.

  3. Electron stimulated desorption of anions and cations from condensed allyl glycidyl ether.

    Science.gov (United States)

    Yildirim, Y; Balcan, M; Bass, A D; Cloutier, P; Sanche, L

    2010-07-28

    We report measurements of the electron stimulated desorption (ESD) of anions and cations from thin films of allyl glycidyl ether (AGE), formed by condensation onto multilayer Kr and Pt substrates using a high sensitivity time of flight mass analyser. Measurements were performed as a function of film thickness, incident electron energy (E(i)) and effective incident current. Below incident electron energies of 20 eV the desorption of anions is dominated by the process of dissociative electron attachment (DEA) via several transient negative ions at E(i) between 5.5 and 16.5 eV. Comparisons between measurements for AGE and ethyl oxirane show that the ESD of anions is essentially that of the glycidyl (epoxide) ring, though DEA occurring at the ether, within the linear part of the AGE molecule is also observed. Cation yields are dominated by the desorption of small fragments formed via scission of the same ether bond.

  4. The action of ether and methoxyflurane on synaptic transmission in isolated preparations of the mammalian cortex.

    Science.gov (United States)

    Richards, C D; Russell, W J; Smaje, J C

    1975-06-01

    1. The actions of ether and methoxyflurane on the evoked potentials of in vitro preparations of the guinea-pig olfactory cortex were studied. Following stimulation of the lateral olfactory tract (l.o.t.) evoked potentials could be recorded from the cortical surface; these potentials consisted of an initial wave (the compound action potential of the l.o.t.) followed by a negative field potential which was associated with the synchronous excitation of many superficial excitatory synapses (population e.p.s.p.). Superimposed on the population e.p.s.p. was a number of positive peaks. These positive peaks reflect the synchronous discharge of many neurones and so have been called population spikes. 2. When ether or methoxyflurane was added to the gas stream that superfused the surface of the preparations, the population e.p.s.p.s. and population spikes were depressed at lower concentrations than those required to depress the compound action potential of the afferent fibres. 3. The evoked activity of individual cells in the cortex was depressed by ether and methoxyflurane. However, five of the twelve cells tested in ether showed an increase in their evoked activity at concentrations below 4-5%, but at higher concentrations these cells also became depressed. 4. Both ether and methoxyflurane depressed the sensitivity of cortical neurones to iontophoretically applied L-glutamate and may similarly depress the sensitivity of the post-synaptic membrane to the released transmitter substance. 5. Neither anaesthetic appeared to increase the threshold depolarization required for nerve impulse generation. Thus, the decrease of the discharge of the post-synaptic cells was primarily caused by a depression of chemical transmission. 6. Ether caused some cells in the cortex to alter their normal pattern of synaptically evoked discharge and both anaesthetics induced similar changes during excitation by glutamate.

  5. Sulfoglucosides as Novel Modified Forms of the Mycotoxins Alternariol and Alternariol Monomethyl Ether.

    Science.gov (United States)

    Soukup, Sebastian T; Kohn, Beate N; Pfeiffer, Erika; Geisen, Rolf; Metzler, Manfred; Bunzel, Mirko; Kulling, Sabine E

    2016-11-23

    The mycotoxins alternariol and alternariol-9-O-methyl ether have recently been reported to be extensively conjugated with glucose and malonyl glucose in tobacco suspension cells. However, only trace amounts of glucosylated conjugates were detected in tomatoes inoculated with Alternaria alternata in the present study. Instead, mostly sulfate conjugates were observed. In studies using cultures of A. alternata and incubations of alternariol and alternariol-9-O-methyl ether with tomato tissue in the absence of the fungus, it was clarified that sulfate conjugates were produced by the fungus, whereas tomato tissues converted alternariol and alternariol-9-O-methyl ether to glucosylated metabolites. Alternariol-3-sulfate, alternariol-9-sulfate, and alternariol-9-O-methyl ether-3-sulfate were unambiguously identified as fungal metabolites using MS and (1)H and (13)C NMR spectroscopy. When these sulfate conjugates were incubated with tobacco suspension cells or ex planta tomato tissues, three sulfoglucosides of alternariol and one sulfoglucoside of alternariol-9-O-methyl ether were formed. Using NMR spectroscopy, the chemical structures of alternariol-3-sulfate-9-glucoside, alternariol-9-sulfate-3-glucoside, and alternariol-9-O-methyl ether-3-sulfate-7-glucoside were established. These conjugates were also detected in the A. alternata-inoculated tomato. This is the first report on a mixed sulfate/glucoside diconjugate of a mycotoxin. Diconjugates of this novel type may be formed by all mycotoxins and their phase I metabolites with two or more hydroxyl groups and should be taken into account in the future analysis of modified mycotoxins.

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

    Directory of Open Access Journals (Sweden)

    M. Farrokhi ، S. Ahmadizad

    2009-04-01

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

  7. The screening of microorganisms capable of methyl tert-butyl ether (MTBE) biodegradation.

    Science.gov (United States)

    Wieczorek, Andrzej; Przybulewska, Krystyna; Karpowicz, Katarzyna; Nowak, Maciej J

    2013-01-01

    As a result of examinations carried out, 16 strains of microorganisms able to grow on mineral media with methyl tert-butyl ether as the sole source of carbon and energy were isolated. Bacteria prevailed among the isolated microorganisms. The growth of microorganisms under laboratory conditions was long and accompanied by low biomass increase. Under the conditions of the experiment, the isolated microorganisms did not show any quantitatively measurable biodegradability of methyl tert-butyl ether (MTBE) under aerobic conditions. This requires far-reaching caution with respect to trading in MTBE-modified petrols in order to protect the natural environment in Poland against contamination with that hard-to-biodegrade substance.

  8. Positron Lifetime Study of the Transition from Glassy to Normal Liquid State for Two Phenyl Ethers

    DEFF Research Database (Denmark)

    Pethrick, R. A.; Jacobsen, F. M.; Mogensen, O. E.

    1980-01-01

    Positron lifetime measurements are reported as a function of temperature for bis[m-(m-phenoxyphenoxy)phenyl] ether and m-phenoxyphenyl-m-(m-phenoxyphenoxy)phenyl ether. The decay curves were analysed in terms of three lifetime components; two short lifetimes of typically 200 and 500 ps associated......, which may be slightly enlarged due to the presence of Ps. Above 313 K Ps is apparently localized in a thermal equilibrated bubble. The size of the bubble is probably independent of the size of the pre-existing holes, as described by the “bubble model”. The transition between those two cases occurs...

  9. The Kinetics of the Trimethoxyboroxine-Induced Thermal Polymerization of Phenyl Glycidyl Ether

    Science.gov (United States)

    Lopata, Eugene S.; Riccitiello, Salvatore R.

    1975-01-01

    The kinetics of the bulk thermal polymerization of phenyl glycidyl ether induced by trimethoxyboroxine were investigated. Infrared absorption spectroscopy and gel permeation chromatography were used to follow the course of polymerization, while proton and boron-2 NMR spectroscopy were used to support the kinetic model developed. The postulated mechanism involves a fast-initiated, non-stationary cationic polymerization with five elementary steps, including spontaneous and monomer transfer as well as a termination reaction. The trimethoxyboroxine was found to be incorporated into the structure of the cured polymer. Tile polymerization was followed at several temperatures and with several ratios of initial concentrations of trimethoxyboroxine to phenyl glycidyl ether.

