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Sample records for lariat crown ethers

  1. Synthesis of Novel C-Pivot Lariat 18-Crown-6 Ethers and their Efficient Purification

    PubMed Central

    Jana, Susovan; Suresh, Vallabh

    2015-01-01

    The syntheses of various lariat ethers including several not previously reported and their efficient purification are presented. The synthesis route brings together reactions from a variety of previous works leading to a robust and generalized approach to these C-pivot lariats. The main steps are condensation of functionalized diols with pentaethylene glycol ditosylate in the presence of potassium as a templating cation. Purification of the final products was achieved without chromatography by extracting from an aqueous potassium hydroxide solution. PMID:26900260

  2. Lanthanide/actinide separations with proton-ionizable lariat ethers

    SciTech Connect

    Bartsch, R.A.; Kim, J.S.; Yang, Y.

    1995-12-01

    Proton-ionizable lariat ethers are crown ethers with pendent ion-exchange sites. Such dual-function extractants provide both ion-exchange and polyether binding sites for metal ion complexation. A series of sym-(OR)-dibenzo-16-crown-5 compounds with R=CH{sub 2}CO{sub 2}H, CH{sub 2}P(O)(OC{sub 2}H{sub 5})OH, CH{sub 2}CH{sub 2}CH{sub 2}CH{sub 2}P(O)(OC{sub 2}H{sub 5})OH and CH{sub 2}CH{sub 2}CH{sub 2}SO{sub 3}Na have been prepared and their application as extractants in lanthanide/actinide separations explored. For solvent extraction of Eu and Am from moderately acidic aqueous solutions into chloroform, the lariat ether phosphonic acid monoethyl esters gave much larger distribution coefficients than did the lariat ether carboxylic and sulfonic acids. Subsequently a more lipophilic lariat ether phosphonic acid monoethyl ester was synthesized and utilized for the solvent extraction of Eu and Am into toluene.

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

    SciTech Connect

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

    1993-01-01

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

  4. Crown ethers in graphene

    DOE PAGES

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I.; ...

    2014-11-13

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

  5. Crown ethers in graphene

    SciTech Connect

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

    2014-11-13

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

  6. Crown ethers in graphene.

    PubMed

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

    2014-11-13

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

  7. Ion flotation of cadmium(II) and zinc(II) in the presence of proton-ionizable lariat ethers.

    PubMed

    Ulewicz, Malgorzata; Walkowiak, Wladyslaw; Jang, Youngchan; Kim, Jong Seung; Bartsch, Richard A

    2003-05-15

    Competitive flotation of Cd(II) and Zn(II) from very dilute aqueous solutions by proton-ionizable lariat ethers in the presence of nonylphenol nona(ethylene glycol) ether as a nonionic foaming agent is reported. Influences of structural variation within the collector (identity of the pendent acidic group and lipophilicity), concentration of the collector, and pH of the aqueous solution are assessed. A monoethyl lariat ether phosphonic acid collector is found to exhibit high Cd(II)/Zn(II) flotation selectivity under certain conditions.

  8. Polymeric Electrolyte Containing 12-Crown-4 Ether

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesa; Distefano, Salvador

    1992-01-01

    Experiments show incorporation of 12-crown-4 ether into solid electrolytes based on polyethylene oxide enhances their electrochemical properties. More specifically, 12-crown-4 ether increases Faradaic efficiency for Li+ ions in low-power secondary Li cells and enables operation of these cells at lower temperatures with higher efficiencies.

  9. Lariat ethers with fluoroaryl side-arms: a study of CFmetal cation interaction in the complexes of N-(o-fluoroaryl)azacrown ethers.

    PubMed

    Sazonov, Petr K; Minacheva, Lidiya Kh; Churakov, Andrei V; Sergienko, Vladimir S; Artamkina, Galina A; Oprunenko, Yuri F; Beletskaya, Irina P

    2009-02-07

    New lariat ethers, N-(o-fluorophenyl)aza-15-crown-5 (F-A15C5) and N,N'-bis(o-fluorophenyl)diaza-18-crown-6 (F(2)-A(2)18C6), were prepared by the N-arylation of the corresponding azacrown ethers. The interaction of the ligands with metal cations was studied in solution by (1)H and (19)F NMR (in acetone-d(6)) and UV spectroscopy (MeOH) confirming the formation of complexes of F(2)-A(2)18C6 with K(+), Na(+), Ag(+), Ba(2+), Pb(2+) and of F-A15C5 with Na(+) and giving evidence of CFmetal cation interaction. Cation binding constants (beta, evaluated by UV titration method), demonstrate that F-A15C5 and F(2)-A(2)18C6 form more stable complexes than their fluorine-free analogs. The effect depends on the nature of the metal cation and is at a maximum for hard, singly charged cations (up to 3 logbeta units for K(+) complex of F(2)-A(2)18C6). The X-ray structures of complexes [Pb(F(2)-A(2)18C6)(H(2)O)](ClO(4))(2) () and [Ba(F(2)-A(2)18C6)(ClO(4))(2)] () reveal short Pb-F (2.805 A) and Ba-F (2.965 A) contacts. Complex is centrosymmetric (C(i)), while complex has C(2) symmetry with one-side coordination of o-fluorophenyl groups to Pb(2+). This "one-side" coordination mode of Pb(2+) is indicative of a partial localization of the Pb(2+) lone pair.

  10. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  11. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  12. Phosphorus-nitrogen compounds. Part 20: Fully substituted spiro-cyclotriphosphazenic lariat (PNP-pivot) ether derivatives

    NASA Astrophysics Data System (ADS)

    Okumuş, Aytuğ; Bilge, Selen; Kılıç, Zeynel; Öztürk, Aslı; Hökelek, Tuncer; Yılmaz, Filiz

    2010-08-01

    The condensation reactions of partly substituted spiro-cyclotriphosphazenic lariat (PNP-pivot) ethers, N 3P 3[( o-NHPhO) 2R]Cl 4 [where R = -CH 2CH 2- ( 1) and -CH 2CH 2OCH 2CH 2- ( 2)] with morpholine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) produce fully substituted morpholino ( 3 and 4) and 1,4-dioxa-8-azaspiro[4,5]deca ( 5 and 6) phosphazenes. These are the new examples of the spiro-cyclophosphazenic lariat ether derivatives with N 2O x ( x = 2 and 3) donor type containing 11- and 14-membered macrocycles. The solid state structures of 3, 5 and 6 have been determined by X-ray diffraction techniques. Compound 3 has intermolecular N-H…O hydrogen bond, compound 5 has intra- and intermolecular N-H…O hydrogen bonds, while compound 6 has intramolecular N-H…O and O-H…N and intermolecular N-H…O and O-H…O hydrogen bonds. The correlations of the endocyclic ( α) and exocyclic ( α') NPN bond angles with δP spiro values are investigated. The structural investigations of 3- 6 have been verified by elemental analyses, MS, FTIR, 1H, 13C and 31P NMR, DEPT and HETCOR techniques.

  13. Characterization of Microsolvated Crown Ethers from Broadband Rotational Spectroscopy

    NASA Astrophysics Data System (ADS)

    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

  14. Photodissociation of Non-Covalent Peptide-Crown Ether Complexes

    PubMed Central

    Wilson, Jeffrey J.; Kirkovits, Gregory J.; Sessler, Jonathan L.; Brodbelt, Jennifer S.

    2008-01-01

    Highly chromogenic 18-crown-6-dipyrrolylquinoxaline coordinates primary amines of peptides, forming non-covalent complexes that can be transferred to the gas phase by electrospray ionization. The appended chromogenic crown ether facilitates efficient energy transfer to the peptide upon ultraviolet irradiation in the gas phase, resulting in diagnostic peptide fragmentation. Collisional activated dissociation (CAD) and infrared multiphoton dissociation (IRMPD) of these non-covalent complexes results only in their disassembly with the charge retained on either the peptide or crown ether, yielding no sequence ions. Upon UV photon absorption the intermolecular energy transfer is facilitated by the fast activation time scale of UVPD (< 10 ns) and by the collectively strong hydrogen bonding between the crown ether and peptide, thus allowing effective transfer of energy to the peptide moiety prior to disruption of the intermolecular hydrogen bonds. PMID:18077179

  15. Secondary li battery incorporating 12-crown-4 ether

    SciTech Connect

    Nagasubramanian, G.; DiStefano, S.

    1992-05-05

    This patent describes a solid electrolyte, it comprises: a solid polyethylene oxide matrix; a dispersion of a lithium salt in the matrix, the ratio of oxygen to lithium in the polyethylene oxide matrix being from 1 to 1 to 10 to 1; and further including 12 Crown-4-ether in an amount effective to increase conductivity.

  16. Synthesis of l-threitol-based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions.

    PubMed

    Rapi, Zsolt; Nemcsok, Tamás; Pálvölgyi, Ádám; Keglevich, György; Grün, Alajos; Bakó, Péter

    2017-06-01

    A few new l-threitol-based lariat ethers incorporating a monoaza-15-crown-5 unit were synthesized starting from diethyl l-tartrate. These macrocycles were used as phase transfer catalysts in asymmetric Michael addition reactions under mild conditions to afford the adducts in a few cases in good to excellent enantioselectivities. The addition of 2-nitropropane to trans-chalcone, and the reaction of diethyl acetamidomalonate with β-nitrostyrene resulted in the chiral Michael adducts in good enantioselectivities (90% and 95%, respectively). The substituents of chalcone had a significant impact on the yield and enantioselectivity in the reaction of diethyl acetoxymalonate. The highest enantiomeric excess (ee) values (99% ee) were measured in the case of 4-chloro- and 4-methoxychalcone. The phase transfer catalyzed cyclopropanation reaction of chalcone and benzylidene-malononitriles using diethyl bromomalonate as the nucleophile (MIRC reaction) was also developed. The corresponding chiral cyclopropane diesters were obtained in moderate to good (up to 99%) enantioselectivities in the presence of the threitol-based crown ethers. © 2017 Wiley Periodicals, Inc.

  17. Perfluoroalkylated 4,13-diaza-18-crown-6 ethers: synthesis, phase-transfer catalysis, and recycling studies.

    PubMed

    Stuart, Alison M; Vidal, José A

    2007-05-11

    A series of N,N'-dialkyl-4,13-diaza-18-crown-6 lariat ethers possessing two C8H17 (2), (CH2)3C8F17 (3), (CH2)3C10F21 (4), and (CH2)2C8F17 (5) side arms were synthesized in good yields by N-alkylation of 4,13-diaza-18-crown-6. Potassium picrate could be extracted from an aqueous solution into an organic phase by all of the perfluoroalkylated macrocycles demonstrating their potential to be used as phase-transfer catalysts, and preliminary studies on a classical nucleophilic substitution established that they each gave higher catalytic activities under solid-liquid than under liquid-liquid phase-transfer conditions. The light fluorous macrocycles gave similar, if not better, catalytic activity compared to the parent, non-fluorinated phase-transfer catalyst 2 under solid-liquid conditions in conventional organic solvents in both an aliphatic and an aromatic nucleophilic substitution. N,N'-Bis(1H,1H,2H,2H,3H,3H-perfluoroundecyl)-4,13-diaza-18-crown-6 (3) was recycled six times in the iodide displacement reaction of 1-bromooctane and four times in the fluoride displacement reaction of 2,4-dinitrochlorobenzene using fluorous solid-phase extraction without any loss in activity.

  18. Thermodynamic and Transport Properties of Crown-Ethers: Force Field Development and Molecular Simulations.

    PubMed

    Jamali, Seyed Hossein; Ramdin, Mahinder; Becker, Tim M; Rinwa, Shwet Kumar; Buijs, Wim; Vlugt, Thijs J H

    2017-09-07

    Crown-ethers have recently been used to assemble porous liquids (PLs), which are liquids with permanent porosity formed by mixing bulky solvent molecules (e.g., 15-crown-5 ether) with solvent-inaccessible organic cages. PLs and crown-ethers belong to a novel class of materials, which can potentially be used for gas separation and storage, but their performance for this purpose needs to be assessed thoroughly. Here, we use molecular simulations to study the gas separation performance of crown-ethers as the solvent of porous liquids. The TraPPE force field for linear ether molecules has been adjusted by fitting a new set of torsional potentials to accurately describe cyclic crown-ether molecules. Molecular dynamics (MD) simulations have been used to compute densities, shear viscosities, and self-diffusion coefficients of 12-crown-4, 15-crown-5, and 18-crown-6 ethers. In addition, Monte Carlo (MC) simulations have been used to compute the solubility of the gases CO2, CH4, and N2 in 12-crown-4 and 15-crown-5 ether. The computed properties are compared with available experimental data of crown-ethers and their linear counterparts, i.e., polyethylene glycol dimethyl ethers.

  19. 12-Crown-4 Ether Improves Rechargeable Lithium Cells

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan; Attia, Alan I.

    1992-01-01

    Experiments show addition of 12-crown-4 ether (12Cr4) to thin film of polyethylene oxide (PEO) and LiBF4 reduces charge-transfer resistance of film and enhances performance of electrochemical cell in which film is electrolyte, anode is lithium, and cathode is LixCoO2. By increasing conductivity of the electrolyte, 12Cr4 reduces polarization loss; enabling cell to sustain higher current. Result is new type of rechargeable lithium cell.

  20. Supramolecular Complexation of Carbon Nanostructures by Crown Ethers.

    PubMed

    Moreira, Luis; Illescas, Beatriz M; Martín, Nazario

    2017-04-07

    Since their discovery, crown ethers as well as the most recent carbon nanostructures, namely fullerenes, carbon nanotubes, and graphene, have received a lot of attention from the chemical community. Merging these singular chemical structures by noncovalent forces has provided a large number of unprecedented supramolecular assemblies with new geometric and electronic properties whose more representative examples are presented in this Synopsis organized according to the different nature of the carbon nanostructures.

  1. Secondary Li battery incorporating 12-Crown-4 ether

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan (Inventor); Distefano, Salvador (Inventor)

    1992-01-01

    A rechargeable lithium battery which utilizes a polyethylene oxide (PEO) solid polymeric electrolyte complexed with a lithium salt is disclosed. The conductivity is increased an order of magnitude and interfacial charge transfer resistance is substantially decreased by incorporating a minor amount of 12-Crown-4 ether in the PEO-lithium salt solid electrolyte film. Batteries containing the improved electrolyte permit operation at a lower temperature with improved efficiency.

  2. Antimutagenic effect of crown ethers on heavy metal-induced sister chromatid exchanges.

    PubMed

    Cai, M Y; Arenaz, P

    1998-01-01

    Macrocyclic polyethers (crown ethers) are a family of compounds that possess the ability to complex with and transport metal ions across membranes. Because of their unique ionophoric characteristic, they have wide application in industry and research, chemistry and biology. In the current investigation the relationship between heavy metal mutagenesis and crown ether co-mutagenicity and/or antimutagenicity in mammalian cells has been examined using sister chromatid exchange (SCE) as the cytogenetic end point. Chinese hamster ovary cells were treated with lead or cadmium, with and without selected crown ethers. Several genotoxic end points, including SCEs were scored and statistically compared. We report here that most of the crown ethers studied had little or no influence on lead- or cadmium-induced SCEs or chromosome aberrations. On the other hand, the substituted crown ether dicyclohexyl 21-crown-7 significantly decreased both spontaneous and metal-induced SCE frequencies, suggesting that this crown ether may possess antimutagenic activity.

  3. Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

    NASA Technical Reports Server (NTRS)

    Irvin, Jennifer A.; Stasko, Daniel; Fallis, Stephen; Guenthner, Andrew J.; Webber, Cynthia; Blackwell, John; Chvalun, Sergei N.

    2003-01-01

    We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.

  4. Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

    NASA Technical Reports Server (NTRS)

    Irvin, Jennifer A.; Stasko, Daniel; Fallis, Stephen; Guenthner, Andrew J.; Webber, Cynthia; Blackwell, John; Chvalun, Sergei N.

    2003-01-01

    We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.

  5. Crown bowl: metallocyclophane by self-assembly of 4'-pyridylmethyl-armed 12-crown-4 ethers with Ag+ ions.

    PubMed

    Habata, Yoichi; Yamada, Sachiko; Osaka, Futoshi

    2006-02-06

    New 3'-pyridylmethyl- and 4'-pyridylmethyl-armed monoaza-12-crown-4 ethers were prepared by the reductive amination of monoaza-12-crown-4 with the appropriate pyridinecarbaldehyde in the presence of NaBH(OAc)3. X-ray crystallography, cold electrospray ionization mass spectrometry, and 1H NMR titration experiments show that Ag+ complexes with 3'-pyridylmethyl- and 4'-pyridylmethyl-armed monoaza-12-crown-4 ethers are dimetallo[3.3]metacyclophane and trimetallo[3.3.3]paracyclophane, respectively (crown bowl). The structure of the metallocyclophanes can be controlled by the positions of the N atoms in the pyridine side arms and the ring size of the crown moiety.

  6. Two crown-ether-coordinated caesium halogen salts.

    PubMed

    Well, Natalija van; Klein, Christian; Ritter, Franz; Assmus, Wolf; Krellner, Cornelius; Bolte, Michael

    2014-05-01

    The crystal structures of two crown-ether-coordinated caesium halogen salt hydrates, namely di-μ-bromido-bis[aqua(1,4,7,10,13,16-hexaoxacyclooctadecane)caesium(I)] dihydrate, [Cs2Br2(C12H24O6)2(H2O)2]·2H2O, (I), and poly[[diaquadi-μ-chlorido-μ-(1,4,7,10,13,16-hexaoxacyclooctadecane)dicaesium(I)] dihydrate], {[Cs2Cl2(C12H24O6)(H2O)2]·2H2O}n, (II), are reported. In (I), all atoms are located on general positions. In (II), the Cs(+) cation is located on a mirror plane perpendicular to the a axis, the chloride anion is located on a mirror plane perpendicular to the c axis and the crown-ether ring is located around a special position with site symmetry 2/m, with two opposite O atoms exactly on the mirror plane perpendicular to the a axis; of one water molecule, only the O atom is located on a mirror plane perpendicular on the a axis, while the other water molecule is completely located on a mirror plane perpendicular to the c axis. Whereas in (I), hydrogen bonds between bromide ligands and water molecules lead to one-dimensional chains running along the b axis, in (II) two-dimensional sheets of water molecules and chloride ligands are formed which combine with the polymeric caesium-crown polymer to give a three-dimensional network. Although both compounds have a similar composition, i.e. a Cs(+) cation with a halogen, an 18-crown-6 ether and a water ligand, the crystal structures are rather different. On the other hand, it is remarkable that (I) is isomorphous with the already published iodide compound.

  7. Dependence of the optical absorption and Na+ binding energies of coumarin-crown ethers on the size and attachment position of ether ring: density functional investigation.

    PubMed

    Kasapbasi, Esra; Yurtsever, Mine

    2013-01-01

    The crowned coumarin complexes are well known compounds for their ion recognition abilities. They undergo photophysical changes upon cation binding. On the basis of density functional theory calculations, we examined the sodium cation (Na+) binding energies of coumarin-crown ethers based on 15-Crown-5 (15 C5) and 18-Crown-6 (18 C6) as well as the optical absorptions of coumarin-crown ethers based on 12-Crown-4 (12 C4), 15 C5 and 18 C6. We explored why the attachment of crown ether ring to coumarin affects the Na+ binding energies of coumarin-crown ethers and also why the optical absorption of coumarin is modified by the crown ethers. Our study reveals that the Na+ ion binding energies of coumarin-crown ethers depend strongly on the size of the crown ether ring and also on the attachment position of the ether ring on coumarin. These factors affect the intramolecular charge transfer and overall stability of the complexes. The absorptions of the coumarin and ether ring parts of coumarin-crown ether are red shifted from those of isolated coumarin and crown ether, respectively. The red-shift of the coumarin ester group absorption is much stronger depending on the attachment position of the ether ring to coumarin. The absorption intensity of the coumarin part in coumarin-crown ethers is reduced for the benzene group absorption, but is enhanced for the ester group absorption.

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

    SciTech Connect

    Shkrob, I.; Marin, T.; Dietz, M.

    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.

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

    SciTech Connect

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

    1991-02-01

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

  10. Sorbents based on crown ethers: preparation and application for the sorption of strontium

    NASA Astrophysics Data System (ADS)

    Bezhin, N. A.; Dovhyi, I. I.

    2015-12-01

    The key approaches to the synthesis of crown ether-based sorbents, including immobilization both with and without covalent bonding, are reviewed. Examples of sorbent preparation using anodic oxidation, chemical modification of polymers, polycondensation reactions, chemical modification of inorganic supports and radiochemical synthesis for covalent bonding of crown ether moieties are considered. Immobilization methods without covalent bonding including support synthesis in the presence of crown ethers, impregnation of supports with a crown ether solution and the use of powdered crown ether as a sorbent are presented. The applications of sorbents for selective removal of strontium from solutions of radioactive waste and spent nuclear fuel, for radiochemical analysis (determination of strontium in water, soil and biological materials) and for separation of strontium and yttrium isotopes are discussed. The bibliography includes 114 references.

  11. Radium separation through complexation by aqueous crown ethers and ion exchange or solvent extraction

    SciTech Connect

    Chiarizia, R.; Dietz, M.L.; Horwitz, E.P.; Burnett, W.C.

    1997-11-01

    The effect of three water-soluble, unsubstituted crown ethers (15-crown-5 (15C5), 18-crown-6 (18C6) and 21-crown-7 (21C7)) on the uptake of Ca, Sr, Ba and Ra cations by a sulfonic acid cation exchange resin, and on the extraction of the same cations by xylene solutions of dinonylnaphthalenesulfonic acid (HDNNS) from aqueous hydrochloric acid solutions has been investigated. The crown ethers enhance the sorption of the larger cations by the ion exchange resin, thereby improving the resin selectivity over calcium, a result of a synergistic interaction between the crown ether and the ionic functional groups of the resin. Similarly, the extraction of the larger alkaline earth cations into xylene by HDNNS is strongly synergized by the presence of the crown ethers in the aqueous phase. Promising results for intra-Group IIa cation separations have been obtained using each of the three crown ethers as the aqueous ligands and the sulfonic acid cation exchange resin. Even greater separation factors for the radium-calcium couple have been measured with the crown-ethers and HDNNS solutions in the solvent extraction mode. The application of the uptake and extraction results to the development of radium separation schemes is discussed and a possible flowchart for the determination of {sup 226}Ra/{sup 228}Ra in natural waters is presented.

  12. Construction of a new selective coated disk electrode for Ag (I) based on modified polypyrrole-carbon nanotubes composite with new lariat ether.

    PubMed

    Abbaspour, A; Tashkhourian, J; Ahmadpour, S; Mirahmadi, E; Sharghi, H; Khalifeh, R; Shahriyari, M R

    2014-01-01

    A poly (vinyl chloride) (PVC) matrix membrane ion-selective electrode for silver (I) ion is fabricated based on modified polypyrrole - multiwalled carbon nanotubes composite with new lariat ether. This sensor has a Nernstian slope of 59.4±0.5mV/decade over a wide linear concentration range of 1.0×10(-7) to 1.0×10(-1)molL(-1) for silver (I) ion. It has a short response time of about 8.0s and can be used for at least 50days. The detection limit is 9.3×10(-8)molL(-1) for silver (I) ion, and the electrode was applicable in the wide pH range of 1.6 -7.7. The electrode shows good selectivity for silver ion against many cations such as Hg (II), which usually imposes serious interference in the determination of silver ion concentration. The use of multiwalled carbon nanotubes (MWCNTs) in a polymer matrix improves the linear range and sensitivity of the electrode. In addition by coating the solid contact with a layer of the polypyrrole (Ppy) before coating the membrane on it, not only did it reduce the drift in potential, but a shorter response time was also resulted. The proposed electrode was used as an indicator electrode for potentiometric titration of silver ions with chloride anions and in the titration of mixed halides. This electrode was successfully applied for the determination of silver ions in silver sulphadiazine as a burning cream.

  13. Ion selectivity of crown ethers investigated by UV and IR spectroscopy in a cold ion trap.

    PubMed

    Inokuchi, Yoshiya; Boyarkin, Oleg V; Kusaka, Ryoji; Haino, Takeharu; Ebata, Takayuki; Rizzo, Thomas R

    2012-04-26

    Electronic and vibrational spectra of benzo-15-crown-5 (B15C5) and benzo-18-crown-6 (B18C6) complexes with alkali metal ions, M(+)•B15C5 and M(+)•B18C6 (M = Li, Na, K, Rb, and Cs), are measured using UV photodissociation (UVPD) and IR-UV double resonance spectroscopy in a cold, 22-pole ion trap. We determine the structure of conformers with the aid of density functional theory calculations. In the Na(+)•B15C5 and K(+)•B18C6 complexes, the crown ethers open the most and hold the metal ions at the center of the ether ring, demonstrating an optimum matching in size between the cavity of the crown ethers and the metal ions. For smaller ions, the crown ethers deform the ether ring to decrease the distance and increase the interaction between the metal ions and oxygen atoms; the metal ions are completely surrounded by the ether ring. In the case of larger ions, the metal ions are too large to enter the crown cavity and are positioned on it, leaving one of its sides open for further solvation. Thermochemistry data calculated on the basis of the stable conformers of the complexes suggest that the ion selectivity of crown ethers is controlled primarily by the enthalpy change for the complex formation in solution, which depends strongly on the complex structure.

  14. Release of Lariat Peanut

    USDA-ARS?s Scientific Manuscript database

    Lariat is a high-oleic runner-type peanut (Arachis hypogaea L. subsp. hypogaea var. hypogaea) that has enhanced Sclerotinia blight and pod rot tolerance when compared to the cultivar Red River Runner. Lariat (experimental designation ARSOK-R35) is the result of a cross between cultivar Red River Ru...

  15. Improvement of chiral stationary phases based on cinchona alkaloids bonded to crown ethers by chiral modification.

    PubMed

    Zhao, Jianchao; Wu, Haixia; Wang, Dongqiang; Wu, Haibo; Cheng, Lingping; Jin, Yu; Ke, Yanxiong; Liang, Xinmiao

    2015-09-17

    To improve the chiral recognition capability of a cinchona alkaloid crown ether chiral stationary phase, the crown ether moiety was modified by the chiral group of (1S, 2S)-2-aminocyclohexyl phenylcarbamate. Both quinine and quinidine-based stationary phases were evaluated by chiral acids, chiral primary amines and amino acids. The quinine/quinidine and crown ether provided ion-exchange sites and complex interaction site for carboxyl group and primary amine group in amino acids, respectively, which were necessary for the chiral discrimination of amino acid enantiomers. The introduction of the chiral group greatly improved the chiral recognition for chiral primary amines. The structure of crown ether moiety was proved to play a dominant role in the chiral recognitions for chiral primary amines and amino acids.

  16. Effect of Crown Ethers on Structure, Stability, Activity, and Enantioselectivity of Subtilisin Carlsberg in Organic Solvents

    PubMed Central

    Santos, Angélica M.; Vidal, Michael; Pacheco, Yamaris; Frontera, Joel; Báez, Carlos; Ornellas, Olivia; Barletta, Gabriel

    2015-01-01

    Colyophilization or codrying of subtilisin Carlsberg with the crown ethers 18-crown-6, 15-crown-5, and 12-crown-4 substantially improved enzyme activity in THF, acetonitrile, and 1,4-dioxane in the transesterification reactions of N-acetyl-L-phenylalanine ethylester and 1-propanol and that of (±)-1-phenylethanol and vinylbutyrate. The acceleration of the initial rate, V0, ranged from less than 10-fold to more than 100-fold. All crown ethers activated subtilisin substantially, which excludes a specific macrocyclic effect from being responsible. The secondary structure of subtilisin was studied by Fourier-transform infrared (FTIR) spectroscopy. 18-Crown-6 and 15-crown-5 led to a more nativelike structure of subtilisin in the organic solvents employed when compared with that of the dehydrated enzyme obtained from buffer alone. However, the high level of activation with 12-crown-4 where this effect was not observed excluded overall structural preservation from being the primary cause of the observed enzyme activation. The conformational mobility of subtilisin was investigated by performing thermal denaturation experiments in 1,4-dioxane. Although only a small effect of temperature on subtilisin structure was observed for the samples prepared with or without 12-crown-4, both 18-crown-6 and 15-crown-5 caused the enzyme to denature at quite low temperatures (38°C and 56°C, respectively). No relationship between this property and V0 was evident, but increased conformational mobility of the protein decreased its storage stability. The possibility of a “molecular imprinting” effect was also tested by removing 18-crown-6 from the subtilisin-18-crown-6 colyophilizate by washing. V0 was only halved as a result of this procedure, an effect insignificant compared with the ca. 80-fold rate enhancement observed prior to washing in THF. This suggests that molecular imprinting is likely the primary cause of sub-tilisin activation by crown ethers, as recently suggested. PMID

  17. Differential Self-Assembly of Novel Redox Crown Ethers

    NASA Astrophysics Data System (ADS)

    Merithew, Andrew William

    Retinal prosthesis relies on the stimulation of living nerve tissue behind the rods and cones of the eye. The current state of the art relies on electrodes controlled by cameras which directly stimulate the nerve tissue to elicit a response to an image. These types of retinal implants have allowed for short-term crude vision in patients but have had limited long term success due to external battery packs and electroplating of the implanted electrodes. Ionic stimulation is one of the principle mechanisms that sensory neurons utilize in the generation of an action potential. In a complex transduction pathway, ionic gradients are constantly altered inside the neuron by voltage sensors or mechanically controlled gates embedded in the neuronal cell membrane; responsible for the open and close state of these ion channels. It has been demonstrated that local concentration increases of K + by direct injection proximal to the nerve can elicit nerve firing at a concentration of 15-20 mM (3-4X normal concentration) increase in K + concentration. As part of a larger concept of integrating biotechnology with nanofabrication, the materials for the development of potassium selective sequestration/storage and delivery were developed in the form of a redox-gated K+ selective crown ether. The structure of the anthraquinone-based crown was deduced by computational simulation and stoichiometry of the complex confirmed by mass spec. along with 2D diffusion NMR techniques. In this instance, the stoichiometry could be controlled by the addition of different salts to give a 1:1 complex with large, aromatic anions and a 2:1 complex with smaller anions such as triflate. The synthesis of the molecule was optimized by computational modeling and simulations of transport through an artificial membrane. The selectivity of the architecture developed was specific for K+ over Na+, the other major ionic species present in the blood. The mechanism influencing the self-assembly of this class of

  18. Ultrasonic Absorption Rate Studies of Crown Ether and 222 Cryptate Complexes of Alkali Metal Cations in Nonaqueous Solutions

    DTIC Science & Technology

    1988-06-30

    Studies of Crown Ether and 222 Cryptate Complexes of Alkali Metal Cations in Nonaqueous Solutions * by Sergio Petrucci and Edward M. Eyring Prepared...STUDIES OF CROWN ETHER AND 222 CRYPTATE COMPLEXES OF ALKALI METAL CATIONS IN NONAQUEOUS SOLUTIONS 12. PERSONAL AUTHOR(S) Sergio Petrucci and Edward M...of Crown Ether and 222 Cryptate Complexes of Alkali Metal Cations in Nonaqueous Solutions Sergio Petrucci and Edward M. Eyring Department of

  19. Metal ion complexation by ionizable crown ethers. Final report, January 1, 1988--June 30, 1994

    SciTech Connect

    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.

  20. Synthesis, characterization and cation-induced dimerization of new aza-crown ether-appended metalloporphyrins.

    PubMed

    Mikhalitsyna, Elena A; Tyurin, Vladimir S; Zamylatskov, Ilia A; Khrustalev, Victor N; Beletskaya, Irina P

    2012-07-07

    New metalloporphyrins bearing one or two aryl-aza-crown ether moieties at meso-positions have been synthesized using a palladium catalyzed amination reaction and fully characterized by spectral techniques. X-Ray structural data have been presented for the zinc and copper complexes of mono-substituted aza-crown ether appended metalloporphyrins. UV-Vis and (1)H NMR spectroscopic studies showed that addition of K(+) cations to a solution of monomeric aza-crowned porphyrins in CHCl(3)/MeOH led to cation-induced dimerization of these porphyrins, whereas addition of Na(+) cations yielded a monomeric complex. Axial coordination of the exobidentate ligand (DABCO) to zinc complexes of aza-crowned porphyrins and following binding metal ions led to formation of sandwich complexes with high stability constants.

  1. Absorption spectroscopic study of synergistic extraction of praseodymium with benzoyl acetone in presence of crown ether.

    PubMed

    Banerjee, Shrabanti; Bhattacharya, Sumanta; Basu, Sukalyan

    2005-04-01

    The extraction behaviour of Pr(III) from aqueous nitric acid medium employing benzoylacetone has been studied in presence of two crown ethers, viz., 15-crown-5 and benzo-15-crown-5 in chloroform medium using UV-vis absorption spectroscopy. The binary equilibrium constant (logk(ex)) for the complex [Pr(benzoylacetonate)(NO3(-))2(H(2)O)] in organic phase was found to be 1.170. The overall equilibrium constants (logK) for the ternary species [Pr(benzoylacetonate)(crown ether)(NO3(-))(2)] were estimated to be 4.01 and 4.41 for 15-crown-5 and benzo-15-crown-5, respectively. The trend in the equilibrium constant values were very much in accordance with the nature of substitution of the donor moiety. The extraction of Pr(III) by the benzoylacetone-crown ether combination was maximum at pH 3.0 and extraction decreases with increase in pH. It has been found that the extent of extraction of Pr(III) in organic phase as the binary as well as ternary complex [Pr(benzoylacetonate)(NO3(-))(2)(H(2)O)] and [Pr(benzoylacetonate)(crown ether)(NO3(-))(2)] increases with increase in concentration of the ligand. Similar trend is observed in the extraction by only donors. Enthalpies and entropies of formation for the ternary extraction process have been estimated. In addition, the effect of NaNO(3) as foreign salt was also studied and it was observed that with increase in ionic strength, percentage extraction increases.

  2. Influence of aza crown ethers on the electric percolation of AOT/isooctane/water (w/o) microemulsions.

    PubMed

    Dasilva-Carvalhal, J; Fernández-Gándara, D; García-Río, L; Mejuto, J C

    2006-09-15

    A study was carried out on the influence of different aza crown ethers on the electric percolation of AOT/isooctane/water microemulsions. A dual behavior of the aza crown ethers with regard to the percolative phenomenon was observed: low additive concentration causes an increase in the percolation temperature, whereas at high additive concentration a reduction in the percolation temperature of the system was observed. This dual behavior allowed us to define the compensation concentration, which corresponds the aza crown ether concentration at which there is no effect on the percolative phenomenon. We observed a correlation between the effect exerted by the aza crown ethers and the size of the cavity. This shows the importance of the capacity to complexate Na(+) and solubilize it in the interface and the continuous medium on the electric percolation. We also observed a correlation between the effect of the aza crown ethers on the percolation temperature and their external size. This shows the importance of their inclusion in the interface on the percolative phenomenon. Such an inclusion modifies the properties of the AOT film, facilitating the exchange of matter between droplets. A satisfactory multiparametric correlation between the compensation concentration, the distribution of the aza crown ether between water and 1-octanol, and the number of electron-donor atoms (O and N) in the crown ether was obtained. The effects have been compared with those corresponding to the crown ethers.

  3. Evaluation of polymer inclusion membranes containing crown ethers for selective cesium separation from nuclear waste solution.

    PubMed

    Mohapatra, P K; Lakshmi, D S; Bhattacharyya, A; Manchanda, V K

    2009-09-30

    Transport behaviour of (137)Cs from nitric acid feed was investigated using cellulose triacetate plasticized polymer inclusion membrane (PIM) containing several crown ether carriers viz. di-benzo-18-crown-6 (DB18C6), di-benzo-21-crown-7 (DB21C7) and di-tert-butylbenzo-18-crown-6 (DTBB18C6). The PIM was prepared from cellulose triacetate (CTA) with various crown ethers and plasticizers. DTBB18C6 and tri-n-butyl phosphate (TBP) were found to give higher transport rate for (137)Cs as compared to other carriers and plasticizers. Effect of crown ether concentration, nitric acid concentration, plasticizer and CTA concentration on the transport rate of Cs was also studied. The Cs selectivity with respect to various fission products obtained from an irradiated natural uranium target was found to be heavily dependent on the nature of the plasticizer. The present work shows that by choosing a proper plasticizer, one can get either good transport efficiency or selectivity. Though TBP plasticized membranes showed good transport efficiency, it displayed poor selectivities. On the other hand, an entirely opposite separation behaviour was observed with 2-nitrophenyloctylether (NPOE) plasticized membranes suggesting the possible application of the later membranes for the removal of bulk (137)Cs from the nuclear waste. The stability of the membrane was tested by carrying out transport runs for nearly 25 days.

  4. A Highly Effective Strategy for Encapsulating Potassium Cations in Small Crown Ether Rings on a Dinuclear Palladium Complex.

    PubMed

    Lucio-Martínez, Fátima; Bermúdez, Brais; Ortigueira, Juan M; Adams, Harry; Fernández, Alberto; Pereira, M Teresa; Vila, José M

    2017-03-16

    The potential of 15-crown-5 ethers to link large cations, such as potassium, is limited by the quasi-parallel arrangement of two oxygen donor moieties upon appropriate orientation of the corresponding ether-ring-containing molecules. Substrates bearing the two crown ethers that are capable of achieving such coordination are hitherto unknown. The synthesis and isolation of a tailor-made dinuclear palladacycle bearing 15-crown-5 ether rings on the metallated phenyls offers such a possibility, providing the adequate environment for the formation of the sandwiched [K(metallacycle-15-crown-5)2 ] moiety. This synthetic strategy also culminates in the isolation of the first palladacycle able to entrap a potassium cation through bonding to two 15-crown-5 ether rings in a single molecule.

  5. Controlling ligand binding for tunable and switchable catalysis: cation-modulated hemilability in pincer-crown ether ligands.

    PubMed

    Miller, Alexander J M

    2017-09-28

    Methods for in situ reversible control over ligand binding processes at transition metal complexes can enable advances in switchable and tunable catalysis. After a brief overview of different approaches to controlling ligand binding, this Perspective details the development of "pincer-crown ether" ligands that contain a rigid pincer backbone and a hemilabile aza-crown ether unit that enables cation-modulated hemilability. Applications of pincer-crown ether complexes in small molecule activation and catalysis are discussed, culminating in a set of design principles for ligands capable of cation-modulated ligand binding.

  6. A basic study on the production of enriched isotope {}^{48}Ca by using crown-ether resin

    NASA Astrophysics Data System (ADS)

    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.

  7. Emergence of symmetry and chirality in crown ether complexes with alkali metal cations.

    PubMed

    Martínez-Haya, Bruno; Hurtado, Paola; Hortal, Ana R; Hamad, Said; Steill, Jeffrey D; Oomens, Jos

    2010-07-08

    Crown ethers provide a valuable benchmark for the comprehension of molecular recognition mediated by inclusion complexes. One of the most relevant crown ethers, 18-crown-6 (18c6), features a flexible six-oxygen cyclic backbone that is well-known for its selective cation binding. This study employs infrared spectroscopy and quantum mechanical calculations to elucidate the structure of the gas-phase complexes formed by the 18c6 ether with the alkali metal cations. It is shown that symmetric and chiral arrangements play a dominant role in the conformational landscape of the 18c6-alkali system. Most stable 18c6-M(+) conformers are found to have symmetries C(3v) and C(2) for Cs(+), D(3d) for K(+), C(1) and D(3d) for Na(+), and D(2) for Li(+). Remarkably, whereas the bare 18c6 ether is achiral, chirality emerges in the C(2) and D(2) 18c6-M(+) conformations, both of which involve pairs of stable atropoisomers capable of acting as enantiomeric selective substrates.

  8. Ring-size and substituent effects in the solvent extraction of alkali metal nitrates by crown ethers in 1,2-dichloroethane and 1-octanol

    SciTech Connect

    Sachleben, R.A.; Deng, Y.; Bailey, D.R.; Moyer, B.A.

    1996-11-01

    The extraction of alkali metal nitrate salts by solutions of crown ethers in each of the two diluents 1,2-dichloroethane and 1-octanol has been surveyed. The crown ethers include 18-crown-6, 21-crown-7, and 24-crown-8 ethers bearing cyclohexano, benzo, t-alkylbenzo, and/or furano substituents. The extraction efficiencies of the different crown ethers are examined in terms of ring-size, substituent, and solvent effects. Partition ratios for the crown ethers between water and either 1,2-dichloroethane or 1-octanol are discussed. The extraction selectivities, expressed as the separation factor for cesium over sodium, are examined in relation to crown ether structure. 62 refs., 5 figs., 4 tabs.

  9. Bis-15-crown-5-ether-pillar[5]arene K(+)-Responsive Channels.

    PubMed

    Feng, Wei-Xu; Sun, Zhanhu; Zhang, Yan; Legrand, Yves-Marie; Petit, Eddy; Su, Cheng-Yong; Barboiu, Mihail

    2017-03-17

    An artificial selective K(+) channel is formed from the supramolecular organization on bis(benzo-15-crown-5- ether-ureido)-pillar[5]arene compound. This channel achieves a selectivity of SK(+)/Na(+) = 5 for an initial transport rate of kK(+) = 3.2 × 10(-3) s(-1). The cation-file diffusion occurs via selective macrocyclic-filters anchored on inactive supporting pillar[5]arene relays. The sandwich-type binding geometry of the K(+) cation by two 15-crown-5 moieties sites is a key feature influencing channel efficiency.

  10. Extractant composition including crown ether and calixarene extractants

    DOEpatents

    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.

  11. Radiolytic degradation of a crown ether for extractability of strontium

    SciTech Connect

    Takagi, Noriaki; Izumi, Yoshinobu; Ema, Kimiko; Yamamoto, Tadashi; Nishizawa, Kazushige

    1999-11-01

    Dicyclohexano-18-crown-6 (DC18C6), dissolved in chloroform, 1-octanol, toluene or cyclohexane, was irradiated by {sup 60}Co {gamma}-rays. Radiolytic destruction of DC18C6, measured by gas chromatography, decreased in the order: chloroform > cyclohexane > 1-octanol > toluene. Distribution coefficients in the solvent extraction of strontium from nitric acid solution were measured. These distribution coefficients were minimally affected by {gamma}-irradiation in toluene solution, but decreased with the absorbed dose in chloroform solution. It was suggested that the distribution coefficient for the liquid-liquid extraction system was influenced by radiolytic products. The effect of radiolytic products on the distribution coefficients was evaluated by considering DC18C6 remaining in the organic phase after irradiation. The distribution coefficient measured for the organic phase with radiolytic products was larger than that without radiolytic products. The radiolytic products were thus shown to contribute to the increase in the distribution coefficient.

  12. Discriminating single-molecule sensing by crown-ether-based molecular junctions

    NASA Astrophysics Data System (ADS)

    Ismael, Ali K.; Al-Jobory, Alaa; Grace, Iain; Lambert, Colin J.

    2017-02-01

    Crown-ether molecules are well known to selectively bind alkali atoms, so by incorporating these within wires, any change in electrical conductance of the wire upon binding leads to discriminating sensing. Using a density functional theory-based approach to quantum transport, we investigate the potential sensing capabilities of single-molecule junctions formed from crown ethers attached to anthraquinone units, which are in turn attached to gold electrodes via alkyl chains. We calculate the change in electrical conductance for binding of three different alkali ions (lithium, sodium, and potassium). Depending on the nature of the ionic analyte, the conductance is enhanced by different amounts. This change in electrical conductance is due to charge transfer from the ion to molecular wire causing the molecular resonances to shift closer to the electrode Fermi energy.

  13. EXAFS investigations of strontium complexation by a polymer-supported crown ether.

    SciTech Connect

    Dietz, M. L.; Jensen, M. P.; Chemistry

    2004-01-09

    Extended X-ray absorption fine-structure (EXAFS) measurements have been used to probe the coordination environment of strontium ion sorbed from aqueous nitric acid solutions on an extraction chromatographic resin comprising a macrocyclic polyether dispersed on a polymeric support. The strontium EXAFS of the metal ions sorbed onto the resin are consistent with a 1:1:2 strontium:crown ether:nitrate stoichiometry in which the strontium is enveloped in the crown ether ring and both nitrate anions are coordinated to the strontium as bidentate ligands. This is the same structure and stoichiometry observed for complexes in liquid-liquid extraction when the macrocyclic polyether is dissolved in a diluent with low water miscibility like 1-octanol.

  14. Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks.