  10. FTIR cryospectroscopic and ab initio studies of desflurane-dimethyl ether H-bonded complexes

    Science.gov (United States)

    Melikova, S. M.; Rutkowski, K. S.; Rospenk, M.

    2017-09-01

    The IR spectra of mixtures of desflurane and dimethyl ether are studied with the help of FTIR cryospectroscopy in liquefied Kr at T 118-158 K. Comparative analysis of the experimental data and results of ab initio calculations show that either of the two C-H groups of desflurane is involved in heterodimer formation of comparable strengths. The blue frequency shift is found for stretching vibrations of those C-H donors which directly participate in H-bond formation. Additionally the complexes are stabilized by weaker contacts between hydrogen atoms of dimethyl ether and fluorine atoms of desflurane.

  11. Catalyst system and process for benzyl ether fragmentation and coal liquefaction

    Science.gov (United States)

    Zoeller, Joseph Robert

    1998-04-28

    Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

  12. Alkyl aryl ethers in lignite solubilization 1. Study of the process

    Energy Technology Data Exchange (ETDEWEB)

    Mastral, A.M.; Cebolla, V.L.; Gavilan, J.M.

    1984-10-01

    The chemistry of solubilization of a lignite has been investigated with anisole, 3-methyl anisole and 1,3dimethoxybenzene catalysed by SbCl/sub 3/, ZnCl/sub 2/, AlCl/sub 3/ and BF/sub 3/ as boron trifluoride etherate, at atmospheric pressure and temperatures <220/sup 0/C. 60% of lignite was solubilized in a toluene-ethanol azeotropic mixture. During the process, the solvent is incorporated as an alkylated substratum. The yield increased with activity of the aromatic ether ring and catalyst acidity.

  13. Alkyl aryl ethers in lignite solubilization. 1. Study of the process

    Energy Technology Data Exchange (ETDEWEB)

    Mastral, A.M.; Cebolla, V.L.; Gavilan, J.M.

    1984-10-01

    The chemistry of solubilization of a lignite has been investigated with anisole, 3-methyl anisole and 13-dimethoxybenzene catalysed by SbCl/sub 3/, ZnCl/sub 2/, AlCl/sub 3/ and BF/sub 3/ as boron trifluoride etherate, at atmospheric pressure and temperatures <220 C. 60% of lignite was solubilized in a toluene-ethanol azeotropic mixture. During the process, the solvent is incorporated as an alkylated substratum. The yield increased with activity of the aromatic ether ring and catalyst acidity. 14 references.

  14. Gold( i )-catalysed dehydrative formation of ethers from benzylic alcohols and phenols

    KAUST Repository

    Veenboer, Richard M. P.

    2015-01-01

    © The Royal Society of Chemistry 2015. We report the cross-dehydrative reaction of two alcohols to form unsymmetrical ethers using NHC-gold(i) complexes (NHC = N-heterocyclic carbene). Our progress in developing this reaction into a straightforward procedure is discussed in detail. The optimised methodology proceeds under mild reaction conditions and produces water as the sole by-product. The synthetic utility of this environmentally benign methodology is exemplified by the formation of a range of new ethers from readily available phenols bearing electron withdrawing substituents and secondary benzylic alcohols with various substituents. Finally, we present experimental results to account for the chemoselectivity obtained in these reactions.

  15. Ring-opening of cyclic ethers with carbon–carbon bond formation by Grignard reagents

    DEFF Research Database (Denmark)

    Christensen, Stig Holden; Holm, Torkil; Madsen, Robert

    2014-01-01

    The ring-opening of cyclic ethers with concomitant C–C bond formation was studied with a number of Grignard reagents. The transformation was performed in a sealed vial by heating to ∼160 °C in an aluminum block or at 180 °C in a microwave oven. Good yields of the product alcohols were obtained...... with allyl- and benzylmagnesium halides when the ether was tetrahydrofuran or 3,3-dimethyloxetane. Lower yields were obtained with substituted tetrahydrofurans while no ring-opening was observed with tetrahydropyran. Only highly reactive allyl and benzyl Grignard reagents participated in the transformation...

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

    Science.gov (United States)

    Jarumaneeroj, Chatchai; Tashiro, Kohji; Chirachanchai, Suwabun

    2014-08-01

    Sulfonated poly(ether ether ketone) (SPEEK) thin film performs reversible thermochromic property by developing the color to be yellowish at the temperature above 190 °C. The detailed analyses based on temperature-dependent techniques suggest the thermal treatment inducing the shifting of the hydrogen bond network between the sulfonated group and the hydrated water molecules to the π-π stacking among aromatic rings in SPEEK chains. Although it is general that the polymer chain packing is unfavorable at high temperature, the present work shows a good example that when the polymer chains can form specific molecular interaction, such as π-π stacking, even in harsh thermal treatment, a rearrangement will effectively occur, which leads to an external stimuli-responsive property. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-02-01

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

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

    Science.gov (United States)

    Kanakasabai, P.; Vijay, P.; Deshpande, Abhijit P.; Varughese, Susy

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

  19. Thermodynamic modeling of ternary and quaternary (liquid + liquid) systems containing water, FeCl3, HCl and diisopropyl ether

    NARCIS (Netherlands)

    Milosevic, M.; Hendriks, I.; Smits, R.E.R.; Schuur, Boelo; de Haan, A.B.

    2013-01-01

    Liquid–liquid extraction using ethers as solvents is a potentially energy saving alternative for the concentration of aqueous ferric chloride solutions. Adequate thermodynamic models that describe the behavior of the resulting quaternary systems (FeCl3, ether, acid and water) are not available in

  20. 40 CFR 63.63 - Deletion of ethylene glycol monobutyl ether from the list of hazardous air pollutants.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 9 2010-07-01 2010-07-01 false Deletion of ethylene glycol monobutyl... Quantity Designations, Source Category List § 63.63 Deletion of ethylene glycol monobutyl ether from the list of hazardous air pollutants. The substance ethylene glycol monobutyl ether (EGBE,2-Butoxyethanol...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-04-15

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

  2. Effects of various elicitors on the accumulation and secretion of spiroketal enol ether diacetylenes in feverfew hairy root culture

    Directory of Open Access Journals (Sweden)

    Anna Stojakowska

    2011-01-01

    Full Text Available In a hairy root culture of Tanacetum parthenium treated with yeast extract (YE, silver nitrate (AgNO3 and microalgal glycoproteins (MGPS, contents of four spiroketal enol ether type diacetylenes were mesured. The elicitors transiently reduced contents of three constitutive spiroketal enol ethers and selectively enhanced accumulation of cis-C13-spiroketal enol ether epoxide ((E-3,4-epoxy-2-(2,4-hexadiynylidene-1,6-dioxaspiro[4.4]nonane in the roots. The most abundant formation of cis-C13-spiroketal enol ether epoxide was observed after 48-96 h of AgNO3 treatment and 96 h of YE treatment (over 3-fold increase compared with the control. The applied elicitors caused enhanced liberation of cis-C13-spiroketal enol ether epoxide to the culture medium. The results show that diacetylene accumulation pattern in the elicited hairy roots is affected in a similar manner, irrespectively of the elicitor applied.

  3. Lewis Acid Accelerated Aryl Ether Bond Cleavage with Nickel: Orders of Magnitude Rate Enhancement Using AlMe3.

    Science.gov (United States)

    Kelley, Paul; Edouard, Guy A; Lin, Sibo; Agapie, Theodor

    2016-11-21

    Study of the kinetics of intramolecular aryl ether C-O bond cleavage by Ni was facilitated by access to a family of metal complexes supported by diphosphines with pendant aryl-methyl ethers. The nature of the aryl substituents was found to have little effect on the rate of cleavage. In contrast, soluble Lewis acidic additives accelerate the aryl ether cleavage dramatically. The effect of AlMe3 was studied in detail, and showed an increase in rate by several orders of magnitude. Low temperature NMR spectroscopy studies demonstrate quantitative coordination of ether to Al. From the Lewis acid-bound precursor, the activation parameters for ether cleavage are significantly lower. These findings provide a mechanistic basis for milder catalyst design for the activation of strong bonds. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Uptake and efflux of rhenium in cells exposed to rhenium diseleno-ether and tissue distribution of rhenium and selenium after rhenium diseleno-ether treatment in mice.

    Science.gov (United States)

    Collery, Philippe; Bastian, Gérard; Santoni, François; Mohsen, Ahmed; Wei, Ming; Collery, Thomas; Tomas, Alain; Desmaele, Didier; D'Angelo, Jean

    2014-04-01

    We proposed a new water-soluble rhenium diseleno-ether compound (with one atom of Re and two atoms of Se) and investigated the uptake of Re into the nucleus of malignant cells in culture exposed to the compound for 48 h and its efflux from the nucleus after a post-exposure period of 48 h, as DNA is the main target of Re. We also studied the distribution of both Re and Se in the main organs after an oral administration of 10 or 40 mg/kg Re diseleno-ether to mice for four weeks, five days-a-week. Re and Se concentrations were assayed by inductively coupled plasma mass spectrometry (ICP-MS). Statistical analysis was performed using the Wilcoxon signed-rank test, comparing two related groups. We observed that Re was well incorporated into the nucleus of malignant cells in the most sensitive cells MCF-7, derived from human breast cancer, and that there was no efflux of Re. In contrast, in MCF-7 resistant cells (MCF-7 Mdr and MCF-7 R), A549 and HeLa cells, there was significant efflux of Re from the nucleus after the wash-out period. In mice, an important and dose-dependent uptake of both Re and Se was observed in the liver, with lower concentrations in kidneys. The lowest concentrations were observed in blood, lung, spleen and bones. There was a significant increase of Re concentrations in the blood, liver and kidney in mice treated with Re diseleno-ether at the dose of 40 mg/kg/24 h versus those treated at the dose of 10 mg/kg/24 h. There was a significant increase of Se concentrations in all tissues with the dose of Re diseleno-ether of 10 mg/kg/24 h versus controls, and a significant increase in the liver in mice treated with dose of Re diseleno-ether of 40 mg/kg/24h versus those treated with 10 mg/kg/24 h. We are the first to demonstrate that a compound combining Re and Se in a single molecule, is able to deliver Re and Se to the organism via an oral route, for cancer treatment.

  5. Study of the interaction of some unsaturated hydrocarbons, simple ethers, and alcohols with sputtered iron surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Losev, V.V.; Chechel, O.V.; Kumpanenko, I.V.; Entelis, S.G.

    1989-01-01

    The method of temperature-programmed reduction has been used to study the interaction of hydrogen, ethylene, acetylene, benzene, water ethanol, ethyl ether, and ethylene oxide with sputtered iron surfaces. For the majority of compounds studied, the sole product of thermal desorption is hydrogen. The stability of the surface compounds formed was evaluated.

  6. Top-down lipidomics reveals ether lipid deficiency in blood plasma of hypertensive patients.

    Science.gov (United States)

    Graessler, Juergen; Schwudke, Dominik; Schwarz, Peter E H; Herzog, Ronny; Shevchenko, Andrej; Bornstein, Stefan R

    2009-07-15

    Dyslipoproteinemia, obesity and insulin resistance are integrative constituents of the metabolic syndrome and are major risk factors for hypertension. The objective of this study was to determine whether hypertension specifically affects the plasma lipidome independently and differently from the effects induced by obesity and insulin resistance. We screened the plasma lipidome of 19 men with hypertension and 51 normotensive male controls by top-down shotgun profiling on a LTQ Orbitrap hybrid mass spectrometer. The analysis encompassed 95 lipid species of 10 major lipid classes. Obesity resulted in generally higher lipid load in blood plasma, while the content of tri- and diacylglycerols increased dramatically. Insulin resistance, defined by HOMA-IR >3.5 and controlled for BMI, had little effect on the plasma lipidome. Importantly, we observed that in blood plasma of hypertensive individuals the overall content of ether lipids decreased. Ether phosphatidylcholines and ether phosphatidylethanolamines, that comprise arachidonic (20:4) and docosapentaenoic (22:5) fatty acid moieties, were specifically diminished. The content of free cholesterol also decreased, although conventional clinical lipid homeostasis indices remained unaffected. Top-down shotgun lipidomics demonstrated that hypertension is accompanied by specific reduction of the content of ether lipids and free cholesterol that occurred independently of lipidomic alterations induced by obesity and insulin resistance. These results may form the basis for novel preventive and dietary strategies alleviating the severity of hypertension.

  7. Top-down lipidomics reveals ether lipid deficiency in blood plasma of hypertensive patients.

    Directory of Open Access Journals (Sweden)

    Juergen Graessler

    Full Text Available BACKGROUND: Dyslipoproteinemia, obesity and insulin resistance are integrative constituents of the metabolic syndrome and are major risk factors for hypertension. The objective of this study was to determine whether hypertension specifically affects the plasma lipidome independently and differently from the effects induced by obesity and insulin resistance. METHODOLOGY/PRINCIPAL FINDINGS: We screened the plasma lipidome of 19 men with hypertension and 51 normotensive male controls by top-down shotgun profiling on a LTQ Orbitrap hybrid mass spectrometer. The analysis encompassed 95 lipid species of 10 major lipid classes. Obesity resulted in generally higher lipid load in blood plasma, while the content of tri- and diacylglycerols increased dramatically. Insulin resistance, defined by HOMA-IR >3.5 and controlled for BMI, had little effect on the plasma lipidome. Importantly, we observed that in blood plasma of hypertensive individuals the overall content of ether lipids decreased. Ether phosphatidylcholines and ether phosphatidylethanolamines, that comprise arachidonic (20:4 and docosapentaenoic (22:5 fatty acid moieties, were specifically diminished. The content of free cholesterol also decreased, although conventional clinical lipid homeostasis indices remained unaffected. CONCLUSIONS/SIGNIFICANCE: Top-down shotgun lipidomics demonstrated that hypertension is accompanied by specific reduction of the content of ether lipids and free cholesterol that occurred independently of lipidomic alterations induced by obesity and insulin resistance. These results may form the basis for novel preventive and dietary strategies alleviating the severity of hypertension.