    PubMed

    Zhao, Yan-Li; Liu, Lihua; Zhang, Wenyu; Sue, Chi-Hau; Li, Qiaowei; Miljanić, Ognjen S; Yaghi, Omar M; Stoddart, J Fraser

    2009-12-14

    To introduce crown ethers into the struts of metal-organic frameworks (MOFs), general approaches have been developed for the syntheses of dicarboxylic acid dibenzo[30]crown-10 (DB30C10DA), dicarboxylic acid di-2,3-naphtho[30]crown-10 (DN30C10DA), dicarboxylic acid bisparaphenylene[34]crown-10 (BPP34C10DA), and dicarboxylic acid 1,5-naphthoparaphenylene[36]crown-10 (NPP36C10DA). These novel crown ethers not only retain the characteristics of their parent crown ethers since they can 1) bind cationic guests and 2) serve as templates for making mechanically interlocked molecules (MIMs), such as catenanes and rotaxanes, but they also present coordination sites to connect with secondary building units (SBUs) in MOFs. The binding behavior of BPP34C10DA with 1,1'-dimethyl-4,4'-bipyridinium bis(hexafluorophosphate) (DMBP2.PF(6)) has been investigated by means of UV/Vis, fluorescence, and NMR spectroscopic techniques. The crystal superstructure of the complex DMBP2.PF(6) subset BPP34C10DA was determined by X-ray crystallography. The NPP36C10DA-based [2]catenane (H(2)NPP36C10DC-CAT4.PF(6)) and the BPP34C10DA-based [2]catenane (H(2)BPP34C10DC-CAT4.PF(6)) were prepared in DMF at room temperature by the template-directed clipping reactions of the planarly chiral NPP36C10DA and BPP34C10DA with 1,1'-[1,4-phenylenebis(methylene)]di-4,4'-bipyridin-1-ium bis(hexafluorophosphate) and 1,4-bis(bromomethyl)benzene, respectively. The crystal structure of the dimethyl ester (BPP34C10DE-CAT4.PF(6)) of the [2]catenane H(2)BPP34C10DC-CAT4.PF(6) was investigated by X-ray crystallography, which revealed racemic R and S isomers with planar chirality present in the crystal in a 1:1 ratio. These crown ether based struts serve as excellent organic ligands to bind with transition metal ions in the construction of MOFs: the crown ethers BPP34C10DA and NPP36C10DA in the presence of Zn(NO(3))(2)4.H(2)O afforded the MOF-1001 and MOF-1002 frameworks, respectively. The crystal structures of MOF-1001 and

  15. Potential of polymethacrylate pseudo crown ethers as solid state polymer electrolytes.

    PubMed

    Moins, S; Martins, J C; Krumpmann, A; Lemaur, V; Cornil, J; Delbosc, N; Decroly, A; Dubois, Ph; Lazzaroni, R; Gohy, J-F; Coulembier, O

    2017-06-22

    The association of kinetic studies, DFT calculations and (1)H-(7)Li NMR analyses allowed the control of the cyclo-ATRP of PEG9DMA and the production of polymethacrylate pseudo crown-ethers of various molar masses. Their potential to act as a solid-state polymer electrolyte in Li-ion batteries has been highlighted and may come from the supramolecular organization of the cyclo-PEG forming a Li(+) diffusion channel.

  16. Schiff's Bases and Crown Ethers as Supramolecular Sensing Materials in the Construction of Potentiometric Membrane Sensors

    PubMed Central

    Faridbod, Farnoush; Ganjali, Mohammad Reza; Dinarvand, Rassoul; Norouzi, Parviz; Riahi, Siavash

    2008-01-01

    Ionophore incorporated PVC membrane sensors are well-established analytical tools routinely used for the selective and direct measurement of a wide variety of different ions in complex biological and environmental samples. Potentiometric sensors have some outstanding advantages including simple design and operation, wide linear dynamic range, relatively fast response and rational selectivity. The vital component of such plasticized PVC members is the ionophore involved, defining the selectivity of the electrodes' complex formation. Molecular recognition causes the formation of many different supramolecules. Different types of supramolecules, like calixarenes, cyclodextrins and podands, have been used as a sensing material in the construction of ion selective sensors. Schiff's bases and crown ethers, which feature prominently in supramolecular chemistry, can be used as sensing materials in the construction of potentiometric ion selective electrodes. Up to now, more than 200 potentiometric membrane sensors for cations and anions based on Schiff's bases and crown ethers have been reported. In this review cation binding and anion complexes will be described. Liquid membrane sensors based on Schiff's bases and crown ethers will then be discussed. PMID:27879786

  17. Bimolecular gas-phase exchange of alkali metals between cationized biomolecules and neutral crown ethers

    SciTech Connect

    Pope, M.; Dearden, D.V.; Hofstadler, S.

    1995-12-31

    Electrospray ionization of polypeptides and nucleic acids often yields ions containing sodium or potassium charge carriers. These alkali adducts are frequently the residue of ionic buffers used to preserve protein conformation in solution or artifacts of a natural matrix such as blood plasma. Measures taken in solution to desalinate these samples are hindered by the desire to maintain native conformation. The authors here show that ion-molecule chemistry is an alternate means of removing alkali metal ions from multiply-charged biomolecules. Ion-molecule reactions of multiply charged polypeptides with crown ethers result in adduction of the crown if protons are the only charge bearing species, or desalting if alkali metals are among the charge carriers. Both product ions, the desalted peptide and the crown/alkali metal complex, are observed in the latter case.

  18. Thermodynamic analysis of alkali metal complex formation of polymer-bonded crown ether.

    PubMed

    Bey, Alexandra; Dreyer, Oliver; Abetz, Volker

    2017-06-21

    The complex formation of two crown ethers with colored alkali metal salts was investigated by UV/Vis spectroscopy. Complexation was accomplished with free benzo-15-crown-5 (B15C5) and 15-crown-5 bonded to a diblock copolymer (Poly15C5). The diblock copolymer was synthesized by two controlled polymerization techniques and copper(i)-catalyzed azide-alkyne cycloaddition. Depending on the inserted cation, 1 : 1- or 1 : 2-complexes are formed. A significant difference of the stability constants was determined by concentration dependence solvent extraction with sodium or potassium salt. For Poly15C5 the stability constants increase for both salts compared to the stability constants of B15C5, which suggests a more effective complexation. Evaluation of the thermodynamics (ΔH, ΔS, ΔG) of cation complexation was achieved by temperature dependence phase extraction on the basis of established thermodynamic equations. Remarkably, in all cases the entropic gain seems to be the major propulsion facilitating the complexation between alkali metal salts and crown ethers. Indeed, by using Poly15C5 a more pronounced dependency of enthalpy and entropy on the complex formation is calculated.

  19. Improvement of Thiolate/Disulfide Mediated Dye-Sensitized Solar Cells through Supramolecular Lithium Cation Assembling of Crown Ether

    PubMed Central

    Liu, Linfeng; Li, Xiong; Chen, Jiangzhao; Rong, Yaoguang; Ku, Zhiliang; Han, Hongwei

    2013-01-01

    A supramolecular lithium cation assemblies of crown ether, [Li⊂12-crown-4]+, has been used to replace conventional tetraalkylammonium counterion in thiolate/disulfide (ET−/BET) mediated dye-sensitized solar cells (DSCs), which exhibit high stability and efficiency of 6.61% under 100 mW·cm−2 simulated sunlight illumination. PMID:23933601

  20. Kinetics of the hydroxyethylation of n-octyl alcohol in the presence of the macrocyclic ether dibenzo-18-crown-6

    SciTech Connect

    Gus'kov, A.K.; Zolotarskii, V.A.; Makarov, M.G.; Shvets, V.F.

    1988-02-01

    A study has been made of the kinetics of the reaction of ethylene oxide with n-octyl alcohol catalyzed by potassium octylate in the presence of the macrocyclic ether dibenzo-18-crown-6. A kinetic model has been proposed, which satisfactorily represents the effect of dibenzo-18-crown-6 on the rate of hydroxyethylation over a wide range of molar ratios of dibenzo-18-crown-6:potassium octylate and initial alcohol concentrations.

  1. Thermal lensing detection of lanthanide ions by solvent extraction using crown ethers

    SciTech Connect

    Tran, C.D.; Zhang, Weifeng )

    1990-04-15

    A novel method has been developed to enhance the sensitivity and selectivity of the thermal lens detection of lanthanide ions. In this method, the rare-earth ions were selectively extracted from water to organic solvent with the use of crown either, e.g., 18-crown-6, 15-crown-5 as synergistic extractant. The thermal lens signal intensity of the extracted ions in the organic phase can be enhanced up to 24-fold. This enhancement is due to the fact that the thermal lens signal is dependent on the thermooptical properties of the solvent, and water is a poor thermooptical solvent (low dn/dT and high thermal conductivity, k, values), whereas organic solvents are good thermooptical media (high dn/dT and low k values). The well-defined cavities of the crown ethers restrict their complex formation (and hence solvent extraction) only with the rare-earth ions whose sizes are comparable to their cavities, and this is the origin for the improvement in the selectivity. For instance, with the use of 18-crown-6, up to 41% of the Er{sup 3+} ion can be extracted from water to chloroform, whereas the extraction yield for the Pr{sup 3+} ion, under the same experimental conditions, was only 28%. The thermal lens technique was used to determine the stoichiometry of the extracted ion pair complexes.

  2. Chiral recognition of amino acid enantiomers by a crown ether: chiroptical IR-VCD response and computational study.

    PubMed

    Avilés-Moreno, Juan Ramón; Quesada-Moreno, María Mar; López-González, Juan Jesús; Martínez-Haya, Bruno

    2013-08-15

    We report on a combined experimental and computational study of the chiral recognition of the amino acid serine in protonated form (L/D-SerH(+)), by the crown ether (all-S)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (S-18c6H4). Infrared and vibrational circular dichroism spectroscopies (IR-VCD) are employed to characterize the chiroptical response of the complexes formed by S-18c6H4 with the L-SerH(+) and D-SerH(+) enantiomers in dried thin films obtained from aqueous solutions. The study focuses on vibrational modes directly related to the intermolecular hydrogen bonds between the crown ether derivative and serine, responsible for crown-serine binding, namely, the C═O and C-O stretching modes, and on the C-O-H bending mode, which yield intense IR and VCD signals in the range of wavenumbers 900-2000 cm(-1). The experimental spectra are analyzed in combination with a computational structural survey and optimization at different levels of density functional theory. The conformational landscape of the complexes is found to be primarily governed by a bowl-like structure of the crown ether host and a tripodal coordination of the protonated R-NH3(+) group of serine with the oxygen atoms of the central ether ring. Additionally, one or two of the carboxylic side groups of the crown ether interact with the -COH and -COOH groups of serine. Chiral selectivity is probed by recording the IR and VCD spectra of dried thin films obtained from aqueous solutions with equimolar concentrations of the two serine enantiomers and the macrocycle. The results demonstrate a marked chiral recognition of L-SerH(+) relative to D-SerH(+) by the S-18c6H4 substrate, which arises from the favorable host-guest coordination through H-bonds at optimum distances and collinear orientations, also involving a limited distortion of the crown ether backbone.

  3. [2]pseudorotaxane formation with N-benzylanilinium axles and 24-crown-8 ether wheels.

    PubMed

    Loeb, Stephen J; Tiburcio, Jorge; Vella, Sarah J

    2005-10-27

    [reaction: see text] As a hybrid of the N,N-dibenzylammonium and 1,2-bis(pyridinium)ethane axles, various N-benzylanilinium cations were investigated as suitable axles for the formation of [2]pseudorotaxanes with the 24-membered crown ethers 24C8 and DB24C8. The effect of electron-donating OCH(3) and electron-withdrawing CF(3) groups on both the anilinium and benzyl aromatic rings was studied. Formation constants and structural details were compared to the [2]pseudorotaxanes formed by the two aforementioned dibenzylammonium and 1,2-bis(pyridinium)ethane axles.

  4. Arginine-responsive terbium luminescent hybrid sensors triggered by two crown ether carboxylic acids.

    PubMed

    Jiang, Lasheng; Tang, Ke; Ding, Xiaoping; Wang, Qianming; Zhou, Zhan; Xiao, Rui

    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. © 2013.

  5. Multipodal coordination of a tetracarboxylic crown ether with NH4+: A vibrational spectroscopy and computational study

    NASA Astrophysics Data System (ADS)

    Hurtado, Paola; Gámez, Francisco; Hamad, Said; Martínez-Haya, Bruno; Steill, Jeffrey D.; Oomens, Jos

    2012-03-01

    The elucidation of the structural requirements for molecular recognition by the crown ether (18-crown-6)-2,3,11,12-tetracarboxylic acid (18c6H4) and its cationic complexes constitutes a topic of current fundamental and practical interest in catalysis and analytical sciences. The flexibility of the central ether ring and its four carboxyl side arms poses important challenges to experimental and theoretical approaches. In this study, infrared action vibrational spectroscopy and quantum mechanical computations are employed to characterize the conformational structure of the isolated gas phase complex formed by the 18c6H4 host with NH_4^+ as guest. The results show that the most stable gas-phase structure is a barrel-like conformation sustained by tetrapodal H-bonding of the ammonia cation with two C=O side groups and with four oxygen atoms of the ether ring in a bifurcated arrangement. Interestingly, a similar structure had been proposed in previous crystallographic studies. The experiment also provides evidence for a significant contribution of a higher energy bowl-like conformer with features resembling those adopted by 18c6H4 in the analogous complexes with secondary amines. Such a conformation displays H-bonding between confronted side carboxyl groups and tetrapodal binding of the NH_4^+ with the ether ring and with one C=O group. Structures involving even more extensive intramolecular H-bonding in the 18c6H4 substrate are found to lie higher in energy and are ruled out by the experiment.

  6. An investigation of the surface chemistry of crown ethers: the adsorption and reaction of 12-crown-4 on palladium ( 1 1 1 )

    NASA Astrophysics Data System (ADS)

    Azad, S.; Laack, B.; Tysoe, W. T.

    2002-01-01

    The adsorption of 12-crown-4 on Pd(1 1 1) is investigated using reflection-absorption infrared spectroscopy and temperature-programmed desorption. Analysis of the infrared spectrum of 12-crown-4 suggests that it adsorbs in a flat-lying geometry with C 4v symmetry with a saturation coverage of 0.073±0.008 monolayers. This implies that the crown ether bonds to the surface via the lone pair orbitals on the ether oxygen atoms. Estimating the saturation coverage for this geometry using Van der Waals' radii yields a value of 0.088 monolayers in good agreement with the measured value. 12-crown-4 thermally decomposes to leave predominantly CO and ethylidyne species on the surface where the desorbing CO removes three of the four crown ether oxygen atoms, the fourth remaining on the surface. Small amounts of ethylene are also found to desorb along with a high molecular weight product which is tentatively assigned to the formation of C 2H 5OCH 2CHO.

  7. Functionalized mesoporous silicas with crown ether moieties for selective adsorption of lithium ions in artificial sea water.

    PubMed

    Sung, Soo Park; Moorthy, Madhappan Santha; Song, Hyun-Jin; Ha, Chang-Sik

    2014-11-01

    Lithium ion has been increasingly recognized in a wide range of industrial applications. In this work, we studied on the adsorption of Li+ in the artificial seawater with high selectivity using methyl-crown ether (AC-SBA-15) and aza-crown ether (HMC-SBA-15) moieties-functionalized mesoporous silica materials. First, methyl-crown ether and aza-crown ether moieties-functionalized mesoporous silica materials were synthesized via two-step post-synthesis process using a grafting method. The functionalized materials were employed to the metal ion adsorption from aqueous solution (artificial seawater) containing Li+, Co2+, Cr3+ and Hg2+. The prepared hybrid material showed high selectivity for Li+ ion in the artificial seawater at pH 8.0. The absorbed amount of Li+ was 73 times higher than Cr3+ for aza-crown ether containing AC-SBA-15 as an absorbent. The absorbed amount of Co2+ (4.5 x 10(-5) mol/g), Cr3+ (1.5 x 10(-5) mol/g) and Hg2+ (2.25 x 10(-4) mol/g) were remarkably lower than the case of Li+. On the other hand, the absorbed amount of various metal ions of HMC-SBA-15 with amine groups in alky chains and crown ether moieties were 1.1 x 10(-3) mol/g for Li+, 5.0 x 10(-5) mol/g for Co2+, 2.9 x 10(-4) mol/g for Cr3+, 2.8 x 10(-4) mol/g for Hg2+ mol/g, respectively.

  8. Computational Study of Nanosized Drug Delivery from Cyclodextrins, Crown Ethers and Hyaluronan in Pharmaceutical Formulations.

    PubMed

    Torrens, Francisco; Castellano, Gloria

    2015-01-01

    The problem in this work is the computational characterization of cyclodextrins, crown ethers and hyaluronan (HA) as hosts of inclusion complexes for nanosized drug delivery vehicles in pharmaceutical formulations. The difficulty is addressed through a computational study of some thermodynamic, geometric and topological properties of the hosts. The calculated properties of oligosaccharides of D-glucopyranoses allow these to act as co-solvents of polyanions in water. In crown ethers, the central channel is computed. Mucoadhesive polymer HA in formulations releases drugs in mucosas. Geometric, topological and fractal analyses are carried out with code TOPO. Reference calculations are performed with code GEPOL. From HA to HA·3Ca and hydrate, the hydrophilic solvent-accessible surface varies with the count of H-bonds. The fractal dimension rises. The dimension of external atoms rises resulting 1.725 for HA. It rises going to HA·3Ca and hydrate. Nonburied minus molecular dimension rises and decays. Hydrate globularity is lower than O(water), Ca(2+) and O(HA). Ca(2+) rugosity is smaller than for hydrate, O(HA) and O(water). Ca(2+) and O(water) accessibilities are greater than hydrate. Conclusions are drawn on: (1) the relative stability of linear/cyclic and shorter/larger polymers; (2) the atomic analysis of properties allows determining the atoms with maximum reactivity.

  9. Alkali-Ion-Crown Ether in Art and Conservation: The Applied Bioinorganic Chemistry Approach

    PubMed Central

    Hilfrich, Uwe; Taylor, Harold; Weser, Ulrich

    2004-01-01

    Dried varnish is rich in many ester moieties, which may be broken down into small, soluble compounds by esterase activity or alkaline hydrolysis. Two methods for varnish removal have been developed, including the treatment of either lipase or RbOH / PEG-400 crown ether which allow aged oil varnishes or paint coverings to be removed or thinned. These techniques are designed to proceed in a controlled manner without damaging lower paint or base layers. Unfortunately, lipase did not react with the aged ester groups of dried linseed oil varnish. Surprisingly, the varnish came off in the presence of Tris buffer alone which, in addition, formed reactive metal complexes. A better choice was the use of high Mr alkali ion polyethylene glycol–400 (PEG-400) crown ether type chelates. PEG-400 complexes alkali ions including rubidium and other alkaliions impeding the diffusion of their basic counter ions into lower varnish or paint layers. Possible migration of alkali metal ions into the paint layer during alkaline varnish removal was determined by labelling the cleansing solutions with 86Rb. Fortunately, varnish is degraded on the surface only. Lower paint or varnish layers are not attacked even if chemically similar to the varnish or over painting to be removed as virtually no 86Rb was detected on the paint surface. PMID:18365066

  10. Alkali-ion-crown ether in art and conservation: the applied bioinorganic chemistry approach.

    PubMed

    Hilfrich, Uwe; Taylor, Harold; Weser, Ulrich

    2004-01-01

    Dried varnish is rich in many ester moieties, which may be broken down into small, soluble compounds by esterase activity or alkaline hydrolysis. Two methods for varnish removal have been developed, including the treatment of either lipase or RbOH / PEG-400 crown ether which allow aged oil varnishes or paint coverings to be removed or thinned. These techniques are designed to proceed in a controlled manner without damaging lower paint or base layers. Unfortunately, lipase did not react with the aged ester groups of dried linseed oil varnish. Surprisingly, the varnish came off in the presence of Tris buffer alone which, in addition, formed reactive metal complexes. A better choice was the use of high M(r) alkali ion polyethylene glycol-400 (PEG-400) crown ether type chelates. PEG-400 complexes alkali ions including rubidium and other alkaliions impeding the diffusion of their basic counter ions into lower varnish or paint layers. Possible migration of alkali metal ions into the paint layer during alkaline varnish removal was determined by labelling the cleansing solutions with (86)Rb. Fortunately, varnish is degraded on the surface only. Lower paint or varnish layers are not attacked even if chemically similar to the varnish or over painting to be removed as virtually no (86)Rb was detected on the paint surface.

  11. Photodissociation of protonated tryptophan and alteration of dissociation pathways by complexation with crown ether

    SciTech Connect

    Kadhane, Umesh; Andersen, Jens Ulrik; Ehlerding, Anneli; Hvelplund, Preben; Kirketerp, Maj-Britt S.; Lykkegaard, Morten Koecks; Nielsen, Steen Broendsted; Panja, Subhasis; Wyer, Jean Ann; Zettergren, Henning

    2008-11-14

    The behavior of protonated tryptophan (TrpH{sup +}) and its complex with 18-crown-6-ether (CE) after photoexcitation has been explored based on measurements of dissociation lifetimes, fragmentation channels, and absorption spectra using an electrostatic ion storage ring. A recent implementation of pulsed power supplies for the ring elements with microsecond response times allows us to identify the daughter ion fragment masses and to disentangle fragmentation that occurs from excited states immediately after photoexcitation from that occurring on a longer time scale of several microseconds to milliseconds. We find that attachment of crown ether significantly alters the dissociation channels since it renders the {pi}{sigma}*(NH{sub 3}) state inaccessible and hence prevents the N-H bond breakage which is an important fragmentation channel of TrpH{sup +}. As a result, on a long time scale (>10 {mu}s), photoexcited TrpH{sup +}(CE) decays exponentially whereas TrpH{sup +} displays a power-law decay. The only ions remaining in the latter case are Trp{sup +{center_dot}} radical cations with a broad internal energy distribution caused by the departing hydrogen. Large changes in the fragment branching ratios as functions of excitation wavelength between 210 and 290 nm were found for both TrpH{sup +} and TrpH{sup +}(CE)

  12. Separation of fission products based on ionic liquids: Task-specific ionic liquids containing an aza-crown ether fragment

    SciTech Connect

    Luo, Huimin; Dai, Sheng; Bonnesen, Peter V; Buchanan III, A C

    2005-01-01

    A new class of task-specific ionic liquids (TSILs) based on the covalent attachment of imidazolium cations to a monoaza-crown ether fragment has been synthesized and characterized. The efficacy of these TSILs for the biphasic extraction of Cs(+) and Sr(2+) from aqueous solutions has been evaluated. The extraction properties of these TSILs can be influenced by the structures of the covalently attached imidazolium cations, which highlight the possibilities to enhance or tune the selectivities of crown ethers toward target ionic species through the covalent coupling with the imidazolium cations. (c) 2005 Elsevier B.V. All rights reserved.

  13. Comparison of chiral separations of aminophosphonic acids and their aminocarboxylic acid analogs using a crown ether column.

    PubMed

    Barnhart, Wesley W; Xia, Xiaoyang; Jensen, Randy; Gahm, Kyung H

    2013-07-01

    Crown ethers are capable of complexing with primary amines and have been utilized in chromatography to separate amino acid racemates. This application has been extended to resolve (1-amino-1-phenylmethyl)phosphonic acid and (1-aminoethyl)phosphonic acid racemates, along with their aminocarboxylic acid analogs (2-phenylglycine and alanine, respectively), via a ChiroSil RCA crown ether based chiral stationary phase. Effects of the organic modifier, temperature, and acid type and concentration on retention and selectivity were also investigated. Trends in retention and selectivity varied between aminophosponic acids and their aminocarboxylic analogs. Computer modeling and (1)H NMR analyses were performed to potentially gain a better understanding of interactions of the aforementioned molecules with the ChiroSil RCA chiral stationary phase. Theoretical predictions of the most stable conformations for (R)- and (S)-enantiomers were compared to elution order; it was found that the elution order agreed with molecular modeling such that the longest retention correlated with the predicted most stable complex between the enantiomer and crown ether. (1)H NMR demonstrated interactions of aminophosphonic and aminocarboxylic racemates with (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid in solution and was utilized to determine enantiomeric excess of (1-amino-1-phenylmethyl)phosphonic acid after its enantioenrichment via crystallization through diastereomeric salt formation with the crown ether followed by filtration.

  14. Creation of a ternary complex between a crown ether, 4-aminobenzoic acid and 3,5-dinitrobenzoic acid.

    PubMed

    Boardman, Nicole D; Munshi, Tasnim; Scowen, Ian J; Seaton, Colin C

    2014-02-01

    The creation of ternary multi-component crystals through the introduction of 18-crown-6 to direct the hydrogen-bonding motifs of the other molecular components was investigated for 3,5-dinitrobenzoic acid (3,5-dnba) with 4-aminobenzoic acid (4-aba). The creation of a binary complex between 18-crown-6 and 4-aba (C12H24O6·2C7H7NO2)2 and a ternary salt between 3,5-dnba, 18-crown-6 and 4-aba (C12H24O6·C7H8NO2(+)·C7H3N2O6(-)·C7H4N2O6) were confirmed by single-crystal structure determination. In both structures, the amino molecules bind to the crown ether through N-H...O hydrogen bonds, leaving available only a single O atom site on the crown with restricted geometry to potentially accept a hydrogen bond from 3,5-dnba. While 3,5-dnba and 4-aba form a binary co-crystal containing neutral molecules, the shape-selective nature of 18-crown-6 preferentially binds protonated amino molecules, thereby leading to the formation of the ternary salt, despite the predicted low concentration of the protonated species in the crystallizing solution. Thus, through the choice of crown ether it may be possible to control both location and nature of the available bonding sites for the designed creation of ternary crystals.

  15. An ab initio study of the selective of alkali and alkaline earth metal cations for crown ethers

    SciTech Connect

    Feller, D.F.; Glendening, E.D.; Thompson, M.A.; Hill, S.E.

    1997-12-31

    Crown ethers are a class of macrocyclic polyether that are known to preferentially bind certain cations in potentially complex mixtures of other cations. They are being considered as candidates for separating radioactive cesium (137Cs) and strontium (90Sr) from the high level waste tanks on the Hanford Nuclear Reservation. We present the results of RHF and Mp2 calculations on a variety of crown ethers, including 12-crown-4, 18-crown-6 and Clark Still`s 18-crown-6 derivative. Gas phase calculations show that 18-crown-6 most strongly blinds lithium, but our results indicate that potassium selectivity is recovered with the inclusion of even a small number of waters of hydration in the calculations. Several polarized Gaussian basis sets were used in an effort to derive convergence estimates for the binding enthalpies. The only available experimental values, obtained from FT-ICR experiments by A.R. Katritzky, et al, are over 30 kcal/mol smaller than our best estimate for K+/18-crown-6.

  16. Temperature, Molecular Weight, and Concentration Dependences of Thermal Diffusion for Ethylene Glycol Oligomers and Crown Ethers

    NASA Astrophysics Data System (ADS)

    Maeda, Kousaku; Kita, Rio; Shinyashiki, Naoki; Yagihara, Shin

    The Soret coefficient ST of ethylene glycol oligomers (EGOs) and crown ethers (CEs) in water were obtained by thermal diffusion forced Rayleigh scattering by changing the temperature, molecular weight, and concentration. The effect of a hydroxyl group on the EGOs and the effect of the cyclic structure of CEs on the thermal diffusion were determined systematically by changing the molecular weights of the EGOs and CEs. For dilute aqueous solutions, EGOs and CEs, except EG, show positive ST values that decrease with increasing temperature, which is similar to the results of previous studies on mixtures of water and organic solvents. The temperature dependence of ST changes its behavior from negative to positive with decreasing number of repeating units of EGOs. This behavior is related to the increase in the number density of the hydroxyl group. The ST values of EG show two different concentration regions, namely, the low concentration (0-2 wt %) and high concentration (2-100 wt %) regions.

  17. Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

    PubMed

    Song, Yingying; Cheng, Chen; Jing, Huanwang

    2014-09-26

    Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions.

  18. Coordination effect-regulated CO2 capture with an alkali metal onium salts/crown ether system

    SciTech Connect

    Yang, Zhen-Zhen; Jiang, Deen; Zhu, Xiang; Tian, Chengcheng; Brown, Suree; Do-Thanh, Chi-Linh; He, Liang-Nian; Dai, Sheng

    2014-01-01

    A coordination effect was employed to realize equimolar CO2 absorption, adopting easily synthesized amino group containing absorbents (alkali metal onium salts). The essence of our strategy was to increase the steric hindrance of cations so as to enhance a carbamic acid pathway for CO2 capture. Our easily synthesized alkali metal amino acid salts or phenolates were coordinated with crown ethers, in which highly sterically hindered cations were obtained through a strong coordination effect of crown ethers with alkali metal cations. For example, a CO2 capacity of 0.99 was attained by potassium prolinate/18-crown-6, being characterized by NMR, FT-IR, and quantum chemistry calculations to go through a carbamic acid formation pathway. The captured CO2 can be stripped under very mild conditions (50 degrees C, N-2). Thus, this protocol offers an alternative for the development of technological innovation towards efficient and low energy processes for carbon capture and sequestration.

  19. Molecular logic gates based on benzo-18-crown-6 ether of styrylquinoline: a theoretical study.

    PubMed

    Tzeli, Demeter; Petsalakis, Ioannis D; Theodorakopoulos, Giannoula

    2016-11-30

    In the present work, we examine the possibility of a benzo-18-crown-6 ether of styrylquinoline molecule (1) in acetonitrile solvent to act as a sensor for the Ca(++) cation and as a molecular logical gate. DFT and TDDFT calculations are carried out using the M06-2X and the PBE0 functionals. The quinoline moiety is an electron donor and an H(+) receptor, while the crown ether is a Ca(++) receptor forming host-guest complexes with Ca(++). The calculations show that there are 8 thermally stable forms, i.e., trans and cis isomers of neutral (1), protonated (1H+), complexed with Ca(++) (1Ca++), and both protonated and Ca(++) complexed (1H+Ca++), with different absorption and emission spectra, and which can be interconverted from one form to another. The addition of H(+) and/or Ca(++) to 1 results in variation of the oscillator strength of the major absorption and emission peaks as well as in significant shifts of the major absorption and emission peaks including shifting from the vis spectral area to UV and vice versa. Consequently, 1 is a candidate for a sensor for the Ca(++) cation. Furthermore it is shown that 1 can act as a molecular optical switch owing to its ability to be reversibly protonated and/or Ca(++) complexed with substantial accompanying differences in the spectral properties. Similarly, 1 can be used as a sensor molecular logic gate, in which using H(+) and Ca(++) and irradiation as input, the emission output at 500, 470, 430, and 407 nm can be utilized as output to build AND, NOR, XOR, XNOR, INHIBIT, and IMPLICATION logic gates.

  20. Laser Spectroscopic Study of Cold Gas-Phase Host-Guest Complexes of Crown Ethers.

    PubMed

    Ebata, Takayuki; Inokuchi, Yoshiya

    2016-06-01

    The structure, molecular recognition, and inclusion effect on the photophysics of guest species are investigated for neutral and ionic cold host-guest complexes of crown ethers (CEs) in the gas phase. Here, the cold neutral host-guest complexes are produced by a supersonic expansion technique and the cold ionic complexes are generated by the combination of electrospray ionization (ESI) and a cryogenically cooled ion trap. The host species are 3n-crown-n (3nCn; n = 4, 5, 6, 8) and (di)benzo-3n-crown-n ((D)B3nCn; n = 4, 5, 6, 8). For neutral guests, we have chosen water and aromatic molecules, such as phenol and benzenediols, and as ionic species we have chosen alkali-metal ions (M(+) ). The electronic spectra and isomer-specific vibrational spectra for the complexes are observed with various laser spectroscopic methods: laser-induced fluorescence (LIF); ultraviolet-ultraviolet hole-burning (UV-UV HB); and IR-UV double resonance (IR-UV DR) spectroscopy. The obtained spectra are analyzed with the aid of quantum chemical calculations. We will discuss how the host and guest species change their flexible structures for forming best-fit stable complexes (induced fitting) and what kinds of interactions are operating for the stabilization of the complexes. For the alkali metal ion•CE complexes, we investigate the solvation effect by attaching water molecules. In addition to the ground-state stabilization problem, we will show that the complexation leads to a drastic effect on the excited-state electronic structure and dynamics of the guest species, which we call a "cage-like effect".

  1. Schiff's Bases and Crown Ethers as Supramolecular Sensing Materials in the Construction of Potentiometric Membrane Sensors.

    PubMed

    Faridbod, Farnoush; Ganjali, Mohammad Reza; Dinarvand, Rassoul; Norouzi, Parviz; Riahi, Siavash

    2008-03-11

    Ionophore incorporated PVC membrane sensors are well-established analyticaltools routinely used for the selective and direct measurement of a wide variety of differentions in complex biological and environmental samples. Potentiometric sensors have someoutstanding advantages including simple design and operation, wide linear dynamic range,relatively fast response and rational selectivity. The vital component of such plasticizedPVC members is the ionophore involved, defining the selectivity of the electrodes' complexformation. Molecular recognition causes the formation of many different supramolecules.Different types of supramolecules, like calixarenes, cyclodextrins and podands, have beenused as a sensing material in the construction of ion selective sensors. Schiff's bases andcrown ethers, which feature prominently in supramolecular chemistry, can be used assensing materials in the construction of potentiometric ion selective electrodes. Up to now,more than 200 potentiometric membrane sensors for cations and anions based on Schiff's bases and crown ethers have been reported. In this review cation binding and anioncomplexes will be described. Liquid membrane sensors based on Schiff's bases and crownethers will then be discussed.

  2. Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

    DOEpatents

    Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.; Presley, Derek J.

    2001-01-01

    A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

  3. Macrocyclic Gd(3+) complexes with pendant crown ethers designed for binding zwitterionic neurotransmitters.

    PubMed

    Oukhatar, Fatima; Meudal, Hervé; Landon, Céline; Logothetis, Nikos K; Platas-Iglesias, Carlos; Angelovski, Goran; Tóth, Éva

    2015-07-27

    A series of Gd(3+) complexes exhibiting a relaxometric response to zwitterionic amino acid neurotransmitters was synthesized. The design concept involves ditopic interactions 1) between a positively charged and coordinatively unsaturated Gd(3+) chelate and the carboxylate group of the neurotransmitters and 2) between an azacrown ether appended to the chelate and the amino group of the neurotransmitters. The chelates differ in the nature and length of the linker connecting the cyclen-type macrocycle that binds the Ln(3+) ion and the crown ether. The complexes are monohydrated, but they exhibit high proton relaxivities (up to 7.7 mM(-1)  s(-1) at 60 MHz, 310 K) due to slow molecular tumbling. The formation of ternary complexes with neurotransmitters was monitored by (1) H relaxometric titrations of the Gd(3+) complexes and by luminescence measurements on the Eu(3+) and Tb(3+) analogues at pH 7.4. The remarkable relaxivity decrease (≈80 %) observed on neurotransmitter binding is related to the decrease in the hydration number, as evidenced by luminescence lifetime measurements on the Eu(3+) complexes. These complexes show affinity for amino acid neurotransmitters in the millimolar range, which can be suited to imaging concentrations of synaptically released neurotransmitters. They display good selectivity over non-amino acid neurotransmitters (acetylcholine, serotonin, and noradrenaline) and hydrogenphosphate, but selectivity over hydrogencarbonate was not achieved.

  4. Equilibria and effect of diluent in the solvent extraction of lithium salts by highly alkylated 14-crown-4-ethers

    SciTech Connect

    Moyer, B.A.; Sachleben, R.A.; Sun, Y.; Driver, J.L.; Chen, Z. Cavenaugh, K.L.; Carter, R.W.; Baes, C.F. Jr.

    1996-12-31

    As shown by survey experiments, 14-crown-4 ethers bearing certain aliphatic substituents exhibit strong selectivity for lithium. Both selectivity and overall extraction efficiency depend markedly on type of ring substituents and on diluent properties. To understand such effects in greater detail, extraction of LiCl by the crown ether 2,2,3,3,6,9,9,10,10-nonamethyl-14-crown-4 (NM14C4) was subjected to equilibrium analysis. By use of the program SXLSQI (a solvent-extraction modeling program), the extraction behavior as determined by ion chromatography has been modeled quantitatively in terms of four equilibrium in 1-octanol. The following neutral and ionic organic-phase species have been considered: LiCl, Li+, Cl{sup {minus}}, LiCECl, and LiCE+ (CE = crown ether). Parallel measurements of the same system by {sup 7}Li NMR techniques agree with the ion-chromatography results. The NMR experiment affords the advantage of distinguishing between free and bound lithium and thus provides a check on the species indicated by the modeling. Extraction of LiCl by NM 14C4 correlates with diluent properties, including the Shmidt-Marcus diluent parameter and Reichardt`s E{sub T} parameter; as diluent polarity increases, LiCl extraction increases steeply.

  5. An ab initio study of the selective binding of alkali and alkaline earth metal cations for crown ethers

    SciTech Connect

    Feller, D.F.; Glendening, E.D.; Thompson, M.A.

    1995-12-31

    Crown ethers are a class of macrocyclic polyether that are known to preferentially bind certain cations in potentially complex mixtures of other cations. They are being considered as candidates for separating radioactive cesium ({sup 137}Cs) and strontium ({sup 90}Sr) from the high level waste tanks on the Hanford Nuclear Reservation. We present the results of RHF and MP2 calculations on a variety of crown ethers, including 18-crown-6, which is known to prefer potassium in polar solvents. Gas phase calculations show that 18-crown-6 most strongly binds lithium, but our results indicate that potassium selectivity is recovered with the inclusion of even a small number of waters of hydration in the calculations. A variety of Gaussian basis sets (3-21G, 6-31+G* and correlation consistent) were employed in an effort to derive convergence estimates for the binding enthalpies. The only available experimental values, obtained from FT-ICR experiments by A.R. Katritzky et al., Rapid Comm. Mass Spect., 6, 25 (1992), are over 30 kcal/mol smaller than our best estimate for K+/18-crown-6.

  6. SYNTHESIS OF NOVEL CROWN ETHERS BEARING THE exo-cis-2,3-NORBORNYL GROUP AS POTENTIAL Na+ AND K+ EXTRACTANTS

    SciTech Connect

    Robeson, R.M.; Bonnesen, P.

    2007-01-01

    The synthesis of a series of novel dinorbornyl-16-crown-5 and dinorbornyl-18-crown-6 ethers that incorporate the exo-cis-2,3-norbornyl moiety within the macrocycle framework is described. The key starting material for the crown ethers, exo-cis-2,3-norbornanediol, was successfully prepared on a large (>30g) scale in 88% yield from norbornylene by osmium tetroxide-catalyzed hydroxylation. The syn and anti isomers of the dinorbornyl-16-crown-5 ether family were prepared using diethylene glycol with ring closure achieved using a methallyl linkage. The isomers cis-syn-cis and cis-anti-cis di-norbornano-15-methyleno-16-crown-5 (6A and 6B) could be separated using column chromatography, and a single crystal of the syn isomer 6A suitable for X-ray crystal structure analysis was obtained, thereby confi rming the syn orientation. The syn and anti isomers of the dinorbornyl-18-crown-6 ether family were successfully prepared employing a different synthetic strategy, involving the potassium–templated cyclization of two bis-hydroxyethoxy-substituted exo-cis-2,3-norbornyl groups under high dilution conditions. Attempts to fully separate cis-syn-cis di-norbornano-18-crown-6 (10A) and cis-anti-cis di-norbornano-18-crown-6 (10B) from one another using column chromatography were unsuccessful. All intermediates and products were checked for purity using either thin layer chromatography or gas chromatography, and characterized by proton and carbon NMR. Crown ethers 6AB and 10AB are to our knowledge the fi rst crown ethers to incorporate the exo-cis-2,3-norbornyl moiety into the crown ring to be successfully synthesized and characterized.

  7. Alkaline-side extraction of technetium from tank waste using crown ethers and other extractants

    SciTech Connect

    Bonnesen, P.V.; Moyer, B.A.; Presley, D.J.; Armstrong, V.S.; Haverlock, T.J.; Counce, R.M.; Sachleben, R.A.

    1996-06-01

    The chemical development of a new crown-ether-based solvent-extraction process for the separation of (Tc) from alkaline tank-waste supernate is ready for counter-current testing. The process addresses a priority need in the proposed cleanup of Hanford and other tank wastes. This need has arisen from concerns due to the volatility of Tc during vitrification, as well as {sup 99}Tc`s long half-life and environmental mobility. The new process offers several key advantages that direct treatability--no adjustment of the waste composition is needed; economical stripping with water; high efficiency--few stages needed; non-RCRA chemicals--no generation of hazardous or mixed wastes; co-extraction of {sup 90}Sr; and optional concentration on a resin. A key concept advanced in this work entails the use of tandem techniques: solvent extraction offers high selectivity, while a subsequent column sorption process on the aqueous stripping solution serves to greatly concentrate the Tc. Optionally, the stripping solution can be evaporated to a small volume. Batch tests of the solvent-extraction and stripping components of the process have been conducted on actual melton Valley Storage Tank (MVST) waste as well as simulants of MVST and Hanford waste. The tandem process was demonstrated on MVST waste simulants using the three solvents that were selected the final candidates for the process. The solvents are 0.04 M bis-4,4{prime}(5{prime})[(tert-butyl)cyclohexano]-18-crown-6 (abbreviated di-t-BuCH18C6) in a 1:1 vol/vol blend of tributyl phosphate and Isopar{reg_sign} M (an isoparaffinic kerosene); 0.02 M di-t-BuCH18C6 in 2:1 vol/vol TBP/Isopar M and pure TBP. The process is now ready for counter-current testing on actual Hanford tank supernates.

  8. Coordination properties of a diarylaza crown ether appended with a luminescent [Ru(bipy)3]2+ unit.

    PubMed

    Charbonnière, Loïc J; Ziessel, Raymond F; Sams, Craig A; Harriman, Anthony

    2003-06-02

    The [Ru(bipy)(2)(1)](PF(6))(2) (bipy refers to 2,2'-bipyridine) complex, comprising a ruthenium(II) tris(2,2'-bipyridine) luminophore covalently linked to a di[(o-triethyleneglycoxy)phenyl]amine crown ether 1, has been synthesized and fully characterized. The photophysical properties of this metal complex have been examined in solution at ambient temperature. Luminescence from the metal complex is enhanced significantly in the presence of various adventitious cations, including protons. In particular, Li(+) cations bind to the crown ether, as evidenced by (1)H NMR and luminescence spectroscopy. Cation binding serves to decrease the rate of reductive quenching of the triplet state of the metal complex, thereby increasing the extent of luminescence. The solution-phase conformation of [Ru(bipy)(2)(1)](PF(6))(2), with and without encapsulated Li(+), has been examined by 2-D NMR and by molecular dynamics simulations.

  9. Fluoroponytailed crown ethers and quaternary ammonium salts as solid-liquid phase transfer catalysts in organic synthesis.

    PubMed

    Pozzi, Gianluca; Fish, Richard H

    2012-01-01

    Fluorous derivatives of dibenzo-18-crown-6 ether were prepared, and then successfully applied in representative solid-liquid phase transfer catalysis reactions, which were performed in standard organic solvents, such as chlorobenzene and toluene, as well as in fluorous solvents, such as perfluoro-1,3-dimethylcyclohexane. It was clearly shown that properly designed fluoroponytailed crown ethers could promote the disintegration of the crystal lattice of alkali salts, and transfer anions from the solid surface into an apolar, non-coordinating perfluorocarbon phase, for phase transfer catalysis reactions in organic synthesis. Furthermore, 3,5-bis(perfluorooctyl)benzyl bromide and triethylamine were reacted under mild conditions to provide an analogue of the versatile phase transfer catalyst, benzyltriethylammonium chloride, containing two fluoroponytails. This fluoroponytailed quaternary ammonium salt was also successfully employed as a catalyst in a variety of organic reactions conducted under solid-liquid phase transfer catalysis conditions, without a perfluorocarbon phase. Thus, being both hydrophobic and lipophobic, fluorous crown ethers and ammonium salts, could be rapidly recovered in quantitative yields, and reused without loss of activity, over several reaction cycles.

  10. Separation of calcium-48 isotope by crown ether chromatography using ethanol/hydrochloric acid mixed solvent.

    PubMed

    Okumura, Shin; Umehara, Saori; Fujii, Yasuhiko; Nomura, Masao; Kaneshiki, Toshitaka; Ozawa, Masaki; Kishimoto, Tadafumi

    2015-10-09

    Benzo-18-crown-6 ether resin embedded in porous silica beads was synthesized and used as the packing material for chromatographic separation of (48)Ca isotope. The aim of the present work is to develop efficient isotope enrichment process for double β decay nuclide (48)Ca. To this end, ethanol/HCl mixed solvent was selected as the medium for the chromatographic separation. Adsorption of calcium on the resin was studied at different HCl concentrations and different ethanol mixing ratios in batch-wise experiments. A very interesting phenomenon was observed; Ca adsorption is controlled not by the overall HCl concentration of the mixed solvent, but by the initial concentration of added HCl solution. Calcium break-through chromatography experiments were conducted by using 75v/v% ethanol/25v/v% 8M HCl mixed solvent at different flow rates. The isotope separation coefficient between (48)Ca and (40)Ca was determined as 3.8×10(-3), which is larger than that of pure HCl solution system. Discussion is extended to the chromatographic HETP, height equivalent to a theoretical plate. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

    PubMed

    Marin, Timothy W; Shkrob, Ilya A; Dietz, Mark L

    2011-04-14

    Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {H(3)O(+)•CE}NO(3)(-) complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.

  12. Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

    SciTech Connect

    Marin, T.; Shkrob, I.; Dietz, M.