  8. 18-Crown[6]ether functionalized reduced graphene oxide for membrane-free ion selective sensing

    DEFF Research Database (Denmark)

    Olsen, Gunnar; Ulstrup, Jens; Chi, Qijin

    The focus of this work is on the synthesis of a 1-Aza-18-crown[6]ether functionalized reduced graphene oxide (RGO-crown[6]) with specific K+ binding sites on the RGO surface. Glassy carbon electrodes (GCE) functionalized with RGO-crown[6] weretested for selective potentiometric sensing of K...

  9. On-board conversion of methanol to dimethyl ether as an alternative diesel fuel

    Energy Technology Data Exchange (ETDEWEB)

    Armbruster, H.; Heinzelmann, G.; Struis, R.; Stucki, S. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The catalytic dehydration of methanol to dimethyl ether was investigated for application on-board a methanol fuelled vehicle. Several catalysts have been tested in a fixed bed reactor. Our approach is to develop a small and efficient reactor converting liquid MeOH under pressure and at low reaction temperatures. (author) 2 figs., 5 refs.

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

    Science.gov (United States)

    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.

  11. Magnetic silica supported palladium catalyst: synthesis of allyl aryl ethers in water

    Science.gov (United States)

    A simple and benign procedure for the synthesis of aryl allyl ethers has been developed using phenols, allyl acetates and magnetically recyclable silica supported palladium catalyst in water; performance of reaction in air and easy separation of the catalyst using an external mag...

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

    NARCIS (Netherlands)

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

    2004-01-01

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

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

    NARCIS (Netherlands)

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

    2004-01-01

    Recently, possible unacceptable harmful effects from Methyl tertiary-Butyl Ether (MTBE) to humans raised political consternation. For this reason the Dutch Ministry of Housing, Spatial Planning and the Environment ("VROM") ordered the RIVM to derive solid risk limits for soil, sediment,

  14. Chemical oxidation of bis(2-chloroethyl) ether in the Fenton process: Kinetics, pathways and toxicity assessment.

    Science.gov (United States)

    Shi, Jiaqi; Long, Tao; Ying, Rongrong; Wang, Lei; Zhu, Xin; Lin, Yusuo

    2017-08-01

    Bis(2-chloroethyl) ether (BCEE) is a common chemical material and a frequently detected contaminant in groundwater. It has a strong toxicity and some other chemicals such as poly(vinyl chloride-co-isobutyl vinyl ether) contain similar chloroaliphatic ether structure. So the effective degradation method and transformation pathways for BCEE need to be learned. The present study compared the degradation rate of BCEE by Fenton's reagent and other common oxidation methods, and optimized the reaction conditions. Oxidation intermediates and pathways were also proposed and toxicities of the intermediates were investigated. Results showed that Fenton was highly effective to degrade BCEE. pH, Fe2+ and H2O2 concentration all affected the oxidation rate, among which Fe2+ was the most significant variable. A total of twelve chlorinated intermediates were detected. Three main reaction pathways involved cleavage of the ether bond, hydroxyl substitution for hydrogen, and radical coupling. The pathways could be well interpreted and supported by theoretical calculations. The reaction mixture showed a decreasing trend in TOC concentration and toxicity until totally harmless to Vibrio fischeri after 15 min, but it was noteworthy that toxicities of some dimeric intermediates were stronger than BCEE by calculation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Oxidation mechanism of diethyl ether: a complex process for a simple molecule.

    Science.gov (United States)

    Di Tommaso, Stefania; Rotureau, Patricia; Crescenzi, Orlando; Adamo, Carlo

    2011-08-28

    A large number of organic compounds, such as ethers, spontaneously form unstable peroxides through a self-propagating process of autoxidation (peroxidation). Although the hazards of organic peroxides are well known, the oxidation mechanisms of peroxidizable compounds like ethers reported in the literature are vague and often based on old experiments, carried out in very different conditions (e.g. atmospheric, combustion). With the aim to (partially) fill the lack of information, in this paper we present an extensive Density Functional Theory (DFT) study of autoxidation reaction of diethyl ether (DEE), a chemical that is largely used as solvent in laboratories, and which is considered to be responsible for various accidents. The aim of the work is to investigate the most probable reaction paths involved in the autoxidation process and to identify all potential hazardous intermediates, such as peroxides. Beyond the determination of a complex oxidation mechanism for such a simple molecule, our results suggest that the two main reaction channels open in solution are the direct decomposition (β-scission) of DEE radical issued of the initiation step and the isomerization of the peroxy radical formed upon oxygen attack (DEEOO˙). A simple kinetic evaluation of these two competing reaction channels hints that radical isomerization may play an unexpectedly important role in the global DEE oxidation process. Finally industrial hazards could be related to the hydroperoxide formation and accumulation during the chain propagation step. The resulting information may contribute to the understanding of the accidental risks associated with the use of diethyl ether.

  16. Claisen rearrangements of benzyl vinyl ethers: theoretical investigation of mechanism, substituent effects, and regioselectivity.

    Science.gov (United States)

    Krenske, Elizabeth H; Burns, Jed M; McGeary, Ross P

    2017-09-26

    Recently we reported the aromatic Claisen rearrangements of benzyl ketene acetals, which form one of the few examples of aromatic Claisen rearrangements involving benzyl vinyl ethers (as opposed to allyl aryl ethers, which are the usual substrates for aromatic Claisen rearrangements). Theoretical calculations predict that these rearrangements proceed via a concerted [3,3]-sigmatropic transition state, which is similar in geometry to the TS for the Claisen rearrangement of an allyl aryl ether but has a 4 kcal mol-1 higher barrier. The effects of donor (OMe) and acceptor (CN) substituents on the kinetics of the [3,3]-rearrangement mirror those reported for allyl vinyl ethers: the largest substituent effects are seen for 1-OMe, 2-OMe, 2-CN, and 4-CN substituents, which lower the barrier by 5-9 kcal mol-1. Substituents on the aromatic ring have smaller effects on the barrier (≤2 kcal mol-1). The regioselectivities of Claisen rearrangements of meta-substituted benzyl ketene acetals favour 1,2,3-trisubstituted products in preference to the less sterically congested 1,2,4-isomers due to favourable orbital interactions in the 1,2,3 transition state.

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

    Science.gov (United States)

    Smith, L.A. Jr.

    1983-03-01

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

  18. 40 CFR 721.7046 - Formaldehyde, polymer with substituted phenols, glycidyl ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Formaldehyde, polymer with substituted... New Uses for Specific Chemical Substances § 721.7046 Formaldehyde, polymer with substituted phenols... substance identified as formaldehyde, polymer with substituted phenols, glycidyl ether (PMN P-93-955) is...

  19. IRIS Toxicological Review of Ethylene Glycol Mono-Butyl Ether (Egbe) (Interagency Science Discussion Draft)

    Science.gov (United States)

    EPA released the draft report, Toxicological Review for Ethylene Glycol Mono-Butyl Ether , that was distributed to Federal agencies and White House Offices for comment during the Science Discussion step of the IRIS Assessment Development Process. Comments received from ot...

  20. Survey of the occurrence of 1,6-hexanediol diglycidyl ether in food contact materials

    DEFF Research Database (Denmark)

    This project is a survey of the occurence of 1,6-hexanediol diglycidyl ether (HDDGE) specifically in food contact material on the Danish market This survey clarifies that HDDGE is listed on an inventory for possible use in printing inks food contact materials, but that is not used by European...

  1. Effects of poly-ether B on proteome and phosphoproteome expression in biofouling Balanus amphitrite cyprids.

    Science.gov (United States)

    Dash, Swagatika; Chandramouli, Kondethimma H; Zhang, Yu; Qian, Pei-Yuan

    2012-01-01

    Biofouling is ubiquitous in marine environments, and the barnacle Balanus amphitrite is one of the most recalcitrant and aggressive biofoulers in tropical waters. Several natural antifoulants that were claimed to be non-toxic have been isolated in recent years, although the mechanism by which they inhibit fouling is yet to be investigated. Poly-ether B has shown promise in the non-toxic inhibition of larval barnacle attachment. Hence, in this study, multiplex two-dimensional electrophoresis (2-DE) was applied in conjunction with mass spectrometry to investigate the effects of poly-ether B on barnacle larvae at the molecular level. The cyprid proteome response to poly-ether B treatment was analyzed at the total proteome and phosphoproteome levels, with 65 protein and 19 phosphoprotein spots found to be up- or down-regulated. The proteins were found to be related to energy-metabolism, oxidative stress, and molecular chaperones, thus indicating that poly-ether B may interfere with the redox-regulatory mechanisms governing the settlement of barnacle larvae. The results of this study demonstrate the usefulness of the proteomic technique in revealing the working mechanisms of antifouling compounds. © 2012 Taylor & Francis

  2. IRIS Toxicological Review and Summary Documents for Tertiary Amyl Ethyl Ether (Taee)

    Science.gov (United States)

    This is EPA's first assessment of the noncancer health effects and carcinogenic potential of tertiary amyl ethyl ether (TAEE). The IRIS program is preparing an assessment that will incorporate health effects information available for TAEE, and current risk assessment methods. T...

  3. Prolinethiol ether catalysis in an asymmetric Michael reaction: solvent-free synthesis of functionalized monohaloalkenes.

    Science.gov (United States)

    Xia, Ai-Bao; Wu, Chao; Xu, Dan-Qian; Wang, Yi-Feng; Du, Xiao-Hua; Li, Zhao-Bo; Xu, Zhen-Yuan

    2013-02-01

    The organocatalytic Michael reaction of ketones with γ-monohalonitrodienes catalyzed by chiral prolinethiol ether under solvent-free conditions was developed. The described method represents a novel approach for accessing highly functionalized monohaloalkenes with α, β-stereocenters of up to >99% ee.

  4. Provisional Peer-Reviewed Toxicity Values for Diphenyl ether (CASRN 101-84-8)

    Science.gov (United States)

    PPRTVs are toxicity values derived for use in EPAs Superfund program when a value is not available in the IRIS database. Superfund site managers use PPRTV in decision making for waste site clean ups. This is a PPRTV for Diphenyl ether.

  5. An Evaluation of the Human Carcinogenic Potential of Ethylene Glycol Butyl Ether (Egbe)

    Science.gov (United States)

    This position paper, An Evaluation of the Human Carcinogenic Potential of Ethylene Glycol Butyl Ether, was developed in support of the EPA's evaluation of a petition from the American Chemistry Council requesting to delist EGBE per the Clean Air Act Amendments (CAAA), Titl...

  6. New coating systems based on vinyl ether- and oxetane-modified hyperbranched polyesters

    NARCIS (Netherlands)

    Schmaljohann, D.; Voit, B.I.; Jansen, J.F.G.A.; Hendriks, Peter; Loontjens, J.A.

    2000-01-01

    A series of hyperbranched aliphatic-aromatic polyesters has been synthesized which contain vinyl ether or oxetane functionalities as curable groups. We investigated the curing behavior of these multifunctional polymers in the presence of reactive diluents in order to analyze the possibility of their

  7. Efficient Deprotection of Phenol Methoxymethyl Ethers Using a Solid Acid Catalyst with Wells-Dawson Structure

    Directory of Open Access Journals (Sweden)

    H. Thomas

    2001-11-01

    Full Text Available Deprotection of various phenols from their respective methoxymethyl ethers using an heteropolyacid catalyst was studied. The catalyst was the Wells-Dawson heteropolyacid, used both in bulk or supported on silica. Yields were high to quantitative after less than one hour reaction time and the catalyst was easily recoverable and reusable.

  8. TREATMENT OF METHYL TERT-BUTYL ETHER CONTAMINATED WATER USING PHOTOCATALYSIS

    Science.gov (United States)

    The feasibility of photo-oxidation treatment of methyl tert-butyl ether (MTBE) in water was investigated in three ways, 1) using a slurry falling film photo-reactor, 2) a batch solar reactor system, and 3) a combination of air-stripping and gas phase photooxidation system. MTBE-c...

  9. Mechanisms of flash pyrolysis of ether lipids isolated from the green microalga Botryococcus braunii race

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Gelin, F.; Gatellier, J-P.L.A.; Metzger, P.; Derenne, S.; Largeau, C.; Leeuw, J.W. de

    1993-01-01

    Two types of ether lipids isolated from the microalga Botryococcus braunii have been subjected to flash pyrolysis. The pyrolysis products were separated and analyzed by GC/MS. The nature and distribution of the pyrolysis compounds gave clues to the different mechanisms involved in the pyrolysis of

  10. 40 CFR 721.1580 - Disubstituted benzene ether, polymer with substituted phenol (generic).

    Science.gov (United States)

    2010-07-01

    ... PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES... chemical substance generically identified as disubstituted benzene ether, polymer with substituted phenol... A of this part apply to this section except as modified by this paragraph. (1) Recordkeeping...

  11. Synthesis and application of polyepoxide cardanol glycidyl ether as biobased polyepoxide reactive diluent for epoxy resin

    Science.gov (United States)

    Polyepoxide cardanol glycidyl ether (PECGE), a novel cardanol derivative, was synthesized and used as reactive diluent for petroleum-based epoxy resin in this work. The synthetic condition was first optimized, and the resultant PECGE diluent was characterized using Fourier transform infrared spectro...

  12. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated ...

  13. Long term studies on the anaerobic biodegradability of MTBE and other gasoline ethers

    DEFF Research Database (Denmark)

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

    2009-01-01

    to investigate the anaerobic biodegradability of MTBE and other gasoline ethers. Inoculums collected from various environments were used, along with different electron acceptors. Only one set of the batch experiments showed a 30-60% conversion of MTBE to tert-butyl alcohol under Fe(III)-reducing conditions...