    2011-04-14

    Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.

  13. Squalyl Crown Ether Self-Assembled Conjugates: An Example of Highly Selective Artificial K(+) Channels.

    PubMed

    Sun, Zhanhu; Gilles, Arnaud; Kocsis, Istvan; Legrand, Yves-Marie; Petit, Eddy; Barboiu, Mihail

    2016-02-01

    The natural KcsA K(+) channel, one of the best-characterized biological pore structures, conducts K(+) cations at high rates while excluding Na(+) cations. The KcsA K(+) channel is of primordial inspiration for the design of artificial channels. Important progress in improving conduction activity and K(+) /Na(+) selectivity has been achieved with artificial ion-channel systems. However, simple artificial systems exhibiting K(+) /Na(+) selectivity and mimicking the biofunctions of the KcsA K(+) channel are unknown. Herein, an artificial ion channel formed by H-bonded stacks of squalyl crown ethers, in which K(+) conduction is highly preferred to Na(+) conduction, is reported. The K(+) -channel behavior is interpreted as arising from discreet stacks of dimers resulting in the formation of oligomeric channels, in which transport of cations occurs through macrocycles mixed with dimeric carriers undergoing dynamic exchange within the bilayer membrane. The present highly K(+) -selective macrocyclic channel can be regarded as a biomimetic alternative to the KcsA channel.

  14. Selective cesium removal from radioactive liquid waste by crown ether immobilized new class conjugate adsorbent.

    PubMed

    Awual, Md Rabiul; Yaita, Tsuyoshi; Taguchi, Tomitsugu; Shiwaku, Hideaki; Suzuki, Shinichi; Okamoto, Yoshihiro

    2014-08-15

    Conjugate materials can provide chemical functionality, enabling an assembly of the ligand complexation ability to metal ions that are important for applications, such as separation and removal devices. In this study, we developed ligand immobilized conjugate adsorbent for selective cesium (Cs) removal from wastewater. The adsorbent was synthesized by direct immobilization of dibenzo-24-crown-8 ether onto inorganic mesoporous silica. The effective parameters such as solution pH, contact time, initial Cs concentration and ionic strength of Na and K ion concentrations were evaluated and optimized systematically. This adsorbent was exhibited the high surface area-to-volume ratios and uniformly shaped pores in case cavities, and its active sites kept open functionality to taking up Cs. The obtained results revealed that adsorbent had higher selectivity toward Cs even in the presence of a high concentration of Na and K and this is probably due to the Cs-π interaction of the benzene ring. The proposed adsorbent was successfully applied for radioactive Cs removal to be used as the potential candidate in Fukushima nuclear wastewater treatment. The adsorbed Cs was eluted with suitable eluent and simultaneously regenerated into the initial form for the next removal operation after rinsing with water. The adsorbent retained functionality despite several cycles during sorption-elution-regeneration operations. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Synergistic ion-pair extraction of lanthanide(III) with thenoyltrifluoroacetone and crown ether into 1,2-dichloroethane

    SciTech Connect

    Kitatsuji, Yoshihiro; Meguro, Yoshihiro; Yoshida, Zenko; Yamamoto, Tadashi; Nishizawa, Kazushige

    1995-03-01

    Synergistic extraction of trivalent lanthanides(Ln) was investigated using thenoyltrifluoroacetone(HTTA) and crown ether(CE). Characteristic ion-pair extraction of the lighter Ln(III) was observed with 1,2-dichloroethane containing HTTA and 18-crown-6 or dicyclohexano-18-crown-6, in which the cationic complex, Ln(TTA){sub 2}CE{sup +}, was formed and extracted. Remarkable increases of an extractability and a selectivity were attained in the synergistic ion-pair extraction of the lighter Ln ions, which could be elucidated on the basis of size-fitting effect in the complex formation of the lighter Ln ions with CE. 19 refs., 2 figs., 3 tabs.

  16. Luminescence detection of rare-earth ions by energy transfer from counteranion to crown ether-lanthanide ion complexes

    SciTech Connect

    Tran, C.D.; Zhang, Weifeng )

    1990-04-15

    A novel method has been developed to enhance the sensitivity and selecitivity of the luminescence detection for lanthanide ions. In this method, the lanthanide ion, crown ether, and benzoate were compartmentalized into an ion pair complex in order to eliminate the quenching and to induce the energy transfer so that the luminescence detection for the lanthanide ions can be selectively enhanced. The molecular organization is achieved by using a crown ether such as 18-crown-6 or 15-crown-5 as the synergistic extracting agent and benzoate as the counterion to selectively extract the rare-earth ions from water into an organic solvent where they are subsequently determined by luminescence technique. Compared to lanthanide ions in aqueous solutions, the luminescence intensity of the extracted ion pair complexes is substantially enhanced. The luminescence intensities of the Tb{sup 3+}, Eu{sup 3+}, and Dy{sup 3+} ions were enhanced up to 4 times when they were extracted into ethyl acetate or into chloroform. The total enhancement by the extraction and energy transfer processes can, therefore, be up to 67 times. The mechanism of energy transfer and the use of this technique to measure the selective extractions of Tb{sup 3+}, Eu{sup 3+}, and Dy{sup 3+} ions are discussed.

  17. Equilibria and speciation in the solvent extraction of lithium chloride by nonamethyl-14-crown-4 ether in 1-octanol

    SciTech Connect

    Sun, Y.; Chen, Z.; Cavenaugh, K.L.; Sachleben, R.A.; Moyer, B.A.

    1996-05-30

    The equilibria and speciation in the solvent extraction of LiCl by nonamethyl-14-crown-4 ether in 1-octanol have been determined by use of ion chromatography (IC) and inductively coupled plasma (ICP) analyses, equilibrium modeling with the program SXLSQI, and {sup 7}Li NMR measurements. SXLSQI modeling of the extraction data indicates the formation of a 1:1 metal:crown complex in the organic phase. The complex apparently exists as an ion-pair Li(crown)Cl, which partially dissociates to the complex cation Li(crown){sup +} and free chloride anion Cl{sup -}. Extraction of LiCl by 1-octanol to give the organic-phase ion-pair LiCl and its dissociated ions Li{sup +} and Cl{sup -} must be included in the data analysis. {sup 7}Li NMR measurements verify the existence of free and crown-complexed lithium species in 1-octanol, and the measurements quantitatively agree with results from the SXLSQI model. 41 refs., 4 figs., 2 tabs.

  18. A taco complex derived from a bis-crown ether capable of executing molecular logic operation through reversible complexation.

    PubMed

    Mandal, Amal Kumar; Das, Priyadip; Mahato, Prasenjit; Acharya, Suhash; Das, Amitava

    2012-08-17

    As learned from natural systems, self-assembly and self-sorting help in interconnecting different molecular logic gates and thus achieve high-level logic functions. In this context, demonstration of important logic operations using changes in optical responses due to the formation of molecular assemblies is even more desirable for the construction of a molecular computer. Synthesis of an appropriate divalent as well as a luminescent crown ether based host 1 and paraquat derivatives, 2(PF(6))(2) and 3(PF(6))(2), as guests helped in demonstrating a reversible [3](taco complex) (1·{2(PF(6))(2)}(2) or 1·{3(PF(6))(2)}(2)) formation in nonpolar solvent. Detailed (1)H NMR studies revealed that two paraquat units were bound cooperatively by the two crown units in 1. Because of preorganization, the flexible host molecule 1 adopts a folded conformation, where each of two paraquat units remain sandwiched between the two aromatic units of each folded crown ether moiety in 1. Disassembly of the "taco" complex in the presence of KPF(6) and reassembly on subsequent addition of DB18C6 was initially demonstrated by (1)H NMR spectral studies, which were subsequently corroborated through luminescence spectral studies. Further, luminescence spectral responses as output signals with appropriate and two independent molecular inputs could be correlated to demonstrate basic logic operation like OR and YES gates, while the results of the three molecular inputs could be utilized to demonstrate important logic operation like an INHIBIT gate.

  19. Characterization of the homologs of flerovium with crown ether based extraction chromatography resins: studies in nitric acid

    DOE PAGES

    Despotopulos, John D.; Kmak, Kelly N.; Gharibyan, Narek; ...

    2016-09-17

    Eichrom’s Pb resin, a crown-ether-based extraction chromatography resin, was characterized for separation of the flerovium (Fl) homologs, Pb and Sn. Batch uptake of Pb(II) and Sn(IV) radionuclides was determined from an HNO3 matrix. Pb(II) was strongly retained on the resin at all HNO3 concentrations, while Sn(IV) showed no uptake. Extraction kinetics for Pb(II) were examined and show suitable uptake on the second time scale. Here, separation methods for the isolation of individual homologs, Pb(II) and Sn(IV), have been established using 2 mL pre-packed vacuum flow Pb resin columns.

  20. 12-crown-4 ether-assisted enhancement of ionic conductivity and interfacial kinetics in polyethylene oxide electrolytes

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Di Stefano, S.

    1990-01-01

    The electrical and electrochemical properties of thin films of polyethylene oxide electrolytes with and without 12-crown-4 ether (12Cr4) are studied as a function of temperature and in the frequency regime from 100 kHz to 0.1 Hz. These measurements were made on electrolytes containing LiCF3SO3, LiBF4, or LiClO4 salts. At a given temperature, the bulk conductivity for a particular salt depends on the 12Cr4 concentration, reaching a maximum for a ratio of 12Cr4 to Li of 0.003.

  1. 12-crown-4 ether-assisted enhancement of ionic conductivity and interfacial kinetics in polyethylene oxide electrolytes

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Di Stefano, S.

    1990-01-01

    The electrical and electrochemical properties of thin films of polyethylene oxide electrolytes with and without 12-crown-4 ether (12Cr4) are studied as a function of temperature and in the frequency regime from 100 kHz to 0.1 Hz. These measurements were made on electrolytes containing LiCF3SO3, LiBF4, or LiClO4 salts. At a given temperature, the bulk conductivity for a particular salt depends on the 12Cr4 concentration, reaching a maximum for a ratio of 12Cr4 to Li of 0.003.

  2. Mapping the Binding Modes of Hemilabile Pincer-Crown Ether Ligands in Solution Using Diamagnetic Anisotropic Effects on NMR Chemical Shift.

    PubMed

    Camp, Andrew M; Kita, Matthew R; Grajeda, Javier; White, Peter S; Dickie, Diane A; Miller, Alexander J M

    2017-09-05

    A protocol for identifying ligand binding modes in a series of iridium pincer complexes bearing hemilabile aza-crown ether ligands has been developed using readily accessible NMR methods. The approach was tested on a collection of 13 structurally diverse pincer-crown ether complexes that include several newly characterized species. New synthetic routes enable facile interconversion of coordination modes and supporting ligands. Detailed structural assignments of five complexes reveal that the difference in chemical shift (Δδ) between geminal protons in the crown ether is influenced by diamagnetic anisotropy arising from halides and other ligands in the primary coordination sphere. The average difference in chemical shift between diastereotopic geminal protons in the crown ether macrocycle (Δδavg), as determined through a single (1)H-(13)C HSQC experiment, provides information on the pincer ligand binding mode by establishing whether the macrocycle is in close proximity to the metal center. The Δδavg values for binding modes that involve chelating ether(s) bound to iridium are roughly 2-fold larger than those for tridentate complexes with no Ir-O bonds.

  3. Design of a new dental adhesive--effect of a water-soluble sodium acylphosphine oxide with crown ether on adhesion to dental hard tissues.

    PubMed

    Ikemura, Kunio; Ichizawa, Kensuke; Fuchigami, Kiyomi; Ito, So; Endo, Takeshi

    2009-05-01

    The behavior of water-soluble photoinitiators with crown ethers in dental adhesives is unknown. This study investigated the effect of sodium acylphosphine oxide (APO-Na) with crown ether in a hydrophobic adhesive on adhesion to teeth. Sodium 2,4,6-trimethylbenzoyl-phenylphosphine oxide (TMPO-Na = APO-Na) was synthesized in 67.1% yield and identified by 1H NMR. APO-Na was dissolved in hydrophobic resins in the presence of a crown ether (ionophore effect). Thirty kinds of experimental single-step adhesives comprising APO-Na, CE, Bis-GMA, 6-methacryloyloxyhexyl phosphonoacetate (6-MHPA), and 4-methacryloyloxyethyl trimellitic acid (4-MET) were thereby prepared. Shear bond strength to unetched ground teeth was measured at a crosshead speed of 1.0 mm/min, and the data were analyzed by ANOVA. The shear bond strength results of bonding resins containing APO-Na with 18-crown-6-ether (CE-6) were significantly higher than that without CE-6 (control) (p<0.05). Higher bond strength values [for enamel: BR24 at 19.3 (3.2) MPa; for dentin: BR29 at 20.2 (4.7) MPa] were achieved with the adhesives containing APO-Na, CE-6, 6-MHPA, and 4-MET. Therefore, it was found that APO-Na with CE-6 contributed to the efficient bonding performance of single-step adhesive to teeth. However, in view of the biosafety hazard posed by crown ethers, the search is still on for reagents that are biologically safer than crown ethers--but with ionophor effects--to be used in dental adhesives.

  4. Water Ionic Liquid-Crown Ether System Controlling Morphologies and Sizes of Soluble Polypyrrole Nanostructures and Their Self-Assembly Behaviors in the System

    NASA Astrophysics Data System (ADS)

    Yavari, Issa; Kowsari, Elaheh

    The present study reports a novel chemical route to synthesize different sizes of conducting polypyrrol (ppy) nanoparticles by hydrogen-bonding directionality in the presence of a crown ether, ionic liquid ([octmim]Br, octhyl-methyl imidazulim bromide) and ammonium persulfate in HCl solution. The morphology of the nanoparticle of PPy was confirmed by SEM images. The effects of reaction conditions on the morphology of the resultant ppy nanostructures were studied. The conductivity of the product varied with the mass ratio of aniline monomer to crown ether and IL. The chemical and electronic structures of the ppy nanoparticle were also studied by FT-IR and UV-Vis spectrometry, respectively.

  5. Extraction of protactinium-233 and separation from thermal neutron-irradiated thorium-232 using crown ethers

    SciTech Connect

    Jalhoom, Moayyed G.; Mohammed, Dawood A.; Khalaf, Jumah S.

    2008-07-01

    A new method was developed for the extraction and separation of {sup 233}Pa from thermal neutron-irradiated {sup 232}Th. Solutions of Pa{sup 233} were prepared in LiCI-HCl solutions from which appreciable extraction was obtained using dibenzo-18-crown-6 in 1,2-dichloroethane. The effects of cavity size, substitutions on the crown ring, type of the organic solvent, and temperature on extraction are discussed. Very high separation factors were obtained for the pairs {sup 233}Pa/{sup 232}Th (>105), {sup 233}Pa/{sup 233}U (> 1000), and {sup 232}U/{sup 232}Th (>60). (authors)

  6. Solvent effect on the complex formation of a crown ether derivative with sodium and potassium ions. Thermodynamic background of selectivity

    NASA Astrophysics Data System (ADS)

    Li, Yin; Huszthy, Péter; Móczár, Ildikó; Szemenyei, Balázs; Kunsági-Máté, Sándor

    2013-01-01

    The complexation properties of dimethyl-pyridino-18-crown-6 ether (M2P18C6) with Na+ and K+ in different primary alcohols including methanol (MeOH), ethanol (EtOH) and n-propanol (n-PrOH) were investigated by UV-vis spectroscopy. Stability constants and thermodynamic parameters have been determined applying the van't Hoff theory. In the cases of both Na+ and K+ the stability constants increase with decreasing permittivity of the solvent used. M2P18C6 always exhibits better affinity to K+ in each alcoholic solution compared to Na+. Thermodynamic studies suggest that in both cases there is a correlation between the permittivity of the solvent and the enthalpy and entropy change of complex formation.

  7. A water soluble fluorescent BODIPY dye with azathia-crown ether functionality for mercury chemosensing in environmental media.

    PubMed

    Isaad, Jalal; El Achari, Ahmida

    2013-07-07

    A novel mercury chemosensor based on water soluble fluorescent BODIPY probe with an azathia-crown ether moiety has been synthesised through condensation of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene as a fluorophore coupled at the 3-position to an azathia macrocycle via an ethenylphenyl linker. Spectroscopic properties and complex formation with several metal ions are investigated in aqueous organic solvent and in water via colorimetric and fluorometric titrations. The binding ratio of chemosensor to Hg(2+) complex was determined to be 1 : 1 according to a Job plot. Hg(2+) binding in chemosensor was 8.19 × 10(3) M(-1). The fluorescence and colorimetric spectroscopic experiments in this study demonstrated that chemosensor can be used as a fluorescent and colorimetric probe for detecting Hg(2+) in water.

  8. Characterization of the homologs of flerovium with crown ether based extraction chromatography resins: studies in nitric acid

    SciTech Connect

    Despotopulos, John D.; Kmak, Kelly N.; Gharibyan, Narek; Henderson, Roger A.; Moody, Kenton J.; Shaughnessy, Dawn A.; Sudowe, Ralf

    2016-09-17

    Eichrom’s Pb resin, a crown-ether-based extraction chromatography resin, was characterized for separation of the flerovium (Fl) homologs, Pb and Sn. Batch uptake of Pb(II) and Sn(IV) radionuclides was determined from an HNO3 matrix. Pb(II) was strongly retained on the resin at all HNO3 concentrations, while Sn(IV) showed no uptake. Extraction kinetics for Pb(II) were examined and show suitable uptake on the second time scale. Here, separation methods for the isolation of individual homologs, Pb(II) and Sn(IV), have been established using 2 mL pre-packed vacuum flow Pb resin columns.

  9. Crown-Ether Derived Graphene Hybrid Composite for Membrane-Free Potentiometric Sensing of Alkali Metal Ions.

    PubMed

    Olsen, Gunnar; Ulstrup, Jens; Chi, Qijin

    2016-01-13

    We report the design and synthesis of newly functionalized graphene hybrid material that can be used for selective membrane-free potentiometric detection of alkali metal ions, represented by potassium ions. Reduced graphene oxide (RGO) functionalized covalently by 18-crown[6] ether with a dense surface coverage is achieved by the introduction of a flexible linking molecule. The resulting hybrid composite is highly stable and is capable of detecting potassium ions down to micromolar ranges with a selectivity over other cations (including Ca(2+), Li(+), Na(+), NH4(+)) at concentrations up to 25 mM. This material can be combined further with disposable chips, demonstrating its promise as an effective ion-selective sensing component for practical applications.

  10. Synthesis and Structural Characterization of Butadienylcalcium-based Heavy Grignard Reagents and a Ca4 [O] Inverse Crown Ether Complex.

    PubMed

    Wei, Baosheng; Liu, Liang; Zhang, Wen-Xiong; Xi, Zhenfeng

    2017-07-24

    The structure elucidation of heavy Grignard reagents (RAeX, Ae=Ca, Sr, and Ba, X=halides) has been greatly strived after, mainly because of their inaccessibility and remarkable instability. The synthesis of a series of butadienylcalcium compounds is presented, including 1-calcio-4-lithio-1,3-butadiene, 1,4-dicalcio-1,3-butadiene, and a Ca4 [O] inverse crown ether complex, via the reaction between 1,4-dilithio-1,3-butadienes and calcium iodide in THF. Single-crystal X-ray analysis of these unprecedented heavy Grignard reagents revealed unique structural characteristics and bonding modes. Preliminary reaction chemistry was investigated. This study provides a novel class of alkenyl heavy Grignard reagents and a useful synthetic strategy for otherwise unavailable reactive organometallic compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Modulation of the Cs2CO3-promoted catalytic amination by a crown ether.

    PubMed

    Torisawa, Y; Nishi, T; Minamikawa, J

    2000-11-06

    The catalytic addition of 18-Crown-6 in some Cs2CO3-promoted amination of triflates and bromides was beneficial to improve sluggish reaction with suppression of the unwanted side products. The protocol was useful for the preparation of chlorinated aryl piperazines from phenol derivatives.

  12. Unexpected structural diversity in alkali metal azide-crown ether complexes: syntheses, X-ray structures, and quantum-chemical calculations.

    PubMed

    Brown, Michael D; Dyke, John M; Ferrante, Francesco; Levason, William; Ogden, J Steven; Webster, Michael

    2006-03-08

    A series of alkali metal azide-crown ether complexes, [Li([12]crown-4)(N3)], [Na([15]crown-5)(N3)], [Na([15]crown-5)(H2O)2]N3, [K([18]crown-6)(N3)(H2O)], [Rb([18]crown-6)(N3)(H2O)], [Cs([18]crown-6)(N3)]2, and [Cs([18]crown-6)(N3)(H2O)(MeOH)], has been synthesised. In most cases, single crystals were obtained, which allowed X-ray crystal structures to be derived. The structures obtained have been compared with molecular structures computed by density functional theory (DFT) calculations. This has allowed the effects of the crystal lattice on the structures to be investigated. Also, a study of the M-N(terminal) metal-azide bond length and charge densities on the metal (M) and terminal nitrogen centre (N(terminal)) in these complexes has allowed the nature of the metal-azide bond to be probed in each case. The bonding in these complexes is believed to be predominantly ionic or ion-dipole in character, with the differences in geometries reflecting the balance between maximising the coordination number of the metal centre and minimising ligand-ligand repulsions. The structures of the crown ether complexes determined in this work show the subtle interplay of such factors. The significant role of hydrogen bonding is also demonstrated, most clearly in the structures of the K and Rb dimers, but also in the chain structure of the hydrated Cs complex.

  13. Theoretical Design and Calculation of a Crown Ether Phase-Transfer-Catalyst Scaffold for Nucleophilic Fluorination Merging Two Catalytic Concepts.

    PubMed

    Carvalho, Nathália F; Pliego, Josefredo R

    2016-09-16

    Fluorinated organic molecules are playing an increased role in the area of pharmaceuticals and agrochemicals. This fact demands the development of efficient catalytic fluorination processes. In this paper, we have designed a new crown ether with four hydroxyl groups strategically positioned. The catalytic activity of this basic scaffold was investigated with high levels of electronic structure theory, such as the ONIOM approach combining MP4 and MP2 methods. On the basis of the calculations, this new structure is able to solubilize potassium fluoride in toluene solution much more efficiently than 18-crown-6 (18C6). In addition, the strong interaction of the new catalyst with the SN2 transition state leads to a very important catalytic effect, with a predicted free energy barrier of 23.3 kcal mol(-1) for potassium fluoride plus ethyl bromide reaction model. Compared with experimental data and previous theoretical studies, this new catalyst is 10(4) times more efficient than 18C6 for nucleophilic fluorination of alkyl halides. The catalysis is predicted to be selective, leading to 97% of fluorination and only 3% of elimination. Catalytic fluorination of the aromatic ring has also been investigated, and although the catalyst is less efficient in this case, our analysis has indicated further development of this strategy can lead to more efficient catalysis.

  14. Probing Supramolecular Interactions between a Crown Ether Appended Zinc Phthalocyanine and an Ammonium Group Appended to a C60 Derivative.

    PubMed

    Lederer, Marcus; Hahn, Uwe; Strub, Jean-Marc; Cianférani, Sarah; Van Dorsselaer, Alain; Nierengarten, Jean-François; Torres, Tomas; Guldi, Dirk M

    2016-02-01

    Self-assembly driven by crown ether complexation of zinc phthalocyanines equipped with one 18-crown-6 moiety and fullerenes bearing an ammonium head group afforded a novel donor-acceptor hybrid. In reference experiments, fullerenes containing a Boc-protected amine functionality have been probed. The circumvention of zinc phthalocyanine aggregation is important for the self-assembly, which required the addition of pyridine. From absorption and fluorescence titration assays, which provided sound and unambiguous evidence for mutual interactions between the electron donor and the electron acceptor within the hybrids, association constants in the order of 8.0×10(5)  m(-1) have been derived. The aforementioned is based on 1:1 stoichiometries, which have been independently confirmed by Job's plot measurements. In the excited state, which has been examined by transient absorption experiments, intermolecular charge separation evolves from the photoexcited zinc phthalocyanine to the fullerene subunit and leads to short-lived charge-separated states. Interestingly, photoexcitation of zinc phthalocyanine dimers/aggregates can also be followed by an intermolecular charge separation between vicinal phthalocyanines. These multicomponent supramolecular ensembles have also been shown by in-depth electrospray ionization mass spectrometry (ESI-MS) studies, giving rise to the formation and detection of a variety of non-covalently linked species.

  15. Design and synthesis of the next generation of crown ethers for waste separations: An inter-laboratory comprehensive proposal. 1998 annual progress report

    SciTech Connect

    Moyer, B.A.; Hay, B.P.; Dietz, M.L.; Alexandratos, S.D.; Sachleben, R.A.; Chiarizia, R.

    1998-06-01

    'The purpose of this task is to undertake the design, synthesis, and characterization of the next generation of crown ethers for metal-ion separations applicable to USDOE''s environmental needs. Target problems include: Li{sup +} ions leaching from burial sites at the Oak Ridge Y-12 Plant; fission products 90 Sr and {sup 137}Cs contaminating high-level tank wastes at Hanford, INEEL, and Savannah River; and radium in wastes at the Niagara Falls Storage Site. Unfortunately, the technologies needed to address these problems either do not exist or exhibit substantial deficiencies. Separation techniques such as solvent extraction and ion exchange promise to play a strong role, especially as enhanced with highly selective crown ethers and calixarenes. This project is midway through year 2 of a 3-year effort. Below is given a summary of progress in the approximate period September, 1997, to May, 1998, for each of the four co-investigators at Pacific Northwest National Laboratory (PNNL), Argonne National Laboratory (ANL), Oak Ridge National Laboratory (ORNL), and the University of Tennessee (UTK). The overall approach entails utilization of theory and molecular modeling (PNNL), organic synthesis of novel crown compounds (ORNL), solvent extraction studies (ORNL and ANL), and studies of polymer-immobilized crown ethers (UTK).'

  16. The interaction between ketamine and some crown ethers in common organic solvents studied by NMR: The effect of donating atoms and ligand structure

    NASA Astrophysics Data System (ADS)

    Chekin, Fereshteh; Bordbar, Maryam; Fathollahi, Yaghoub; Alizadeh, Naader

    2006-02-01

    1H NMR spectroscopy was used to investigate the stoichiometry and stability of the drug ketamine cation complexes with some crown ethers, such as 15-crown-5 (15C5), aza-15-crown-5 (A15C5), 18-crown-6 (18C6), aza-18-crown-6 (A18C6), diaza-18-crown-6 (DA18C6), dibenzyl-diaza-18-crown-6 (DBzDA18C6) and cryptant [2,2,2] (C222) in acetonitrile (AN), dimethylsulfoxide (DMSO) and methanol (MeOH) at 27 °C. In order to evaluate the formation constants of the ketamine cation complexes, the CH 3 protons chemical shift (on the nitrogen atom of ketamine) was measured as function of ligand/ketamine mole ratio. The formation constant of resulting complexes were calculated by the computer fitting of chemical shift versus mole ratio data to appropriate equations. A significant chemical shift variation was not observed for 15C5 and 18C6. The stoichiometry of the mono aza and diaza ligands are 1:1 and 1:2 (ligand/ketamine), respectively. In all of the solvents studied, DA18C6 formed more stable complexes than other ligands. The solvent effect on the stability of these complexes is discussed.

  17. Cesium and strontium extraction using a mixed extractant solvent including crown ether and calixarene extractants

    DOEpatents

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

    2007-11-06

    A mixed extractant solvent including 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 mixed extractant solvent may be used to remove cesium and strontium from an acidic solution. The DtBu18C6 may be present from approximately 0.01 M to approximately 0.4M, such as 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 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 mixed extractant solvent may form an organic phase in an extraction system that also includes an aqueous phase. Methods of extracting cesium and strontium as well as strontium alone are also disclosed.

  18. Chiroptical properties of cation complexes of chiral phenazino-18-crown-6 ether-type hosts.

    PubMed

    Szarvas, Szilvia; Szalay, Luca; Vass, Elemér; Hollósi, Miklós; Samu, Erika; Huszthy, Péter

    2005-06-01

    Herein we report CD spectroscopic studies on complexes of (R,R)-dimethyl-, (R,R)-diisobutyl-, and (S,S)-di-sec-butyl-phenazino-18-crown-6 ligands (Scheme 1) with selected alkali (Na+, K+), alkaline earth (Mg2+, Ca2+), and transition-metal (Ag+, Zn2+, Ni2+, Cd2+, Pb2+) cations. The complexation was monitored in the 300- to 240-nm region of the CD spectra comprising mainly the 1Bb band of the heteroaromatic subunit. The CD spectra of the complexes showed an unexpected diversity. In the most characteristic 1Bb spectral region, the number, position, and intensity of band(s) depend not only on the heteroaromatic subunit and the size of the substituents but also on the diameter, ion strength, and coordination geometry of the cation. The appearance of two weak 1Bb CD bands (type-I spectra) with the sign pattern of the host is an indication of two complexes of comparable stability. The "type-II" spectra differ from that of the host in the number, sign pattern, and intensity of the bands. Complexes of transition-metal cations generally show CD spectra with more intense bands. The CD spectra of complexes of (S,S)-di-sec-butyl-phenazino-18-crown-6 ligand with Na+, K+, and Pb2+ (type III) strongly suggest exciton coupling caused by the closeness of the heteroaromatic rings of two 1:1 complex molecules.

  19. Liquid-liquid extraction, separation recovery and transport of tantalum by crown-ether.

    PubMed

    Agrawal, Y K

    2002-11-12

    A solvent extraction, separation, preconcentration method and recovery of tantalum is reported. Tantalum is extracted with dibenzo-18-crown-6 (DB18C6) in dichloromethane in presence of niobium from 4 M hydrochloric acid. The transport of tantalum(V) ions through a supported liquid membrane containing DB18C6 has been studied. The influence of molarity of acid, carrier concentration, temperature and kinetics of transport is discussed. Tantalum-DB18C6 extract was directly inserted in the plasma for ICP-AES measurement which enhances the sensitivity to 20-folds with the detection limit 1 ng. The mixed compelxes of tantalum-DB18C6 with methyl violet and thiocyanate have also been studied. Tantalum was recovered from tin scrap and determined in standard and sea water samples.

  20. Mono- and ditopic models of binding of a photochromic chromene annelated with an 18-crown-6 ether with protonated amino acids.

    PubMed

    Paramonov, Sergey; Fedorov, Yury; Lokshin, Vladimir; Tulyakova, Elena; Vermeersch, Gaston; Delbaere, Stéphanie; Fedorova, Olga

    2012-01-21

    In this work, the interaction of protonated amino acids with a chromene bearing a fused 18-crown-6 ether moiety was studied by UV-vis and NMR spectroscopy. Initial closed forms of the chromene form monotopic 1 : 1 complexes, the ammonium group being localized inside the crown ether cavity. UV-irradiation leads to transformation of the ring-closed species into the ring-opened form. Depending on the amino acid length, either ditopic or monotopic 1 : 1 complexes are formed. Such complexes are stabilized by the additional H-bonding between the carboxylic group of the acid and the carbonyl oxygen atom of the ring-opened form. Cessation of the irradiation results in ring-closure to the chromene with concomitant change of the complexation mode.

  1. MRI sensing of neurotransmitters with a crown ether appended Gd(3+) complex.

    PubMed

    Oukhatar, Fatima; Même, Sandra; Même, William; Szeremeta, Frédéric; Logothetis, Nikos K; Angelovski, Goran; Tóth, Éva

    2015-02-18

    Molecular magnetic resonance imaging (MRI) approaches that detect biomarkers associated with neural activity would allow more direct observation of brain function than current functional MRI based on blood-oxygen-level-dependent contrast. Our objective was to create a synthetic molecular platform with appropriate recognition moieties for zwitterionic neurotransmitters that generate an MR signal change upon neurotransmitter binding. The gadolinium complex (GdL) we report offers ditopic binding for zwitterionic amino acid neurotransmitters, via interactions (i) between the positively charged and coordinatively unsaturated metal center and the carboxylate function and (ii) between a triazacrown ether and the amine group of the neurotransmitters. GdL discriminates zwitterionic neurotransmitters from monoamines. Neurotransmitter binding leads to a remarkable relaxivity change, related to a decrease in hydration number. GdL was successfully used to monitor neural activity in ex vivo mouse brain slices by MRI.

  2. Ammonium-crown ether supramolecular cation-templated assembly of an unprecedented heterobicluster-metal coordination polymer with enhanced NLO properties.

    PubMed

    Zhang, Jinfang; Jia, Ding; Humphrey, Mark G; Meng, Suci; Zaworotko, Michael J; Cifuentes, Marie P; Zhang, Chi

    2016-03-07

    An ammonium-crown ether host-guest supramolecular cation-templated synthetic methodology has been developed to construct a structurally unprecedented heterobicluster-metal coordination polymer (HCM-CP 1) based on tetranuclear clusters [WS4Cu3](+) with different connection environments, pentanuclear clusters [WS4Cu4](2+), and Cu(+) building metal ions. HCM-CP 1 exhibits enhanced NLO properties, which may be ascribed to the incorporation of diverse building cluster components.

  3. Monolayer detection of ion binding at a crown ether-functionalised supramolecular surface via an integrated optical Bragg grating.

    PubMed

    Parker, Richard M; Wales, Dominic J; Gates, James C; Frey, Jeremy G; Smith, Peter G R; Grossel, Martin C

    2014-06-07

    There have been significant recent developments in the field of integrated optical Bragg grating sensors for use in the biological domain, where changes in the thickness of a surface layer upon specific binding of biological targets allows quantitative detection. However in the chemical domain less work has been reported. We present here an integrated optical Bragg grating sensor, capable of evanescently detecting small changes in refractive index down to 10(-6) RIU at infrared wavelengths, within a microfluidic system. The high spectral fidelity of the Bragg gratings combined with precise thermal compensation enables direct monitoring of the surface throughout the experiment. This allows the sensor to probe surface changes in situ and in real-time, from preparation through to chemical modification of the surface, so that the progress of dynamic surface-localized interactions can be followed. Here we describe confirmatory studies to validate this approach, including a comparison with the modelled optical system, before assessing the ability to detect binding of Group I cations at a crown ether-functionalised supramolecular surface. Unlike larger biological entities, for these small chemical species, simple additive changes in film-thickness no longer prevail.

  4. Effects of 12-Crown-4 ether on the ionic conductivity and electrode kinetics of electrolytes in polyethylene oxide

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Di Stefano, S.

    1990-01-01

    Results are described of investigations of the electrical and electrochemical properties of thin films of polyethylene oxide (PEO) electrolytes with and without 12-Crown-4 ether (12Cr4) as a function of temperature and in the frequency regime 100 kHz-0.1 Hz. These measurements were made for LiCF3SO3, LiBF4, and LiClO4 salts. At a given temperature, the bulk conductivity, sigma, (S/cm), for a particular salt, depends on the 12Cr4 concentration with sigma reaching a maximum at about 3 mM 12Cr4. Of the three salts studied, the sigma is the highest for PEO/LiBF4 with 3 mM 12Cr4. The ac and dc measurements yield a lower charge transfer resistance for 12Cr4-incorporated samples than for samples without. Plating/stripping of Li occurs at a potential closer to Li(+)/Li for 12Cr4 samples than those without. The conductivities of a thin (about 100 microns) and a thick (400 microns) films are similar.

  5. Effects of 12-Crown-4 ether on the ionic conductivity and electrode kinetics of electrolytes in polyethylene oxide

    NASA Astrophysics Data System (ADS)

    Nagasubramanian, G.; di Stefano, S.

    Results are described of investigations of the electrical and electrochemical properties of thin films of polyethylene oxide (PEO) electrolytes with and without 12-Crown-4 ether (12Cr4) as a function of temperature and in the frequency regime 100 kHz-0.1 Hz. These measurements were made for LiCF3SO3, LiBF4, and LiClO4 salts. At a given temperature, the bulk conductivity, sigma, (S/cm), for a particular salt, depends on the 12Cr4 concentration with sigma reaching a maximum at about 3 mM 12Cr4. Of the three salts studied, the sigma is the highest for PEO/LiBF4 with 3 mM 12Cr4. The ac and dc measurements yield a lower charge transfer resistance for 12Cr4-incorporated samples than for samples without. Plating/stripping of Li occurs at a potential closer to Li(+)/Li for 12Cr4 samples than those without. The conductivities of a thin (about 100 microns) and a thick (400 microns) films are similar.

  6. Supramolecular interaction of 18-crown-6 ether with mesalazine and spectrofluorimetric determination of mesalazine in pharmaceutical formulations.

    PubMed

    Elbashir, Abdalla A; Abdalla, Fatima Altayib Alasha; Aboul-Enein, Hassan Y

    2015-12-01

    The supramolecular interaction of protonated mesalazine (MSZ) and 18-crown-6 ether (18C6) has been examined by Ultraviolet-visible, FT-IR and fluorescence spectroscopy. The formation of the inclusion complex has been confirmed based on the changes of the spectral properties. The MSZ-18C6 host-guest complex formed in (1:1) stoichiometry and the inclusion constant (K = 1.411 × 10(2) L mol(-1)) was ascertained by the typical double reciprocal plots. Furthermore, the thermodynamic parameters (ΔG°, ΔH° and ΔS°) of (MSZ-18C6) were obtained. Based on the remarkable enhancement of the fluorescence intensity of MSZ produced through complex formation, a simple, accurate, rapid and highly sensitive spectrofluorometric method for the determination of MSZ in aqueous solution in the presence of 18C6 was developed. The measurement of relative fluorescence intensity was carried with excitation at 298 nm, emission 410 nm. All variables affecting the reactions were studied and optimized. Beer's law was obeyed in the concentration range of 0.1-0.9 µg/mL. The absorbance was found to increase linearly with increasing concentration of MSZ. The molar absorptivity, Sandell sensitivity, limit of detection (LOD) and limit of quantification (LOQ) were calculated. The validity of the described method was assessed, and the method was successfully applied to the determination of MSZ in its pharmaceutical formulation. In addition, a solid inclusion complex was synthesized by the coprecipitation method.

  7. Effects of 12-Crown-4 ether on the ionic conductivity and electrode kinetics of electrolytes in polyethylene oxide

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Di Stefano, S.

    1990-01-01

    Results are described of investigations of the electrical and electrochemical properties of thin films of polyethylene oxide (PEO) electrolytes with and without 12-Crown-4 ether (12Cr4) as a function of temperature and in the frequency regime 100 kHz-0.1 Hz. These measurements were made for LiCF3SO3, LiBF4, and LiClO4 salts. At a given temperature, the bulk conductivity, sigma, (S/cm), for a particular salt, depends on the 12Cr4 concentration with sigma reaching a maximum at about 3 mM 12Cr4. Of the three salts studied, the sigma is the highest for PEO/LiBF4 with 3 mM 12Cr4. The ac and dc measurements yield a lower charge transfer resistance for 12Cr4-incorporated samples than for samples without. Plating/stripping of Li occurs at a potential closer to Li(+)/Li for 12Cr4 samples than those without. The conductivities of a thin (about 100 microns) and a thick (400 microns) films are similar.

  8. Binding and selectivity of phenazino-18-crown-6-ether with alkali, alkaline earth and toxic metal species: A DFT study

    NASA Astrophysics Data System (ADS)

    Islam, Nasarul; Chimni, Swapandeep Singh

    2017-02-01

    The interactions of phenazino-crown ether ligands with alkali, alkaline earth and selected toxic species were investigated using density functional theory modelling by employing B3PW91/6-311G ++ (d, p) level of theory. The complex stability was analysed in terms of binding energies, perturbation energies, position of highest molecular orbital and energy gap values. In general, the complexes formed by P18C6-1a ligand with metal cations were found to be more stable than those with P18C6-1b. Among alkali and alkaline earth metals complexes having highest stability was observed for the complex formed by P18C6-1a with Be2+. Computational calculations of P18C6 ligand with toxic metal ions reveals that the P18C6-Cr6+ metal complexes acquire envelop like geometry, leading to higher binding energy values. Comparing the binding energies of neutral and monocations of Ag and Hg, the former had higher value both in neutral as well as monocation state. Thus, the stability of metal complexes is determined not only by the ligand but also by the type of metal ion. In solvent systems the stability constants of metal complexes were found increasing with decreasing permittivity of the solvent. This reflects the inherited polar character of the protic solvents stabilises the cation, resulting in decrease of effective interaction of ligand with the metal ion.

  9. Anion effect on selectivity in solvent extraction of alkali metal salts by crown ethers

    SciTech Connect

    Hankins, M.G.; Bartsch, R.A.; Olsher, U.

    1995-11-01

    The influence of the co-extracted anion upon competitive solvent extraction of five alkali metal cations from aqueous solutions into organic diluents by the cis-syn-cis and cis-anti-cis isomers of dicyclohexano-18-crown-6 has been assessed. The anions are bromide, chloride, iodide, nitrate, perchlorate, and thiocyanate and the organic diluents are chloroform and 1-octanol. The extraction efficiency is markedly influenced by the identity of the anion and exhibits some correlation with the inverse of the hydration enthalpy of the anion. Although potassium is the best exctracted cation with all anions, the selectivities for potassium over lithium, sodium, rubidium, and cesium are strongly affected by anion variation in chloroform, but not in 1-octanol. The selectivity ordering in chloroform does not correlate with the hydration enthalpy or softness parameter for the anion. Instead it appears to result from variation of the dimensional structure and the availability of specific binding sites in the anion. 21 refs., 1 fig., 5 tabs.

  10. The LArIAT experiment at Fermilab

    SciTech Connect

    Nutini, Irene

    2016-03-01

    The LArIAT experiment at Fermilab is part of the International Neutrino program recently approved in the US. LArIAT aims to measure the main features of charged particles interactions in argon in the energy range (0.2 - 2.0 GeV) corresponding to the energy spectrum of the same particles when produced in a neutrino-argon interaction (neutrino energies of few GeV) typical of the short- and long-baseline neutrino beams of the Neutrino Program. Data collected from the 1st Run are being analyzed for both Physics studies and a technical characterization of the scintillation light collection system. Furthermore, two analysis topics are reported: the method developed for charged pion cross section measurement, based on the specific features of the LArTPC, and the development and test of the LArIAT custom-designed cold front-end electronics for SiPM devices to collect LAr scintillation light.

  11. The LArIAT experiment at Fermilab

    DOE PAGES

    Nutini, Irene

    2016-03-01

    The LArIAT experiment at Fermilab is part of the International Neutrino program recently approved in the US. LArIAT aims to measure the main features of charged particles interactions in argon in the energy range (0.2 - 2.0 GeV) corresponding to the energy spectrum of the same particles when produced in a neutrino-argon interaction (neutrino energies of few GeV) typical of the short- and long-baseline neutrino beams of the Neutrino Program. Data collected from the 1st Run are being analyzed for both Physics studies and a technical characterization of the scintillation light collection system. Furthermore, two analysis topics are reported: themore » method developed for charged pion cross section measurement, based on the specific features of the LArTPC, and the development and test of the LArIAT custom-designed cold front-end electronics for SiPM devices to collect LAr scintillation light.« less

  12. Design, synthesis, characterization, and OFET properties of amphiphilic heteroleptic tris(phthalocyaninato) europium(III) complexes. The effect of crown ether hydrophilic substituents.

    PubMed

    Gao, Yingning; Ma, Pan; Chen, Yanli; Zhang, Ying; Bian, Yongzhong; Li, Xiyou; Jiang, Jianzhuang; Ma, Changqin

    2009-01-05

    Two amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic crown ether heads and hydrophobic octyloxy tails [Pc(mCn)(4)]Eu[Pc(mCn)(4)]Eu[Pc(OC(8)H(17))(8)] [m = 12, n = 4, H(2)Pc(12C4)(4) = 2,3,9,10,16,17,23,24-tetrakis(12-crown-4)phthalocyanine; m = 18, n = 6, H(2)Pc(18C6)(4) = 2,3,9,10,16,17,23,24-tetrakis(18-crown-6)phthalocyanine; H(2)Pc(OC(8)H(17))(8) = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] (1, 2) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound [Pc(mCn)(4)]Eu[Pc(mCn)(4)] (m = 12, n = 4; m = 18, n = 6) and metal-free H(2)Pc(OC(8)H(17))(8) in the presence of Eu(acac)(3).H(2)O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene. These novel sandwich triple-decker complexes were characterized by a wide range of spectroscopic methods and electrochemically studied. With the help of the Langmuir-Blodgett technique, these typical amphiphilic triple-decker complexes were fabricated into organic field effect transistors (OFET) with top contact configuration on bare SiO(2)/Si substrate, hexamethyldisilazane-treated SiO(2)/Si substrate, and octadecyltrichlorosilane (OTS)-treated SiO(2)/Si substrate, respectively. The device performance is revealed to be dependent on the species of crown ether substituents and substrate surface treatment. OFETs fabricated from the triple decker with 12-crown-4 hydrophilic substituents, 1, allow the hole transfer in the direction parallel to the aromatic phthalocyanine rings. In contrast, the devices of a triple-decker compound containing 18-crown-6 as hydrophilic heads, 2, transfer holes in a direction along the long axis of the assembly composed of face-to-face aggregated triple-decker molecules, revealing the effect of molecular structure, specifically the crown ether substituents on the film structure and OFET functional properties. The carrier mobility for hole as high as 0.33 cm(2) V(-1) s(-1) and current modulation of 7.91 x 10

  13. Electrochemical, spectral, and computational studies of metalloporphyrin dimers formed by cation complexation of crown ether cavities.

    PubMed

    Chitta, Raghu; Rogers, Lisa M; Wanklyn, Amber; Karr, Paul A; Kahol, Pawan K; Zandler, Melvin E; D'Souza, Francis

    2004-11-01

    The effect on the electrochemical oxidation and reduction potentials of 5,10,15,20-tetrakis(benzo-15-crown-5)porphyrin (TCP) and its metal derivatives (MTCP; M = Mg(II), VO(IV), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II)) upon potassium ion induced dimerization of the porphyrins was systematically performed in benzonitrile containing 0.1 M (TBA)ClO(4) by differential pulse voltammetry technique. The HOMO--LUMO energy level diagram constructed from the electrochemical data revealed destabilization of the HOMO level and stabilization of the LUMO level upon dimer formation while such a perturbation was larger for the HOMO level than the LUMO level. The geometry and electronic structure of a representative ZnTCP and its dimer, K(4)(ZnTCP)(2), were evaluated by the ab initio B3LYP method utilizing a mixed basis set of 3-21G(*) for Zn, K, O, and N and STO-3G for C and H. The inter-porphyrin ring distance of the dimer calculated from the optimized geometry agreed with the spectroscopically determined one, and the calculated HOMO and LUMO frontier orbitals revealed delocalization on both of the porphyrins rings. The metal-metal distances calculated from the triplet ESR spectra of the K(+) induced porphyrin dimers bearing paramagnetic metal ions in the cavity followed the trend Cu--Cu < VO--VO < Ag--Ag. However, the spectral shifts resulting from the exciton coupling of the interacting porphyrin pi-systems revealed no specific trend with respect to the metal ion in the porphyrin cavity. Additionally, linear trends in the electrochemically measured HOMO--LUMO gap and the energy corresponding to the most intense visible band of both MTCP and K(4)(MTCP)(2) were observed. A reduced HOMO--LUMO gap predicted for the dimer by B3LYP/(3-21G(), STO-3G) calculations was confirmed by the results of optical absorption and electrochemical studies.

  14. Design and synthesis of the next generation of crown ethers for waste separations: An interlaboratory comprehensive proposal. 1997 annual progress report

    SciTech Connect

    Moyer, B.A.; Dietz, M.L.; Alexandratos, S.D.; Hay, B.P.

    1997-09-01

    'The purpose of this task is to undertake the design, synthesis, and characterization of the next generation of crown ethers for metal-ion separations applicable to the US Department of Energy''s (DOE''s) environmental needs. The general target problem is the removal of alkali and alkaline-earth metal contaminants from certain environmental and waste streams. Although not a radioactivity hazard, Li{sup +} ions leaching from burial sites containing more than 12 metric tons of lithium compounds contaminate the groundwater at the Oak Ridge Y-12 Plant and have raised noncompliance concerns because of the resultant toxicity to aquatic biota. A more highly visible problem has been treatment of high-level wastes stored in underground tanks at Oak Ridge National Laboratory (ORNL), Idaho National Engineering and Environmental Laboratory, and especially the Hanford Site. The fission products {sup 90}Sr and {sup 137}Cs have been explicitly targeted for removal by the following DOE programs: the Office of Environmental Management, the Office of Science and Technology, the Tank Waste Remediation System, the Tanks Focus Area, and the Efficient Separations and Processing Cross-Cutting Program. These seemingly ubiquitous fission products also appear in soil and groundwater at numerous DOE sites. In addition, radium has recently been named as a target contaminant at the Niagara Falls Storage Site. Unfortunately, the separations technologies needed to address these problems either do not exist or exhibit substantial deficiencies. Established techniques such as solvent extraction and ion exchange certainly have a strong role to play, especially as enhanced with the use of the new highly selective metal-ion hosts such as crown ethers and calixarenes. Recently applied results in the United States, France, Russia, and elsewhere have demonstrated the effective performance of crown ethers under realistic or actual process conditions for the removal of alkali and alkaline-earth metal ions

  15. Release of Lariat Peanut (ARSOK-R35)

    USDA-ARS?s Scientific Manuscript database

    'Lariat' is a high-oleic runner-type peanut (Arachis hypogaea L. subsp. hypogaea var. hypogaea) that has enhanced Sclerotinia blight and pod rot tolerance when compared to the cultivar Red River Runner. 'Lariat' (experimental designation ARSOK-R35) is the result of a cross between cultivar Red Rive...

  16. Variational first hyperpolarizabilities of 2,3-naphtho-15-crown-5 ether derivatives with cation-complexing: a potential and selective cation detector.

    PubMed

    Yu, Hai-Ling; Wang, Wen-Yong; Hong, Bo; Zong, Ying; Si, Yan-Ling; Hu, Zhong-Qiang

    2016-09-29

    Crown ethers, as a kind of heterocycle, have been the subject of great interest over recent decades due to their selective capability to bind to metal cations. The use of a constant crown ether, such as naphtho-15-crown-5 (N15C5), and varied metal cations (Li(+), Na(+), K(+), Be(2+), Mg(2+), Ca(2+), Co(2+), Ni(2+), Cu(2+)) makes it possible to determine the contributions of the metal cations to nonlinear optical (NLO) responses and to design an appropriate NLO-based cation detector. N15C5 and its metal cation derivatives have been systematically investigated by density functional theory. It is found that the dependency of the first hyperpolarizability relies on the metal cation, especially for transition metals. The decrease of the first hyperpolarizabilities for alkali metal cation derivatives is due to their relatively low oscillator strengths, whereas the significant increase of the first hyperpolarizabilities for transition metal cation derivatives can be further illustrated by their low transition energies, large amplitudes and separate distributions of first hyperpolarizability density. Thus, the alkali metal and transition metal cations are distinguishable and the transition metal cations are easier to detect by utilizing the variations in NLO responses.

  17. Ludwig-Soret effect of aqueous solutions of ethylene glycol oligomers, crown ethers, and glycerol: Temperature, molecular weight, and hydrogen bond effect

    NASA Astrophysics Data System (ADS)

    Maeda, Kousaku; Shinyashiki, Naoki; Yagihara, Shin; Wiegand, Simone; Kita, Rio

    2015-09-01

    The thermal diffusion, also called the Ludwig-Soret effect, of aqueous solutions of ethylene glycol oligomers, crown ethers, and glycerol is investigated as a function of temperature by thermal diffusion forced Rayleigh scattering. The Soret coefficient, ST, and the thermal diffusion coefficient, DT, show a linear temperature dependence for all studied compounds in the investigated temperature range. The magnitudes and the slopes of ST and DT vary with the chemical structure of the solute molecules. All studied molecules contain ether and/or hydroxyl groups, which can act as acceptor or donor to form hydrogen bonds, respectively. By introducing the number of donor and acceptor sites of each solute molecule, we can express their hydrogen bond capability. ST and DT can be described by an empirical equation depending on the difference of donor minus acceptor sites and the molecular weight of the solute molecule.

  18. RNA splicing and debranching viewed through analysis of RNA lariats.

    PubMed

    Cheng, Zhi; Menees, Thomas M

    2011-12-01

    Intron lariat RNAs, created by pre-mRNA splicing, are sources of information on gene expression and structure. Although produced equivalently to their corresponding mRNAs, the vast majority of intron lariat RNAs are rapidly degraded. However, their levels are enhanced in cells deficient for RNA debranching enzyme, which catalyzes linearization of these RNAs, the rate-limiting step in their degradation. Furthermore, RNA lariats are resistant to degradation by the 3' exonuclease polynucleotide phosphorylase (PNPase), providing a means to enrich for lariat RNAs. Working with the yeast Saccharomyces cerevisiae as a model organism, our goal was to develop novel combinations of methods to enhance the use of intron lariat RNAs as objects of study. Using RT-PCR assays developed for detecting and quantifying specific lariat RNAs, we demonstrate the resistance of RNA lariats to degradation by PNPase and their sensitivity to cleavage by RNA debranching enzyme. We also employ sequential treatments with these two enzymes to produce characteristic effects on linear and lariat RNAs. We establish the utility of the methods for analyzing RNA debranching enzyme variants and in vitro debranching reactions and discuss several possible applications, including measuring relative rates of transcription and combining these methods with non-gene-specific RNA sequencing as a novel approach for genome annotation. In summary, enzymatic treatments that produce characteristic effects on linear and lariat RNAs, combined with RT-PCR or RNA sequencing, can be powerful tools to advance studies on gene expression, alternative splicing, and any process that depends on the RNA debranching enzyme.

  19. Enhanced isosteric heat of H2 adsorption by inclusion of crown ethers in a porous metal-organic framework.

    PubMed

    Park, Hye Jeong; Suh, Myunghyun Paik

    2012-04-07

    Inclusion of 18-crown-6 or 15-crown-5 in a porous MOF increased the isosteric heats of H(2) adsorption significantly, which are comparable to MOFs containing open metal sites. This journal is © The Royal Society of Chemistry 2012

  20. Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

    DOE PAGES

    Motokawa, Ryuhei; Kobayashi, Tohru; Endo, Hitoshi; ...

    2015-10-26

    This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs+). SANS profiles obtained for the complex of ace-DB20C6 and Cs+ (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs+ coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Furthermore, we conclude that the SANS analysis experimentallymore » supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs+ is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs+ above the center of the crown ether ring of ace-DB20C6.« less

  1. Investigation by mass spectrometry of metal complexes of new molecular hosts: cyclic oligomer of sugar amino acid and sugar-aza-crown ethers.

    PubMed

    Fournier, Françoise; Afonso, Carlos; Ménand, Mickaël; Hamon, Louis; Xie, Juan; Tabet, Jean-Claude

    2008-01-01

    The affinity of cyclic oligomers of sugar amino acid and sugar-aza-crown ether compounds towards various transition metal cations (Cu(II), Ni(II), Co(II), Fe(II) and Zn(II)) was investigated with positive-ion electrospray mass spectrometry. The binding between the receptors (M) and the different metals (Met) is evidenced mainly by the presence of the [M + Met(II)Cl](+) ion. The experimental results showed that all studied receptors present specificity to Cu(II). An attempt has been made with CuI but no complexation was obtained. The formation of these complexes can be rationalized by considering the presence of two oxygens and two nitrogens on the receptor rim. The lone electron pair can serve as the electron donor to Cu(II). Theoretical calculations were carried out in order to show the structure of the complex and, in particular, to determine if Cu(2+) is situated either on the outer surface, on the rim of the receptor or inside the cavity. Comparison of complex formation was carried out by mixing the four receptors with various amounts of Cu(II) (one equivalent and five equivalents). It appears that the best complexation was obtained with the sugar-aza-crown ethers (amine linker) for both benzylated and methylated compounds. In addition, the stereochemical effects have been investigated.

  2. Vibrational Signatures of Large Amplitude Motions for the Shackled Hydronium Ion Nested in 18-CROWN-6 Ether Using D2 Tagging

    NASA Astrophysics Data System (ADS)

    Duong, Chinh H.; Menges, Fabian; Craig, Stephanie; Wolke, Conrad T.; Johnson, Mark

    2016-06-01

    The diffuse spectra arising from the excess proton in dilute acids suggests that its behavior is highly dependent on the local environment surrounding it. In this work, we report how the spectra of the H3O+, NH4+, and CH3NH3+ ions respond when docked to the rigid, tri-coordinated binding pocket of the 18-crown-6 ether using cryogenic ion vibrational predissociation (CIVP) spectroscopy with D2 tagging at 10 K. The H3O+{tiny^bullet}18-crown-6 ether complex displays a broad (350 cm-1 FWHM) unstructured band arising from the OH stretching fundamentals, which is significantly broader than the corresponding band (125 cm-1 FWHM) in the Eigen cation (H9O4+) spectrum. Perdeuterated isotopologue studies for both systems yield sharper bands with clear multiplet structures, indicating that the broadening arises from nuclear quantum effects. The key displacements underlying this coupling were explored using the vibrationally adiabatic scheme introduced by McCoy in the context of similar broadening in the Ca2+OH-(H2O)n system. Christopher J. Johnson, Laura C. Dzugan, Arron B. Wolk, Christopher M. Leavitt, Joseph A. Fournier, Anne B. McCoy, Mark A. Johnson, J. Phys. Chem. A 118, 2014.

  3. Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

    SciTech Connect

    Motokawa, Ryuhei; Kobayashi, Tohru; Endo, Hitoshi; Ikeda, Takashi; Yaita, Tsuyoshi; Suzuki, Shinichi; Narita, Hirokazu; Akutsu, Kazuhiro; Heller, William T.

    2015-10-26

    This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs+). SANS profiles obtained for the complex of ace-DB20C6 and Cs+ (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs+ coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Furthermore, we conclude that the SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs+ is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs+ above the center of the crown ether ring of ace-DB20C6.

  4. Nonaqueous synthesis of a selectively modified, highly anionic sulfopropyl ether derivative of cyclomaltoheptaose (beta-cyclodextrin) in the presence of 18-crown-6.

    PubMed

    Kirschner, Daniel L; Green, Thomas K

    2005-08-15

    A highly anionic cyclomaltooligosaccharide (cyclodextrin, CD) derivative containing sulfopropyl functional groups on the primary face of the CD was synthesized. Heptakis(2,3-di-O-methyl)cyclomaltoheptaose [heptakis(2,3-di-O-methyl)-beta-cyclodextrin] was reacted with 1,3-propane sultone and potassium hydride (KH) in anhydrous tetrahydrofuran in the presence of 18-crown-6 to yield highly substituted potassium heptakis(2,3-di-O-methyl-6-O-sulfopropyl)cyclomaltoheptaose [heptakis(KSPDM)-beta-CD] with an average degree of substitution (DSCE) of 6.9 as determined by inverse detection capillary electrophoresis (CE). The principal species in the product is the fully substituted heptakis(KSPDM)-beta-CD. Complete NMR assignments of the hydrogen and carbon atoms are made using a combination of gCOSY and gHSQC. In the absence of 18-crown-6, the reaction generates a mixture of multiply charged derivatives with average DSCE of 4.1. The possible roles of the crown ether in the reaction are discussed. The ROESY NMR spectrum of the inclusion complex that forms between heptakis(KSPDM)-beta-CD and 2-naphthoic acid in D2O reveals that 2-naphthoic acid inserts with the carboxyl group toward the derivatized primary rim of the cyclodextrin.

  5. Hydrogen storage in a potassium-ion-bound metal-organic framework incorporating crown ether struts as specific cation binding sites.

    PubMed

    Lim, Dae-Woon; Chyun, Seung An; Suh, Myunghyun Paik

    2014-07-21

    To develop a metal-organic framework (MOF) for hydrogen storage, SNU-200 incorporating a 18-crown-6 ether moiety as a specific binding site for selected cations has been synthesized. SNU-200 binds K(+), NH4(+), and methyl viologen (MV(2+)) through single-crystal to single-crystal transformations. It exhibits characteristic gas-sorption properties depending on the bound cation. SNU-200 activated with supercritical CO2 shows a higher isosteric heat (Qst) of H2 adsorption (7.70 kJ mol(-1)) than other zinc-based MOFs. Among the cation inclusions, K(+) is the best for enhancing the isosteric heat of the H2 adsorption (9.92 kJ mol(-1)) as a result of the accessible open metal sites on the K(+) ion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A Focus on Triazolium as a Multipurpose Molecular Station for pH-Sensitive Interlocked Crown-Ether-Based Molecular Machines.

    PubMed

    Coutrot, Frédéric

    2015-10-01

    The control of motion of one element with respect to others in an interlocked architecture allows for different co-conformational states of a molecule. This can result in variations of physical or chemical properties. The increase of knowledge in the field of molecular interactions led to the design, the synthesis, and the study of various systems of molecular machinery in a wide range of interlocked architectures. In this field, the discovery of new molecular stations for macrocycles is an attractive way to conceive original molecular machines. In the very recent past, the triazolium moiety proved to interact with crown ethers in interlocked molecules, so that it could be used as an ideal molecular station. It also served as a molecular barrier in order to lock interlaced structures or to compartmentalize interlocked molecular machines. This review describes the recently reported examples of pH-sensitive triazolium-containing molecular machines and their peculiar features.

  7. A Focus on Triazolium as a Multipurpose Molecular Station for pH-Sensitive Interlocked Crown-Ether-Based Molecular Machines

    PubMed Central

    Coutrot, Frédéric

    2015-01-01

    The control of motion of one element with respect to others in an interlocked architecture allows for different co-conformational states of a molecule. This can result in variations of physical or chemical properties. The increase of knowledge in the field of molecular interactions led to the design, the synthesis, and the study of various systems of molecular machinery in a wide range of interlocked architectures. In this field, the discovery of new molecular stations for macrocycles is an attractive way to conceive original molecular machines. In the very recent past, the triazolium moiety proved to interact with crown ethers in interlocked molecules, so that it could be used as an ideal molecular station. It also served as a molecular barrier in order to lock interlaced structures or to compartmentalize interlocked molecular machines. This review describes the recently reported examples of pH-sensitive triazolium-containing molecular machines and their peculiar features. PMID:26491633

  8. The influence of water-ethanol mixture on the thermodynamics of complex formation between 18-crown-6 ether and L-phenylalanine

    NASA Astrophysics Data System (ADS)

    Usacheva, T. R.; Sharnin, V. A.; Chernov, I. V.; Matteoli, E.; Terekhova, I. V.; Kumeev, R. S.

    2012-08-01

    The influence of water-ethanol mixture composition on the complex formation between 18-crown-6 ether and L-phenylalanine was studied by titration calorimetry at Т = 298.15 K. The standard thermodynamic parameters (ΔrGо, ΔrHо, ТΔrSо) of formation of [Phe18C6] molecular complex were calculated from data obtained by means of the microcalorimetric system TAM III (TA Instruments, USA) at X(EtOH) = 0.0/0.6 mol fraction. The stability of [Phe18C6] and the mechanism of complexation in water were investigated using the 1Н and 13С NMR spectroscopy. The increase of EtOH concentration results in an increase of the complex stability and of the exothermicity of complexation.

  9. Synthesis, supramolecular behavior, and in vitro photodynamic activities of novel zinc(II) phthalocyanines "side-strapped" with crown ether bridges.

    PubMed

    Chen, Xing-Wei; Ke, Mei-Rong; Li, Xing-Shu; Lan, Wen-Liang; Zhang, Miao-Fen; Huang, Jian-Dong

    2013-12-01

    Two new tetra- or di-α-substituted zinc(II) phthalocyanines 5 and 6 have been prepared through a "side-strapped" method. In the molecules, the adjacent benzene rings of the phthalocyanine core are linked at α-position through a triethylene glycol bridge to form a hybrid aza-/oxa-crown ether. The tetra-α-substituted phthalocyanine 5 shows an eclipsed self-assembly property in CH2Cl2 and the effect on the di-α-substituted analogue 6 is significantly weakened. Furthermore, the crown ethers of these compounds can selectively complex with Fe(3+) or Cu(2+) ion in DMF, leading to formation of J-aggregated nano-assemblies, which can be disaggregated in the presence of some organic or inorganic ligands, such as triethylamine, tetramethylethylenediamine, CH3COO(-), or OH(-). In addition, both compounds are efficient singlet oxygen generators with the singlet oxygen quantum yields (Φ(Δ)) of 0.54-0.74 in DMF relative to unsubstituted zinc(II) phthalocyanine (Φ(Δ)=0.56). They exhibit photodynamic activities toward HepG2 human hepatocarcinoma cells, but the compound 6, which has more than 40-fold lower IC50 value (0.08 μM) compared to the analogue 5 (IC50=3.31 μM), shows remarkablely higher in vitro photocytotoxicity due to its significantly higher cellular uptake and singlet oxygen generation efficiency. The results suggest that these compounds can serve as promising multifunctional materials both in (opto)electronic field and photodynamic therapy.

  10. Utilization of different crown ethers impregnated polymeric resin for treatment of low level liquid radioactive waste by column chromatography.

    PubMed

    Attallah, M F; Borai, E H; Hilal, M A; Shehata, F A; Abo-Aly, M M

    2011-11-15

    The main goal of this study was to find a novel impregnated resin as an alternative for the conventional resin (KY-2 and AN-31) used for low and intermediate level liquid radioactive waste treatment. Novel impregnated ion exchangers namely, poly (acrylamide-acrylic acid-acrylonitril)-N,N'-methylenedi-acrylamide-4,4'(5')di-t-butylbenzo 18 crown 6 [P(AM-AA-AN)-DAM/DtBB18C6], poly (acrylamide-acrylic acid-acrylonitril)-N,N'-methylenediacrylamide-dibenzo 18 crown 6 [P(AM-AA-AN)-DAM/DB18C6], and poly (acrylamide-acrylic acid-acrylonitril)-N,N'-methylenediacrylamide-18 crown 6 [P(AM-AA-AN)-DAM/18C6] were prepared and their removal efficiency of some radionuclides was investigated. Preliminary batch experiments were performed in order to study the influence of the different derivatives of 18 crown 6 on the characteristic removal performance. Separation of (134)Cs, (60)Co, (65)Zn and ((152+154))Eu radionuclides from low level liquid radioactive waste was investigated by using column chromatography with P(AM-AA-AN)-DAM/DtBB18C6 and metal salt solutions traced with the corresponding radionuclides. Breakthrough data was obtained in a fixed bed column at room temperature (298K) using different bed heights and flow rates. The breakthrough capacities were found to be 94.7, 83.3, 58.7, 43.1 (mg/g) for (60)Co, (65)Zn, (134)Cs, and ((152+154))Eu, respectively. Pre-concentration and separation of all radionuclides under study have been carried out using different concentration of nitric and/or oxalic acids.

  11. Extraction of Cesium by a Calix[4]arene-Crown-6 Ether Bearing a Pendant amine Group

    SciTech Connect

    Harmon, Ben; Ensor, Dale; Delmau, Laetitia Helene; Moyer, Bruce A

    2007-01-01

    The goal of this work was to evaluate the role of the amino group of 5-aminomethylcalix[4]arene-[bis-4-(2-ethylhexyl)benzo-crown-6] (AMBEHB) in the extraction of cesium from acidic and basic mixtures of sodium nitrate and other concentrated salts. The extraction of cesium from nitrate media was measured as a function of extractant concentration, nitrate concentration, cesium concentration, and pH over the range 1-13. The initial studies showed a moderate decrease in the extraction of cesium in acidic media, which indicated the binding of cesium by the calixarene-crown was weakened by the protonation of the amine group. The results also indicated that a 1:1:1 Cs-ligand-nitrate complex is formed in the organic phase. To further evaluate AMBEHB, the empirical data were mathematically modeled to determine the formation constants of the complexes formed in the organic phase. The resulting formation constants showed that the attachment of the amine group to the calixarene-crown molecule reduced the binding stability for the cesium ion upon contact with an acidic solution. This supports the hypothesis of charge repulsion as the basis for more efficient stripping of cesium via pH-switching.

  12. Microwave irradiation-assisted synthesis of a novel crown ether crosslinked chitosan as a chelating agent for heavy metal ions (M(+n)).

    PubMed

    Radwan, Awwad A; Alanazi, Fars K; Alsarra, Ibrahim A

    2010-09-06

    Microwave irradiation was used to obtain a di-Schiff base type crosslinked chitosan dibenzocrown ether (CCdBE) via the reaction between the -NH(2) and -CHO groups in chitosan and 4,4'-diformyldibenzo-18-c-6, respectively. The structure of the synthesized compound was characterized by elemental analysis, solid state 13C-NMR and FT-IR spectra analysis. The results showed that the mass fraction of nitrogen in the CCdBE derivative was much lower than those of chitosan. The FT-IR spectra of CCdBE revealed the expected chitosan-crown ether structure, as evidenced by the presence of the characteristic C=N and Ar peaks. The adsorption properties of CCdBE for Pd2+ and Hg2+ were investigated and the results demonstrated that the adsorbent has both desirable adsorption properties with a high particular adsorption selectivity for Hg2+ when in the presence of Pb2+ as well as selectivity coefficients for metal ions of K(Hg(2+)/Pb(2+)) = 8.00 and K(Hg(2+)/Pb(2+)) = 10.62 at pH values of 4 and 6, respectively. The reusability tests for CCdBE for Pb2+ adsorption showed that complete recovery of the ion was possible with CCdBE after 10-multiple reuses while CTS had no reusability at acidic solution because of its higher dissolution. The studied features of CCdBE suggested that the material could be considered as a new adsorbent. It is envisaged that the crosslinking of CTS into CCdBE would enhance practicality and effectiveness of adsorption in ion separation and removal procedures.

  13. Comparative studies of various run buffers for chiral capillary electrophoresis using chiral crown ether as a chiral selector.

    PubMed

    Jang, J; Cho, S I; Chung, D S

    2001-12-01

    In the capillary electrophoretic separation of primary amine enantiomers using (+)-(18-crown-6)-tetracarboxylic acid (18C6H4) as a chiral selector, the presence of run buffer constituents such as tris(hydroxymethyl)aminomethane (Tris) or Na+ competing with analytes for 18C6H4, diminishes the effectiveness of 18C6H4. In order to determine appropriate buffer systems for 18C6H4, various run buffer cationic components including Tris, 1,3-bis[tris(hydroxymethyl)methylamino]propane, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, triethanolamine, tetramethylammonium, and Na+ were compared. Quantitative studies of the effects of the competitive constituents were carried out by measuring the electrophoretic mobilities of histidine as a function of the 18C6H4 concentration. We also derived a simple equation to estimate the optimal chiral selector concentration for a maximum mobility difference in the presence of a competitive inhibitor.

  14. Solvent extraction of silver picrate by 3m-crown-m ethers (m = 5, 6) and its mono-benzo-derivative from water into benzene or chloroform: elucidation of an extraction equilibrium using component equilibrium constants.

    PubMed

    Kudo, Yoshihiro; Usami, Jun; Katsuta, Shoichi; Takeda, Yasuyuki

    2004-03-10

    Ion-pair formation constant (K(AgPic) in mol(-1)dm(3)) of silver picrate (AgPic), those (K(AgLPic)) of its ion-pair complexes (AgLPic) with crown ethers (L) and complex formation constants (K(AgL)) of Ag(+) with L (15-crown-5 ether (15C5) and benzo-15C5) in water (w) were determined potentiometrically at 25 degrees C. Compounds used as L were 18-crown-6 ether (18C6), its benzo-derivative (B18C6) and the two 15C5 derivatives. Extraction constants (K(ex) in mol(-1)dm(3)) of AgPic with L (15C5, 18C6, B18C6) from acidic w-phases into either C(6)H(6) or CHCl(3) were recalculated from K(AgPic), K(AgL), K(AgLPic) and data opened in previous papers. Thus obtained K(ex) was divided into five component equilibrium constants containing K(AgL) and K(AgLPic) anew. Then, contributions of the component constants, K(AgL), K(AgLPic) and distribution constants of AgLPic between the w- and C(6)H(6)-phases, to K(ex) were discussed and compared with corresponding extraction systems of NaPic and KPic with18C6.

  15. High performance planar p-i-n perovskite solar cells with crown-ether functionalized fullerene and LiF as double cathode buffer layers

    NASA Astrophysics Data System (ADS)

    Liu, Xiaodong; Lei, Ming; Zhou, Yi; Song, Bo; Li, Yongfang

    2015-08-01

    Double cathode buffer layers (CBLs) composed of fullerene derivative functionalized with a crown-ether end group in its side chain (denoted as PCBC) and a LiF layer were introduced between the PCBM acceptor layer and the top cathode in planar p-i-n perovskite solar cells (pero-SCs) based on CH3NH3PbI3-XClX. The devices with the PCBC/LiF double CBLs showed significant improvements in power conversion efficiency (PCE) and long-term stability when compared to the device with LiF single CBL. Through optimizing the spin-coating speed of PCBC, a maximum PCE of 15.53% has been achieved, which is approximately 15% higher than that of the device with single LiF CBL. The remarkable improvement in PCE can be attributed to the formation of a better ohmic contact in the CBL between PCBC and LiF/Al electrode arising from the dipole moment of PCBC, leading to the enhanced fill factor and short-circuit current density (Jsc). Besides the PCE, the long-term stability of the devices with PCBC interlayer is also superior to that of the device with LiF single CBL, which is due to the more effective protection for the perovskite/PCBM interface.

  16. A novel fluorescent probe for Cr3 + based on rhodamine-crown ether conjugate and its application to drinking water examination and bioimaging

    NASA Astrophysics Data System (ADS)

    Diao, Quanping; Ma, Pinyi; Lv, Linlin; Li, Tiechun; Wang, Xinghua; Song, Daqian

    2016-03-01

    A trivalent chromium (Cr3 +) fluorescence probe (RhC) was designed and synthesized via Schiff base reaction based on rhodamine-crown ether conjugate. This probe displayed a favorable selectivity for Cr3 + over a range of other common metal ions in DMF/H2O (3:7, v/v; PBS buffer 50 mmol L- 1; pH = 6.8) solution, leading to prominent fluorescence "OFF-ON" switching of the rhodamine fluorophore. The limit of detection was calculated to be 1.5 μmol L- 1 (S/N = 3). The binding ratio of RhC-Cr3 + complex was determined to be 1:2 according to the Job's plot and HR-MS. The probe was successfully applied to examination of Cr3 + in drinking water spiked samples. The average recoveries ranged from 104.9% to 106.9% at spiked concentration level of 10.00 μmol L- 1, and the obtained results were consistent with those obtained using atomic absorption spectrometry (AAS). Moreover, bioimaging experiments showed that RhC can sense the Cr3 + in living cells with a fluorescence enhancement signal.

  17. High performance planar p-i-n perovskite solar cells with crown-ether functionalized fullerene and LiF as double cathode buffer layers

    SciTech Connect

    Liu, Xiaodong; Zhou, Yi E-mail: songbo@suda.edu.cn Song, Bo E-mail: songbo@suda.edu.cn; Lei, Ming; Li, Yongfang E-mail: songbo@suda.edu.cn

    2015-08-10

    Double cathode buffer layers (CBLs) composed of fullerene derivative functionalized with a crown-ether end group in its side chain (denoted as PCBC) and a LiF layer were introduced between the PCBM acceptor layer and the top cathode in planar p-i-n perovskite solar cells (pero-SCs) based on CH{sub 3}NH{sub 3}PbI{sub 3−X}Cl{sub X}. The devices with the PCBC/LiF double CBLs showed significant improvements in power conversion efficiency (PCE) and long-term stability when compared to the device with LiF single CBL. Through optimizing the spin-coating speed of PCBC, a maximum PCE of 15.53% has been achieved, which is approximately 15% higher than that of the device with single LiF CBL. The remarkable improvement in PCE can be attributed to the formation of a better ohmic contact in the CBL between PCBC and LiF/Al electrode arising from the dipole moment of PCBC, leading to the enhanced fill factor and short-circuit current density (J{sub sc}). Besides the PCE, the long-term stability of the devices with PCBC interlayer is also superior to that of the device with LiF single CBL, which is due to the more effective protection for the perovskite/PCBM interface.

  18. Lead (II) ion detection in surface water with pM sensitivity using aza-crown-ether-modified silver nanoparticles via dynamic light scattering.

    PubMed

    Zhang, Liang; Yao, Yao; Shan, Jin; Li, Haibing

    2011-07-08

    In this paper, we reported ultrasensitive lead ion detection in environmental water with pM sensitivity using aza-crown-ether-modified silver nanoparticles (ACE-Ag NPs) through dynamic light scattering (DLS). The colorimetric method based on ACE-Ag NPs is not capable of detecting Pb2+ ions over other metal ions (Fe3+, Co2+, Cu2+, Hg2+, Cd2+, Ag+, Li+, Na+, K+ and Cs+) with high sensitivity. But DLS has improved the selectivity and sensitivity of the Pb2+ detection system (50-fold or more) over colorimetric method, and its detection limit is 0.25 pM (1.03 ppt). The Pb2+ DLS assay can be applied to detect Pb2+ in the environmental water, such as in Yangtze and East Lake water samples with a detection limit of 0.20 and 0.22 pM, which is much lower than the maximum contamination level of 4.8×10(-8) M for lead in surface water defined by the national environmental quality standards of China (GB 3838-2002). Also, this method has a good performance in the determination of Pb2+ in drinking water, which is much lower than the maximum contamination level (MCL) of 72 nM for lead as defined by the US Environmental Protection Agency (EPA).

  19. Effects of 12-crown-4 ether on the electrochemical performance of CoO2 and TiS2 cathodes in Li polymer electrolyte cells

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Attia, Alan I.; Halpert, G.

    1992-01-01

    The effect of adding 12-crown-4 ether (12Cr4) to the polyethylene oxide (PEO) electrolyte on the electrochemical properties of cells with Li(x)CoO2 or TiS2 as the cathode was investigated. The polymer electrolyte films were: (1) PEO, LiBF4; (2) PEO, LiBF4 with 12Cr4; (3) Li(x)CoO2, PEO, and LiBF4; and (4) Li(x)CoO2, PEO, LiBF4, and 12Cr4. It was found that, although 12Cr4 improved the cell performance over cells without 12Cr4 in the shallow c/d cycles (cyclic voltammetric behavior), it did not seem to prolong the active life of the cell. The cells with CoO2 as the cathode failed after a few c/d cycles, while similar cells with TiS2 did not fail even after 12 c/d cycles. The probable cause of failure in the case of CoO2 is ascribed to the instability of the CoO2 cathode.

  20. A novel fluorescent probe for Cr(3+) based on rhodamine-crown ether conjugate and its application to drinking water examination and bioimaging.

    PubMed

    Diao, Quanping; Ma, Pinyi; Lv, Linlin; Li, Tiechun; Wang, Xinghua; Song, Daqian

    2016-03-05

    A trivalent chromium (Cr(3+)) fluorescence probe (RhC) was designed and synthesized via Schiff base reaction based on rhodamine-crown ether conjugate. This probe displayed a favorable selectivity for Cr(3+) over a range of other common metal ions in DMF/H2O (3:7, v/v; PBS buffer 50 mmol L(-1); pH=6.8) solution, leading to prominent fluorescence "OFF-ON" switching of the rhodamine fluorophore. The limit of detection was calculated to be 1.5 μmol L(-1) (S/N=3). The binding ratio of RhC-Cr(3+) complex was determined to be 1:2 according to the Job's plot and HR-MS. The probe was successfully applied to examination of Cr(3+) in drinking water spiked samples. The average recoveries ranged from 104.9% to 106.9% at spiked concentration level of 10.00 μmol L(-1), and the obtained results were consistent with those obtained using atomic absorption spectrometry (AAS). Moreover, bioimaging experiments showed that RhC can sense the Cr(3+) in living cells with a fluorescence enhancement signal. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Sorption reaction mechanism of some hazardous radionuclides from mixed waste by impregnated crown ether onto polymeric resin.

    PubMed

    Shehata, F A; Attallah, M F; Borai, E H; Hilal, M A; Abo-Aly, M M

    2010-02-01

    A novel impregnated polymeric resin was practically tested as adsorbent material for removal of some hazardous radionuclides from radioactive liquid waste. The applicability for the treatment of low-level liquid radioactive waste was investigated. The material was prepared by loading 4,4'(5')di-t-butylbenzo 18 crown 6 (DtBB18C6) onto poly(acrylamide-acrylic acid-acrylonitril)-N, N'-methylenediacrylamide (P(AM-AA-AN)-DAM). The removal of (134)Cs, (60)Co, (65)Zn , and ((152+154))Eu onto P(AM-AA-AN)-DAM/DtBB18C6 was investigated using a batch equilibrium technique with respect to the pH, contact time, and temperature. Kinetic models are used to determine the rate of sorption and to investigate the mechanism of sorption process. Five kinetics models, pseudo-first-order, pseudo-second-order, intra-particle diffusion, homogeneous particle diffusion (HPDM), and Elovich models, were used to investigate the sorption process. The obtained results of kinetic models predicted that, pseudo-second-order is applicable; the sorption is controlled by particle diffusion mechanism and the process is chemisorption. The obtained values of thermodynamics parameters, DeltaH degrees , DeltaS degrees , and DeltaG degrees indicated that the endothermic nature, increased randomness at the solid/solution interface and the spontaneous nature of the sorption processes. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  2. Alkaline-Side Extraction of Cesium from Savannah River Tank Waste Using a Calixarene-Crown Ether Extractant

    SciTech Connect

    Bonnesen, P.V.; Delmau, L.H.; Haverlock, T.J.; Moyer, B.A.

    1998-12-01

    Results are presented supporting the viability of the alkaline-side CSEX process as a potential replacement for the In-Tank Precipitation process for removal of cesium from aqueous high-level waste (HLW) at the Savannah River Site (SRS). Under funding from the USDOE Efficient Separations and Crosscutting program, a flowsheet was suggested in early June of 1998, and in the following four months, this flowsheet underwent extensive testing, both in batch tests at ORNL and ANL and in two centrifugal-contactor tests at ANL. To carry out these tests, the initial ESP funding was augmented by direct funds from Westinghouse Savannah River Corporation. The flowsheet employed a solvent containing a calixarene-crown hybrid compound called BoBCalixC6 that was invented at ORNL and can now be obtained commercially for government use from IBC Advanced Technologies. This special extractant is so powerful and selective that it can be used at only 0.01 M, compensating for its expense, but a modifier is required for use in an aliphatic diluent, primarily to increase the cesium distribution ratio D{sub Cs} in extraction. The modifier selected is a relatively economical fluorinated alcohol called Cs3, invented at ORNL and so far available. only from ORNL. For the flowsheet, the modifier is used at 0.2 M in the branched aliphatic kerosene Isopar{reg_sign} L. Testing at ORNL and ANL involved simulants of the SRS HLW. After extraction of the Cs from the waste simulant, the solvent is scrubbed with 0.05 M HNO{sub 3} and stripped with a solution comprised of 0.0005 M HNO{sub 3} and 0.0001 M CsNO{sub 3}. The selection of these conditions is justified in this report, both on the basis of experimental data and underlying theory.

  3. Synergistic adsorption of heavy metal ions and organic pollutants by supramolecular polysaccharide composite materials from cellulose, chitosan and crown ether.

    PubMed

    Mututuvari, Tamutsiwa M; Tran, Chieu D

    2014-01-15

    We have developed a simple one-step method to synthesize novel supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS) and benzo-15-crown 5 (B15C5). Butylmethylimidazolium chloride [BMIm(+)Cl(-)], an ionic liquid (IL), was used as a sole solvent for dissolution and preparation of the composites. Since majority of [BMIm(+)Cl(-)] used was recovered for reuse, the method is recyclable. The [CEL/CS+B15C5] composites obtained retain properties of their components, namely superior mechanical strength (from CEL), excellent adsorption capability for heavy metal ions and organic pollutants (from B15C5 and CS). More importantly, the [CEL/CS+B15C5] composites exhibit truly supramolecular properties. By itself CS, CEL and B15C5 can effectively adsorb Cd(2+), Zn(2+) and 2,4,5-trichlorophenol. However, adsorption capability of the composite was substantially and synergistically enhanced by adding B15C5 to either CEL and/or CS. That is, the adsorption capacity (qe values) for Cd(2+) and Zn(2+) by [CS+B15C5], [CEL+B15C5] and [CEL+CS+B15C5] composites are much higher than combined qe values of individual CS, CEL and B15C5 composites. It seems that B15C5 synergistically interact with CS (or CEL) to form more stable complexes with Cd(2+) (or Zn(2+)), and as a consequence, the [CS+B15C5] (or the [CEL+B15C5]) composite can adsorb relatively larger amount Cd(2+) (or Zn(2+)). Moreover, the pollutants adsorbed on the composites can be quantitatively desorbed to enable the [CS+CEL+B15C5] composites to be reused with similar adsorption efficiency.

  4. Synergistic adsorption of heavy metal ions and organic pollutants by supramolecular polysaccharide composite materials from cellulose, chitosan and crown ether

    PubMed Central

    Mututuvari, Tamutsiwa M.; Tran, Chieu D.

    2013-01-01

    We have developed a simple one-step method to synthesize novel supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS) and benzo-15-crown 5 (B15C5). Butylmethylimidazolium chloride [BMIm+Cl−], an ionic liquid (IL), was used as a sole solvent for dissolution and preparation of the composites. Since majority of [BMIm+Cl−] used was recovered for reuse, the method is recyclable. The [CEL/CS + B15C5] composites obtained retain properties of their components, namely superior mechanical strength (from CEL), excellent adsorption capability for heavy metal ions and organic pollutants (from B15C5 and CS). More importantly, the [CEL/CS + B15C5] composites exhibit truly supramolecular properties. By itself CS, CEL and B15C5 can effectively adsorb Cd2+, Zn2+ and 2,4,5-trichlorophenol. However, adsorption capability of the composite was substantially and synergistically enhanced by adding B15C5 to either CEL and/or CS. That is, the adsorption capacity (qe values) for Cd2+ and Zn2+ by [CS + B15C5], [CEL + B15C5] and [CEL + CS + B15C5] composites are much higher than combined qe values of individual CS, CEL and B15C5 composites. It seems that B15C5 synergistically interact with CS (or CEL) to form more stable complexes with Cd2+ (or Zn2+), and as a consequence, the [CS + B15C5] (or the [CEL + B15C5]) composite can adsorb relatively larger amount Cd2+ (or Zn2+). Moreover, the pollutants adsorbed on the composites can be quantitatively desorbed to enable the [CS + CEL + B15C5] composites to be reused with similar adsorption efficiency. PMID:24333678

  5. LArIAT: Worlds First Pion-Argon Cross-Section

    SciTech Connect

    Hamilton, Pip

    2016-11-02

    The LArIAT experiment has performed the world's first measurement of the total charged-current pion cross-section on an argon target, using the repurposed ArgoNeuT detector in the Fermilab test beam. Presented here are the results of that measurement, along with an overview of the LArIAT experiment and details of the LArIAT collaboration's plans for future measurements.

  6. Multistate λ-local-elevation umbrella-sampling (MS-λ-LEUS): method and application to the complexation of cations by crown ethers.

    PubMed

    Bieler, Noah S; Tschopp, Jan P; Hünenberger, Philippe H

    2015-06-09

    An extension of the λ-local-elevation umbrella-sampling (λ-LEUS) scheme [ Bieler et al. J. Chem. Theory Comput. 2014 , 10 , 3006 ] is proposed to handle the multistate (MS) situation, i.e. the calculation of the relative free energies of multiple physical states based on a single simulation. The key element of the MS-λ-LEUS approach is to use a single coupling variable Λ controlling successive pairwise mutations between the states of interest in a cyclic fashion. The Λ variable is propagated dynamically as an extended-system variable, using a coordinate transformation with plateaus and a memory-based biasing potential as in λ-LEUS. Compared to other available MS schemes (one-step perturbation, enveloping distribution sampling and conventional λ-dynamics) the proposed method presents a number of important advantages, namely: (i) the physical states are visited explicitly and over finite time periods; (ii) the extent of unphysical space required to ensure transitions is kept minimal and, in particular, one-dimensional; (iii) the setup protocol solely requires the topologies of the physical states; and (iv) the method only requires limited modifications in a simulation code capable of handling two-state mutations. As an initial application, the absolute binding free energies of five alkali cations to three crown ethers in three different solvents are calculated. The results are found to reproduce qualitatively the main experimental trends and, in particular, the experimental selectivity of 18C6 for K(+) in water and methanol, which is interpreted in terms of opposing trends along the cation series between the solvation free energy of the cation and the direct electrostatic interactions within the complex.

  7. Novel 15-crown-5 ether or beta-diketone incorporated gadolinium complexes for the detection of potassium ions or magnesium and calcium ions.

    PubMed

    Hifumi, Hiroki; Tanimoto, Akihiro; Citterio, Daniel; Komatsu, Hirokazu; Suzuki, Koji

    2007-11-01

    Novel gadolinium complexes (KMR-series: KMR-K and KMR-Mg), which have a bis-15-crown-5 ether or a charged beta-diketone structure as a recognition site, have been designed, synthesized and applied for the detection of K(+) or of Mg(2+) and Ca(2+) using MRI or NMR techniques. The measurements are based on the modulation of the longitudinal relaxation time (T(1)) of water protons in proximity of the gadolinium complexes. Relaxivity measurements of KMR-K1 in aqueous solution showed that the initial longitudinal relaxivity value (r(1)) of 5.05 mM(-1) s(-1) is monotonously decreasing with increasing K(+) concentrations, reaching a final value of 4.78 mM(-1) s(-1). This decrease is attributed to a change in the second sphere of hydration of the gadolinium (Gd(3+)) complex (KMR-K), resulting in a K(+) concentration-dependent contrast in MR images. From stoichiometric analysis using mass spectrometry and UV/VIS spectrometry, a 1 : 1 complex formation between KMR-K1 and K(+) in a sandwich-type manner with a log K of 3.20 was confirmed. In the case of KMR-Mg, the initial r(1) value of 4.98 mM(-1) s(-1) is monotonously decreasing with increasing Mg(2+) or Ca(2+) concentrations, reaching a final value of 3.95 or 4.16 mM(-1) s(-1), respectively, resulting in Mg(2+) and Ca(2+) concentration-dependent contrast in MR images. The formation of a 1:1 complex with a log K of 2.33 for Mg(2+) and 1.91 for Ca(2+) was confirmed. KMR-K1 and KMR-Mg are the first ion-selective or ion-sensitive gadolinium complexes for K(+) or Mg(2+) and Ca(2+), respectively.