  14. Information draft on the development of air standards for ethyl ether

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-01-01

    Ethyl ether is a clear, volatile liquid with a sweet, pungent odour. It is used as a solvent for waxes, fats, oils, perfumes, alkaloids and gums. It is an easily removable extractant of hormones from animal and plant tissues. Therapeutically, it is used as an inhalation anesthetic and antispasmodic. Ethyl ether can be absorbed via inhalation or ingestion. From the blood it passes quickly into the brain. It is partly metabolized to carbon dioxide and to urinary metabolites, but over 90 per cent is excreted unchanged through exhaled air. Inhalation may cause dizziness, giddiness, euphoria, skin, eye and mucous membrane irritation, and rarely death, due to respiratory failure. Release into the environment is usually from its industrial application. Ethyl ether is not a candidate substance in the National Pollutant Release Inventory for the reporting of environmental releases. No data in ambient air concentrations was found for Ontario or Canada. This report discusses the scientific and technical evidence relevant to the setting of a revised air standard for ethyl ether. The available evidence has been gathered from world-wide sources. Only three of the agencies reviewed have derived ambient air quality criteria. These were based on the occupational exposure limit of the American Conference of Governmental Industrial Hygienists. Odour thresholds have been found to be in the range of 700 to 3,000 microgram/cubic meter, which may provide an appropriate effect to consider for developing air quality limits for Ontario. 42 refs., 1 tab., appendix

  15. Elevated Serum Polybrominated Diphenyl Ethers and Alteration of Thyroid Hormones in Children from Guiyu, China

    NARCIS (Netherlands)

    Xu, Xijin; Liu, Junxiao; Zeng, Xiang; Lu, Fangfang; Chen, Aimin; Huo, Xia

    2014-01-01

    Informal electronic waste (e-waste) recycling results in serious environmental pollution of polybrominated diphenyl ethers (PBDEs) and heavy metals. This study explored whether there is an association between PBDEs, heavy metal and key growth-and development-related hormones in children from Guiyu,

  16. Unusual selectivity-determining factors in the phosphine-free Heck arylation of allyl ethers

    DEFF Research Database (Denmark)

    Ambrogio, I.; Fabrizi, G.; Cacchi, S.

    2008-01-01

    The Heck reaction of aryl iodides and bromides with allyl ethers has been investigated. Using phosphinefree Pd(OAc)(2) in DNIF at 90 degrees C in the presence of Bu4NOAc, the reaction gave cinnamyl derivatives, usually in good to high yields, with a wide range of aryl halides. The reaction...

  17. Rapid and selective lead (II) colorimetric sensor based on azacrown ether-functionalized gold nanoparticles

    Science.gov (United States)

    Alizadeh, A.; Khodaei, M. M.; Karami, Ch; Workentin, M. S.; Shamsipur, M.; Sadeghi, M.

    2010-08-01

    A gold nanoparticle (AuNPs)-based simple and fast colorimetric sensor for selective detecting of Pb(II) in aqueous solution has been developed. Monodisperse AuNPs (approx. 2.0 nm diameter) has been prepared facilely and further modified with an alkanethiol-bearing monoazacrown ether terminus. These AuNPs are shown to selectively sense Pb2 + through color change, which is visually discernible by an appearance of the surface plasmon band (SPB) at 520 nm. The recognition mechanism is attributed to the unique structure of the monoazacrown ether attached to AuNPs and metal sandwich coordination between two azacrown ether moieties that are attached to separate nanoparticles. This inter-particle cross-linking results in an aggregation and apparent color change from brown to purple. Additionally, TEM experiments support the optical absorption data proving the aggregation between azacrown ether-capped gold nanoparticles. This AuNP-based colorimetric assay is a facile and robust method and allows fast detection of Pb2 + at ambient temperatures. More importantly, the developed technique does not utilize enzymatic reactions, light-sensitive dye molecules, lengthy protocols or sophisticated instrumentation.

  18. Polycation-Sodium Lauryl Ether Sulfate-Type Surfactant Complexes : Influence of Ethylene Oxide Length

    NARCIS (Netherlands)

    Vleugels, Leo F. W.; Pollet, Jennifer; Tuinier, Remco

    2015-01-01

    Poiyelectrolyte-surfactant complexes (PESC) are a class of materials which form spontaneously by self-assembly driven by electrostatic and hydrophobic interactions. PESC containing sodium lauryl ether Sulfates (SLES) have found wide application in hair care products like shampoo. Typically, SLES

  19. Novel Naphthalene Based Lariat-Type Crown Ethers Using Direct Single Electron Transfer Photochemical Strategy

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hea Jung; Sung, Nam Kyung; Kim, Su Rhan; Kim, Su Rhan; Ahn, So Hyun; Yoon, Ung Chan [Pusan National Univ., Busan (Korea, Republic of); Cho, Dae Won [Yeungnam Univ., Geoungsan (Korea, Republic of); Mariano, Patrick S. [Univ. of New Mexico, Albuquerque (United States)

    2013-12-15

    This study explored a direct SET-photochemical strategy to construct a new family of thioene conjugated-naphthalamide fluorophore based lariat-crown ethers which show strong binding properties towards heavy metal ions. Irradiations of designed nitrogen branched (trimethylsilyl)methylthio-terminated polyethylenoxy-tethered naphthalimides in acidic methanol solutions have led to highly efficient photocyclization reactions to generate naphthalamide based lariat type thiadiazacrown ethers directly in chemo- and regio-selective manners which undergo very facile secondary dehydration reactions during separation processes to produce their corresponding amidoenethio ether cyclic products tethered with electron donating diethyleneoxy- and diethyenethio-side arm chains. Fluorescence and metal cation binding properties of the lariat type enamidothio products were examined. The photocyclized amidoenethio products, thioene conjugated naphthalamide fluorophore containing lariat-thiadiazacrowns exhibited strong fluorescence emissions in region of 330-450 nm along with intramolecular exciplex emissions in region of 450-560 nm with their maxima at 508 nm. Divalent cation Hg{sup 2+} and Pb{sup 2+} showed strong binding to sulfur atom(s) in side arm chain and atoms in enethiadiazacrown ether rings which led to significant enhancement of fluorescence from its chromophore singlet excited state and concomitant quenching of exciplex emission. The dual fluorescence emission responses towards divalent cations might provide a new guide for design and development of fluorescence sensors for detecting those metals.

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

    Science.gov (United States)

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

    2017-04-12

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

  1. A new bile acid-derived lariat-ether: Design, synthesis and cation ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. A new chola lariat ether (1, a 21-crown-6) was constructed from readily available precursors. The association constant of compound 1 with alkali metal picrates was measured using Cram's extraction protocol. Evidence is presented for the involvement of the 3-methoxy group for the complexation. Energy minimised.

  2. A novel guanidinium grafted poly(aryl ether sulfone) for high-performance hydroxide exchange membranes.

    Science.gov (United States)

    Zhang, Qiang; Li, Shenghai; Zhang, Suobo

    2010-10-28

    A novel poly(aryl ether sulfone) ionomer containing hexaalkylguanidinium groups was synthesized, and membranes formed from this polymer displayed large ionic clusters, high hydroxide conductivity, and excellent solubility in low boiling point water-soluble solvents such as ethanol and methanol.

  3. Electrochemically reduced graphene oxide / sulfonated polyether ether ketone composite membrane for electrochemical applications

    Science.gov (United States)

    Seetharaman, S.; Ramya, K.; Dhathathreyan, K. S.

    2013-06-01

    A simple and effective method for the preparation of sulfonated polyether ether ketone (SPEEK) based composites with electrochemical reduced graphene oxide (EGO) as inorganic fillers has been described. The resulting dispersions are homogeneous and the cast membranes show significant improvement on tensile strength and thermal properties. It has high ionic conductivity and is cost effective making it a promising alternative membrane for electrochemical applications.

  4. Poly(ether amide) segmented block copolymers with adipicacid based tetra amide segments

    NARCIS (Netherlands)

    Biemond, G.J.E.; Feijen, Jan; Gaymans, R.J.

    2007-01-01

    Poly(tetramethylene oxide)-based poly(ether ester amide)s with monodisperse tetraamide segments were synthesized. The tetraamide segment was based on adipic acid, terephthalic acid, and hexamethylenediamine. The synthesis method of the copolymers and the influence of the tetraamide concentration,

  5. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated ...... acetic acid (CH2DCOOD), when D2O is introduced in the feed during the carbonylation reaction....