  8. Scintillation Light Detection System in LArIAT

    SciTech Connect

    Kryczynski, Pawel

    2016-02-29

    The LArIAT experiment is currently taking data at Fermilab using a Liquid Argon TPC, with the aim of studying particle interactions and characterizing detector response for neutrino detectors using argon. In parallel, it serves as a test-bench to develop and evaluate the performance of the simulation, reconstruction, and analysis software used in LAr neutrino experiments. LArIAT also takes advantage of the scintillating capabilities of liquid argon and will evaluate the feasibility of using the light signal to determine calorimetric information and particle identification. To test this possibility, a scintillation light detection system consisting of high Quantum Efficiency (QE) PMT and Silicon Photomultiplier (SiPM) devices is installed in the cryostat, viewing the interior of the TPC. Light collection efficiency is maximized by means of lining the walls with reflector foils covered by a wavelength shifter layer. Collecting the light reflected at the boundaries of the active volume greatly improves also the uniformity of the light yield. Presented here are initial results of the LArIAT light detection system calibration together with the preliminary results of the dedicated simulation and its application in future LAr TPC experiments

  9. Liquid argon scintillation light studies in LArIAT

    SciTech Connect

    Kryczynski, Pawel

    2016-10-12

    The LArIAT experiment is using its Liquid Argon Time Projection Chamber (LArTPC) in the second run of data-taking at the Fermilab Test Beam Facility. The goal of the experiment is to study the response of LArTPCs to charged particles of energies relevant for planned neutrino experiments. In addition, it will help to develop and evaluate the performance of the simulation, analysis, and reconstruction software used in other LAr neutrino experiments. Particles from a tertiary beam detected by LArIAT (mainly protons, pions and muons) are identified using a set of beamline detectors, including Wire Chambers, Time of Flight counters and Cherenkov counters, as well as a simplified sampling detector used to detect muons. In its effort towards augmenting LArTPC technology for other neutrino experiments, LArIAT also takes advantage of the scintillating capabilities of LAr and is testing the possibility of using the light signal to help reconstruct calorimetric information and particle ID. In this report, we present results from these studies of the scintillation light signal to evaluate detector performance and calorimetry.

  10. Liquid argon scintillation light studies in LArIAT

    NASA Astrophysics Data System (ADS)

    Kryczynski, Pawel; LArIAT Collaboration

    2017-09-01

    The LArIAT experiment is using its Liquid Argon Time Projection Chamber (LArTPC) in the second run of data-taking at the Fermilab Test Beam Facility. The goal of the experiment is to study the response of LArTPCs to charged particles of energies relevant for planned neutrino experiments. In addition, it will help to develop and evaluate the performance of the simulation, analysis, and reconstruction software used in other LAr neutrino experiments. Particles from a tertiary beam detected by LArIAT (mainly protons, pions and muons) are identified using a set of beamline detectors, including Wire Chambers, Time of Flight counters and Cherenkov counters, as well as a simplified sampling detector used to detect muons. In its effort towards augmenting LArTPC technology for other neutrino experiments, LArIAT also takes advantage of the scintillating capabilities of LAr and is testing the possibility of using the light signal to help reconstruct calorimetric information and particle ID. In this report, we present results from these studies of the scintillation light signal to evaluate detector performance and calorimetry.

  11. New NO donor ligands and complexes containing furfuryl or crown ether moiety: Syntheses, crystal structures and tautomerism in ortho-hydroxy substituted compounds as studied by UV-vis spectrophotometry

    NASA Astrophysics Data System (ADS)

    Şahin, Duygu; Koçoğlu, Serhat; Şener, Öznur; Şenol, Cemal; Dal, Hakan; Hökelek, Tuncer; Hayvalı, Zeliha

    2015-12-01

    NO donor ligands were prepared by the condensation of methoxy substituted salicylaldehyde with 5-methylfurfurylamine (1 and 2) and 4‧-aminobenzo-15-crown 5 (3-5). New crown ether ligands of Schiff base type (3-5) containing recognition sites for alkali metal and transition guest cations. Ni(II) complexes (1a-5a) have been synthesized with bidentate NO donor Schiff base ligands (1-5) with Ni(CH3COO)2.·4H2O. Monotopic crystalline 1:1 (Na+:ligand) sodium complexes (3b-5b) of the crown ether ligands were also prepared. Schiff bases (1-5) and complexes (1a-5a, 3b-5b) were characterized by elemental analyses, FT-IR, 1H-, 13C-NMR and mass spectroscopies. The crystal structures of 1, 1a and 2 were verified by X-ray diffraction analysis. The tautomeric equilibria (phenol-imine, O-H⋯N and keto-amine, O⋯H-N forms) have been systematically studied by using UV-vis spectrophotometry for the o-hydroxy substituted compounds (1-5). The UV-visible spectra of these ligands (1-5) were recorded and commented in polar, non-polar, acidic and basic media.

  12. Intron Lariat RNA Inhibits MicroRNA Biogenesis by Sequestering the Dicing Complex in Arabidopsis

    PubMed Central

    Cheng, Jinping; Su, Chuanbin; Zhong, Songxiao; Liu, Qi; Fang, Yuda; Yu, Yao; Lv, Hong; Zheng, Yun

    2016-01-01

    Lariat RNAs formed as by-products of splicing are quickly degraded by the RNA debranching enzyme 1 (DBR1), leading to their turnover. Null dbr1 mutants in both animals and plants are embryo lethal, but the mechanism underlying the lethality remains unclear. Here we characterized a weak mutant allele of DBR1 in Arabidopsis, dbr1-2, and showed that a global increase in lariat RNAs was unexpectedly accompanied by a genome-wide reduction in miRNA accumulation. The dbr1-2 mutation had no effects on expression of miRNA biogenesis genes or primary miRNAs (pri-miRNAs), but the association of pri-miRNAs with the DCL1/HYL1 dicing complex was impaired. Lariat RNAs were associated with the DCL1/HYL1 dicing complex in vivo and competitively inhibited the binding of HYL1 with pri-miRNA. Consistent with the impacts of lariat RNAs on miRNA biogenesis, over-expression of lariat RNAs reduced miRNA accumulation. Lariat RNAs localized in nuclear bodies, and partially co-localize with HYL1, and both DCL1 and HYL1 were mis-localized in dbr1-2. Together with our findings that nearly four hundred lariat RNAs exist in wild type plants and that these lariat RNAs also associate with the DCL1/HYL1 dicing complex in vivo, we thus propose that lariat RNAs, as decoys, inhibit miRNA processing, suggesting a hitherto unknown layer of regulation in miRNA biogenesis. PMID:27870853

  13. Widespread alternative and aberrant splicing revealed by lariat sequencing

    PubMed Central

    Stepankiw, Nicholas; Raghavan, Madhura; Fogarty, Elizabeth A.; Grimson, Andrew; Pleiss, Jeffrey A.

    2015-01-01

    Alternative splicing is an important and ancient feature of eukaryotic gene structure, the existence of which has likely facilitated eukaryotic proteome expansions. Here, we have used intron lariat sequencing to generate a comprehensive profile of splicing events in Schizosaccharomyces pombe, amongst the simplest organisms that possess mammalian-like splice site degeneracy. We reveal an unprecedented level of alternative splicing, including alternative splice site selection for over half of all annotated introns, hundreds of novel exon-skipping events, and thousands of novel introns. Moreover, the frequency of these events is far higher than previous estimates, with alternative splice sites on average activated at ∼3% the rate of canonical sites. Although a subset of alternative sites are conserved in related species, implying functional potential, the majority are not detectably conserved. Interestingly, the rate of aberrant splicing is inversely related to expression level, with lowly expressed genes more prone to erroneous splicing. Although we validate many events with RNAseq, the proportion of alternative splicing discovered with lariat sequencing is far greater, a difference we attribute to preferential decay of aberrantly spliced transcripts. Together, these data suggest the spliceosome possesses far lower fidelity than previously appreciated, highlighting the potential contributions of alternative splicing in generating novel gene structures. PMID:26261211

  14. Crown ether-modified electrodes for the simultaneous stripping voltammetric determination of Cd(II), Pb(II) and Cu(II).

    PubMed

    Serrano, Núria; González-Calabuig, Andreu; del Valle, Manel

    2015-06-01

    This work describes the immobilization of 4-carboxybenzo-18-crown-6 (CB-18-crown-6) and 4-carboxybenzo-15-crown-5 (CB-15-crown-5) assisted by lysine on aryl diazonium salt monolayers anchored to the surface of graphite-epoxy composite electrodes (GEC), and their use for the simultaneous determination of Cd(II), Pb(II) and Cu(II) by differential pulse anodic stripping voltammetry (DPASV). These modified electrodes display a good repeatability and reproducibility with detection and quantification limits at levels of µg L(-1) (ppb), confirming their suitability for the determination of Cd(II), Pb(II) and Cu(II) ions in environmental samples. The overlapped nature of the multimetal stripping measurements was resolved by employing the two-sensor array CB-15-crown-5-GEC and CB-18-crown-6-GEC, since the metal complex selectivity exhibited by the considered ligands could add some discrimination power. For the processing of the voltammograms, Discrete Wavelet Transform and Causal Index were selected as preprocessing tools for data compression coupled with an artificial neural network for the modeling of the obtained responses, allowing the resolution of mixtures of these metals with good prediction of their concentrations (correlation with expected values for an external test subset better than 0.942).

  15. The First Pion-Ar Cross-Section Measurement with the LArIAT Experiment

    SciTech Connect

    Nutini, Irene

    2016-01-01

    A complete understanding of neutrinos properties requires a study and a characterization of the interactions of the daughter particles created in a neutrino-nucleus interaction. The Liquid Argon In A Testbeam (LArIAT) experiment is a small-scale liquid argon detector situated in the Fermilab Test Beam Facility. The LArIAT experiment is exposed to a tertiary beam comprised of mostly pions along with a mix of muons, protons, kaons, and electrons. LArIAT's goal is to characterize the response of the LArTPC to known incoming charged particles and measure their interactions in Argon, in order to understand their cross-sections and to help developing and tuning simulations and reconstruction algorithms for LArTPC neutrino experiments. The world's rst measurement of a pion cross-section on an Argon target, made with the LArIAT detector, is presented here.

  16. Dental crowns

    MedlinePlus

    ... off when the child loses the baby tooth. Metal crowns: Hold up to chewing and teeth grinding ... porcelain crowns: Wear down opposing teeth more than metal crowns Match the color of other teeth May ...

  17. Supramolecular photochemistry and photophysics. Mutual inhibition of host and guest photochemistry and luminescence in the adduct of an anthraceno-crown ether with Pt(bpy)(NH sub 3 ) sub 2 sup 2+

    SciTech Connect

    Prodi, L.; Gandolfi, M.T.; Balzani, V. ); Ballardini, R. ); Desvergne, J.P.; Bouas-Laurent, H. )

    1991-03-07

    Pt(bpy)(NH{sub 3}){sub 2}{sup 2+} forms a 1:1 adduct with the anthraceno-crown ether 2. The adduct formation causes (i) strong changes in the absorption spectra of the two components, (ii) the quenching of the luminescence and photoreactivity of both Pt(bpy)(NH{sub 3}){sub 2}{sup 2+} and 2, and (iii) the appearance of a new, broad, low-energy emission band at 77 K. It is suggested that the adduct exhibits a sandwich-type conformation in which the Pt complex is inserted between the two aromatic moieties of 2. Such a structure allows the stabilization of the adduct via both hydrogen bonds and {pi}-{pi} interactions and accounts for the mutual protection of the two components toward their luminescence and photoreactivity.

  18. Studies of a pyridino-crown ether-based chiral stationary phase on the enantioseparation of biogenic chiral aralkylamines and α-amino acid esters by high-performance liquid chromatography.

    PubMed

    Lévai, Sándor; Németh, Tamás; Fődi, Tamás; Kupai, József; Tóth, Tünde; Huszthy, Péter; Balogh, György Tibor

    2015-11-10

    This paper reports the enantioseparation ability of a pyridino-18-crown-6 ether-based chiral stationary phase [(S,S)-CSP-1]. The enantiomeric discrimination of chiral stationary phase (S,S)-CSP-1 was evaluated by HPLC using the mixtures of enantiomers of various protonated primary aralkylamines [1-phenylethylamine hydrogen perchlorate (PEA), 2,3-dihydro-1H-inden-1-amine (1-aminoindan), 2,2'-(1,2-diaminoethane-1,2-diyl) diphenol (HPEN)] and perchlorate salts of α-amino acid esters [alanine benzyl ester (Ala-OBn), phenylalanine benzyl ester (Phe-OBn), phenylalanine methyl ester (Phe-OMe), phenylglycine methyl ester (PhGly-OMe), glutamic acid dibenzyl ester (Glu-diOBn), and valine benzyl ester (Val-OBn)]. The best enantioseparation was achieved in the case of PEA. The high enantioselectivity was rationalized by the strong π-π interaction of the extended π system of the aryl-substituted pyridine unit.

  19. Selective O-Alkylation of the Crown Conformer of Tetra(4-hydroxyphenyl)calix[4]resorcinarene to the Corresponding Tetraalkyl Ether.

    PubMed

    Castillo-Aguirre, Alver; Rivera-Monroy, Zuly; Maldonado, Mauricio

    2017-10-04

    Reactions of glycidyl methacrylate with the crown and chair conformers of tetra(4-hydroxyphenyl)calix[4]resorcinarene were studied. The reactions were done over epoxide groups present in the ester, which can easily undergo an opening reaction with hydroxyl groups in the macrocyclic system. Initially, epoxidation reactions were carried out with pure conformers, and it was observed that the reaction between tetra(4-hydroxyphenyl)calix[4]resorcinarene fixed in the chair conformation does not occur, while for the molecule fixed in the crown conformation only one tetraalkylated derivative was obtained. The obtained product was characterized using IR, ¹H-NMR, (13)C-NMR, COSY, HMQC and HMBC techniques. An exhaustive NMR study showed that the reaction is selective at the hydroxyl groups in the lower rim, without affecting the hydroxyl groups in the upper rim. In addition, the RP-HPLC analysis of the epoxidation reaction mixture, using both crown and chair conformers, showed that only the crown conformer reacted under tested conditions. Finally, a comparative study of the reactivity of tetranonylcalix[4]resorcinarene with glycidyl methacrylate showed that the reaction does not take place. Instead, the formation of the tetranonylcalix[4]resorcinarene tetrasodium salt was observed, which confirms that the hydroxyl groups in the upper rim are unreactive under these conditions.

  20. An Alternative Method for Generating Arynes from ortho-Silylaryl Triflates: Activation by Cesium Carbonate in the Presence of a Crown Ether.

    PubMed

    Yoshida, Suguru; Hazama, Yuki; Sumida, Yuto; Yano, Takahisa; Hosoya, Takamitsu

    2015-06-01

    An alternative method for generating arynes from ortho-silylaryl triflates using cesium carbonate and 18-crown-6 is reported. The method was efficiently applied to a variety of reactions between several arynes and arynophiles. We also demonstrated that the efficiency of aryne generation is significantly affected by the alkali metal countercation of the carbonate.

  1. Absorption and biotransformation of polybrominated diphenyl ethers DE-71 and DE-79 in chicken (Gallus gallus), mallard (Anas platyrhynchos), American kestrel (Falco sparverius) and black-crowned night-heron (Nycticorax nycticorax) eggs

    USGS Publications Warehouse

    McKernan, Moira A.; Rattner, Barnett A.; Hatfield, Jeff S.; Hale, Robert C.; Ottinger, Mary Ann

    2010-01-01

    We recently reported that air cell administration of penta-brominated diphenyl ether (penta-BDE; DE-71) evokes biochemical and immunologic effects in chicken (Gallus gallus) embryos at very low doses, and impairs pipping (i.e., stage immediately prior to hatching) and hatching success at 1.8 ug g-1 egg (actual dose absorbed) in American kestrels (Falco sparverius). I n the present study, absorption of polybrominated diphenyl ether (PBDE) congeners was measured following air cell administration of a penta-BDE mixture (11.1 ug DE-71 g-1 egg) or an octa-brominated diphenyl ether mixture (octa-BDE; DE-79; 15.4 ug DE-79 g-1 egg). Uptake of PBDE congeners was measured at 24 h post-injection, midway through incubation, and at pipping in chicken, mallard (Anas platyrhynchos), and American kestrel egg contents, and at the end of incubation in black-crowned night-heron (Nycticorax nycticorax) egg contents. Absorption of penta-BDE and octa-BDE from the air cell into egg contents occurred throughout incubation; at pipping, up to 29.6% of penta-BDE was absorbed, but only 1.40-6.48% of octa-BDE was absorbed. Higher brominated congeners appeared to be absorbed more slowly than lower brominated congeners, and uptake rate was inversely proportional to the log Kow of predominant BDE congeners. Six congeners or co-eluting pairs of congeners were detected in penta-BDE-treated eggs that were not found in the dosing solution suggesting debromination in the developing embryo, extraembryonic membranes, and possibly even in the air cell membrane. This study demonstrates the importance of determining the fraction of xenobiotic absorbed into the egg following air cell administration for estimation of the lowest-observed-effect level.

  2. Modulation of the Excited-State Dynamics of 2,2'-Bipyridine-3,3'-diol in Crown Ethers: A Possible Way To Control the Morphology of a Glycine Fibril through Fluorescence Lifetime Imaging Microscopy.

    PubMed

    Banik, Debasis; Roy, Arpita; Kundu, Niloy; Sarkar, Nilmoni

    2016-11-03

    In this article, we have investigated the modulation of excited-state intramolecular double proton transfer (ESIDPT) dynamics of 2,2'-bipyridine-3,3'-diol (BP(OH)2) in two crown ethers (CEs), namely, 18-Crown-6 (18C6) and 15-Crown-5 (15C5). From steady-state UV-visible measurements, we have shown that there is no significant interaction between the dienol tautomeric form of BP(OH)2 and two CEs. However, in the presence of CEs, an additional emission band (∼415 nm) is generated along with the diketo tautomer band (∼465 nm). In time-resolved analysis, we have observed the generation of ∼260 ps rise component in the presence of 18C6. Therefore, by combining the results of steady-state and time-resolved emissions, we have proposed that the water-assisted ESIDPT route of BP(OH)2 generates a hydronium ion (H3O(+)) in the excited state. 18C6 binds nicely to this H3O(+) ion. As a result, retarded ESIDPT dynamics is observed in 18C6. However, as 15C5 cannot bind H3O(+) properly, no rise component is found. With the addition of potassium chloride (KCl), the contribution of the rise component decreases due to unavailability of free 18C6 cavity to capture the H3O(+) ion generated in the excited state. Addition of calcium chloride (CaCl2) leads to complete removal of the rise component due to the inhibition of the water-assisted ESIDPT route. From wavelength-dependent behavior, we have observed that the rise component is present only at 465 nm in 18C6. We have also shown that the fibrillar morphology of glycine can be successfully probed through fluorescence lifetime imaging microscopy using BP(OH)2 as an imaging agent. Modulation of fibrillar morphology has been found in the presence of two CEs. The interaction of glycine fiber with CEs can be explained by lifetime distribution analysis.

  3. Crown Gall

    USDA-ARS?s Scientific Manuscript database

    Crown gall disease occurs on diverse dicotyledonous and gymnospermous plant species worldwide. Reports of crown gall on hop date back to at least 1929, and the disease has been reported from most countries where hop is or has been grown commercially. The epidemiology of the causal bacterium, Agrob...

  4. Application of lariat lock catch knot suture in the achilles tendon rupture

    PubMed Central

    Wang, Baocang; Feng, Xiaona; Yan, Ming; Wang, Hui; Li, Yong

    2015-01-01

    The aim of this study was to summarize the clinical experience of repairing the Achilles tendon rupture by lariat lock catch knot suture. Between January 2011 and February, 2014, 32 cases of the Achilles tendon rupture were treated by lariat lock catch knot suture. There were 26 males and 6 females, with the average age of 39 years (range 17-53 years), including 13 left knees and 19 right knees. 29 wounds healed by first intention, and 3 cases who were performed local flap transfer due to necrosis of skin were healed by second intention. Thirty-two cases were followed up 10-25 months (13 months on average). No re-rupture of Achilles tendon or deep infection occurred during follow-up period. According to Arner-Lindholm assessment standard, the results were excellent in 19 cases and good in 13 cases, the excellent and good rate was 100%. Lariat lock catch knot suture is a safe and effective method for repairing Achilles tendon. PMID:26770612

  5. Speciation of a group I intron into a lariat capping ribozyme

    PubMed Central

    Meyer, Mélanie; Nielsen, Henrik; Oliéric, Vincent; Roblin, Pierre; Johansen, Steinar D.; Westhof, Eric; Masquida, Benoît

    2014-01-01

    The lariat-capping (LC) ribozyme is a natural ribozyme isolated from eukaryotic microorganisms. Despite apparent structural similarity to group I introns, the LC ribozyme catalyzes cleavage by a 2′,5′ branching reaction, leaving the 3′ product with a 3-nt lariat cap that functionally substitutes for a conventional mRNA cap in the downstream pre-mRNA encoding a homing endonuclease. We describe the crystal structures of the precleavage and postcleavage LC ribozymes, which suggest that structural features inherited from group I ribozymes have undergone speciation due to profound changes in molecular selection pressure, ultimately giving rise to an original branching ribozyme family. The structures elucidate the role of key elements that regulate the activity of the LC ribozyme by conformational switching and suggest a mechanism by which the signal for branching is transmitted to the catalytic core. The structures also show how conserved interactions twist residues, forming the lariat to join chemical groups involved in branching. PMID:24821772

  6. Multiple functionalities of polyfluorene grafted with metal ion-intercalated crown ether as an electron transport layer for bulk-heterojunction polymer solar cells: optical interference, hole blocking, interfacial dipole, and electron conduction.

    PubMed

    Liao, Sih-Hao; Li, Yi-Lun; Jen, Tzu-Hao; Cheng, Yu-Shan; Chen, Show-An

    2012-09-05

    We present a novel electron transport (ET) polymer composed of polyfluorene grafted with a K(+)-intercalated crown ether involving six oxygen atoms (PFCn6:K(+)) for bulk-heterojunction polymer solar cells (PSCs) with regioregular poly(3-hexylthiophene) (P3HT) as the donor and indene-C(60) bisadduct (ICBA) or indene-[6,6]-phenyl-C(61)-butyric acid methyl ester (IPCBM) as the acceptor in the active layer and with Al or Ca/Al as the cathode. A remarkable improvement in the power conversion efficiency (PCE) (measured in air) was observed upon insertion of this ET layer, which increased the PCE from 5.78 to 7.5% for a PSC with ICBA and Ca/Al (5.53 to 6.63% with IPCBM) and from 3.87 to 6.88% for a PSC with ICBA and Al (3.06 to 6.21% with IPCBM). This ET layer provides multiple functionalities: (1) it generates an optical interference effect for redistribution of light intensity as an optical spacer; (2) it blocks electron-hole recombination at the interface with the cathode; (3) it forms an interfacial dipole that promotes the vacuum level of the cathode metal; and (4) it enhances electron conduction, as evidenced by (1) the increase in total absorption of 1:1 w/w P3HT:ICBA by a factor of 1.3; (2) the reduction in the hole-only current density profile by a factor of 3.3 at 2.0 × 10(5) V/cm; (3) the decrease of 0.81 eV in the work function of Al from 4.28 to 3.47 eV, as determined by UV photoelectron spectroscopy; and (4) the decrease in the series resistance of PSCs with ICBA and Al by a factor of 4.5, as determined by the current-voltage characteristic under dark conditions; respectively. The PSC of 7.5% is the highest among the reported values for PSC systems with the simplest donor polymer, P3HT.

  7. Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems.

    PubMed

    Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie; Di Bernardo, Plinio; Grenthe, Ingmar

    2015-10-07

    The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-) is slow on the (17)O chemical shift time-scale, while the exchange between TMA[(UO2)(O2)(CO3)]6(11-) and Na[(UO2)(O2)(CO3)]6(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed.

  8. Crown wart

    USDA-ARS?s Scientific Manuscript database

    Crown wart has been found widely distributed in Australia, New Zealand, and European countries. It has been recorded sporadically in India (Punjab), South Africa, South America (Ecuador, Chile, Peru), Panama, Mexico, and Canada (British Columbia). In the United States, it has been found more frequ...

  9. Molecular characterization of a new member of the lariat capping twin-ribozyme introns

    PubMed Central

    2014-01-01

    Background Twin-ribozyme introns represent a complex class of mobile group I introns that harbour a lariat capping (LC) ribozyme and a homing endonuclease gene embedded in a conventional self-splicing group I ribozyme (GIR2). Twin-ribozyme introns have so far been confined to nucleolar DNA in Naegleria amoeboflagellates and the myxomycete Didymium iridis. Results We characterize structural organization, catalytic properties and molecular evolution of a new twin-ribozyme intron in Allovahlkampfia (Heterolobosea). The intron contains two ribozyme domains with different functions in ribosomal RNA splicing and homing endonuclease mRNA maturation. We found Allovahlkampfia GIR2 to be a typical group IC1 splicing ribozyme responsible for addition of the exogenous guanosine cofactor (exoG), exon ligation and circularization of intron RNA. The Allovahlkampfia LC ribozyme, by contrast, represents an efficient self-cleaving ribozyme that generates a small 2′,5′ lariat cap at the 5′ end of the homing endonuclease mRNA, and thus contributes to intron mobility. Conclusions The discovery of a twin-ribozyme intron in a member of Heterolobosea expands the distribution pattern of LC ribozymes. We identify a putative regulatory RNA element (AP2.1) in the Allovahlkampfia LC ribozyme that involves homing endonuclease mRNA coding sequences as an important structural component. PMID:25342998

  10. Inhibition of RNA lariat debranching enzyme suppresses TDP-43 toxicity in ALS disease models

    PubMed Central

    Armakola, Maria; Higgins, Matthew J.; Figley, Matthew D.; Barmada, Sami J.; Scarborough, Emily A.; Diaz, Zamia; Fang, Xiaodong; Shorter, James; Krogan, Nevan J.; Finkbeiner, Steven; Farese, Robert V.; Gitler, Aaron D.

    2012-01-01

    ALS is a devastating neurodegenerative disease primarily affecting motor neurons. Mutations in TDP-43 cause some forms of the disease, and cytoplasmic TDP-43 aggregates accumulate in degenerating neurons of most ALS patients. Thus, strategies aimed at targeting the toxicity of cytoplasmic TDP-43 aggregates may be effective. Here we report results from two genome-wide loss-of-function TDP-43 toxicity suppressor screens in yeast. The strongest suppressor of TDP-43 toxicity was deletion of Dbr1, which encodes RNA lariat debranching enzyme. We show that in the absence of Dbr1 enzymatic activity intronic lariats accumulate in the cytoplasm and likely act as decoys to sequester TDP-43 away from interfering with essential cellular RNAs and RNA-binding proteins. Knockdown of Dbr1 in a human neuronal cell line or in primary rodent neurons is also sufficient to rescue TDP-43 toxicity. Our findings provide insight into TDP-43 cytotoxicity and suggest decreasing Dbr1 activity could be a potential therapeutic approach for ALS. PMID:23104007

  11. Structural basis of lariat RNA recognition by the intron debranching enzyme Dbr1

    PubMed Central

    Montemayor, Eric J.; Katolik, Adam; Clark, Nathaniel E.; Taylor, Alexander B.; Schuermann, Jonathan P.; Combs, D. Joshua; Johnsson, Richard; Holloway, Stephen P.; Stevens, Scott W.; Damha, Masad J.; Hart, P. John

    2014-01-01

    The enzymatic processing of cellular RNA molecules requires selective recognition of unique chemical and topological features. The unusual 2′,5′-phosphodiester linkages in RNA lariats produced by the spliceosome must be hydrolyzed by the intron debranching enzyme (Dbr1) before they can be metabolized or processed into essential cellular factors, such as snoRNA and miRNA. Dbr1 is also involved in the propagation of retrotransposons and retroviruses, although the precise role played by the enzyme in these processes is poorly understood. Here, we report the first structures of Dbr1 alone and in complex with several synthetic RNA compounds that mimic the branchpoint in lariat RNA. The structures, together with functional data on Dbr1 variants, reveal the molecular basis for 2′,5′-phosphodiester recognition and explain why the enzyme lacks activity toward 3′,5′-phosphodiester linkages. The findings illuminate structure/function relationships in a unique enzyme that is central to eukaryotic RNA metabolism and set the stage for the rational design of inhibitors that may represent novel therapeutic agents to treat retroviral infections and neurodegenerative disease. PMID:25123664

  12. Structural basis of lariat RNA recognition by the intron debranching enzyme Dbr1.

    PubMed

    Montemayor, Eric J; Katolik, Adam; Clark, Nathaniel E; Taylor, Alexander B; Schuermann, Jonathan P; Combs, D Joshua; Johnsson, Richard; Holloway, Stephen P; Stevens, Scott W; Damha, Masad J; Hart, P John

    2014-01-01

    The enzymatic processing of cellular RNA molecules requires selective recognition of unique chemical and topological features. The unusual 2',5'-phosphodiester linkages in RNA lariats produced by the spliceosome must be hydrolyzed by the intron debranching enzyme (Dbr1) before they can be metabolized or processed into essential cellular factors, such as snoRNA and miRNA. Dbr1 is also involved in the propagation of retrotransposons and retroviruses, although the precise role played by the enzyme in these processes is poorly understood. Here, we report the first structures of Dbr1 alone and in complex with several synthetic RNA compounds that mimic the branchpoint in lariat RNA. The structures, together with functional data on Dbr1 variants, reveal the molecular basis for 2',5'-phosphodiester recognition and explain why the enzyme lacks activity toward 3',5'-phosphodiester linkages. The findings illuminate structure/function relationships in a unique enzyme that is central to eukaryotic RNA metabolism and set the stage for the rational design of inhibitors that may represent novel therapeutic agents to treat retroviral infections and neurodegenerative disease.

  13. Crystal structure of the inverse crown ether tetra­kis­[μ2-bis­(tri­methyl­sil­yl)amido]-μ4-oxido-dicobalt(II)disodium, [Co2Na2{μ2-N(SiMe3)2}4](μ4-O)

    PubMed Central

    Hansen, Christopher B.; Filatov, Alexander S.; Hillhouse, Gregory L.

    2016-01-01

    The title compound, [Co2Na2{μ2-N(SiMe3)2}4](μ4-O), (I), represents a new entry in the class of inverse crown ethers. In the mol­ecule, each Co atom is formally in the oxidation state +II. The structure contains one half of a unique mol­ecule per asymmetric unit with the central μ4-oxido ligand residing on an inversion center, leading to a planar coordination to the Na and Co atoms. In the crystal, bulky tri­methyl­silyl substituents prevent additional inter­actions with cobalt. However, weak inter­molecular Na⋯H3C—Si inter­actions form an infinite chain along [010]. The structure is isotypic with its Mg, Mn and Zn analogues. PMID:27308041

  14. Light-Based Triggering and Reconstruction of Michel Electrons in LArIAT

    SciTech Connect

    Foreman, W.

    2016-01-19

    The LArIAT Experiment aims to calibrate the liquid argon time projection chamber (LArTPC) using a beam of charged particles at the Fermilab Test Beam Facility. It is equipped with a novel scintillation light readout system using PMTs and custom SiPM preamplifier boards to detect light from reflector foils coated with wavelength-shifting TPB. A trigger on delayed secondary flashes of light captures events containing stopping cosmic muons together with the Michel electrons coming from their subsequent decay. This dedicated Michel trigger supplies an abundant sample of low-energy electrons throughout the detector's active volume, providing opportunities to study the combined calorimetric capabilities of the light system and the TPC. Preliminary results using scintillation light to study properties of the Michel electron sample are presented.

  15. Regiospecific solid-phase synthesis of branched oligoribonucleotides that mimic intronic lariat RNA intermediates.

    PubMed

    Katolik, Adam; Johnsson, Richard; Montemayor, Eric; Lackey, Jeremy G; Hart, P John; Damha, Masad J

    2014-02-07

    We have developed new solid phase methods for the synthesis of branched RNAs that mimic intronic lariat RNA intermediates. These methods produce branched oligoribonucleotide sequences of arbitrary length, base composition, and regiochemistry at the branchpoint junction. The methods utilize branching monomers that allow for the growth of each branch regioselectively from any of the hydroxyl positions (5′, 3′, or 2′) at the branch-point junction. The integrity and branchpoint connectivity of the synthetic products have been confirmed by HPLC and MS analysis, and cleavage of the 2′,5′ linkage by recombinant debranching enzyme. Nonhydrolyzable branched RNA analogues containing arabinose instead of ribose at the branchpoint junction were shown to inhibit debranching activity and, hence, represent “decoys” for sequestering RNA binding proteins thought to drive amyotrophic lateral sclerosis (ALS).

  16. Nonabromodiphenyl ether

    Integrated Risk Information System (IRIS)

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

  17. Pentabromodiphenyl ether

    Integrated Risk Information System (IRIS)

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

  18. Octabromodiphenyl ether

    Integrated Risk Information System (IRIS)

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

  19. Tribromodiphenyl ether

    Integrated Risk Information System (IRIS)

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

  20. Hexabromodiphenyl ether

    Integrated Risk Information System (IRIS)

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

  1. Ethyl ether

    Integrated Risk Information System (IRIS)

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

  2. Tetrabromodiphenyl ether

    Integrated Risk Information System (IRIS)

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

  3. 18-crown-6-sodium cholate complex: thermochemistry, structure, and stability.

    PubMed

    Mihelj, Tea; Tomašić, Vlasta; Biliškov, Nikola

    2014-06-03

    18-Crown-6, one of the most relevant crown ethers, and sodium cholate, a steroidal surfactant classified as a natural bile salt, are components of a novel, synthesized coordination complex: 18-crown-6-sodium cholate (18C6·NaCh). Like crown ethers, bile salts act as building blocks in supramolecular chemistry to design new functionalized materials with a desired structure and properties. In order to obtain thermal behavior of this 1:1 coordination complex, thermogravimetry and differential thermal analysis were used, as well as microscopic observations and differential scanning calorimetry. Temperature dependent infrared (IR) spectroscopy gave a detailed view into phase transitions. The structures during thermal treatment were observed with powder X-ray diffraction, and molecular models of the phases were made. Hard, glassy, colorless compound 18C6·NaCh goes through crystalline-crystalline polymorphic phase transitions at higher temperatures. The room temperature phase is indexed to a triclinic lattice, while in the high temperature phases molecules take randomly one of the two different configurations in the unit cell, resulting in the 2-fold symmetry. The formation of cholesteric liquid crystalline phase occurs simultaneously with partial decomposition, followed by the isotropization with simultaneous and complete decomposition at much higher temperature, as obtained by IR. The results provide valuable information about the relationship between molecular structure, thermal properties, and stability of the complex, indicating the importance of an appropriate choice of cation, amphiphilic, and crown ether unit in order to synthesize compounds with desired behavior.

  4. The Influence of Crown Ether and Alcohol on Unsaturation and Molar Mass of Poly(propylene oxide)s Prepared by Use of Potassium t-Butoxide: Reinvestigation of Chain Transfer Reactions

    PubMed Central

    Jurek-Suliga, Justyna; Skrzeczyna, Kinga; Gabor, Jadwiga; Łężniak, Marta

    2016-01-01

    Potassium t-butoxide dissolved in tetrahydrofuran effectively initiates homogeneous polymerization of propylene oxide at room temperature. Unsaturation and molar mass (Mn) of the polymers prepared depend on the presence of additives, such as macrocyclic ligand 18-crown-6 (L) and t-butanol. Application of the ligand alone results in distinct increase of unsaturation and decrease of Mn, whereas use of t-BuOH leads to simultaneous decrease of unsaturation and Mn. Activation of t-BuOK/t-BuOH system with the ligand causes further decrease of unsaturation, that is, from 12.0 to 3.5 mol % for OK/OH (1/3) and OK/OH/L (1/3/2) systems, respectively. Unexpectedly, Mn of the polymers obtained does not practically change (~4800). This result differs from that reported earlier for neat PO polymerization initiated potassium 1-methoxy-2-propoxide/1-methoxy-2-propanol, in which in the presence of the same ligand Mn increases to ~12 400 for the same ratio of reagents. The mechanism of studied processes was discussed. PMID:27528874

  5. Strontium nitrate extraction to ionic liquids by a crown ether: a molecular dynamics study of aqueous interfaces with C4mim+- vs C8mim+-based ionic liquids.

    PubMed

    Chaumont, A; Wipff, G

    2010-11-04

    In order to gain microscopic insights into the extraction mechanism of strontium cations by 18-crown-6 (18C6) to room temperature ionic liquids (ILs), we simulated by molecular dynamics (MD) strontium complexes in neat ionic liquids and at their interfaces with water. We compared two ILs, based on the PF(6)(-) anion and either 1-butyl-3-methylimidazolium (C(4)mim(+)) or 1-octyl-3-methylimidazolium (C(8)mim(+)) cations. Regarding the complexes, two states were considered: charged [Sr⊂18C6](2+) vs neutral [Sr⊂18C6,(NO(3))(2)], where the nitrates are either fully dissociated or coordinated to Sr. In "dry" or "humid" [C(4)mim][PF(6)] and in "dry" [C(8)mim][PF(6)] IL, the neutral complex is found to be the most stable one. In the binary IL/water solutions, the charged complexes mostly partition to the aqueous phase, whereas the neutral [Sr⊂18C6,(NO(3))(2)] complexes are more concentrated in the interfacial domain. The aqueous solutions in contact with the ionic liquids contain C(4)mim(+), but almost no C(8)mim(+) ions, supporting a classical extraction mechanism to [C(8)mim][PF(6)] and an ion exchange mechanism to [C(4)mim][PF(6)]. Furthermore, remarkable events occurred during the dynamics, where complexes were extracted to the IL phases. When compared to the interfacial landscapes obtained with the same solutes at a classical organic liquid (chloroform)/water interface, those with ILs allow us to better understand specific features of liquid-liquid extraction to ILs.

  6. Safety and Procedural Success of Left Atrial Appendage Exclusion With the Lariat Device: A Systematic Review of Published Reports and Analytic Review of the FDA MAUDE Database.

    PubMed

    Chatterjee, Saurav; Herrmann, Howard C; Wilensky, Robert L; Hirshfeld, John; McCormick, Daniel; Frankel, David S; Yeh, Robert W; Armstrong, Ehrin J; Kumbhani, Dharam J; Giri, Jay

    2015-07-01

    The Lariat device has received US Food and Drug Administration (FDA) 510(k) clearance for soft-tissue approximation and is being widely used off-label for left atrial appendage (LAA) exclusion. A comprehensive analysis of safety and effectiveness has not been reported. To perform a systematic review of published literature to assess safety and procedural success, defined as successful closure of the LAA during the index procedure, of the Lariat device. We performed a formal analytic review of the FDA MAUDE (Manufacturer and User Facility Device Experience) database to compile adverse event reports from real-world practice with the Lariat. For the systematic review, PubMed, EMBASE, CINAHL, and the Cochrane Library were searched from January 2007 through August 2014 to identify all studies reporting use of the Lariat device in 3 or more patients. The FDA MAUDE database was queried for adverse events reports related to Lariat use. Data were abstracted in duplicate by 2 physician reviewers. Events from published literature were pooled using a generic inverse variance weighting with a random effects model. Cumulative and individual adverse events were also reported using the FDA MAUDE data set. Procedural adverse events and procedural success. In the systematic review, 5 reports of Lariat device use in 309 participants were identified. Specific complications weighted for inverse of variance of individual studies were urgent need for cardiac surgery (2.3%; 7 of 309 procedures) and death (0.3%; 1 of 309 procedures). Procedural success was 90.3% (279 of 309 procedures). In the FDA MAUDE database, there were 35 unique reports of adverse events with use of the Lariat device. Among these, we identified 5 adverse event reports that noted pericardial effusion and death and an additional 23 reported urgent cardiac surgery without mention of death. This review of published reports and case reports identified risks of adverse events with off-label use of the Lariat device for LAA

  7. Metal dependence and branched RNA cocrystal structures of the RNA lariat debranching enzyme Dbr1

    SciTech Connect

    Clark, Nathaniel E.; Katolik, Adam; Roberts, Kenneth M.; Taylor, Alexander B.; Holloway, Stephen P.; Schuermann, Jonathan P.; Montemayor, Eric J.; Stevens, Scott W.; Fitzpatrick, Paul F.; Damha, Masad J.; Hart, P. John

    2016-12-06

    Intron lariats are circular, branched RNAs (bRNAs) produced during pre-mRNA splicing. Their unusual chemical and topological properties arise from branch-point nucleotides harboring vicinal 2',5'- and 3',5'-phosphodiester linkages. The 2',5'-bonds must be hydrolyzed by the RNA debranching enzyme Dbr1 before spliced introns can be degraded or processed into small nucleolar RNA and microRNA derived from intronic RNA. Here, we measure the activity of Dbr1 from Entamoeba histolytica by using a synthetic, dark-quenched bRNA substrate that fluoresces upon hydrolysis. Purified enzyme contains nearly stoichiometric equivalents of Fe and Zn per polypeptide and demonstrates turnover rates of ~3 s-1. Similar rates are observed when apo-Dbr1 is reconstituted with Fe(II)+Zn(II) under aerobic conditions. Under anaerobic conditions, a rate of ~4.0 s-1 is observed when apoenzyme is reconstituted with Fe(II). In contrast, apo-Dbr1 reconstituted with Mn(II) or Fe(II) under aerobic conditions is inactive. Diffraction data from crystals of purified enzyme using X-rays tuned to the Fe absorption edge show Fe partitions primarily to the β-pocket and Zn to the α-pocket. Structures of the catalytic mutant H91A in complex with 7-mer and 16-mer synthetic bRNAs reveal bona fide RNA branchpoints in the Dbr1 active site. A bridging hydroxide is in optimal position for nucleophilic attack of the scissile phosphate. The results clarify uncertainties regarding structure/function relationships in Dbr1 enzymes, and the fluorogenic probe permits high-throughput screening for inhibitors that may hold promise as treatments for retroviral infections and neurodegenerative disease.

  8. Metal dependence and branched RNA cocrystal structures of the RNA lariat debranching enzyme Dbr1.

    PubMed

    Clark, Nathaniel E; Katolik, Adam; Roberts, Kenneth M; Taylor, Alexander B; Holloway, Stephen P; Schuermann, Jonathan P; Montemayor, Eric J; Stevens, Scott W; Fitzpatrick, Paul F; Damha, Masad J; Hart, P John

    2016-12-20

    Intron lariats are circular, branched RNAs (bRNAs) produced during pre-mRNA splicing. Their unusual chemical and topological properties arise from branch-point nucleotides harboring vicinal 2',5'- and 3',5'-phosphodiester linkages. The 2',5'-bonds must be hydrolyzed by the RNA debranching enzyme Dbr1 before spliced introns can be degraded or processed into small nucleolar RNA and microRNA derived from intronic RNA. Here, we measure the activity of Dbr1 from Entamoeba histolytica by using a synthetic, dark-quenched bRNA substrate that fluoresces upon hydrolysis. Purified enzyme contains nearly stoichiometric equivalents of Fe and Zn per polypeptide and demonstrates turnover rates of ∼3 s(-1) Similar rates are observed when apo-Dbr1 is reconstituted with Fe(II)+Zn(II) under aerobic conditions. Under anaerobic conditions, a rate of ∼4.0 s(-1) is observed when apoenzyme is reconstituted with Fe(II). In contrast, apo-Dbr1 reconstituted with Mn(II) or Fe(II) under aerobic conditions is inactive. Diffraction data from crystals of purified enzyme using X-rays tuned to the Fe absorption edge show Fe partitions primarily to the β-pocket and Zn to the α-pocket. Structures of the catalytic mutant H91A in complex with 7-mer and 16-mer synthetic bRNAs reveal bona fide RNA branchpoints in the Dbr1 active site. A bridging hydroxide is in optimal position for nucleophilic attack of the scissile phosphate. The results clarify uncertainties regarding structure/function relationships in Dbr1 enzymes, and the fluorogenic probe permits high-throughput screening for inhibitors that may hold promise as treatments for retroviral infections and neurodegenerative disease.

  9. Structural aspects of rubidium ion selectivity by tribenzo-21-crown-7

    SciTech Connect

    Bryan, J.C.; Sachleben, R.A.; Lavis, J.M.; Davis, M.C.; Burns, J.H.; Hay, B.P.

    1998-06-01

    The structural origins of the selectivity of rubidium ion over other alkali metal ions (Cs, Rb, Na, Re) by tribenzo-21-crown-7 is investigated from single-crystal X-ray diffraction. The structures reported here are the first reported for a tribenzo-21-crown-7, and the alkali metal ion complexes are the first reported structures of these ions with any 21-crown-7 ether. Different crown conformations are observed for each structure. Molecular mechanics calculations were performed on all conformers, and the results are related to the observed extraction selectivity for rubidium.