  6. Effects of poly-ether B on proteome and phosphoproteome expression in biofouling Balanus amphitrite cyprids

    KAUST Repository

    Dash, Swagatika

    2012-04-01

    Biofouling is ubiquitous in marine environments, and the barnacle Balanus amphitrite is one of the most recalcitrant and aggressive biofoulers in tropical waters. Several natural antifoulants that were claimed to be non-toxic have been isolated in recent years, although the mechanism by which they inhibit fouling is yet to be investigated. Poly-ether B has shown promise in the non-toxic inhibition of larval barnacle attachment. Hence, in this study, multiplex two-dimensional electrophoresis (2-DE) was applied in conjunction with mass spectrometry to investigate the effects of poly-ether B on barnacle larvae at the molecular level. The cyprid proteome response to poly-ether B treatment was analyzed at the total proteome and phosphoproteome levels, with 65 protein and 19 phosphoprotein spots found to be up- or down-regulated. The proteins were found to be related to energy-metabolism, oxidative stress, and molecular chaperones, thus indicating that poly-ether B may interfere with the redox-regulatory mechanisms governing the settlement of barnacle larvae. The results of this study demonstrate the usefulness of the proteomic technique in revealing the working mechanisms of antifouling compounds. © 2012 Copyright Taylor and Francis Group, LLC.

  7. Diels-Alder Reactions Using 5 M LiClO4 -Diethyl Ether Catalyst

    OpenAIRE

    KACAN, M.; KARABULUT, H. R. F.

    2014-01-01

    The rate acceleration of Diels-Alder reactions in 5.0 M lithium perchlorate-diethyl ether was re-examined using itaconic anhydride and itaconic acid. Rate acceleration was observed for non-functionalised dienes, but functionalised dienes gave the starting or polymeric materials.

  8. The Rod Contraction-Clock Retardation Ether Theory and the Special Theory of Relativity

    Science.gov (United States)

    Erlichson, Herman

    1973-01-01

    Discusses the historical rod contraction-block retardation (RC-CR) ether theory to illustrate its relationship to the special theory of relativity and the possibility of experimental differences between them. Indicates that the RC-CR theory is worthy of the attention of both physicists and science philosophers. (CC)

  9. Sodium lauryl ether sulfate (SLES) degradation by nitrate-reducing bacteria

    NARCIS (Netherlands)

    Silva Paulo, da Ana; Aydin, Rozelin; Dimitrov, Mauricio R.; Vreeling, Harm; Cavaleiro, Ana J.; García-Encina, Pedro A.; Stams, Fons; Plugge, Caroline M.

    2017-01-01

    The surfactant sodium lauryl ether sulfate (SLES) is widely used in the composition of detergents and frequently ends up in wastewater treatment plants (WWTPs). While aerobic SLES degradation is well studied, little is known about the fate of this compound in anoxic environments, such as

  10. A new bile acid-derived lariat-ether: Design, synthesis and cation ...

    Indian Academy of Sciences (India)

    A new chola lariat ether (1, a 21-crown-6) was constructed from readily available precursors. The association constant of compound 1 with alkali metal picrates was measured using Cram's extraction protocol. Evidence is presented for the involvement of the 3-methoxy group for the complexation. Energy minimised ...

  11. Selective crystallization of cations with crown ethers; Selektive Kristallisation von Kationen mit Kronenethern

    Energy Technology Data Exchange (ETDEWEB)

    Heffels, Dennis Egidius

    2014-07-04

    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

  12. Fast liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and their derivatives in canned food and beverages.

    Science.gov (United States)

    Gallart-Ayala, H; Moyano, E; Galceran, M T

    2011-03-25

    In this work a fast liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method using a C18 Fused Core™ column, was developed for the simultaneous analysis of bisphenol A diglycidyl ether (BADGE), bisphenol A (2,3-dihydroxypropyl) glycidyl ether (BADGE·H(2)O), bisphenol A bis(2,3-dihydroxypropyl) ether (BADGE·2H(2)O), bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether (BADGE·HCl), bisphenol A bis(3-chloro-2-hydroxypropyl) ether (BADGE·2HCl) and bisphenol A (3-chloro-2-hydroxypropyl)(2,3-dihydroxypropyl ether) (BADGE·HCl·H(2)O) and bisphenol F diglycidyl ether (BFDGE), bisphenol F bis(2,3-dihydroxypropyl) ether (BFDGE·2H(2)O), bisphenol F bis(3-chloro-2-hydroxypropyl) ether (BFDGE·2HCl). The LC method was coupled with a triple quadrupole mass spectrometer, using an ESI source in positive mode and using the [M+NH(4)](+) adduct as precursor ion for tandem mass spectrometry experiments. The method developed was applied to the determination of these compounds in canned soft drinks and canned food. OASIS HLB solid phase extraction (SPE) cartridges were used for the analysis of soft drinks, while solid canned food was extracted with ethyl acetate. Method limits of quantitation ranged from 0.13 μgL(-1) to 1.6 μgL(-1) in soft drinks and 1.0 μgkg(-1) to 4.0 μgkg(-1) in food samples. BADGE·2H(2)O was detected in all the analyzed samples, while other BADGEs such as BADGE·H(2)O, BADGE·HCl·H(2)O, BADGE·HCl and BADGE·2HCl were also detected in canned foods. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Assessment of ether and alcohol fuels from coal. Volume 2. Technical report

    Energy Technology Data Exchange (ETDEWEB)

    1983-03-01

    A unique route for the indirect liquefaction of coal to produce transportation fuel has been evaluated. The resultant fuel includes alkyl tertiary alkyl ethers and higher alcohols, all in the gasoline boiling range. When blended into gasoline, the ether fuel provides several advantages over the lower alcohols: (1) lower chemical oxygen content, (2) less-severe water-separation problems, and (3) reduced front-end volatility effects. The ether fuel also has high-octane quality. Further, it can be utilized as a gasoline substitute in all proportions. Production of ether fuel combines several steps, all of which are or have been practiced on an industrial scale: (1) coal gasification, (2) gas cleanup and shift to desired H/sub 2/:CO ratio, (3) conversion of synthesis gas to isobutanol, methanol, and higher alcohols, (4) separation of alcohols, (5) chemical dehydration of isobutanol to isobutylene, and (6) etherification of isobutylene with methanol. A pilot-plant investigation of the isobutanol synthesis step was performed. Estimates of ether-fuel manufacturing costs indicate this process route is significantly more costly than synthesis of methanol. However, the fuel performance features provide incentive for developing the necessary process and catalyst improvements. Co-production of higher-molecular-weight co-solvent alcohols represents a less-drastic form of methanol modification to achieve improvement in the performance of methanol-gasoline blends. Costs were estimated for producing several proportions of methanol plus higher alcohols from coal. Estimated fuel selling price increases regularly but modestly with higher alcohol content.