  10. An mRNA is capped by a 2', 5' lariat catalyzed by a group I-like ribozyme.

    PubMed

    Nielsen, Henrik; Westhof, Eric; Johansen, Steinar

    2005-09-02

    Twin-ribozyme introns are formed by two ribozymes belonging to the group I family and occur in some ribosomal RNA transcripts. The group I-like ribozyme, GIR1, liberates the 5' end of a homing endonuclease messenger RNA in the slime mold Didymium iridis. We demonstrate that this cleavage occurs by a transesterification reaction with the joining of the first and the third nucleotide of the messenger by a 2',5'-phosphodiester linkage. Thus, a group I-like ribozyme catalyzes an RNA branching reaction similar to the first step of splicing in group II introns and spliceosomal introns. The resulting short lariat, by forming a protective 5' cap, might have been useful in a primitive RNA world.

  11. Radiation-chemical synthesis of poly(vinyl alcohol) hydrogel containing dicyclohexano-18-crown-6

    NASA Astrophysics Data System (ADS)

    Zakurdaeva, O. A.; Nesterov, S. V.; Shmakova, N. A.; Semenova, G. K.; Sozontova, E. O.; Feldman, V. I.

    2007-12-01

    Radiation-chemical synthesis of poly(vinyl alcohol) hydrogels containing physically immobilized dicyclohexano-18-crown-6 was carried out. Remarkable gel fraction of 40-70% was observed at absorbed dose of about 5 kGy. Increasing degree of poly(vinyl alcohol) crosslinking led to growth of the efficiency of crown ether immobilization. Post-irradiation thermal annealing of the hydrogel samples at 120 °C for 0.5-5 h resulted in an increase of crown ether retention as compared with non-annealed samples by approximately 20% at the same absorbed dose. Preliminary results on a sorption behavior of the crown-containing hydrogels with respect to Sr 2+ cations in 2.4 M HNO 3 solution are presented.

  12. Proton-Ionizable Crown Ethers. A Short Review

    DTIC Science & Technology

    1989-05-30

    Gloe, and P. Muhl, Anal. Chim. Acta, 1986, 185, 279. 56. R.J. Adaic, B.A. Lloyd. E.M. Eyring, S. Petrucci , L.A. lBartach, N.J. Pugia, B.E. Knudsen, Y...R.A. Bartsch, J. GrandJean, and P. Laszlo, Eioches- Riophys- gas, Comm, 1983, 117, 340. 70. R.J. Adamic, E.M. Eyring, S. Petrucci , and L.A. Bartsch...J. Ph_ - Chem., 1985, 89, 3752. 71. R.J. Adamic,. B.A. Lloyd, E.M. Eyring. S. Petrucci , and R.A. Bartsch, J. Ph_, Chem.. 1986, 90, 1659. 72. K.E

  13. The Crown Ether Promoted Base Degradation of p-Carborane.

    DTIC Science & Technology

    1982-04-20

    containing a magnetic stirring bar. The flask was fitted with a condenser and the system flushed with nitrogen for 15 min. Deoxygenated ethanol (100 ml) was...472 Attn: CRD-AA-IP 800 North Quincy Street P.O. Box 1211 Arlington, Virginia 22217 2 Research Triangle Park, N.C. 27709 ONR Branch Office Naval Ocean ...21401 Washington, D.C. 20360 1 Naval Ocean Systems Center Defense Documentation Center Attn: Dr. S. Yamamoto, Marine Building 5, Cameron Station Sciences

  14. High Resolution Rotational Spectroscopy of a Flexible Cyclic Ether

    NASA Astrophysics Data System (ADS)

    Gámez, F.; Martínez-Haya, B.; Blanco, S.; López, J. C.; Alonso, J. L.

    2011-06-01

    Crown ethers stand as one cornerstone molecular class inhost-guest Supramolecular Chemistry and constitute building blocks for a broad range of modern materials. We report here the first high resolution rotational study of a crown ether: 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5 ether,15c5). Molecular beam Fourier transform microwave spectroscopy has been employed. The liquid sample of 15c5 has been vaporized using heating methods. The considerable size of 15c5 and the broad range of conformations allowed by the flexibility of its backbone pose important challenges to spectroscopy approaches. In fact, the ab-initio computational study for isolated 15c5, yields at least six stable conformers with relative free energies within 2 kJ Mol-1 (167 Cm-1). Nevertheless, in this investigation it has been possible to identify and characterize in detail one stable rotamer of the 15c5 molecule and to challenge different quantum methods for the accurate description of this system. The results pave the ground for an extensive description of the conformational landscape of 15c5 and related cyclic ethers in the near term. J. L. Alonso, F. J. Lorenzo, J. C. López, A. Lesarri, S. Mata and H. Dreizler, Chem. Phys., 218, 267 (1997) S. Blanco, J.C López, J.L. Alonso, P. Ottaviani, W. Caminati, J. Chem. Phys. 119, 880 (2003) S.E. Hill, D. Feller, Int. J. Mass Spectrom. 201, 41 (2000)

  15. All-ceramic crowns.

    PubMed

    Lehner, C R; Schärer, P

    1992-06-01

    Despite the good appearance and biocompatibility of dental porcelains, failures are still of considerable concern because of some limited properties common to all-ceramic crown systems. As in the years before, pertinent scientific articles published between November 1990 and December 1991 focused on strengthening mechanisms and compared fracture toughness for different ceramic systems by using various test methods. Some evaluated the clinical implications thereon for seating and loading crowns and measured wear against different ceramic surface conditions. Recently introduced with pleasing aesthetic qualities, IPS-Empress (Ivoclar, Schaan, Liechtenstein), a new European leucite-reinforced glass-ceramic, has finally drawn attention in some journals and has been reviewed with promising in vitro test results. Using a simple press-molding technique, well-fitting crowns, inlays, and veneers can be fabricated without an additional ceramming procedure. Again, only long-term clinical trials will validate achievements compared with other all-ceramic systems and with well-established metal ceramics.

  16. Pd-catalyzed amination in the synthesis of a new family of macropolycyclic compounds comprising diazacrown ether moieties.

    PubMed

    Yakushev, Alexei A; Chernichenko, Nataliya M; Anokhin, Maxim V; Averin, Alexei D; Buryak, Alexei K; Denat, Franck; Beletskaya, Irina P

    2014-01-15

    N,N'-bis(bromobenzyl) and N,N'-bis(halopyridinyl) derivatives of diaza-12-crown-4, diaza-15-crown-5 and diaza-18-crown-6 ethers were synthesized in high yields. The Pd-catalyzed macrocyclization reactions of these compounds were carried out using a variety of polyamines and oxadiamines were carried out to give novel macrobicyclic and macrotricyclic compounds of the cryptand type. The dependence of the yields of macropolycycles on the nature of the starting diazacrown derivatives and polyamines was established. Generally N,N'-bis(3-bromobenzyl)-substituted diazacrown ethers and oxadiamines provided better yields of the target products. The highest yield of the macrobicyclic products reached 57%.

  17. Aesthetic Surgical Crown Lengthening Procedure

    PubMed Central

    de Oliveira, Pablo Santos; Chiarelli, Fabio; Rodrigues, José A.; Shibli, Jamil A.; Zizzari, Vincenzo Luca; Piattelli, Adriano; Iezzi, Giovanna; Perrotti, Vittoria

    2015-01-01

    The aim of this case report was to describe the surgical sequence of crown lengthening to apically reposition the dentogingival complex, in addition to an esthetic restorative procedure. Many different causes can be responsible for short clinical crown. In these cases, the correct execution of a restorative or prosthetic rehabilitation requires an increasing of the crown length. According to the 2003 American Academy of Periodontology (Practice Profile Survey), crown lengthening is the most habitual surgical periodontal treatment. PMID:26609452

  18. Precision porcelain jacket crown technique.

    PubMed

    Riley, E J; Sozio, R B; Casthely, F; Wilcko, M T; Sotera, A J

    1975-09-01

    A simple technique for construction of an aluminous porcelain crown has been described. An aluminous core is fabricated without platinum foil on a ceramic refractory die and, when retrieved, serves as a coping on the master cast. The technique and accuracy of fit are illustrated with the fabrication of an aluminous porcelain crown on the Bureau of Standards' full-crown die.

  19. Extraction of short-lived zirconium and hafnium isotopes usingcrown ethers: A model system for the study of rutherfordium

    SciTech Connect

    Sudowe, Ralf; Calvert, Michael G.; Dullmann, Christoph E.; Farina, Lindsy M.; Folden III, Charles M.; Gregorich, Kenneth E.; Gallaher, Sarah E.H.; Nelson, Sarah L.; Phillips, Diana C.; Schwantes,Jon M.; Wilson, Richard E.; Zielinski Peter M.; Hoffman, Darleane C.; Nitsche Heino

    2005-07-06

    The extraction of zirconium and hafnium from hydrochloric acid media was studied using the crown ethers dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DC18C6) and dicyclohexano-24-crown-8 (DC24C8) as extractants. The goal was to find an extraction system that exhibits a high selectivity between the members of group 4 of the periodic table and is suitable for the study of rutherfordium. It was found that Zr and Hf are both extracted using DB18C6, DC18C6 and DC24C8. The extraction yield increases with increasing acid concentration and increasing concentration of crown ether. The extracted species most likely consists of an ion-association complex formed between a Zr or Hf chloro complex and a hydronium crown ether complex. Conditions can be found for each extractant that provide for the separation of Zr from Hf. This selective separation between Zr and Hf makes the extraction with crown ethers from HCl well suited to study the extraction behavior of Rf and compare it to the behavior of Zr and Hf. These extraction systems can be used to determine whether the extraction behavior of Rf is similar to Zr, similar to Hf or follows the trend established by the lighter homologs. The extraction kinetics are fast enough for the study of the 78-s isotope {sup 261}Rf.

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

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  1. Lariat sequencing in a unicellular yeast identifies regulated alternative splicing of exons that are evolutionarily conserved with humans.

    PubMed

    Awan, Ali R; Manfredo, Amanda; Pleiss, Jeffrey A

    2013-07-30

    Alternative splicing is a potent regulator of gene expression that vastly increases proteomic diversity in multicellular eukaryotes and is associated with organismal complexity. Although alternative splicing is widespread in vertebrates, little is known about the evolutionary origins of this process, in part because of the absence of phylogenetically conserved events that cross major eukaryotic clades. Here we describe a lariat-sequencing approach, which offers high sensitivity for detecting splicing events, and its application to the unicellular fungus, Schizosaccharomyces pombe, an organism that shares many of the hallmarks of alternative splicing in mammalian systems but for which no previous examples of exon-skipping had been demonstrated. Over 200 previously unannotated splicing events were identified, including examples of regulated alternative splicing. Remarkably, an evolutionary analysis of four of the exons identified here as subject to skipping in S. pombe reveals high sequence conservation and perfect length conservation with their homologs in scores of plants, animals, and fungi. Moreover, alternative splicing of two of these exons have been documented in multiple vertebrate organisms, making these the first demonstrations of identical alternative-splicing patterns in species that are separated by over 1 billion y of evolution.

  2. Aurora Australis, Red Crown

    NASA Technical Reports Server (NTRS)

    1991-01-01

    This view of the Aurora Australis or Southern Lights (location unknown) shows a spiked band of red airglow called a 'Red Crown' above the Earth Limb. Calculated to be in the 80 - 120 km altitude region, auroral activity is due to exitation of atomic oxygen in the upper atmosphere by radiation from the van Allen Radiation Belts and is most common above the 65 degree north and south latitude range during the spring and fall of the year.

  3. Synthesis and crystal structure of copper complex of 7,16-bis(2-hydroxy-5-methyl-3-nitrobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane

    NASA Astrophysics Data System (ADS)

    Ma, Shu-lan; Zhu, Wen-xiang

    2002-12-01

    A lariat crown ether compound 7,16-bis(2-hydroxy-5-methylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane has been prepared via one-pot Mannich reaction. A copper(II) complex with the ligand 7,16-bis(2-hydroxy-5-methyl-3-nitrobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane was unexpectedly synthesized and characterized by elemental analysis, IR and UV spectra. The crystal structure of the complex has been determined by X-ray diffraction. Both crystal structure analysis and spectroscopy study indicated that the side-arm phenols of lariat crown ether are nitrated while complexing with Cu(NO 3) 2. Structure shows that the copper(II) ion is coordinated to two nitrogen and four oxygen atoms, two from the crown ether and other two from the deprotonated phenolate groups. The coordination polyhedron is a distorted octahedron.

  4. Catalytic oxidation of dimethyl ether

    SciTech Connect

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

    2016-05-10

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

  5. Advanced hybrid fluoropolymers from the cycloaddition of aryl trifluorovinyl ethers

    NASA Astrophysics Data System (ADS)

    Ligon, S. Clark, Jr.

    This dissertation discusses the synthesis of aryl trifluorovinyl ethers and their cycloaddition polymerization to give perfluorocyclobutyl (PFCB) polymers. To explore the stereochemistry of these polymers, simple monomfunctional aryl trifluorovinyl ethers were dimerized and the resultant cis and trans isomers were separated. Differences in structure help to improve understanding of the amorphous nature of the bulk PFCB polymeric material. To apply this knowledge, crown ether containing perfluorocyclobutyl (PFCB) polymers were synthesized for use in lithium ion battery applications. While poor solubility has hindered further development of these materials, slight modifications to structure may provide a solution. Also described is a fluorinated aryl vinyl ether and its attempted copolymerization with chlorotrifluoroethylene. While this copolymerization did not yield the desired materials, novel semifluorinated phenol precursors have been utilized in reactions with carboxylic acids to give polyesters and most recently with phosgene like species to give polycarbonates. Next, PFCB polymers were post functionalized with fluoroalkyl tethers to improve oleophobicity and hydrophobicity without decreasing thermal stability or optical clarity. In addition, various silica nanostructures were functionalized with aryl trifluorovinyl ethers. This includes the reaction of aryl silanes to give trifluorovinyl ether functional POSS and their polymerization to provide PFCB hybrid materials. Silane coupling agents were also used to functionalize colloidal silica and fumed silica nanoparticles. These procedures allow excellent dispersion of the silica nanoparticles throughout the fluoropolymer matrix. Finally, the reaction of aryl trifluorovinyl ether with nonfluorinated alkenes and alkynes was explored. In these reactions, the fluorinated olefin adds with the hydrocarbon olefin to give semifluorinated cyclobutanes (SFCB) and with the alkyne to give semifluorinated cyclobutene. The

  6. Design, Synthesis, and Properties of Phosphoramidate 2',5'-Linked Branched RNA: Toward the Rational Design of Inhibitors of the RNA Lariat Debranching Enzyme.

    PubMed

    Tago, Nobuhiro; Katolik, Adam; Clark, Nathaniel E; Montemayor, Eric J; Seio, Kohji; Sekine, Mitsuo; Hart, P John; Damha, Masad J

    2015-10-16

    Two RNA fragments linked by means of a 2',5' phosphodiester bridge (2' hydroxyl of one fragment connected to the 5' hydroxyl of the other) constitute a class of nucleic acids known as 2'-5' branched RNAs (bRNAs). In this report we show that bRNA analogues containing 2'-5' phosphoramidate linkages (bN-RNAs) inhibit the lariat debranching enzyme, a 2',5'-phosphodiesterase that has recently been implicated in neurodegenerative diseases associated with aging. bN-RNAs were efficiently generated using automated solid-phase synthesis and suitably protected branchpoint building blocks. Two orthogonally removable groups, namely the 4-monomethoxytrityl (MMTr) group and the fluorenylmethyl-oxycarbonyl (Fmoc) groups, were evaluated as protecting groups of the 2' amino functionality. The 2'-N-Fmoc methodology was found to successfully produce bN-RNAs on solid-phase oligonucleotide synthesis. The synthesized bN-RNAs resisted hydrolysis by the lariat debranching enzyme (Dbr1) and, in addition, were shown to attenuate the Dbr1-mediated hydrolysis of native bRNA.

  7. ASTER Views California Crown Fire

    NASA Image and Video Library

    2010-08-03

    NASA Terra spacecraft captured this image of the wildfire near Palmdale, Calif. on August 1, 2010 called the Crown fire. The burned areas appear in shades of gray in this simulated natural color image.

  8. Horizontal Roll Vortices and Crown Fires.

    NASA Astrophysics Data System (ADS)

    Haines, Donald A.

    1982-06-01

    Observational evidence from nine crown fires suggests that horizontal roll vortices are a major mechanism in crown-fire spread. Post-burn aerial photography indicates that unburned tree-crown streets are common with crown fire. Investigation of the understory of these crown streets after two fires showed uncharred tree trunks along a center line. This evidence supports a hypothesis of vortex action causing strong downward motion of air along the streets. Additionally, photographs of two ongoing crown fires show apparent horizontal roll vortices. Discussion also includes laboratory and numerical studies in fluid dynamics that may apply to crown fires.

  9. Crown Position and Light Exposure Classification-An Alternative to Field-Assigned Crown Class

    Treesearch

    William A. Bechtold

    2003-01-01

    Crown class, an ordinal tree-level mensuration attribute used extensively by foresters, is difficult to assign in the field because definitions of individual classes are confounded by ambiguous references to the position the tree in the canopy and amount of light received by its crown. When crown class is decomposed into its two elements-crown position and crown light...

  10. Triethylene glycol monoethyl ether

    Integrated Risk Information System (IRIS)

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

  11. Triethylene glycol monobutyl ether

    Integrated Risk Information System (IRIS)

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

  12. p-Bromodiphenyl ether

    Integrated Risk Information System (IRIS)

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

  13. Propylene glycol monoethyl ether

    Integrated Risk Information System (IRIS)

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

  14. Chloromethyl methyl ether (CMME)

    Integrated Risk Information System (IRIS)

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

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Propenyl ether monomers for photopolymerization

    DOEpatents

    Crivello, J.V.

    1996-10-22

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

  17. Propenyl ether monomers for photopolymerization

    DOEpatents

    Crivello, James V.

    1996-01-01

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

  18. Glycol Ethers As Groundwater Contaminants

    NASA Astrophysics Data System (ADS)

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

    1992-01-01

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

  19. Removal of failed crown and bridge

    PubMed Central

    Rahul, G R.; Poduval, Soorya T.; Shetty, Karunakar

    2012-01-01

    Crown and bridge have life span of many years but they fail for a number of reasons. Over the years, many devices have been designed to remove crowns and bridges from abutment teeth. While the removal of temporary crowns and bridges is usually very straightforward, the removal of a definitive cast crown with unknown cement is more challenging. Removal is often by destructive means. There are a number of circumstances, however, in which conservative disassembly would aid the practitioner in completing restorative/endodontic procedures. There are different mechanisms available to remove a failed crown or bridge. But there is no information published about the classification of available systems for crown and bridge removal. So it is logical to classify these systems into different groups which can help a clinician in choosing a particular type of system depending upon the clinical situation. The aim of this article is to provide a classification for various crown and bridge removal systems; describe how a number of systems work; and when and why they might be used. A PubMed search of English literature was conducted up to January 2010 using the terms: Crown and bridge removal, Crown and bridge disassembly, Crown and bridge failure. Additionally, the bibliographies of 3 previous reviews, their cross references as well as articles published in various journals like International Endodontic Journal, Journal of Endodontics and were manually searched. Key words:Crown and bridge removal, Crown and bridge disassembly, Crown and bridge failure. PMID:24558549

  20. Removal of failed crown and bridge.

    PubMed

    Sharma, Ashu; Rahul, G R; Poduval, Soorya T; Shetty, Karunakar

    2012-07-01

    Crown and bridge have life span of many years but they fail for a number of reasons. Over the years, many devices have been designed to remove crowns and bridges from abutment teeth. While the removal of temporary crowns and bridges is usually very straightforward, the removal of a definitive cast crown with unknown cement is more challenging. Removal is often by destructive means. There are a number of circumstances, however, in which conservative disassembly would aid the practitioner in completing restorative/endodontic procedures. There are different mechanisms available to remove a failed crown or bridge. But there is no information published about the classification of available systems for crown and bridge removal. So it is logical to classify these systems into different groups which can help a clinician in choosing a particular type of system depending upon the clinical situation. The aim of this article is to provide a classification for various crown and bridge removal systems; describe how a number of systems work; and when and why they might be used. A PubMed search of English literature was conducted up to January 2010 using the terms: Crown and bridge removal, Crown and bridge disassembly, Crown and bridge failure. Additionally, the bibliographies of 3 previous reviews, their cross references as well as articles published in various journals like International Endodontic Journal, Journal of Endodontics and were manually searched. Key words:Crown and bridge removal, Crown and bridge disassembly, Crown and bridge failure.

  1. Marchantin M trimethyl ether.

    PubMed

    Mombrú, A W; Suescun, L; Pandolfi, E; Seoane, G; López, G; Mariezcurrena, R

    2000-11-01

    The title macrocycle, C(31)H(30)O(5), is comprised of two bibenzyl ether moieties linked cyclically by spacers which each consist of two-carbon alkyl chains. The observed conformation of the macrocycle may be partly stabilized by intramolecular C-H.O close contacts. The packing appears to be directed by van der Waals forces. This work explains the occurrence of a signal found in the (1)H NMR spectra of both marchantinquinone and marchantin M trimethyl ether at delta = 5. 49 and 5.56 p.p.m., respectively. The shift in the position of the expected peak can be explained by the proximity of an H atom belonging to one of the aromatic rings to another ring in the same molecule.

  2. Equations to convert compacted crown ratio to uncompacted crown ratio for trees in the Interior West

    Treesearch

    Chris Toney; Matthew C. Reeves

    2009-01-01

    Crown ratio is the proportion of total tree length supporting live foliage. Inventory programs of the US Forest Service generally define crown ratio in terms of compacted or uncompacted measurements. Measurement of compacted crown ratio (CCR) involves envisioning the transfer of lower branches of trees with asymmetric crowns to fill holes in the upper portion of the...

  3. Assessing crown fire potential by linking models of surface and crown fire behavior

    Treesearch

    Joe H. Scott; Elizabeth D. Reinhardt

    2001-01-01

    Fire managers are increasingly concerned about the threat of crown fires, yet only now are quantitative methods for assessing crown fire hazard being developed. Links among existing mathematical models of fire behavior are used to develop two indices of crown fire hazard-the Torching Index and Crowning Index. These indices can be used to ordinate different forest...

  4. Digital photo monitoring for tree crown

    Treesearch

    Neil Clark; Sang-Mook Lee

    2007-01-01

    Assessing change in the amount of foliage within a tree’s crown is the goal of crown transparency estimation, a component in many forest health assessment programs. Many sources of variability limit analysis and interpretation of crown condition data. Increased precision is needed to detect more subtle changes that are important for detection of health problems....

  5. A surprising host-guest relationship between 1,2-dichloroethane and the cesium complex of tetrabenzo-24-crown-8

    SciTech Connect

    Levitskaia, T.G.; Bryan, J.C.; Sachleben, R.A.; Lamb, J.D.; Moyer, B.A.

    2000-02-02

    The structure of the complex [Cs(tetrabenzo-24-crown-8)(1,2-dichloroethane){sub 2}](NO{sub 3}){sm{underscore}bullet}H{sub 2}O was shown by X-ray crystallography to involve an unprecedented bidentate coordination of two 1,2-dichloroethane solvent molecules to the Cs{sup +} cation via the four chlorine atoms. The coordination of the solvent molecules occurs within two clefts between facing benzo groups, one pair of benzo groups related to the other pair by an improper noncrystallographic 90{degree} rotation. Resembling the seam on a tennis ball, the crown ether envelops the metal cation within a cagelike arrangement of eight crown ether oxygen atoms. Good geometric and electronic complimentarily characterizes the apparent host-guest relationship between the cleft environment and the solvent molecules. The complete encapsulation of the cation by the crown ether and two solvent molecules explains well the speciation behavior observed in liquid-liquid extraction of CsNO{sub 3} or CsClO{sub 4} from aqueous solution to 1,2-dichloroethane solutions of the alkylated analogues 4,4{double{underscore}prime}- or 4,5{double{underscore}prime}-bis(tert-octylbenzo)dibenzo-24-crown-8. In the extraction process studied at 25 C, simple 1:1 metal/crown complexes form in the solvent phase, as modeled by the program SXLSQI. The complex cation and counteranion are present both as ion-pairs, postulated to be ligand-separated ion-pairs as suggested by the crystal structure, and as dissociated ions. In agreement with a theoretical treatment of ion-pairing, the ion-pairs possess unusually low stability and exhibit no discrimination between the anions, largely ascribed to the large effective radius of the complex metal cation. Values of log K{sub f} corresponding to the formation of the complex cations Cs[bis(tert-octylbenzo)-dibenzo-24-crown-8]{sup +} in 1,2-dichloroethane at 25 C average 10.5 {+-} 0.2 for both positional isomers of the crown ether and for their 3:2 mixture. Overall, these

  6. UrbanCrowns: an assessment and monitoring tool for urban trees

    Treesearch

    Matthew F. Winn; Philip A. Araman; Sang-Mook. Lee

    2011-01-01

    UrbanCrowns is a Windows®-based computer program used to assess the crown characteristics of urban trees. The software analyzes side-view digital photographs of trees to compute several crown metrics, including crown height, crown diameter, live crown ratio, crown volume, crown density, and crown transparency. Potential uses of the UrbanCrowns program include...

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  8. Comparison of the arithmetic and geometric means in estimating crown diameter and crown cross-sectional area

    Treesearch

    KaDonna Randolph

    2010-01-01

    The use of the geometric and arithmetic means for estimating tree crown diameter and crown cross-sectional area were examined for trees with crown width measurements taken at the widest point of the crown and perpendicular to the widest point of the crown. The average difference between the geometric and arithmetic mean crown diameters was less than 0.2 ft in absolute...

  9. Allene ether Nazarov cyclization.

    PubMed

    Tius, Marcus A

    2014-05-07

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

  10. Assessment of crown angulations, crown inclinations, and tooth size discrepancies in a South Indian population

    PubMed Central

    Doodamani, Geeta Maruti; Khala, Anmol S; Manohar, Mala; Umashankar

    2011-01-01

    Aims and Objective: The aim of this study was to assess crown angulations, crown inclinations, and tooth size discrepancy in a sample population from Davangere, South India. Materials and Methods: One hundred adults (50 male and 50 female) of age 18–30 years, with Angle's class I ideal occlusion and balanced profiles, were selected for the study. Study models were prepared and crown angulations and crown inclinations were measured using a customized protractor device. Bolton's analysis was used to measure the tooth size discrepancies. Results: Maxillary and mandibular teeth had less crown angulations. Maxillary and mandibular incisors and maxillary molars showed increased crown inclinations, whereas mandibular molars and premolars had less crown inclinations than the original Andrews sample. The mean maxillary and mandibular tooth size ratios, overall and anterior, were similar to Bolton's ratios. Conclusions: The finding of this study indicates that there are possible racial and ethnic factors contributing to variations in crown angulations and crown inclinations. PMID:22090760

  11. [Sunrise gold foil jacket crown].

    PubMed

    Lecardonnel, A

    1989-09-01

    This technique permits the preparation of ceramic jacket crowns made on Sunrise laminated precious metal alloy. The Sunrise foil is gold-colored, made of 99% of precious metals and is 50 microns thick. The die is prepared in order to display a moderate and regular undercut beyond the cervical limit. The margin will be underlined with a red pencil. The Sunrise foil is cut according to predetermined templates. Then the foil is applied without burnishing, according to the technique of jacket crowns on platinum foil only by finger pressure. The double folding on closure is preferably done distally or mesially. Then, the metal base is disinserted, sandblasted with 100 microns aluminum oxide, replaced on its die, and placed in a rubber casing before being placed in the isostatic press, to be subjected to a pressure of 2,000 TSI (14 kg par cm2). Sunrise's orange color reinforces rather subtetly the overall color, making these reconstructions particularly esthetic. The color of the Sunrise metal does not require, therefore a too thick opaque. Any ceramic intended to be fired on a metal base, may be used in respecting its firing protocol. Sunrise, as any other technique of this type, require a careful preparation with a shoulder that has a rounded gingivoaxial line angle. Bridges may be built on the "thimbles" crowns, fitted on Sunrise cores, the pontics being made as a ceramo-metal framework.

  12. Endogenous U2·U5·U6 snRNA complexes in S. pombe are intron lariat spliceosomes

    PubMed Central

    Chen, Weijun; Shulha, Hennady P.; Ashar-Patel, Ami; Yan, Jing; Green, Karin M.; Query, Charles C.; Rhind, Nick; Weng, Zhiping; Moore, Melissa J.

    2014-01-01

    Excision of introns from pre-mRNAs is mediated by the spliceosome, a multi-megadalton complex consisting of U1, U2, U4/U6, and U5 snRNPs plus scores of associated proteins. Spliceosome assembly and disassembly are highly dynamic processes involving multiple stable intermediates. In this study, we utilized a split TAP-tag approach for large-scale purification of an abundant endogenous U2·U5·U6 complex from Schizosaccharomyces pombe. RNAseq revealed this complex to largely contain excised introns, indicating that it is primarily ILS (intron lariat spliceosome) complexes. These endogenous ILS complexes are remarkably resistant to both high-salt and nuclease digestion. Mass spectrometry analysis identified 68, 45, and 43 proteins in low-salt-, high-salt-, and micrococcal nuclease-treated preps, respectively. The protein content of a S. pombe ILS complex strongly resembles that previously reported for human spliced product (P) and Saccharomyces cerevisiae ILS complexes assembled on single pre-mRNAs in vitro. However, the ATP-dependent RNA helicase Brr2 was either substoichiometric in low-salt preps or completely absent from high-salt and MNase preps. Because Brr2 facilitates spliceosome disassembly, its relative absence may explain why the ILS complex accumulates logarithmically growing cultures and the inability of S. pombe extracts to support in vitro splicing. PMID:24442611

  13. Endogenous U2·U5·U6 snRNA complexes in S. pombe are intron lariat spliceosomes.

    PubMed

    Chen, Weijun; Shulha, Hennady P; Ashar-Patel, Ami; Yan, Jing; Green, Karin M; Query, Charles C; Rhind, Nick; Weng, Zhiping; Moore, Melissa J

    2014-03-01

    Excision of introns from pre-mRNAs is mediated by the spliceosome, a multi-megadalton complex consisting of U1, U2, U4/U6, and U5 snRNPs plus scores of associated proteins. Spliceosome assembly and disassembly are highly dynamic processes involving multiple stable intermediates. In this study, we utilized a split TAP-tag approach for large-scale purification of an abundant endogenous U2·U5·U6 complex from Schizosaccharomyces pombe. RNAseq revealed this complex to largely contain excised introns, indicating that it is primarily ILS (intron lariat spliceosome) complexes. These endogenous ILS complexes are remarkably resistant to both high-salt and nuclease digestion. Mass spectrometry analysis identified 68, 45, and 43 proteins in low-salt-, high-salt-, and micrococcal nuclease-treated preps, respectively. The protein content of a S. pombe ILS complex strongly resembles that previously reported for human spliced product (P) and Saccharomyces cerevisiae ILS complexes assembled on single pre-mRNAs in vitro. However, the ATP-dependent RNA helicase Brr2 was either substoichiometric in low-salt preps or completely absent from high-salt and MNase preps. Because Brr2 facilitates spliceosome disassembly, its relative absence may explain why the ILS complex accumulates logarithmically growing cultures and the inability of S. pombe extracts to support in vitro splicing.

  14. Analysis of geophysical logs from six boreholes at Lariat Gulch, former U.S. Air Force site PJKS, Jefferson County, Colorado

    USGS Publications Warehouse

    Paillet, Frederick L.; Hodges, Richard E.; Corland, Barbara S.

    2002-01-01

    This report presents and describes geophysical logs for six boreholes in Lariat Gulch, a topographic gulch at the former U.S. Air Force site PJKS in Jefferson County near Denver, Colorado. Geophysical logs include gamma, normal resistivity, fluid-column temperature and resistivity, caliper, televiewer, and heat-pulse flowmeter. These logs were run in two boreholes penetrating only the Fountain Formation of Pennsylvanian and Permian age (logged to depths of about 65 and 570 feet) and in four boreholes (logged to depths of about 342 to 742 feet) penetrating mostly the Fountain Formation and terminating in Precambrian crystalline rock, which underlies the Fountain Formation. Data from the logs were used to identify fractures and bedding planes and to locate the contact between the two formations. The logs indicated few fractures in the boreholes and gave no indication of higher transmissivity in the contact zone between the two formations. Transmissivities for all fractures in each borehole were estimated to be less than 2 feet squared per day.

  15. Developmental toxicity of diphenyl ether herbicides in birds

    USGS Publications Warehouse

    Hoffman, D.J.; Rattner, B.A.; Bunck, C.M.

    1991-01-01

    Diphenyl ether herblcldes, includlng nitrofen, have been identified as mammalian teratogens and cause perinatal mortality. American kestrel (Falco sparverius) nestlings were orally dosed for 10 days w1th 5 ul/g of corn oil (controls) or one of the diphenyl ether herbicides (nitrofen, bifenox, or oxyfluorofen). At 500 mg/kg, nitrofen resulted in complete mortality, bifenox in high (66%) mortality, and oxyfluorofen in no mortality. Nitrofen, at 250 mg/kg, reduced nestling growth, as reflected by decreased body weight and bone length. Bifenox at 250 mg/kg had less effect on growth than nitrofen but crown rump, humerus, radiusulna and femur lengths were significantly less than controls. Liver welght (percent of body welght) increased with 50 mg/kg nitrofen. Other manifestations of hepatotoxicity following nitrofen ingestion included increased hepatic GSH peroxidase activity with 0 mg/kg nitrofen, and increased plasma enzyme activities for ALT, AST. and LDHL with 250 mg/kg. Blfenox lngestion (50 mg/kg) resulted in increased hepatlc GSH peroxidase activity. Nitrofen exposure increased total plasma thyroxlne (T4) concentratlon. These findings suggest that altricial nestllng kestrels are more sensitive to diphenyl ether herbicides than precocial young or adult birds.

  16. Invariom-model refinement and Hirshfeld surface analysis of well-ordered solvent-free dibenzo-21-crown-7.

    PubMed

    Wiedemann, Dennis; Kohl, Julia

    2017-09-01

    Crown ethers and their supramolecular derivatives are well-known chelators and scavengers for a variety of cations, most notably heavier alkali and alkaline-earth ions. Although they are widely used in synthetic chemistry, available crystal structures of uncoordinated and solvent-free crown ethers regularly suffer from disorder. In this study, we present the X-ray crystal structure analysis of well-ordered solvent-free crystals of dibenzo-21-crown-7 (systematic name: dibenzo[b,k]-1,4,7,10,13,16,19-heptaoxacycloheneicosa-2,11-diene, C22H28O7). Because of the quality of the crystal and diffraction data, we have chosen invarioms, in addition to standard independent spherical atoms, for modelling and briefly discuss the different refinement results. The electrostatic potential, which is directly deducible from the invariom model, and the Hirshfeld surface are analysed and complemented with interaction-energy computations to characterize intermolecular contacts. The boat-like molecules stack along the a axis and are arranged as dimers of chains, which assemble as rows to form a three-dimensional structure. Dispersive C-H...H-C and C-H...π interactions dominate, but nonclassical hydrogen bonds are present and reflect the overall rather weak electrostatic influence. A fingerprint plot of the Hirshfeld surface summarizes and visualizes the intermolecular interactions. The insight gained into the crystal structure of dibenzo-21-crown-7 not only demonstrates the power of invariom refinement, Hirshfeld surface analysis and interaction-energy computation, but also hints at favourable conditions for crystallizing solvent-free crown ethers.

  17. Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  18. Polyarylene Ethers with Improved Properties

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  19. [Artificial crowns influence upon edge parodontium status].

    PubMed

    Zhulev, E N; Serov, A B

    2010-01-01

    With the aim of prosthetic treatment efficacy increase study of edge parodontium tissue reaction upon different types of artificial crowns was done and methods of chronic localized parodontitis prevention were developed. Changes of the main gingival fluid characteristics (amount, acidity, interleukine-1beta concentration) and indicators of microcirculation in edge parodontium of the teeth under the artificial crowns influence were disclosed. There were developed methods of chronic localized parodontitis prevention produced by artificial crowns edge.

  20. Stereoisomeric effect in low temperature radiolysis of dicyclohexano-18-crown-6 complexes with BaCl2

    NASA Astrophysics Data System (ADS)

    Zakurdaeva, Olga A.; Nesterov, Sergey V.; Feldman, Vladimir I.

    2017-01-01

    Effect of syn/anti-stereoisomerism of the macrocycle on radiation-chemical transformations of dicyclohexano-18-crown-6 complexes with BaCl2 was studied by EPR spectroscopy. It was found that the stereoisomerism affected the composition of radicals produced under radiolysis at 77 K. In addition, it was demonstrated that the yield of post-radiation macrocycle cleavage after annealing the irradiated complexes at 333 K was also different for the two studied stereoisomers. The radiation-induced destruction of both cis-syn-cis- and cis-anti-cis-complex was predominately localized at the crown ether moiety, and the Cl2- radical anions were not detected in irradiated samples. The last finding was ascribed to a high reactivity of chlorine atoms towards the crown ether. Generally, it may be concluded that the macrocyclic complex with anti-configuration had a lower radiation stability. Thus, it is very important to characterize the stereoisomeric composition of dicyclohexano-18-crown-6 and its complexes in the radiation-chemical tests for practical purposes.

  1. A method of evaluating crown fuels in forest stands.

    Treesearch

    Rodney W. Sando; Charles H. Wick

    1972-01-01

    A method of describing the crown fuels in a forest fuel complex based on crown weight and crown volume was developed. A computer program is an integral part of the method. Crown weight data are presented in graphical form and are separated into hardwood and coniferous fuels. The fuel complex is described using total crown weight per acre, mean height to the base of...

  2. Tree crown conditions in Missouri, 2000-2003

    Treesearch

    KaDonna C. Randolph; W. Keith Moser

    2009-01-01

    The Forest Service, U.S. Department of Agriculture, Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes three FIA tree crown condition indicators (crown dieback, crown density, and foliage transparency) and sapling crown vigor measured in Missouri between 2000...

  3. Hydrogen bonding assemblies in host guest complexes with 18-crown-6

    NASA Astrophysics Data System (ADS)

    Fonari, M. S.; Simonov, Yu. A.; Kravtsov, V. Ch.; Lipkowski, J.; Ganin, E. V.; Yavolovskii, A. A.

    2003-02-01

    Recent X-ray crystal structural data for two novel 1:2 host-guest complexes of 18-crown-6 with neutral organic molecules, thiaamide hydrazide of 2-aminobenzoic acid and thiaamide hydrazide of 4-amino-1,2,5-thiadiazole-3-carbonic acid are reported. The supramolecular structures of these two and five relative complexes are discussed from the point of view of participation of donor groups in coordination with the crown ether, and donor and acceptor groups in the self-assembly of the guest molecules. Guest molecules have incorporated amine and hydrazine moieties as proton donors and carbonyl oxygen and sulfur (in thiadiazole and in thiaamine moieties) as proton acceptors. The guest-guest interactions appeared to be crucial in the final architecture.

  4. Equations for predicting uncompacted crown ratio based on compacted crown ratio and tree attributes.

    Treesearch

    Vicente J. Monleon; David Azuma; Donald. Gedney

    2004-01-01

    Equations to predict uncompacted crown ratio as a function of compacted crown ratio, tree diameter, and tree height are developed for the main tree species in Oregon, Washington, and California using data from the Forest Health Monitoring Program, USDA Forest Service. The uncompacted crown ratio was modeled with a logistic function and fitted using weighted, nonlinear...

  5. Complexation of mercury(I) and mercury(II) by 18-crown-6: hydrothermal synthesis of the mercuric nitrite complex.

    PubMed

    Williams, Neil J; Hancock, Robert D; Riebenspies, Joseph H; Fernandes, Manuel; de Sousa, Alvaro S

    2009-12-21

    A dimercury(I) 18-crown-6 complex is isolated, and its possible role in the hydrothermal preparation of the mercuric nitrite complex is discussed. The reported structures are of [Hg(2)(18-crown-6)(2)(H(2)O)(2)](ClO(4))(2) (1), monoclinic, C2/c, a = 21.0345(9), b = 12.1565(5), c = 16.8010(7) A, beta = 113.2000(10) degrees , V = 3948.7(3) A(3), Z = 16, R = 0.0230; [Hg(18-crown-6)](NO(2))(2) (2), monoclinic, P2(1)/c, a = 8.027(5), b = 14.437(9), c = 7.827(5) A, beta = 95.165(11) degrees , V = 905.6(10) A(3), Z = 2, R = 0.0175. The complex cation in compound 1 consists of a mercurous dimer exhibiting a Hg-Hg bond length of 2.524(2) A. Non-bonding interactions between adjacent crown ether macrocycles across the Hg-Hg bond result in large variations in mercury to oxygen distances within equatorial coordination sites. At low pH compound 1 is proposed to be preferentially formed under hydrothermal conditions affording compound 2 upon disproportionation. Nitrite ions ligate via a unidentate nitrito (cis to metal) coordination mode as interpreted using vibrational (infrared) spectroscopy. The conformation adopted by 18-crown-6 in compounds 1 and 2 is closely related to a D(3d) conformation as evidenced by X-ray crystallography. Band splitting readily observed in vibrational spectra of the metal free crown ether, attributed to vibrational modes of oxyethylene fragments, is absent in spectra of 1 and 2 confirming a regular D(3d) macrocyclic orientation. Short Hg-O bonds observed for axially coordinated water molecules in 1 and coordinated nitrite ligands in 2, illustrate the prevalence of relativistic effects commonly observed in mercury complexes.

  6. Imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  7. A potassium-18-crown-6 salt of a cyclic myo-inositol phosphate.

    PubMed

    Kumara Swamy, K C; Kumaraswamy, S

    2001-10-01

    The six-membered phosphorinane ring in (1,4,7,10,13,16-hexaoxacyclooctadecane)potassium 2-O-benzoyl-1,3,5-O-methylidyne-myo-inositol 4,6-cyclophosphate trihydrate, [K(C(12)H(24)O(6))](C(14)H(12)O(9)P).3H(2)O, has a boat rather than a chair conformation. The K(+) ion is eight-coordinate and is connected to one of the phosphate O atoms, one of the O atoms of the myo-inositol residue and the six O atoms of the crown ether.

  8. Conformational effect of dicyclo-hexano-18-crown-6 on isotopic fractionation of zinc: DFT approach

    SciTech Connect

    Boda, A.; Singha Deb, A. K.; Ali, Sk. M.; Shenoy, K. T.; Ghosh, S. K.

    2014-04-24

    Generalized gradient approximated BP86 density functional employing triple zeta valence plus polarization (TZVP) basis set has been used to compute the reduced partition function ratio and isotopic separation factor for zinc isotopes. The isotopic separation factor was found to be in good agreement with the experimental results. The isotopic separation factor was found to depend on the conformation of the crown ether ligand. The trans-trans conformation shows the highest fractionation compared to cis-cis conformer. The present theoretical results can thus be used to plan the isotope separation experiments.

  9. Pipe weld crown removal device

    SciTech Connect

    Sword, C.K.; Sette, P.J.

    1992-11-24

    A device is provided for grinding down the crown of a pipe weld joining aligned pipe sections so that the weld is substantially flush with the pipe sections joined by the weld. The device includes a cage assembly comprising a pair of spaced cage rings adapted to be mounted for rotation on the respective pipe sections on opposite sides of the weld, a plurality of grinding wheels, supported by the cage assembly for grinding down the crown of the weld, and a plurality of support shafts, each extending longitudinally along the joined pipe sections, parallel thereto, for individually mounting respective grinding wheels. Each end of the support shafts is mounted for rotation in a bearing assembly housed within a radially directed opening in a corresponding one of the cage rings so as to provide radial movement of the associated shaft, and thus of the associated grinding wheel, towards and away from the weld. A first drive sprocket provides rotation of the cage assembly around the pipe sections while a second drive unit, driven by a common motor, provides rotation of the grinding wheels. 2 figs.

  10. Pipe weld crown removal device

    SciTech Connect

    Sword, C.K.; Sette, P.J.

    1991-12-31

    This invention is comprised of a device that provides for grinding down the crown of a pipe weld joining aligned pipe sections so that the weld is substantially flush with the pipe sections joined by the weld. The device includes a cage assembly comprising a pair of spaced cage rings adapted to be mounted for rotation on the respective pipe sections on opposite sides of the weld, a plurality of grinding wheels, supported by the cage assembly for grinding down the crown of the weld, and a plurality of support shafts, each extending longitudinally along the joined pipe sections, parallel thereto, for individually mounting respective grinding wheels. Each end of the support shafts is mounted for rotation in a bearing assembly housed within a radially directed opening in a corresponding one of the cage rings so as to provide radial movement of the associated shaft, and thus of the associated grinding wheel, towards and away from the weld. A first drive sprocket provides rotation of the cage assembly around the pipe sections while a second drive unit, driven by a common motor, provides rotation of the grinding wheels.

  11. Pipe weld crown removal device

    DOEpatents

    Sword, Charles K.; Sette, Primo J.

    1992-01-01

    A device is provided for grinding down the crown of a pipe weld joining aligned pipe sections so that the weld is substantially flush with the pipe sections joined by the weld. The device includes a cage assembly comprising a pair of spaced cage rings adapted to be mounted for rotation on the respective pipe sections on opposite sides of the weld, a plurality of grinding wheels, supported by the cage assembly for grinding down the crown of the weld, and a plurality of support shafts, each extending longitudinally along the joined pipe sections, parallel thereto, for individually mounting respective grinding wheels. Each end of the support shafts is mounted for rotation in a bearing assembly housed within a radially directed opening in a corresponding one of the cage rings so as to provide radial movement of the associated shaft, and thus of the associated grinding wheel, towards and away from the weld. A first drive sprocket provides rotation of the cage assembly around the pipe sections while a second drive unit, driven by a common motor, provides rotation of the grinding wheels.

  12. Transport Properties of Cation Exchange Membranes in the Presence of Ether Compounds in Electrodialysis.

    PubMed

    Sata; Tanimoto; Kawamura; Matsusaki

    1999-11-15

    Ether compounds such as ethylene glycols with different molecular weights and crown ethers have good affinity to the cation exchange membranes, sulfonated styrene-divinylbenzene membrane (sodium ion form) and perfluorocarbon sodium sulfonate membrane. The impregnated amount of ethylene glycols in the membranes was higher than the water content of the membranes. After the ether compounds had been impregnated in the cation exchange membranes, electrodialysis of mixed salt solutions (1:1 mixture of alkaline earth metal ions or potassium ions and sodium ions) was carried out in the presence of the compounds to observe the change in permselectivity between two cations. Though current efficiency did not change in the presence of the compounds, transport numbers of alkaline earth metal ions relative to sodium ions decreased. Namely, sodium ions permeated through the membrane more selectively than alkaline earth metal ions. This is due mainly to a decrease in the mobility of alkaline earth metal ions in the membrane phase and partially to a decrease in the ion exchange equilibrium constant of alkaline earth metal ions to sodium ions with the membrane. This originates from the difference in ion-dipole interaction between cations and ether groups. The transport number of potassium ions relative to sodium ions also decreased in the presence of the compounds. In particular, the permeation of potassium ions relative to sodium ions remarkably decreased in the presence of 18-crown-6 in the membrane and in the solution due to the formation of a strong complex between potassium ions and 18-crown-6. Copyright 1999 Academic Press.

  13. Structure and conformation of (dibenzyldiaza-18-crown-6)-Nd(III) and Eu(III) thiocyanates: infrared spectroscopic and X-ray crystallographic studies

    NASA Astrophysics Data System (ADS)

    Saleh, Muhammad Idiris; Salhin, Abdussalam; Saad, Bahruddin; Fun, Hoong-Kun

    1999-01-01

    Dibenzyldiaza-18-crown-6 was utilised as a host to accommodate Nd(III) and Eu(III) metal ions together with thiocyanate as counter ion. The crystalline complexes formed were studied for their absorption in the infrared region and their crystalline structure by X-ray diffraction. The coordination of the metal ions to the counter ion and also to the donor atoms of the crown ether was clearly seen from the shift of the absorption band of the pure compound by up to nearly 15 cm -1. From these absorption it was found that each lanthanide ion was coordinated to six donor atoms (2 N and 4 O) from crown ether and three donor atoms, N from NCS -. This nine coordination number complex was found to have the stoichiometry of 1:1:3 (crown ether:lanthanide; NCS -). This ratio was further confirmed by X-ray crystallographic method. The lanthanide thiocyanate salts existed as an isolated (separate) entity in the center of the macrocyclic cavity. The three N atoms surrounded the Ln cation in a nearly planar trigonal arrangement with Ln ion being slightly out of plane. The trigonal plane was perpendicular to and bisects the plane of the macrocycle.

  14. FRACTURE-RESISTANT MONOLITHIC DENTAL CROWNS

    PubMed Central

    Zhang, Yu; Mai, Zhisong; Barani, Amir; Bush, Mark; Lawn, Brian

    2016-01-01

    Objective To quantify the splitting resistance of monolithic zirconia, lithium disilicate and nanoparticle-composite dental crowns. Methods Fracture experiments were conducted on anatomically-correct monolithic crown structures cemented to standard dental composite dies, by axial loading of a hard sphere placed between the cusps. The structures were observed in situ during fracture testing, and critical loads to split the structures were measured. Extended finite element modeling (XFEM), with provision for step-by-step extension of embedded cracks, was employed to simulate full failure evolution. Results Experimental measurements and XFEM predictions were self consistent within data scatter. In conjunction with a fracture mechanics equation for critical splitting load, the data were used to predict load-sustaining capacity for crowns on actual dentin substrates and for loading with a sphere of different size. Stages of crack propagation within the crown and support substrate were quantified. Zirconia crowns showed the highest fracture loads, lithium disilicate intermediate, and dental nanocomposite lowest. Dental nanocomposite crowns have comparable fracture resistance to natural enamel. Significance The results confirm that monolithic crowns are able to sustain high bite forces. The analysis indicates what material and geometrical properties are important in optimizing crown performance and longevity. PMID:26792623

  15. Coast redwood live crown and sapwood

    Treesearch

    John-Pascal Berrill; Jesse L. Deffress; Jessica M. Engle

    2012-01-01

    Understanding crown rise and sapwood taper will help meet management objectives such as producing long branch-free boles for clear wood and old-growth restoration, or producing sawlogs with a high proportion of heartwood. Coast redwood (Sequoia sempervirens) tree crown ratio data were collected 20 years after partial harvesting in a 65-year-old second growth stand....

  16. 21 CFR 872.3330 - Preformed crown.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Preformed crown. 872.3330 Section 872.3330 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3330 Preformed crown. (a) Identification. A preformed...

  17. Crown development: an index of stand density

    Treesearch

    John E. Krajicek; Kenneth A. Brinkman

    1957-01-01

    A study of crown characteristics of several hundred open-grown oak, hickory, and Norway spruce trees in Iowa revealed a high correlation between stem diameter and crown area. Consideration of this relationship led to the idea that perhaps here was a realistic way to measure and evaluate stand density or stocking. If, given unlimited growing space, trees of a certain...

  18. Space, Time, Ether, and Kant

    NASA Astrophysics Data System (ADS)

    Wong, Wing-Chun Godwin

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

  19. Fracture resistance of zirconia-composite veneered crowns in comparison with zirconia-porcelain crowns.

    PubMed

    Alsadon, Omar; Patrick, David; Johnson, Anthony; Pollington, Sarah; Wood, Duncan

    2017-02-11

    The objectives were to evaluate the fracture resistance and stress concentration in zirconia/composite veneered crowns in comparison to zirconia/porcelain crowns using occlusal fracture resistance and by stress analysis using finite element analysis method. Zirconia substructures were divided into two groups based on the veneering material. A static load was applied occlusally using a ball indenter and the load to fracture was recorded in Newtons (N). The same crown design was used to create 3D crown models and evaluated using FEA. The zirconia/composite crowns subjected to static occlusal load showed comparable results to the zirconia/porcelain crowns. Zirconia/composite crowns showed higher stress on the zirconia substructure at 63.6 and 50.9 MPa on the zirconia substructure veneered with porcelain. In conclusion, zirconia/composite crowns withstood high occlusal loads similar to zirconia/porcelain crowns with no significant difference. However, the zirconia/composite crowns showed higher stress values than the zirconia/porcelain crowns at the zirconia substructure.

  20. Evaluating ceramic crown margins with digital radiography.

    PubMed

    Wahle, William Maxwell; Masri, Radi; Driscoll, Carl; Romberg, Elaine

    2017-09-29

    Radiographs aid in clinically determining crown fit, specifically interproximal margins where tactile and visual methods may be limited. However, investigations of the utility of digital radiographs as a tool for evaluating the marginal openings of ceramic crowns are lacking. The purpose of this in vitro study was to assess whether marginal adaptation for ceramic crowns and for metal-ceramic crowns with a metal collar can be identified with digital radiographs. One lithium disilicate crown, 1 fluorapatite crown, and 1 metal-ceramic crown were fabricated for a maxillary premolar. The crowns were attached to a custom-designed device that allowed the marginal discrepancy to be changed. A total of 10 increments were measured starting at 0 to 20 μm and increasing every 20 μm to a maximum opening of 180 to 200 μm. At each increment, 2 radiographs were made of the crowns, using a digital sensor, 1 perpendicular to and 1 at 80 degrees to the long axis of the tooth. To test whether digital radiographs could be used to accurately identify "acceptable" and "unacceptable" margins, 21 dentists were asked to rate the radiographs as "acceptable" or "unacceptable." The chi square test was used to analyze differences between the dentists' evaluations and the actual marginal opening (α=.05). For the purposes of this study, a marginal discrepancy greater than 80 μm was considered "unacceptable." Of all marginal discrepancies exceeding 80 μm, 78.6% of the metal-ceramic crown radiographs were incorrectly scored as "acceptable" (P<.001). These radiographs were identified as false positives. Lithium disilicate (66.1%) and fluorapatite (45.8%) crowns were more likely to be incorrectly evaluated as "unacceptable" (P<.001) and identified as false negatives. Using digital radiographs to evaluate marginal adaptation without clinical examination is not by itself an accurate method of evaluating the marginal fit of complete coverage crowns. The marginal fit of the tested metal

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

    DOEpatents

    Hofmann, Michael A.

    2006-11-14

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

  2. Colorimetric values of esthetic stainless steel crowns.

    PubMed

    Hosoya, Yumiko; Omachi, Koichi; Staninec, Michal

    2002-01-01

    The colorimetric values of two different kinds of esthetic stainless steel crowns were measured and compared with the colorimetric values of primary anterior teeth in Japanese children. The colorimetric values of resin composite-faced stainless steel crowns (Kinder Krown) and epoxy-coated stainless steel crowns (White Steel Crown) were measured with a color difference meter. The Commission Internationale de Eclairage L*, a*, b*, and delta E*ab values and Munsell value, chroma, and hue were calculated. The data were compared with previously reported colorimetric values of Japanese primary anterior teeth measured with the same color difference meter used in this study. Compared to Japanese primary anterior teeth, Kinder Krown Pedo I and Pedo II showed much higher L* values and lower hue; on the other hand, White Steel Crown showed much higher L*, a*, b* values, much higher value and chroma, and much lower hue. Color analysis revealed that the colors of the White Steel Crown and Kinder Krown Pedo I were substantially different from the color of Japanese primary anterior teeth. The color difference between Pedo II crowns and Japanese primary anterior teeth was relatively high, but the color of Pedo II might be acceptable for clinical use.

  3. Fracture strength of monolithic all-ceramic crowns made of high translucent yttrium oxide-stabilized zirconium dioxide compared to porcelain-veneered crowns and lithium disilicate crowns.

    PubMed

    Johansson, Camilla; Kmet, Gratiela; Rivera, Johnny; Larsson, Christel; Vult Von Steyern, Per

    2014-02-01

    The aim of the study was to provide data on the fracture strength of monolithic high translucent Y-TZP crowns and porcelain-veneered high translucent Y-TZP crown cores and to compare that data with the fracture strength of porcelain-veneered Y-TZP crown cores and monolithic lithium disilicate glass-ceramic crowns. Sixty standardized crowns divided into six groups (n = 10) were fabricated: monolithic high translucent Y-TZP crowns, brand A, monolithic high translucent Y-TZP crowns, brand B, veneered high translucent Y-TZP crown cores, brand A, veneered high translucent Y-TZP crown cores, brand B, heat-pressed monolithic lithium disilicate crowns and veneered Y-TZP crown cores. All crowns were thermocycled, cemented onto dies, cyclically pre-loaded and finally loaded to fracture. The monolithic Y-TZP groups showed significantly higher fracture strength (2795 N and 3038 N) compared to all other groups. The fracture strength in the veneered Y-TZP group (2229 N) was significantly higher than the monolithic lithium disilicate group (1856 N) and the veneered high translucent Y-TZP groups (1480 N and 1808 N). The fracture strength of monolithic high translucent Y-TZP crowns is considerably higher than that of porcelain-veneered Y-TZP crown cores, porcelain-veneered high translucent Y-TZP crown cores and monolithic lithium disilicate crowns. The fracture strength of a crown made of monolithic high translucent Y-TZP is, with a large safety margin, sufficient for clinical use for the majority of patients. Porcelain-veneered Y-TZP crown cores show higher fracture resistance than monolithic lithium disilicate crowns.

  4. Crown-rise and crown-length dynamics: applications to loblolly pine

    Treesearch

    Harry T. Valentine; Ralph L. Amateis; Jeffrey H. Gove; Annikki. Makela

    2013-01-01

    The original crown-rise model estimates the average height of a crown-base in an even-aged mono-species stand of trees. We have elaborated this model to reduce bias and prediction error, and to also provide crown-base estimates for individual trees. Results for the latter agree with a theory of branch death based on resource availability and allocation.We use the...

  5. A numerical rating system for crown classes of southern hardwoods

    Treesearch

    James S. Meadows; E.C. Burkhardt; Robert L. Johnson; John D. Hodges

    2001-01-01

    A numerical rating system to delineate crown classes of southern hardwoods is described. The system is based on four criteria: (1) amount of direct sunlight from above, (2) amount of direct sunlight from the sides, (3) crown balance, and (4) relative crown size. The total point value assigned places the tree within one of the four crown classes. The rating system can...

  6. Experimental and numerical modeling of shrub crown fire initiation

    Treesearch

    Watcharapong Tachajapong; Jesse Lozano; Shakar Mahalingam; Xiangyang Zhou; David Weise

    2009-01-01

    The transition of fire from dry surface fuels to wet shrub crown fuels was studied using laboratory experiments and a simple physical model to gain a better understanding of the transition process. In the experiments, we investigated the effects of varying vertical distances between surface and crown fuels (crown base height), and of the wind speed on crown fire...

  7. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a...

  8. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a device...

  9. Induction of Crown Gall on Carrot Slices.

    ERIC Educational Resources Information Center

    Babich, H.; Fox, K. D.

    1998-01-01

    Argues that the transfer of plasmid from a bacterium to a plant cell has received little attention. Presents an experiment for studying this type of genetic transformation using the causative agent of crown gall, a malignant plant tumor. (DDR)

  10. 21 CFR 872.3330 - Preformed crown.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... crown is a prefabricated device made of plastic or austenitic alloys or alloys containing 75 percent or greater gold and metals of the platinum group intended to be affixed temporarily to a tooth after...

  11. Success of Hall technique crowns questioned.

    PubMed

    Nainar, S M Hashim

    2012-01-01

    Hall technique is a method of providing stainless steel crowns for primary molars without tooth preparation and requires no local anesthesia. Literature review showed inconclusive evidence and therefore this technique should not be used in clinical practice.

  12. Induction of Crown Gall on Carrot Slices.

    ERIC Educational Resources Information Center

    Babich, H.; Fox, K. D.

    1998-01-01

    Argues that the transfer of plasmid from a bacterium to a plant cell has received little attention. Presents an experiment for studying this type of genetic transformation using the causative agent of crown gall, a malignant plant tumor. (DDR)

  13. The Crown Bite Jumping Herbst.

    PubMed

    Owen, Reuel

    2003-01-01

    The Crown Bite Jumping Herbst Appliance is evaluated and combined with Straight Wire Arch Fixed Orthodontics in treatment of Class II, Division I malocclusions. This article will evaluate a combined orthodontic approach of "straightening teeth" and an orthognathic approach of "moving jaws or making skeletal changes." Orthodontic treatment cannot be accomplished well without establishing a healthy temporomandibular joint. This is defined by Keller as a joint that is "noiseless, painless and has a normal range of motion without deviation and deflection." It is not prudent to separate orthodontic treatment as its own entity without being aware of the changes in the temporomandibular joint before, during and after treatment. In other words, "If you're doing orthodontics you're doing TMJ treatment." One should treat toward a healthy, beautiful face asking, "Will proposed treatment achieve this goal?" Treatment should be able to be carried out in an efficient manner, minimizing treatment time, be comfortable and affordable for the patient, and profitable for the dentist. The finished treatment should meet Andrews' Six Keys of Occlusion, or Loudon's Twelve Commandments. Above all, do no harm to the patient. We think that a specific treatment plan can embrace these tenets. The focus will be to show Class II treatment using a modified Herbst Appliance and fixed straight wire orthodontics.

  14. Propylene glycol monomethyl ether (PGME)

    Integrated Risk Information System (IRIS)

    Propylene glycol monomethyl ether ( PGME ) ; CASRN 107 - 98 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

  15. Desoxyhemigossypol-6-methyl-ether

    USDA-ARS?s Scientific Manuscript database

    Desoxyhemigossypol-6-methyl ether is an antimicrobial compound produced by the cotton plant in response to attack by pathogens. For the first time, we now report the crystal structure of this compound. This may prove useful in studies on the interaction of the compound with pathogenic fungal cells...

  16. Lacinilene C 7-methyl ether

    USDA-ARS?s Scientific Manuscript database

    Lacinilene C 7-methyl ether is an antimicrobial compound produced by the cotton plant in response to attack by pathogens. For the first time, we now report the crystal structure of this compound. This may prove useful in studies on the interaction of the compound with pathogenic fungal cells....

  17. p,p\\'-Dibromodiphenyl ether

    Integrated Risk Information System (IRIS)

    p , p ' - Dibromodiphenyl ether ; CASRN 2050 - 47 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for

  18. Bis(chloroethyl)ether (BCEE)

    Integrated Risk Information System (IRIS)

    Bis ( chloroethyl ) ether ( BCEE ) ; CASRN 111 - 44 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  19. Bis(chloromethyl)ether (BCME)

    Integrated Risk Information System (IRIS)

    Bis ( chloromethyl ) ether ( BCME ) ; CASRN 542 - 88 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

  20. An investigation of crown fuel bulk density effects on the dynamics of crown fire initiation in shrublands

    Treesearch

    Watcharapong Tachajapong; Jesse Lozano; Shankar Mahalingam; Xiangyang Zhou; David R. Weise

    2008-01-01

    Crown fire initiation is studied by using a simple experimental and detailed physical modeling based on Large Eddy Simulation (LES). Experiments conducted thus far reveal that crown fuel ignition via surface fire occurs when the crown base is within the continuous flame region and does not occur when the crown base is located in the hot plume gas region of the surface...

  1. Ionizable calixarene-crown ethers with high selectivity for radium over light alkaline earth metal ions

    SciTech Connect

    Chen, X.; Ji, M.; Fisher, D.R.; Wai, C.M.

    1999-11-15

    {alpha} particle emitters are of increasing interest as the radionuclide attached to monoclonal antibodies of other targeting mechanisms for applications in cell-directed therapy of cancer. {alpha} particles are more effective than {beta}{sup {minus}} particles for cell-killing and promise a more effective treatment of cancer than other forms of radiation. This is because {alpha} particles have high initial energy (4--8 MeV), short path lengths (40--80 {micro}m, or several cell diameters), and consequently greater energy dissipation per unit length. Cell-directed immunotherapy can help improve irradiation of tumor cells while sparing normal tissues. The success of this approach will require effective chemistry for attaching the radionuclide to the antibody. Therefore, a concerted effort has been directed toward the design of chelating agents capable of holding the desired {alpha}-emitting radionuclide, both selectively and with high stability, to the antibody.

  2. Rates and Mechanisms of Complexation Reactions of Cations with Crown Ethers and Related Macrocycles

    DTIC Science & Technology

    1989-01-23

    as stability constants and entropies of solvation t, be of paramount importance. Complexation rate constants alone seldom disclose a great deal more...sample equilibrium to assure detectability of the reaction. Disadvantages include 1) the need for high solute concentrations in order to detect small...ultrasonic techniques. In principle, the stability constants of macrocycles complexing various cations can be deduced from the amplitudes of the experimental

  3. Cation or Solvent-Induced Supermolecular Phthalocyanine Formation: Crown Ether Substituted Phthalocyanines.

    DTIC Science & Technology

    1987-06-01

    DISTRIBUTION LIST, 051A Dr. M. A. El-Sayed Dr. Carmen Ortiz Department of Chemistry Consejo Superior de University of California Investigaciones ... Cientificas Los Angeles, California 90024 Serrano 121 Madrid 6, SPAIN Dr. E. R. Bernstein Department of Chemistry Dr. Kent R. Wilson Colorado State

  4. Preformed crowns for decayed primary molar teeth.

    PubMed

    Innes, Nicola P T; Ricketts, David; Chong, Lee Yee; Keightley, Alexander J; Lamont, Thomas; Santamaria, Ruth M

    2015-12-31

    Crowns for primary molars are preformed and come in a variety of sizes and materials to be placed over decayed or developmentally defective teeth. They can be made completely of stainless steel (know as 'preformed metal crowns' or PMCs), or to give better aesthetics, may be made of stainless steel with a white veneer cover or made wholly of a white ceramic material. In most cases, teeth are trimmed for the crowns to be fitted conventionally using a local anaesthetic. However, in the case of the Hall Technique, PMCs are pushed over the tooth with no local anaesthetic, carious tissue removal or tooth preparation. Crowns are recommended for restoring primary molar teeth that have had a pulp treatment, are very decayed or are badly broken down. However, few dental practitioners use them in clinical practice. This review updates the original review published in 2007. Primary objectiveTo evaluate the clinical effectiveness and safety of all types of preformed crowns for restoring primary teeth compared with conventional filling materials (such as amalgam, composite, glass ionomer, resin modified glass ionomer and compomers), other types of crowns or methods of crown placement, non-restorative caries treatment or no treatment. Secondary objectiveTo explore whether the extent of decay has an effect on the clinical outcome of primary teeth restored with all types of preformed crowns compared with those restored with conventional filling materials. We searched the following electronic databases: Cochrane Oral Health Group Trials Register (to 21 January 2015), Cochrane Central Register of Controlled Trials (CENTRAL; The Cochrane Library, 2014, Issue 12), MEDLINE via Ovid (1946 to 21 January 2015) and EMBASE via Ovid (1980 to 21 January 2015). We searched the US National Institutes of Health Trials Register (http://clinicaltrials.gov) and the World Health Organization (WHO) International Clinical Trials Registry Platform for ongoing trials and Open Grey for grey literature (to

  5. Persistent organic pollutants in red-crowned cranes (Grus japonensis) from Hokkaido, Japan.

    PubMed

    Kakimoto, Kensaku; Akutsu, Kazuhiko; Nagayoshi, Haruna; Konishi, Yoshimasa; Kajimura, Keiji; Tsukue, Naomi; Yoshino, Tomoo; Matsumoto, Fumio; Nakano, Takeshi; Tang, Ning; Hayakawa, Kazuichi; Toriba, Akira

    2017-09-01

    The red-crowned crane (Grus japonensis) from eastern Hokkaido is classified as a Special Natural Monument in Japan. In this study, we determined the concentrations of persistent organic pollutants (POPs) in red-crowned crane muscle tissues (n = 47). Polychlorinated biphenyls (PCBs) had the highest median concentration (240ng/g lipid weight), followed by dichlorodiphenyltrichloroethane and its metabolites (DDTs) (150ng/g lipid weight), chlordane-related compounds (CHLs) (36ng/g lipid weight), hexachlorobenzene (HCB) (16ng/g lipid weight), hexachlorocyclohexanes (HCHs) (4.4ng/g lipid weight), polybrominated diphenyl ethers (PBDEs) (1.8ng/g lipid weight), and finally, Mirex (1.5ng/g lipid weight). Additionally, a positive correlation was found among POP concentrations. No sex differences beyond body parameters were observed. Additionally, red-crowned cranes exhibited a high enantiomeric excess of (+)-alpha-HCH, with enantiomer fractions varying from 0.51 to 0.87 (average: 0.69). Copyright © 2017 Elsevier Inc. All rights reserved.

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

    PubMed

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

    2010-12-07

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

  7. Urban Crowns: crown analysis software to assist in quantifying urban tree benefits

    Treesearch

    Matthew F. Winn; Sang-Mook Lee Bradley; Philip A. Araman

    2010-01-01

    UrbanCrowns is a Microsoft® Windows®-based computer program developed by the U.S. Forest Service Southern Research Station. The software assists urban forestry professionals, arborists, and community volunteers in assessing and monitoring the crown characteristics of urban trees (both deciduous and coniferous) using a single side-view digital photograph. Program output...

  8. Retrospective Study of Retention of Stainless Steel Crowns and Pre-veneered Crowns on Primary Anterior Teeth.

    PubMed

    Lopez-Loverich, Angela M; Garcia, Maria Minerva; Donly, Kevin J

    2015-01-01

    The purpose of this retrospective chart review was to explore the retention of anterior pre-veneered stainless steel crowns (NuSmile) and conventional stainless steel crowns (3M ESPE) placed on primary anterior teeth. Records for children were reviewed over four years using the electronic record system axiUm. Data collected included child's age at time of crown placement, date of placement, tooth number, type of crown, patient behavior, treatment environment, provider type, crown presence, absence, and cementation success or failure at subsequent recall visits. A total of 637 anterior crowns in children treated with either or both crown types met this study's inclusion criteria. Of these crowns, 483 were NuSmile Signature crowns and 154 were stainless steel crowns. There was a nine percent failure rate for the NuSmile Signature crowns and a seven percent failure rate for the stainless steel crowns. There was no statistically significant difference in crown retention rates between the two groups (P<0.05). A full-coverage restoration that can follow the lifespan of the primary anterior dentition in high-risk children is needed. The results from this study indicate good crown retention rates for both crown types with no statistically significant difference between them (P<0.05).

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

    PubMed

    Demir, Teyfik

    2015-05-01

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

  10. Structural investigation into the steric control of polyether complexation in the lanthanide series: Macrocyclic 18-crown-6 versus acyclic pentaethylene glycol

    SciTech Connect

    Rogers, R.D.; Rollins, A.N.; Etzenhouser, R.D.; Voss, E.J.; Bauer, C.B. )

    1993-08-04

    The complexation reactions of MCl[sub 3][center dot]nH[sub 2]O (M = Y, La-Pr, Sm-Lu) with pentaethylene glycol (EO5) and MCl[sub 3][center dot]nH[sub 2]O (M = La, Ce, Pr, Eu, Gd) with 18-crown-6 in 1:1 molar ratios in 3:1 CH[sub 3]CN:CH[sub 3]OH were investigated. X-ray structural analysis of 21 crystalline complexes were carried out. Comparison of all the crystalline complexes studied reveals that polyethylene glycols exhibit a helical wrapping pattern around the lanthanide ions, while the crown ethers attempt to fold around these cations. This feature of polyether complexation of the lanthanide(III) chlorides may be responsible for the ready isolation of EO5 complexes for all lanthanides and the lack of direct coordination of 18-crown-6 past M = Tb in normal 1:1 complexation reactions.

  11. Measuring exposures to glycol ethers.

    PubMed

    Clapp, D E; Zaebst, D D; Herrick, R F

    1984-08-01

    In 1981, NIOSH began investigating the potential reproductive health effects resulting from exposures to a class of organic solvents known generically as glycol ethers (GE). This research was begun as a result of the NIOSH criteria document development program which revealed little data available on the health effects of glycol ether exposure. Toxicologic research was begun by NIOSH and other researchers which suggested substantial reproductive effects in animals. These animal data motivated a study of human exposures in the occupational setting. In 1981 and 1982 NIOSH conducted several walk-through surveys which included preliminary measurements of exposures in a variety of industries including painting trades, coal mining, production blending and distribution facilities, aircraft fueling, and communications equipment repair facilities. The human exposure data from these surveys is summarized in this paper with most results well below 1 parts per million (ppm) and only a few values approaching 10 ppm. Blood samples were collected at one site resulting in GE concentrations below the limit of detection. Exposures to airborne glycol ethers, in the industries investigated during the collection of this data, revealed several problems in reliably sampling GE at low concentrations. It became apparent, from the data and observations of work practices, that air monitoring alone provided an inadequate index of GE exposure. Further field studies of exposure to GE are anticipated, pending location of additional groups of exposed workers and development of more reliable methods for characterizing exposure, especially biological monitoring.

  12. Crown cover chart for oak savannas. Forest Service technical brief

    SciTech Connect

    Law, J.R.; Johnson, P.S.; Houf, G.

    1994-07-01

    Although oak savannas have been defined in many ways, they are characterized by scattered trees, largely comprised of oaks, and a sparse ground layer rich in grasses and forbs. The crown cover chart can be used to estimate the crown cover of trees as a percent of total area. Potential applications of the chart include monitoring changes in savanna crown cover, determining needed reductions in crown cover, and defining the savanna state. in restoring savannas that have grown into closed canopy stands, one can use the chart to estimate initial crown cover before restoration work is begun and again after crown cover has been reduced.

  13. Clinical Evaluation and Parental Satisfaction with Pediatric Zirconia Anterior Crowns.

    PubMed

    Holsinger, Daniel M; Wells, Martha H; Scarbecz, Mark; Donaldson, Martin

    2016-01-01

    The purpose of this study was to evaluate the clinical success of and parental satisfaction with anterior pediatric zirconia crowns. A retrospective analysis of maxillary anterior pediatric zirconia crowns was performed. Crowns were evaluated for retention, gingival health, color match, contour, marginal integrity, and opposing tooth wear. Parental satisfaction regarding the esthetics of the crowns and parental perception of the impact of treatment on the child's appearance and oral health were evaluated by questionnaire. Fifty-seven crowns were evaluated in 18 children. Eight teeth were lost to exfoliation, three were extracted due to pathology, and two crowns debonded, leaving 44 available for examination. The average crown age at time of examination was 20.8 months. Sixteen crowns (36 percent) displayed gingival inflammation and color mismatch. No recurrent caries or opposing tooth wear was noted. Parents reported high satisfaction with the color, size, and shape of the crowns. The majority of parents reported that crowns improved the appearance and oral health of their child (78 percent and 83 percent, respectively). Eight-nine percent of parents reported that they would highly recommend these crowns. Zirconia crowns are clinically acceptable restorations in the primary maxillary anterior dentition. Parental satisfaction with zirconia crowns is high.

  14. Forest management manual for Crown lands 1994

    SciTech Connect

    Not Available

    1994-01-01

    The forest management plan describes the objectives for which Crown lands and the resources of Crown lands are used by the licensee and sublicensees. The operating plan describes all the proposed activities of the licensee, constituting an implementation plan for the management plan. This document describes the contents of the operating plan in relation to roads, harvest, silviculture, fish and wildlife habitat, recreation, required letters of agreement, and DNR amendments; operating plan approval and maintenance; and annual report requirements for each operating plan element.

  15. [The method of esthetic crown restoration with composite resin jacket crown in primary molars].

    PubMed

    Doi, K; Shibui, N; Suda, M; Uehara, M; Karibe, H; Kondou, K

    1990-10-01

    The term "esthetics" has recently been also used in the dental field, and a field called esthetic dentistry is increasingly being noted. The number of not only adult but also pediatric patients who visit for treatment aiming at esthetic recovery is being increased. Inpedodontics, composite resin of the coronal color is generally used in the restoration of deciduous incisors. However, the method using metal crowns for the deciduous teeth is used for the deciduous molars at present. We applied a composite resin jacket crown to the deciduous molar in a way similar to that of esthetic crown restoration for the anterior teeth. The surgical procedure before crown preparation varied slightly according to the presence or absence of pulpal treatment of vital teeth and with non-vital teeth, but the application was performed as follows: 1) Desensitization of pulp, pulpal treatment and core construction. 2) Preparation of crown. 3) Selection, trial set and occlusal equilibration of a metal crown for the deciduous tooth. 4) Precision impression with a silicone impression material. 5) Removal of the metal crown for the deciduous tooth from the impression material. 6) Making of an under-cut to the abutment tooth on the buccal lingual side. 7) Filling of the impression with chemical polymerization resin. 8) Application of pressure in the oral cavity. 9) Adjustment of edge and crown forms. Thus, the preparation method for the composite resin jacket crown was relatively simple. Since this surgery, the patient has been followed up for 1 year and 6 months, and no specifically troublesome points have been observed clinically. The patient and her parents are satisfied with the results.(ABSTRACT TRUNCATED AT 250 WORDS)

  16. Crystalline Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    Series of imide/arylene ether block copolymers prepared by using arylene ether blocks to impart low melt viscosity, and imide blocks to provide high strength and other desirable mechanical properties. Work represents extension of LAR-14159 on imide/arylene ether copolymers in form of films, moldings, adhesives, and composite matrices. Copolymers potentially useful in variety of high-temperature aerospace and microelectronic applications.

  17. Polyphenylene ethers with imide linking groups

    NASA Technical Reports Server (NTRS)

    St.clair, T. L.; Burks, H. D. (Inventor)

    1984-01-01

    Novel polyphenylene ethers with imide linking units are disclosed. These polymers incorporate the solvent and thermal resistance of polyimides and the processability of polyphenylene ethers. Improved physical properties over those of the prior art are obtained by incorporating meta linked ethers and/or polyphenylene oxides into the polymer backbone. A novel process for making polymers of this type is also disclosed. The process is unique in that the expected need of high process temperatures and/or special atmospheres are eliminated.

  18. Is the ether group hydrophilic or hydrophobic?

    PubMed

    Menger, Fredric M; Chlebowski, Mary E

    2005-03-29

    A series of six surfactants, each with two ether oxygens within otherwise all-hydrocarbon chains, were synthesized and examined for their colloidal properties. Since an ether oxygen is sterically and conformationally similar to the methylene group it has replaced, the ether effect on micellization should stem mainly from solvation of the oxygen and, possibly, disrupted hydrophobicity of its adjacent carbons. It was found that critical aggregation values among the surfactants differ only modestly despite the total length of the ether-separated carbon segments ranging from 12 to 18. Shorter ether surfactants with only 12 or 14 total carbons appear to form small, loose aggregates owing, presumably, to a mild hydrophilicity of the ether groups. A surfactant with 18 chain carbons has a greater tendency to associate hydrophobically, but this is counterbalanced by a relatively water-free environment encountered by the ether groups within a more conventional micelle interior. The result is a leveling effect in which the critical aggregation concentration (cac) loses it sensitivity to chain length. Above their cac's, none of the ether surfactants is a good solubilizer of tetramethysilane or mesitylene. This is not necessarily a predictable finding since it was conceivable that the presence of interior ether groups might actually enhance solubilization (much as ether is a better solvent than hexane). Foamability and solid adsorption studies also indicate that the ethers impair surface activity. In response to the question posed in the paper's title, two ether groups are not sufficiently hydrophilic to prevent aggregation, but they do manage to alter the micelles' morphology and properties considerably.

  19. LaRC-ITPI/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Working, Dennis C.

    1991-01-01

    As part of an effort to develop high performance structural resins for aerospace applications, work has continued on block copolymers containing imide and arylene ether segments. The arylene ether block used in this study contains a bulky fluorene group in the polymer backbone while the imide block contains an arylene ketone segment similar to that in the arylene ether block and has been named LaRC-ITPI. A series of imide/arylene ether block and segmented copolymers were prepared and characterized. Films were prepared from these copolymers and mechanical properties were measured.

  20. 21 CFR 872.3330 - Preformed crown.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... greater gold and metals of the platinum group intended to be affixed temporarily to a tooth after removal of, or breakage of, the natural crown (that portion of the tooth that normally protrudes above the...) tooth until the adult tooth erupts. (b) Classification. Class I (general controls). The device is...

  1. 21 CFR 872.3330 - Preformed crown.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... greater gold and metals of the platinum group intended to be affixed temporarily to a tooth after removal of, or breakage of, the natural crown (that portion of the tooth that normally protrudes above the...) tooth until the adult tooth erupts. (b) Classification. Class I (general controls). The device is...

  2. Crown ratio influences allometric scaling in trees

    Treesearch

    Annikki Makela; Harry T. Valentine

    2006-01-01

    Allometric theories suggest that the size and shape of organisms follow universal rules, with a tendency toward quarter-power scaling. In woody plants, however, structure is influenced by branch death and shedding, which leads to decreasing crown ratios, accumulation of heartwood, and stem and branch tapering. This paper examines the impacts on allometric scaling of...

  3. Crowning achievement: a case of dental aspiration.

    PubMed

    Mark, Nicholas M; Lessing, Juan N; Çoruh, Başak

    2015-12-01

    Aspiration of foreign bodies during dental procedures is a rare but potentially serious complication. We present a case of a 75-year-old man who aspirated a dental crown requiring flexible bronchoscopic retrieval. We discuss the risk factors for aspiration, the radiographic features of diagnosis, and the techniques for management and retrieval.

  4. Crowning achievement: a case of dental aspiration

    PubMed Central

    Mark, Nicholas M.; Lessing, Juan N.; Çoruh, Başak

    2015-01-01

    Aspiration of foreign bodies during dental procedures is a rare but potentially serious complication. We present a case of a 75-year-old man who aspirated a dental crown requiring flexible bronchoscopic retrieval. We discuss the risk factors for aspiration, the radiographic features of diagnosis, and the techniques for management and retrieval. PMID:26649115

  5. PREFORMED METAL CROWNS FOR THE PERMANENT DENTITION.

    PubMed

    Millar, Lynsey M; Cairns, Alison M; Fowler, Lauren

    2015-11-01

    Preformed metal crowns have a range of uses in paediatric dentistry in both the primary and permanent dentition. This article provides an overview of their use in permanent teeth, including teeth that have been affected by molar incisor hypomineralisation, caries, developmental defects and tooth surface loss. The indications for use are described, along with the clinical technique for placement

  6. Aspergillosis in a red-crowned crane

    USGS Publications Warehouse

    Stroud, R.K.; Duncan, R.M.

    1983-01-01

    An unusual form of pulmonary aspergillosis in a red-crowned crane (Grus japonensis) is described in this report. The major lesion is unique because it closely resembles a lesion referred to as an aspergilloma. An aspergilloma is a single large granulomatous lesion that resembles a tumor and is caused by fungi of the genus Aspergillus.

  7. 21 CFR 872.3330 - Preformed crown.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Preformed crown. 872.3330 Section 872.3330 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL... greater gold and metals of the platinum group intended to be affixed temporarily to a tooth after removal...

  8. INTERNAL ADAPTATION OF CAST TITANIUM CROWNS

    PubMed Central

    da Rocha, Sicknan Soares; Adabo, Gelson Luis; Ribeiro, Ricardo Faria; Fonseca, Renata Garcia

    2007-01-01

    As the adaptation of titanium crowns obtained by Rematitan Plus investment, specific for titanium, is not recognized to be suitable, this study evaluated the effect of the concentration of the specific liquid and the temperature of the mold of investments on the internal misfit of crowns cast on commercially pure titanium. Individual dies of epoxy resin were obtained, representing teeth prepared for full-crown restoration with a 6-degree axial surface convergence angle and shoulder (1.0 mm). For the waxing of each crown, a ring-shaped stainless steel matrix (8.0mm internal diameter; 7.5 mm height) was adapted above the individual dies of epoxy resin. The Rematian Plus investment was mixed according to the manufacturer's instructions using two different concentrations of the specific liquid: 100%, 75%. Casting was performed in a Discovery Plasma Ar-arc vacuum-pressure casting machine with molds at temperatures of 430°C, 515°C and 600°C. The crowns were cleaned individually in a solution (1% HF + 13% HNO3) for 10 min using a ultrasonic cleaner, with no internal adaptations, and luted with zinc phosphate cement under a 5 kg static load. The crown and die assemblies were embedded in resin and sectioned longitudinally. The area occupied by cement was observed using stereoscopic lens (10X) and measured by the Leica Qwin image analysis system (mm2). The data for each experimental condition (n=8) were analyzed by Kruskal-Wallis non-parametric test (á=0.05). The results showed that liquid dilution and the increase in mold temperature did not significantly influence the levels of internal fit of the cast titanium crowns. The lowest means (±SD) of internal misfit were obtained for the 430°C/100%: (7.25 mm2 ±1.59) and 600°C/100% (8.8 mm2 ±2.25) groups, which presented statistically similar levels of internal misfit. PMID:19089139

  9. Evaluation of wild juglans species for crown gall resistance

    USDA-ARS?s Scientific Manuscript database

    A. tumefaciens is a soil-borne Gram-negative bacterium which causes crown gall on many dicotyledonous plant species including walnut. Crown gall symptoms on walnut are characterized by large tumors located near the crown of the tree but can occur near wounds caused by bleeding cuts or at the graft u...

  10. 21 CFR 872.3770 - Temporary crown and bridge resin.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Temporary crown and bridge resin. 872.3770 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3770 Temporary crown and bridge resin. (a) Identification. A temporary crown and bridge resin is a device composed of a material, such as...

  11. 21 CFR 872.3770 - Temporary crown and bridge resin.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Temporary crown and bridge resin. 872.3770 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3770 Temporary crown and bridge resin. (a) Identification. A temporary crown and bridge resin is a device composed of a material, such as...

  12. 21 CFR 872.3770 - Temporary crown and bridge resin.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Temporary crown and bridge resin. 872.3770 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3770 Temporary crown and bridge resin. (a) Identification. A temporary crown and bridge resin is a device composed of a material, such as...

  13. 21 CFR 872.3770 - Temporary crown and bridge resin.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Temporary crown and bridge resin. 872.3770 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3770 Temporary crown and bridge resin. (a) Identification. A temporary crown and bridge resin is a device composed of a material, such as...

  14. 21 CFR 872.3770 - Temporary crown and bridge resin.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Temporary crown and bridge resin. 872.3770 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3770 Temporary crown and bridge resin. (a) Identification. A temporary crown and bridge resin is a device composed of a material, such as...

  15. Using crown condition variables as indicators of forest health

    Treesearch

    Stanley J. Zarnoch; William A. Bechtold; K.W. Stolte

    2004-01-01

    Indicators of forest health used in previous studies have focused on crown variables analyzed individually at the tree level by summarizing over all species. This approach has the virtue of simplicity but does not account for the three-dimensional attributes of a tree crown, the multivariate nature of the crown variables, or variability among species. To alleviate...

  16. Thinning guidelines from crown area relationships for young hardwood plantations

    Treesearch

    Jeffrey W. Stringer; Luke Cecil

    2010-01-01

    Crown closure in hardwood plantations signals the first opportunity to apply density control treatments such as thinning or release. The proper timing of these treatments is a function of stocking levels and is generally scheduled within several years after initial crown closure. Predicting crown closure for a plantation provides practitioners with the ability to plan...

  17. Digital photography for urban street tree crown conditions

    Treesearch

    Neil A. Clark; Sang-Mook Lee; William A. Bechtold; Gregory A. Reams

    2006-01-01

    Crown variables such as height, diameter, live crown ratio, dieback, transparency, and density are all collected as part of the overall crown assessment (USDA 2004). Transparency and density are related to the amount of foliage and thus the photosynthetic potential of the tree. These measurements are both currently based on visual estimates and have been shown to be...

  18. 28. Photocopy of Crown Roller Mill illustration; originally published in ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    28. Photocopy of Crown Roller Mill illustration; originally published in The Crown Roller Mill, Northwestern Miller 9 (May 21, 1880): 321; SHOWING WEST SIDE, LOOKING EAST - Crown Roller Mill, 105 Fifth Avenue, South, West Side Milling District, Minneapolis, Hennepin County, MN

  19. Evaluation of sampling strategies to estimate crown biomass

    Treesearch

    Krishna P Poudel; Hailemariam Temesgen; Andrew N Gray

    2015-01-01

    Depending on tree and site characteristics crown biomass accounts for a significant portion of the total aboveground biomass in the tree. Crown biomass estimation is useful for different purposes including evaluating the economic feasibility of crown utilization for energy production or forest products, fuel load assessments and fire management strategies, and wildfire...

  20. Updating histological data on crown initiation and crown completion ages in southern Africans.

    PubMed

    Reid, Donald J; Guatelli-Steinberg, Debbie

    2017-04-01

    To update histological data on crown initiation and completion ages in southern Africans. To evaluate implications of these data for studies that: (a) rely on these data to time linear enamel hypoplasias (LEHs), or, (b) use these data for comparison to fossil hominins. Initiation ages were calculated on 67 histological sections from southern Africans, with sample sizes ranging from one to 11 per tooth type. Crown completion ages for southern Africans were calculated in two ways. First, actual derived initiation ages were added to crown formation times for each histological section to obtain direct information on the crown completion ages of individuals. Second, average initiation ages from this study were added to average crown formation times of southern Africans from the Reid and coworkers previous studies that were based on larger samples. For earlier-initiating tooth types (all anterior teeth and first molars), there is little difference in ages of initiation and crown completion between this and previous studies. Differences increase as a function of initiation age, such that the greatest differences between this and previous studies for both initiation and crown completion ages are for the second and third molars. This study documents variation in initiation ages, particularly for later-initiating tooth types. It upholds the use of previously published histological aging charts for LEHs on anterior teeth. However, this study finds that ages of crown initiation and completion in second and third molars for this southern African sample are earlier than previously estimated. These earlier ages reduce differences between modern humans and fossil hominins for these developmental events in second and third molars. © 2017 Wiley Periodicals, Inc.