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

    DEFF Research Database (Denmark)

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

    2008-01-01

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

  15. Lewis Acid Accelerated Aryl Ether Bond Cleavage with Nickel: Orders of Magnitude Rate Enhancement Using AlMe_3

    OpenAIRE

    Kelley, Paul; Edouard, Guy A.; Lin, Sibo; Agapie, Theodor

    2016-01-01

    Study of the kinetics of intramolecular aryl ether C−O bond cleavage by Ni was facilitated by access to a family of metal complexes supported by diphosphines with pendant aryl-methyl ethers. The nature of the aryl substituents was found to have little effect on the rate of cleavage. In contrast, soluble Lewis acidic additives accelerate the aryl ether cleavage dramatically. The effect of AlMe3 was studied in detail, and showed an increase in rate by several orders of magnitude. Low temperatur...

  16. A basic study on the production of enriched isotope {}^{48}Ca by using crown-ether resin

    Science.gov (United States)

    Umehara, S.; Kishimoto, T.; Kakubata, H.; Nomura, M.; Kaneshiki, T.; Suzuki, T.; Fujii, Y.; Nemoto, S.

    2015-05-01

    The use of enriched ^{48}Ca is expected to improve the sensitivity of ^{48}Ca double beta decay measurements. We have studied the enrichment of ^{48}Ca with chemical exchange isotope separation using benzo-18-crown-6-ether resin. Chromatographic migrations of the calcium adsorption band were carried out at different migration lengths, 1 m, 20 m, and 200 m, using glass columns. Separation coefficients were observed as approximately 3 × 10^{-3}. Efforts have been made towards the production of benzo-18-crown-6-ether monomer at reasonable cost for the production of crown-ether resin for the separation of ^{48}Ca.

  17. Long-chain ethers as solvents can amplify the enantioselectivity of the Carica papaya lipase-catalyzed transesterification of 2-(substituted phenoxy)propanoic acid esters.

    Science.gov (United States)

    Miyazawa, Toshifumi; Iguchi, Wakana

    2013-10-01

    The enantioselectivity of the transesterification of the 2,2,2-trifluoroethyl esters of 2-(substituted phenoxy)propanoic acids, as catalyzed by the lipase from Carica papaya, was greatly improved by using long-chain ethers, such as di-n-hexyl ether, as solvents instead of the conventional diisopropyl ether. Thus, for example, the E value was enhanced from 21 [in diisopropyl ether (0.8 ml)] to 57 [in di-n-hexyl ether (0.8 ml)] in the reaction of 2,2,2-trifluoroethyl(RS)-2-phenoxypropanoate (0.1 mmol) with methanol (0.4 mmol) in the presence of the plant lipase preparation (10 mg); it was also improved from 13 (in diisopropyl ether) to 44 (in di-n-hexyl ether) in the reaction of 2,2,2-trifluoroethyl(RS)-2-(2-chlorophenoxy)propanoate with methanol under the same reaction conditions.

  18. Evaluation of atmospheric solid analysis probe ionization coupled to ion mobility mass spectrometry for characterization of poly(ether ether ketone) polymers

    Energy Technology Data Exchange (ETDEWEB)

    Cossoul, Emilie; Hubert-Roux, Marie; Sebban, Muriel [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France); Churlaud, Florence [Arkema, Centre d’Etude de Recherche et Développement, 27470 Serquigny (France); Oulyadi, Hassan [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France); Afonso, Carlos, E-mail: carlos.afonso@univ-rouen.fr [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France)

    2015-01-26

    Highlights: • Solvent free approach. • Production of intact small oligomers of PEEK with ASAP ionization. • Comparison of the MS/MS spectra from M{sup +}· and [M + H]{sup +} precursor ions. • Identification of end-groups using tandem mass spectrometry. - Abstract: Recently, the interest of the coupling between atmospheric solid analysis probe (ASAP) and ion mobility–mass spectrometry has been revealed in the field of polymers. This method associates a direct ionization technique with a bi-dimensional separation method. Poly(ether ether ketones) (PEEK) belong to the family of the poly(aryl ether ketones) (PAEK) which are high performance aromatic polymers usually used in aerospace, electronics and nuclear industries. PEEK are important commercial thermoplastics with excellent chemical resistance and good mechanical properties. Because of their low solubility, few structural characterization studies of PEEK have been reported. In mass spectrometry, only MALDI-TOF analyses for polymer synthesis monitoring have been described with the use of strong acids such as sulfuric acid. This work demonstrates that ASAP is particularly efficient for analysis of PEEK in a solvent free approach with the production of intact small oligomers (n ≤ 2). Five types of PEEK oligomers with different end-groups were evidenced. With MALDI-TOF, the same end-groups with almost the same relative abundance were obtained which support the hypothesis that the oligomers detected in ASAP are intact small oligomers and not fragments or pyrolysis products. This is particularly interesting as generally the ASAP analysis of polymers yields pyrolysis products with the loss of end-group information. The end-groups assignments have been confirmed by tandem mass spectrometry (MS/MS) experiments on the M{sup +}· molecular ions, which allowed highlighting some specific neutral or radical losses as well as two diagnostic product ions. Thus, ASAP-IM/MS/MS proves to be a fast and efficient

  19. The surface modifications of multi-walled carbon nanotubes for multi-walled carbon nanotube/poly(ether ether ketone) composites

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Zongshuang [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); Research Center of Advanced Material Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Qiu, Li [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Yang, Yongzhen, E-mail: yyztyut@126.com [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); Research Center of Advanced Material Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Chen, Yongkang, E-mail: y.k.chen@herts.ac.uk [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); University of Hertfordshire, School of Engineering and Technology, Hatfield, Hertfordshire AL10 9AB (United Kingdom); Liu, Xuguang [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China)

    2015-10-30

    Graphical abstract: Multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites incorporating surface modified multi-walled carbon nanotubes (MWCNTs) as fillers were fabricated in a solution blending method in order to explore the dynamic mechanical and tribological properties of MWCNT/PEEK composites systematically. It is evident that surface modifications of MWCNTs have a significant impact on dispersibility of MWCNTs in PEEK, dynamic mechanical and tribological properties of MWCNT/PEEK composites. Typically, a clear effect of surface modifications of MWCNTs on tribological properties of MWCNT/PEEK composites was observed. A significant reduction in frictional coefficient of MWCNT/PEEK composites with the MWCNTs modified with ethanolamine has been achieved and the self-lubricating film on their worn surfaces was also observed. - Highlights: • The dispersibility of surface modified MWCNTs in PEEK has been studied. • MWCNTs modified with ethanolamine have showed a good dispersion in PEEK. • Surface modifications of MWCNTs have a significant impact on both dynamic mechanical and tribological properties of MWCNT/PEEK composites. - Abstract: The effects of surface modifications of multi-walled carbon nanotubes (MWCNTs) on the morphology, dynamic mechanical and tribological properties of multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites have been investigated. MWCNTs were treated with mixed acids to obtain acid-functionalized MWCNTs. Then the acid-functionalized MWCNTs were modified with ethanolamine (named e-MWCNTs). The MWCNT/PEEK composites were prepared by a solution-blending method. A more homogeneous distribution of e-MWCNTs within the composites was found with scanning electron microscopy. Dynamic mechanical analysis demonstrated a clear increase in the storage modulus of e-MWCNT/PEEK composites because of the improved interfacial adhesion strength between e-MWCNTs and PEEK. Furthermore, the presence of e

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

    Directory of Open Access Journals (Sweden)

    A. Sadezky

    2006-01-01

    Full Text Available 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(OH, 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