  1. Noncovalent interactions between ([18]crown-6)-tetracarboxylic acid and amino acids: electrospray-ionization mass spectrometry investigation of the chiral-recognition processes.

    PubMed

    Gerbaux, Pascal; De Winter, Julien; Cornil, David; Ravicini, Katia; Pesesse, Gaëlle; Cornil, Jérôme; Flammang, Robert

    2008-01-01

    Chiral recognition of enantiomers by host compounds is one of the most challenging topics in modern host-guest chemistry. Amongst the well-established methods, mass spectrometry (MS) is increasingly used nowadays, due to its low detection limit, short analysis time, and suitability for analyzing mixtures and for studying chiral effects in the gas phase. The development of electrospray-ionization (ESI) techniques provides an invaluable tool to study, in the gas phase, diastereoisomeric complex ions prepared from enantiomer ions and a chiral selector. This paper reports on an ESIMS and ESIMSMS study of the molecular mechanisms that intervene in the chiral-recognition phenomena observed between amino acids and a chiral crown ether. The modified crown ether, namely (+)-([18]crown-6)-2,3,11,12-tetracarboxylic acid, is used as the chiral selector when covalently bound on a stationary phase in liquid chromatography. This study was stimulated by the fact that, except with threonine and proline, consistent elution orders were observed, which indicates that the D enantiomers interact more strongly with the chiral selector than the L enantiomers. For proline, the lack of a primary amino group is likely to be responsible for the nonresolution of the two forms, whereas the second stereogenic center on threonine could explain the reversed elution order. In light of those observations, we performed mass spectrometry experiments to understand more deeply the enantiomeric recognition phenomena, both in solution by the enantiomer-labeled guest method and in the gas phase by gas-phase ligand-exchange ion/molecule reactions. The results have been further supported by quantum chemical calculations. One of the most interesting features of this work is the identification of a nonspecific interaction between proline and the crown ether upon ESIMS analysis.

  2. Estimating the weight of crown segments for old-growth Douglas-fir and western hemlock.

    Treesearch

    J.A. Kendall Snell; Timothy A. Max

    1985-01-01

    The purpose of this study was to develop and validate estimators to predict total crown weight and weight of any segment of crown for old-growth felled and bucked Douglas-fir and western hemlock trees. Equations were developed for predicting weight of continuous live crown, total live crown, dead crown, any segment of live crown, and individual branches for old-growth...

  3. Conformational Study of Dibenzyl Ether

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

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

  4. Purification of aqueous cellulose ethers

    SciTech Connect

    Bartscherer, K.A.; de Pablo, J.J.; Bonnin, M.C.; Prausnitz, J.M.

    1990-07-01

    Manufacture of cellulose ethers usually involves high amounts of salt by-products. For application of the product, salt must be removed. In this work, we have studied the injection of high-pressure CO{sub 2} into an aqueous polymer-salt solution; we find that upon addition of isopropanol in addition to CO{sub 2}, the solution separates into two phases. One phase is rich in polymer and water, and the other phase contains mostly isopropanol, water and CO{sub 2}. The salt distributes between the two phases, thereby offering interesting possibilities for development of a new purification process for water-soluble polymers. This work presents experimental phase-equilibrium data for hydroxyethyl cellulose and sodium carboxymethyl cellulose with sodium acetate and potassium sulfate, respectively, in the region 40{degree}C and 30 to 80 bar. Based on these data, we suggest a process for the manufacture and purification of water-soluble cellulose ethers. 15 refs., 14 figs., 9 tabs.

  5. Bacterial Utilization of Ether Glycols

    PubMed Central

    Fincher, Edward L.; Payne, W. J.

    1962-01-01

    A soil bacterium capable of using oligo- and polyethylene glycols and ether alcohols as sole sources of carbon for aerobic growth was isolated. The effects of substituent groups added to the ether bonds on the acceptability of the compounds as substrates were studied. Mechanisms for the incorporation of two-carbon compounds were demonstrated by the observation that acetate, glyoxylate, ethylene glycol, and a number of the tricarboxylic acid cycle intermediates served as growth substrates in minimal media. The rate of oxidation of the short-chained ethylene glycols by adapted resting cells varied directly with increasing numbers of two-carbon units in the chains from one to four. The amount of oxygen consumed per carbon atom of oligo- and polyethylene glycols was 100% of theoretical, but only 67% of theoretical for ethylene glycol. Resting cells oxidized oligo- and polyethylene glycols with 2 to 600 two-carbon units in the chains. Longer chained polyethylene glycols (up to 6,000) were oxidized at a very slow rate by these cells. Dehydrogenation of triethylene glycol by adapted cells was observed, coupling the reaction with methylene blue reduction. PMID:13945208

  6. 27 CFR 21.108 - Ethyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

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

  7. An expedient synthesis of linden ether.

    PubMed

    Serra, Stefano; Cominetti, Alessandra A

    2014-03-01

    We here describe a comprehensive study on the preparation of the intensive flavor 3,9-epoxy-p-mentha-1,4(8)-diene (1). Key steps of the presented synthesis are the selective addition of MeLi to the keto-ester 7, the regioselective cyclization of the obtained triol to give the ethers 4 and 8 and the selective dehydration of ether 4 through the use of POCI3 and pyridine. It is worth noting that the presented synthesis represents the first expedient and reliable entry to ether 1. Being present in linden honey, 1 is also known as linden ether and it has been regarded as a potential marker for the authentication of the linden honey origin. Therefore, ether 1 can be used as a useful reference standard for the analysis of the natural flavors, as we demonstrated by means of its identification in a sample ofunifloral linden honey.

  8. Cerec anterior crowns: restorative options with monolithic ceramic materials.

    PubMed

    Reich, Sven; Fiedlar, Kurt

    2013-01-01

    The aim of this article is to discuss the different types of monolithic ceramic crowns that can be placed on anterior teeth with existing shoulder preparations. Anterior crowns were indicated for the teeth 12 to 22 in the present case. The patient, a 65-year-old male, had received all-ceramic crowns 20 years earlier, which had started to develop cracks and palatal fractures over the last few years. The patient's teeth were prepared and four sets of crowns were fabricated using different monolithic ceramic materials: IPS e.max CAD, Cerec Blocs C In, VITABLOCS Real Life, and ENAMIC. Both shade characterization and crystallization firing were performed on the monolithic lithium disilicate glass ceramic crowns. The silicate ceramic crowns received glaze firing alone. The crowns made of hybrid ceramic (ENAMIC) were treated with a polymer sealant.

  9. Crown Features Extraction from Low Altitude AVIRIS Data

    NASA Astrophysics Data System (ADS)

    Ogunjemiyo, S. O.; Roberts, D.; Ustin, S.

    2005-12-01

    Automated tree recognition and crown delineations are computer-assisted procedures for identifying individual trees and segmenting their crown boundaries on digital imagery. The success of the procedures is dependent on the quality of the image data and the physiognomy of the stand as evidence by previous studies, which have all used data with spatial resolution less than 1 m and average crown diameter to pixel size ratio greater than 4. In this study we explored the prospect of identifying individual tree species and extracting crown features from low altitude AVIRIS (Airborne Visible/Infrared Imaging Spectrometer) data with spatial resolution of 4 m. The test site is a Douglas-fir and Western hemlock dominated old-growth conifer forest in the Pacific Northwest with average crown diameter of 12 m, which translates to a crown diameter pixel ratio less than 4 m; the lowest value ever used in similar studies. The analysis was carried out using AVIRIS reflectance imagery in the NIR band centered at 885 nm wavelength. The analysis required spatial filtering of the reflectance imagery followed by application of a tree identification algorithm based on maximum filter technique. For every identified tree location a crown polygon was delineated by applying crown segmentation algorithm. Each polygon boundary was characterized by a loop connecting pixels that were geometrically determined to define the crown boundary. Crown features were extracted based on the area covered by the polygons, and they include crown diameters, average distance between crowns, species spectral, pixel brightness at the identified tree locations, average brightness of pixels enclosed by the crown boundary and within crown variation in pixel brightness. Comparison of the results with ground reference data showed a high correlation between the two datasets and highlights the potential of low altitude AVIRIS data to provide the means to improve forest management and practices and estimates of critical

  10. Crystal structures of two solvates of (18-crown-6)potassium acetate

    PubMed Central

    Liebing, Phil; Zaeni, Ahmad; Olbrich, Falk; Edelmann, Frank T.

    2016-01-01

    The crystal and mol­ecular strutures of two solvated forms of [K(18c6)]OAc (18c6 = 18-crown-6 = 1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane and OAc = acetate) were determined by single-crystal X-ray diffraction, namely (acetato-κ2 O,O′)(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-κ6 O)potassium dihydrate, [K(CH3COO)(C12H24O6)]·2H2O (1) and (acetato-κ2 O,O′)aqua­(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-κ6 O)potassium acetic acid monosolvate [K(CH3COO)(C12H24O6)(H2O)]·CH3COOH (2). In both compounds, the acetate anion is bonded to the potassium ion in a chelating fashion and the metal atom is consequently slightly displaced from the O6 plane of the crown ether. In the crystals, O—H⋯O hydrogen bonds lead to a polymeric ladder structure in the dihydrate 1, while the acetic acid hydrate 2 features inversion dimers. PMID:27980824

  11. Crystal structures of two solvates of (18-crown-6)potassium acetate.

    PubMed

    Liebing, Phil; Zaeni, Ahmad; Olbrich, Falk; Edelmann, Frank T

    2016-12-01

    The crystal and mol-ecular strutures of two solvated forms of [K(18c6)]OAc (18c6 = 18-crown-6 = 1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane and OAc = acetate) were determined by single-crystal X-ray diffraction, namely (acetato-κ(2)O,O')(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ(6)O)potassium dihydrate, [K(CH3COO)(C12H24O6)]·2H2O (1) and (acetato-κ(2)O,O')aqua-(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ(6)O)potassium acetic acid monosolvate [K(CH3COO)(C12H24O6)(H2O)]·CH3COOH (2). In both compounds, the acetate anion is bonded to the potassium ion in a chelating fashion and the metal atom is consequently slightly displaced from the O6 plane of the crown ether. In the crystals, O-H⋯O hydrogen bonds lead to a polymeric ladder structure in the dihydrate 1, while the acetic acid hydrate 2 features inversion dimers.

  12. Treatment of crown fractures with pulp exposure.

    PubMed

    de Blanco, L P

    1996-11-01

    Thirty permanent incisors with vital pulps and complicated crown fractures were treated by a partial pulpotomy (Cvek technique). This consisted of amputation of 1 to 2 mm of the exposed pulp, placement of calcium hydroxide powder, and a temporary restoration. Clinical and radiographic assessment of the hard tissue barrier was done after 3 months and again after 1 to 8 years. The treatment was successful in all incisors. No differences were found in stage of root development, size of exposure, and length of time exposed. In conclusion, the partial pulpotomy technique is a successful and permanent treatment for crown fractures with pulp exposure regardless of the size of exposure, the maturity of the root, or the interval between accident and dental treatment.

  13. Accuracy of Casting Single Crowns in Titanium

    DTIC Science & Technology

    1990-04-01

    denture bases were cast by pouring molten metal into a mold by Dr. Edward Hudson of Philadelphia in 1820 ( Hagman , 1976). In 1906, Dr. Solbrig of Paris...fabrication of crowns and fixed partial dentures . Wax patterns are injected into molds that have been machined from aluminum. The patterns are sprued and...as removable partial denture frameworks (Szurgot,et.al., 1988). The other system commercially available is a vertical centrifugal casting machine

  14. Stabilizing distressed glass furnace melter crowns

    SciTech Connect

    1997-08-01

    Before the advent of pump casting, hot patching a melter or regenerator crown was extremely time and labor intensive. During these installations, known to many as the bucket brigade, the slurry was mixed on floor level and hauled in 50--65 lb batches up to 100 ft to the top of the crown. Today, in a single shift, a crew of seven can accomplish what took two days and a crew of {approximately}25 in the past. The first application of pump-casting zircon patch occurred on the AZS crown of an insulation-wool-glass furnace. For this application, 23 in. of insulating firebrick had to be removed to gain access to the fused AZS surface. The zircon patch was applied by pumping the mix from floor level up {approximately}60 ft to the crown by means of a concrete pump. Postmortems were performed on samples from two of the gas-fired TV-panel-glass furnaces. These postmortems were performed to determine if alterations occurred on the hot face of exposed zircon patch and, if so, how much alteration did occur. There was no destructive alteration because of alkali penetration into the patch. In fact, only trace amounts of lead, barium and strontium were detected, no further than 1 in. from the hot face. There was slight loss of P{sub 2}O{sub 5} on the hot face because of migration of phosphate toward the cold face, but it did not decrease the integrity of the patch. The dissociation of zircon was <3% baddelyite detected, all within an in. of the hot face.

  15. The use of stainless steel crowns.

    PubMed

    Seale, N Sue

    2002-01-01

    The stainless steel crown (SSC) is an extremely durable restoration with several clear-cut indications for use in primary teeth including: following a pulpotomy/pulpectomy; for teeth with developmental defects or large carious lesions involving multiple surfaces where an amalgam is likely to fail; and for fractured teeth. In other situations, its use is less clear cut, and caries risk factors, restoration longevity and cost effectiveness are considerations in decisions to use the SSC. The literature on caries risk factors in young children indicates that children at high risk exhibiting anterior tooth decay and/or molar caries may benefit by treatment with stainless steel crowns to protect the remaining at-risk tooth surfaces. Studies evaluating restoration longevity, including the durability and lifespan of SSCs and Class II amalgams demonstrate the superiority of SSCs for both parameters. Children with extensive decay, large lesions or multiple surface lesions in primary molars should be treated with stainless steel crowns. Because of the protection from future decay provided by their feature of full coverage and their increased durability and longevity, strong consideration should be given to the use of SSCs in children who require general anesthesia. Finally, a strong argument for the use of the SSC restoration is its cost effectiveness based on its durability and longevity.

  16. A novel pollution pattern: Highly chlorinated biphenyls retained in Black-crowned night heron (Nycticorax nycticorax) and Whiskered tern (Chlidonias hybrida) from the Yangtze River Delta.

    PubMed

    Zhou, Yihui; Yin, Ge; Asplund, Lillemor; Qiu, Yanling; Bignert, Anders; Zhu, Zhiliang; Zhao, Jianfu; Bergman, Åke

    2016-05-01

    Contamination of organochlorine pesticides (OCPs), polychlorinated diphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and their methylated counterparts (MeO-PBDEs) were determined in Black-crowned night heron (Nycticorax nycticorax) and Whiskered tern (Chlidonias hybrida) from two drinking water sources, e.g. Tianmu lake and East Tai lake in Yangtze River Delta, China. A novel PCBs contamination pattern was detected, including 11% and 6.9% highly chlorinated biphenyls (PCBs with eight to ten chlorines) in relation to total PCB concentrations in the Black-crowned night heron and Whiskered tern eggs, respectively. The predominating OCPs detected in the present study were 4,4'-DDE, with concentration range 280-650 ng g(-1) lw in Black-crowned night heron and 240-480 ng g(-1) lw in Whiskered tern, followed by β-HCH and Mirex. 6-MeO-BDE-90 and 6-MeO-BDE-99 are the two predominant congeners of MeO-PBDEs whereas 6-OH-BDE-47 contributes mostly to the OH-PBDEs in both species. Contamination level was considered as median or low level compared global data.

  17. Development of a carbon paste electrode containing benzo-15-crown-5 for trace determination of the uranyl ion by using a voltammetric technique.

    PubMed

    Agrahari, Sunil K; Kumar, Sangita D; Srivastava, Ashwini K

    2009-01-01

    The interaction of macrocyclic compounds like crown ethers and UO2(2+) has been studied by electrochemical methods. A modified carbon paste electrode incorporating benzo-15-crown-5 (B15C5) was used to evaluate the electron transfer reaction of UO2(2+) by cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy. Electrochemical impedance studies showed that charge transfer resistance was less for the B15C5-modified electrode than for the plain carbon paste electrode (PCPE). On the basis of these observations, a UO2(2+)-sensitive crown ether chemically modified electrode (CME) for trace analysis was fabricated and investigated in aqueous solutions. It was found that a 5% B15C5-CME for UO2(2+) showed a better voltammetric response than did the PCPE. UO2(2+) could be quantified at sub-microg/mL levels by differential pulse voltammetry with a detection limit of 0.03 microg/mL. By differential pulse adsorptive stripping voltammetry, UO2(2+) could be quantified in the working range of 0.002-0.2 microg/mL, with a detection limit of 1.1 microg/L. Simultaneous determination of UO2(2+), Pb(2+), and Cd(2+) was possible. The method was successfully applied to the determination of UO2(2+) in synthetic, as well as real, samples; the results were found to be comparable to those obtained by inductively coupled plasma-atomic emission spectroscopy.

  18. Fracture strength of ceramic monolithic crown systems of different thickness.

    PubMed

    Nordahl, Niklas; Vult von Steyern, Per; Larsson, Christel

    2015-09-01

    The objective of this study was to evaluate fracture strength of high-translucent (HTZ) and low-translucent (LTZ) zirconia and glass-ceramic (LDS) crowns. HTZ and LTZ crowns were made with thicknesses of; 0.3 mm, 0.5 mm, 0.7 mm, 1.0 mm, and 1.5 mm; and LDS crowns of 1.0 mm and 1.5 mm thicknesses. Each group consisted of 10 crowns. All crowns underwent artificial aging before loading until fracture. Mean fracture strengths varied from 450 N to 3,248 N in the LTZ group, 438 N to 3,487 N in the HTZ group, and 1,030 N to 1,431 N in the LDS group. The load at fracture of HTZ and LTZ crowns was equal. The load at fracture of yttria-stabilized tetragonal zirconia polycrystals crowns was significantly greater than LDS crowns (P = 0.000). Two types of fractures were recorded; complete and partial crack-like fracture. The crack type fracture occurred most frequently in all groups except in the thicker LTZ groups (1.0 mm and 1.5 mm). According to this study, there is no difference in strength between crowns made of high-translucent or low-translucent zirconia. At equal thickness, the strength of zirconia crowns was significantly greater than that of lithium-disilicate glass-ceramic.

  19. An Investigation Into the Integrity of Fit of Provisional Crowns Using Current Proprietary Temporary Crown Materials.

    PubMed

    Taylor, Philip D; Georgakis, Georgios; Niggli, Jason

    2016-06-01

    Three methods of direct provisional crown construction were investigated for accuracy of marginal fit. A modified proprietary crown coping was compared to Bis GMA and isobutyl methacrylate resin provisional crowns with margins modified by using a flowable composite and 'bead on' isobutyl methacrylate respectively. Measurement was at 50x magnification at seven sites over the fit surface. Data was analyzed using SPSS version 13.0.1 and measurement compared using the Mann Whitney test set at a significance level of 0.05. Reliability was checked using the Bland Altman test. Statistical significant differences were found between the three groups. The order of best fit was Bis-GMA and flowable composite > isobutyl methacrylate with 'bead on' margins > Bis-GMA modified implant temporary coping. The clinical significance is that the Bis GMA and flowable composite combination can be used with equal confidence to traditional methods of temporarisation.

  20. Microcin J25 uptake: His5 of the MccJ25 lariat ring is involved in interaction with the inner membrane MccJ25 transporter protein SbmA.

    PubMed

    de Cristóbal, Ricardo E; Solbiati, Jose O; Zenoff, Ana M; Vincent, Paula A; Salomón, Raul A; Yuzenkova, Julia; Severinov, Konstantin; Farías, Ricardo N

    2006-05-01

    Escherichia coli microcin J25 (MccJ25) is a plasmid-encoded antibiotic peptide consisting of 21 L-amino acid residues (G1-G-A-G-H5-V-P-E-Y-F10-V-G-I-G-T15-P-I-S-F-Y20-G). E. coli RNA polymerase (RNAP) is the intracellular target of MccJ25. MccJ25 enters cells after binding to specific membrane transporters: FhuA in the outer membrane and SbmA in the inner membrane. Here, we studied MccJ25 mutants carrying a substitution of His5 by Lys, Arg, or Ala. The inhibitory effects on cellular growth and in vitro RNAP activity were determined for each mutant microcin. The results show that all mutants inhibited RNAP in vitro. However, the mutants were defective in their ability to inhibit cellular growth. Experiments in which the FhuA protein was bypassed showed that substitutions of MccJ25 His5 affected the SbmA-dependent transport. Our results thus suggest that MccJ25 His5 located in the lariat ring is involved, directly or indirectly, in specific interaction with SbmA and is not required for MccJ25 inhibition of RNAP.

  1. Alternative crown systems. Is the metal-ceramic crown always the restoration of choice?

    PubMed

    Wall, J G; Cipra, D L

    1992-07-01

    The metal-ceramic crown system still is selected the most frequently because of its strength and versatility. The ability to select metals for color or strength for single units or fixed partial dentures gives great flexibility, but when esthetics of the anterior region are a prime concern, the all-ceramic crown is still an excellent choice. Choice of which all-ceramic system to use is dependent on the strength demands, esthetic needs, amount of tooth structure that can be preserved, and laboratory support available. Where good tooth structure remains but some color, contour, or incisal length changes are desired, the porcelain laminate veneer is an outstanding esthetic and restorative choice. When good labial tooth structure remains but lingual structure is inadequate, a partial veneer gold crown can be an excellent esthetic choice. If moderate tooth structure is lost or moderate staining is present, the Dicor crown is a superb choice. In those instances in which heavy staining is present, a foil or core system should be considered to completely block out the background colors. As the occlusal forces become more of a factor, selection of a restorative system will depend more on strength than esthetic demands. The aluminous porcelain jacket crown still offers great strength and esthetics at a reasonable price. When most of the color is on the surface of the teeth, or when there is a high translucency to the teeth, Dicor can provide very esthetic results, and the Dicor Plus crown offers the opportunity to develop intrinsic shading. When greater strength is required, selection of a foil and core system is suggested, as might be a system that provides a stronger core material, like Alceram or Inceram. These stronger core materials will render improved flexural and compressive strengths, but some increases in brightness may occur with the increased alumina content of the cores. The future in ceramic restorative dentistry may be in the computer-generated crown if ways

  2. A transferable force field to predict phase equilibria and surface tension of ethers and glycol ethers.

    PubMed

    Ferrando, Nicolas; Lachet, Véronique; Pérez-Pellitero, Javier; Mackie, Allan D; Malfreyt, Patrice; Boutin, Anne

    2011-09-15

    We propose a new transferable force field to simulate phase equilibrium and interfacial properties of systems involving ethers and glycol ethers. On the basis of the anisotropic united-atom force field, only one new group is introduced: the ether oxygen atom. The optimized Lennard-Jones (LJ) parameters of this atom are identical whatever the molecule simulated (linear ether, branched ether, cyclic ether, aromatic ether, diether, or glycol ether). Accurate predictions are achieved for pure compound saturated properties, critical properties, and surface tensions of the liquid-vapor interface, as well as for pressure-composition binary mixture diagrams. Multifunctional molecules (1,2-dimethoxyethane, 2-methoxyethanol, diethylene glycol) have also been studied using a recently proposed methodology for the calculation of the intramolecular electrostatic energy avoiding the use of additional empirical parameters. This new force field appears transferable for a wide variety of molecules and properties. It is furthermore worth noticing that binary mixtures have been simulated without introducing empirical binary parameters, highlighting also the transferability to mixtures. Hence, this new force field gives future opportunities to simulate complex systems of industrial interest involving molecules with ether functions.

  3. [Comparison of the clinical effects of selective laser melting deposition basal crowns and cobalt chromium alloy base crowns].

    PubMed

    Li, Jing-min; Wang, Wei-qian; Ma, Jing-yuan

    2014-06-01

    To evaluate the clinical effects of selective laser melting (SLM) deposition basal crowns and cobalt chromium alloy casting base crowns. One hundred and sixty eight patients treated with either SLM deposition basal crowns (110 teeth) or cobalt chromium alloy casting basal crowns (110 teeth) were followed-up for 1 month, 6 months, 12 months and 24 months. The revised standard of American Public Health Association was used to evaluate the clinical effect of restoration, including the color of porcelain crowns, gingival inflammation, gingival margin discoloration, and crack or fracture. Data analysis was conducted with SPSS 20 software package for Student's t test and Chi-square test. Six cases were lost to follow-up. The patients who were treated with SLM deposition basal crowns (104 teeth) and cobalt chromium alloy casting base crowns (101 teeth) completed the study. Patients were more satisfied with SLM deposition cobalt chromium alloy porcelain crowns. There was 1 prosthesis with poor marginal fit after 24 months of restoration in SLM crowns. There were 6 prostheses with edge coloring and 8 with poor marginal fit in cobalt chromium alloy casting base crowns, which was significantly different between the 2 groups(P<0.05). The SLM deposition copings results in smaller edge coloring and better marginal fit than those of cobalt-chrome copings. Patients are pleased with short-term clinical results.

  4. Polybrominated Diphenyl Ethers (PBDEs) Action Plan

    EPA Pesticide Factsheets

    Polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants in a number of applications. EPA is concerned that some of the component congeners are persistent, bioaccumulative and toxic.

  5. Triethylene Glycol Monomethyl Ether; Final Test Rule

    EPA Pesticide Factsheets

    EPA is issuing a final test rule under section 4 of the Toxic Substances Control Act (TSCA) requiring manufacturers and processors of triethylene glycol monomethyl ether (TGME, CAS No. 112-35-6) to perform developmental neurotoxicity tasting.

  6. Effect of Base-Acid Properties of Mixtures of Ethanol with Water on the Enthalpy of Solution of Cyclic Ethers in these Mixtures at T = 298.15 K.

    PubMed

    Jóźwiak, Małgorzata

    2017-01-01

    The enthalpies of solution of the cyclic ethers 1,4-dioxane, 12-crown-4 and 18-crown-6 in mixtures of ethanol and water have been measured within the whole mole fraction range at T = 298.15 K. The enthalpy of solvation has been calculated. In pure ethanol and pure water, the solvation enthalpy of the investigated cyclic ethers depends linearity on the number of -CH2CH2- groups in the cyclic ether molecules. Based on the analysis of the preferential solvation model proposed by Waghorne, it can be concluded that the 1,4-dioxane, 15C5 and 18C6 molecules are preferentially solvated by water molecules in the range of low water content in these mixtures. The effect of base-acid properties of ethanol-water mixtures on the enthalpy of solution of cyclic ethers in these mixtures has been analyzed. The enthalpy of solution of cyclic ethers correlates with the acidic properties of ethanol-water mixtures in the range of high and medium water content. The results presented are compared with analogous data obtained for the methanol-water and propan-1-ol-water mixtures.

  7. Crosslinkage of collagen by polyglycidyl ethers.

    PubMed

    Tang, Z; Yue, Y

    1995-01-01

    Calcification is the principal cause of failure of glutaraldehyde treated bioprosthetic heart valves. This article reports the crosslinkage of several polyglycidyl ethers. Calcification of yak pericardium with polyglycidyl ethers was significantly decreased compared with that crosslinked with glutaraldehyde. The process of calcification of crosslinked yak pericardium was studied using 21 day subdermal implants in rats. The uptake of calcium with ethane diglycidyl ether was reduced (0.57 +/- 0.19 vs 4.28 +/- 1.62 micrograms/mg) over that with glutaraldehyde. Four polyglycidyl ethers were developed and compared. The best compound for raising the shrinkage temperature was the shortest chain compound without steric hindrance. In the polyglycidyl ether process, a suitable amount of alcohol was necessary to promote crosslinking; the catalyst, 2, 4, 6 -tris (dimethyl aminomethyl) phenol (TDAMP) and salicylic acid, were not favorable for long-term treatment of tissues because of the unnecessarily deep dyeing of the tissue, in addition to raising the shrinkage temperature. Unlike glutaraldehyde treatment, which reacts with lysine, polyglycidyl ether treated tissues maintained flexibility of the pericardial tissue, while binding amino acids such as lysine, methionine, tyrosine, aspartic acid and glutamic acid. The authors conclude that the ethane diglycidyl ether process combined with formaldehyde would further raise the shrinkage temperature from 78 degrees C to 87.5 degrees C and sustain it above 80 degrees C. Reverse treatment was not as effective. Compared with glutaraldehyde, polyglycidyl ether treatment renders tissue more flexible, increases the thermal stability of collagen, and decreases the incidence of calcification in vivo.

  8. Zirconia crowns - the new standard for single-visit dentistry?

    PubMed

    Wiedhahn, Klaus; Fritzsche, Günter; Wiedhahn, Claudine; Schenk, Olaf

    2016-01-01

    Zirconia crowns combine the advantages of metal restorations, such as minimally invasive tooth preparation and ease of cementation, with those of full ceramic crowns, such as low thermal conductivity and tooth color. With the introduction of a high-speed sintering procedure, it is possible to produce and cement zirconia crowns and small monolithic bridges in a Cerec Single Visit procedure. This new procedure is compared to established chairside methods.

  9. Fatigue Resistance of CAD/CAM Resin Composite Molar Crowns

    PubMed Central

    Shembish, Fatma A.; Tong, Hui; Kaizer, Marina; Janal, Malvin N.; Thompson, Van P.; Opdam, Niek J.; Zhang, Yu

    2016-01-01

    Objective To demonstrate the fatigue behavior of CAD/CAM resin composite molar crowns using a mouth-motion step-stress fatigue test. Monolithic leucite-reinforced glass-ceramic crowns were used as a reference. Methods Fully anatomically shaped monolithic resin composite molar crowns (Lava Ultimate, n = 24) and leucite reinforced glass-ceramic crowns (IPS Empress CAD, n = 24) were fabricated using CAD/CAM systems. Crowns were cemented on aged dentin-like resin composite tooth replicas (Filtek Z100) with resin-based cements (RelyX Ultimate for Lava Ultimate or Multilink Automix for IPS Empress). Three step-stress profiles (aggressive, moderate and mild) were employed for the accelerated sliding-contact mouth-motion fatigue test. Twenty one crowns from each group were randomly distributed among these three profiles (1:2:4). Failure was designated as chip-off or bulk fracture. Optical and electronic microscopes were used to examine the occlusal surface and subsurface damages, as well as the material microstructures. Results The resin composite crowns showed only minor occlusal damage during mouth-motion step-stress fatigue loading up to 1700 N. Cross-sectional views revealed contact-induced cone cracks in all specimens, and flexural radial cracks in 2 crowns. Both cone and radial cracks were relatively small compared to the crown thickness. Extending these cracks to the threshold for catastrophic failure would require much higher indentation loads or more loading cycles. In contrast, all of the glass-ceramic crowns fractured, starting at loads of approximately 450 N. Significance Monolithic CAD/CAM resin composite crowns endure, with only superficial damage, fatigue loads 3 – 4 times higher than those causing catastrophic failure in glass-ceramic CAD crowns. PMID:26777092

  10. Fatigue resistance of CAD/CAM resin composite molar crowns.

    PubMed

    Shembish, Fatma A; Tong, Hui; Kaizer, Marina; Janal, Malvin N; Thompson, Van P; Opdam, Niek J; Zhang, Yu

    2016-04-01

    To demonstrate the fatigue behavior of CAD/CAM resin composite molar crowns using a mouth-motion step-stress fatigue test. Monolithic leucite-reinforced glass-ceramic crowns were used as a reference. Fully anatomically shaped monolithic resin composite molar crowns (Lava Ultimate, n=24) and leucite reinforced glass-ceramic crowns (IPS Empress CAD, n=24) were fabricated using CAD/CAM systems. Crowns were cemented on aged dentin-like resin composite tooth replicas (Filtek Z100) with resin-based cements (RelyX Ultimate for Lava Ultimate or Multilink Automix for IPS Empress). Three step-stress profiles (aggressive, moderate and mild) were employed for the accelerated sliding-contact mouth-motion fatigue test. Twenty one crowns from each group were randomly distributed among these three profiles (1:2:4). Failure was designated as chip-off or bulk fracture. Optical and electron microscopes were used to examine the occlusal surface and subsurface damages, as well as the material microstructures. The resin composite crowns showed only minor occlusal damage during mouth-motion step-stress fatigue loading up to 1700N. Cross-sectional views revealed contact-induced cone cracks in all specimens, and flexural radial cracks in 2 crowns. Both cone and radial cracks were relatively small compared to the crown thickness. Extending these cracks to the threshold for catastrophic failure would require much higher indentation loads or more loading cycles. In contrast, all of the glass-ceramic crowns fractured, starting at loads of approximately 450N. Monolithic CAD/CAM resin composite crowns endure, with only superficial damage, fatigue loads 3-4 times higher than those causing catastrophic failure in glass-ceramic CAD crowns. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  11. Quantitative characterization of clumping in Scots pine crowns

    PubMed Central

    Stenberg, Pauline; Mõttus, Matti; Rautiainen, Miina; Sievänen, Risto

    2014-01-01

    Background and Aims Proper characterization of the clumped structure of forests is needed for calculation of the absorbed radiation and photosynthetic production by a canopy. This study examined the dependency of crown-level clumping on tree size and growth conditions in Scots pine (Pinus sylvestris), and determined the ability of statistical canopy radiation models to quantify the degree of self-shading within crowns as a result of the clumping effect. Methods Twelve 3-D Scots pine trees were generated using an application of the LIGNUM model, and the crown-level clumping as quantified by the crown silhouette to total needle area ratio (STARcrown) was calculated. The results were compared with those produced by the stochastic approach of modelling tree crowns as geometric shapes filled with a random medium. Key Results Crown clumping was independent of tree height, needle area and growth conditions. The results supported the capability of the stochastic approach in characterizing clumping in crowns given that the outer shell of the tree crown is well represented. Conclusions Variation in the whole-stand clumping index is induced by differences in the spatial pattern of trees as a function of, for example, stand age rather than by changes in the degree of self-shading within individual crowns as they grow bigger. PMID:24431344

  12. Anaerobic biodegradation of ether compounds by ether bond-cleaving bacteria and methanogenic consortia

    SciTech Connect

    Dwyer, D.F.

    1989-01-01

    Ether compounds are manufactured for use in nonionic detergents, plastics, pesticides and other products and occur as toxic organic compounds, the most famous being tetrachlorodibenzo-p-dioxin. Ether compounds were considered recalcitrant to anaerobic biodegradation due to the lack of an appropriate oxidant for ether bond-cleavage in reducing environments. Many of these compounds reside in anaerobic environments or are exposed to anaerobic waste treatment processes. Thus, it is of interest to identify: (i) whether ether compounds are anaerobically biodegradable, (ii) the anaerobic microorganisms able to degrade these compounds, and (iii) the mechanism(s) of anaerobic ether bond-cleavage. The ether bonds of polyethylene glycol (PEG; HO-(CH{sub 2}CH{sub 2}-O-){sub n}H), phenyl ether ((C{sub 6}H{sub 5}){sub 2}O), and dibenzo-p-dioxin ((C{sub 6}H{sub 4}){sub 2}O{sub 2}) were shown to be degraded in methanogenic consortia enriched with these compounds and polyethoxylate (nonionic) surfactants as substrates. Two anaerobic microorganisms which used PEGs as sole substrates were isolated and characterized. Desulfovibrio desulfuricans strain DG2 degraded the monomer ethylene glycol and oligomers up to tetraethylene glycol (HO-(CH{sub 2}CH{sub 2}-O-){sub 4}H) in length. Bacteroides sp. strain PG1 degraded diethylene glycol and all other polymer lengths of PEG. PEGs were degraded by Bacteroides sp. strain PG1 via an external depolymerization which was either a hydrolytic or a reductive cleavage of the ether bond. The ether bond of diaryl ethers was apparently cleaved by a reductive mechanism which produced benzene and phenol as products from phenyl ether degradation and benzene and, by indirect analysis, catechol from dibenzo-dioxin.

  13. Descriptive statistics of tree crown condition in California, Oregon, and Washington

    Treesearch

    KaDonna C. Randolph; Sally J. Campbell; Glenn Christensen

    2010-01-01

    The U.S. Forest Service Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes four tree crown condition indicators (crown dieback, crown density, foliage transparency, and sapling crown vigor) measured in California, Oregon, and Washington between 1996 and 1999....

  14. Descriptive statistics of tree crown condition in the Northeastern United States

    Treesearch

    KaDonna C. Randolph; Randall S. Morin; Jim Steinman

    2010-01-01

    The U.S. Forest Service Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes four crown condition indicators (crown dieback, crown density, foliage transparency, and sapling crown vigor) measured in Connecticut, Delaware, Maine, Maryland, Massachusetts, New...

  15. Descriptive statistics of tree crown condition in the North Central United States

    Treesearch

    KaDonna C. Randolph; Randall S. Morin; Jim Steinman

    2010-01-01

    The U.S. Forest Service Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes four crown condition indicators (crown dieback, crown density, foliage transparency, and sapling crown vigor) measured in Illinois, Indiana, Michigan, Minnesota, Missouri, and Wisconsin...

  16. Descriptive statistics of tree crown condition in the United States Interior West

    Treesearch

    KaDonna C. Randolph; Mike T. Thompson

    2010-01-01

    The U.S. Forest Service Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes four crown condition indicators (crown dieback, crown density, foliage transparency, and sapling crown vigor) measured in Colorado, Idaho, Nevada, Utah, and Wyoming between 1996 and...

  17. Correlations between tree crown condition and shade tolerance, crown form, and light availability

    Treesearch

    KaDonna C. Randolph

    2007-01-01

    Individual tree crown condition is the result of a combination of many factors including genetic traits, growing site characteristics, and past and present external stresses (e.g., drought, insect outbreaks, fire, etc.). Shade tolerance and the extent to which terminal buds control the length and orientation of lateral branches (epinastic control) are the two primary...

  18. Geometric-optical bidirectional reflectance modeling of the discrete crown vegetation canopy - Effect of crown shape and mutual shadowing

    NASA Technical Reports Server (NTRS)

    Li, Xiaowen; Strahler, Alan H.

    1992-01-01

    Many natural vegetation covers can be regarded as assemblages of plant crowns, on a background, which interact with light as discrete objects. On this basis, geometric optics furnish an approach to the modeling of vegetation canopies that captures the most important features of such growths' bidirectional measurements. Attention is presently given to models which approximate these phenomena and relate the size, shape, and count density of plant crowns to viewing and illumination positions and to crown-background reflectance contrasts.

  19. Conformations and Barriers to Methyl Group Internal Rotation in Two Asymmetric Ethers: Propyl Methyl Ether and Butyl Methyl Ether

    NASA Astrophysics Data System (ADS)

    Long, B. E.; Dechirico, F.; Cooke, S. A.

    2012-06-01

    The conformational preferences of the O-C-C-C unit are important in many biological systems with the unit generally preferring a gauche configuration compared to an anti configuration. Butyl methyl ether and propyl methyl ether provide very simple systems for this phenomenom to manifest. Pure rotational spectra of the title molecules have been recorded using chirped pulse Fourier transform microwave spectroscopy (CP-FTMW). In the case of butyl methyl ether, only one conformer has been observed. This conformer has torsional angles of COCC = 180°, OCCC = 62° and CCCC = 180° (anti-gauche-anti) and rotational constants of A = 10259.4591(33) MHz, B = 1445.6470(13) MHz, and C = 1356.2944(14) MHz. The rotational spectrum was doubled and has been analyzed to produce an effective barrier to methyl group internal rotation of 780(35) cm-1. A prior rotational spectroscopic study on propyl methyl ether had focused only on the high energy anti-anti conformer. We have analyzed spectra from the lowest energy anti-gauche conformer and the spectroscopic constants will be presented. A summary of the differences in conformational energies and methyl group internal rotation barriers for the class of aliphatic asymmetric ethers will be presented. K. N. Houk, J. E. Eksterowicz, Y.-D. Wu, C. D. Fuglesang, D. B. Mitchell. J. Am. Chem. Soc. 115 (4170), 1993. Hiroshi Kato, Jun Nakagawa, Michiro Hayashi. J. Mol. Spectrosc. 80 (272), 1980.

  20. Effect of framework design on crown failure.

    PubMed

    Bonfante, Estevam A; da Silva, Nelson R F A; Coelho, Paulo G; Bayardo-González, Daniel E; Thompson, Van P; Bonfante, Gerson

    2009-04-01

    This study evaluated the effect of core-design modification on the characteristic strength and failure modes of glass-infiltrated alumina (In-Ceram) (ICA) compared with porcelain fused to metal (PFM). Premolar crowns of a standard design (PFMs and ICAs) or with a modified framework design (PFMm and ICAm) were fabricated, cemented on dies, and loaded until failure. The crowns were loaded at 0.5 mm min(-1) using a 6.25 mm tungsten-carbide ball at the central fossa. Fracture load values were recorded and fracture analysis of representative samples were evaluated using scanning electron microscopy. Probability Weibull curves with two-sided 90% confidence limits were calculated for each group and a contour plot of the characteristic strength was obtained. Design modification showed an increase in the characteristic strength of the PFMm and ICAm groups, with PFM groups showing higher characteristic strength than ICA groups. The PFMm group showed the highest characteristic strength among all groups. Fracture modes of PFMs and of PFMm frequently reached the core interface at the lingual cusp, whereas ICA exhibited bulk fracture through the alumina core. Core-design modification significantly improved the characteristic strength for PFM and for ICA. The PFM groups demonstrated higher characteristic strength than both ICA groups combined.

  1. Stereocontrolled Cyanohydrin Ether Synthesis through Chiral Brønsted Acid-Mediated Vinyl Ether Hydrocyanation

    PubMed Central

    Lu, Chunliang; Su, Xiaoge; Floreancig, Paul E.

    2013-01-01

    Vinyl ethers can be protonated to generate oxocarbenium ions that react with Me3SiCN to form cyanohydrin alkyl ethers. Reactions that form racemic products proceed efficiently upon converting the vinyl ether to an α-chloro ether prior to cyanide addition in a pathway that proceeds through Brønsted acid-mediated chloride ionization. Enantiomerically enriched products can be accessed by directly protonating the vinyl ether with a chiral Brønsted acid to form a chiral ion pair. Me3SiCN acts as the nucleophile and PhOH serves as a stoichiometric proton source in a rare example of an asymmetric bimolecular nucleophilic addition reaction into an oxocarbenium ion. Computational studies provide a model for the interaction between the catalyst and the oxocarbenium ion. PMID:23968162

  2. Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis

    NASA Astrophysics Data System (ADS)

    Semelsberger, Troy A.; Borup, Rodney L.

    The production of a hydrogen-rich fuel-cell feed by dimethyl ether (DME) steam reforming was investigated using calculations of thermodynamic equilibrium as a function of steam-to-carbon ratio (0.00-4.00), temperature (100-600 °C), pressure (1-5 atm), and product species. Species considered were acetone, acetylene, carbon dioxide, carbon monoxide, dimethyl ether, ethane, ethanol, ethylene, formaldehyde, formic acid, hydrogen, isopropanol, methane, methanol, methyl-ethyl ether, n-propanol and water. Thermodynamic equilibrium calculations of DME steam reforming indicate complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide at temperatures greater than 200 °C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure ( P = 1 atm). Increasing the operating pressure shifts the equilibrium toward the reactants; increasing the pressure from 1 to 5 atm decreases the conversion of dimethyl ether from 99.5 to 76.2%. The trend of thermodynamically stable products in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol-formaldehyde, formic acid, and acetylene were not observed. Based on the equilibrium calculations, the optimal processing conditions for dimethyl ether steam reforming occur at a steam-to-carbon ratio of 1.50, a pressure of 1 atm, and a temperature of 200 °C. These thermodynamic equilibrium calculations show dimethyl ether processed with steam will produce hydrogen-rich fuel-cell feeds—with hydrogen concentrations exceeding 70%. The conversion of dimethyl ether via hydrolysis (considering methanol as the only product) is limited by thermodynamic equilibrium. Equilibrium conversion increases with temperature and steam-to-carbon ratio. A maximum dimethyl ether conversion of 62% is achieved at a steam-to-carbon ratio of 5.00 and a processing temperature of 600 °C.

  3. Ether and the atmospheric chemistry data assimilation

    NASA Astrophysics Data System (ADS)

    Ricaud, P.; Phulpin, T.; Girod, F.; Boonne, C.

    The French atmospheric chemistry data base Ether has been developed and funded by the French Space Agency (CNES) and the Institut National des Sciences de l'Univers (INSU/CNRS) for about 6 years. The role of Ether is to assist French atmospheric researchers, European scientists, as long as they are involved in co-operation agreements with French scientists, to locate, access and interpret atmospheric data. This centre gathers data from satellite, balloon campaigns linked to satellite validation, aircraft and model results for stratospheric and tropospheric purposes and from different levels of production (raw data, physical data, interpolated or assimilated data). All Ether data are available on-line through a World Web interface (http://ether.ipsl.jussieu.fr). Software and added-value services are provided to assist in the manipulation of the data or to generate higher levels standard data products. Extensive information is also provided on the data collection procedures, formats, contact names and references to scientific papers. In addition to data support activities, a major goal of Ether is to promote the creation of different expertise networks on varying atmospheric chemistry topics. The first working group has been created on data assimilation. It consists in gathering expertises in different themes (satellites, assimilation techniques, modelling, real-time processing) in order to optimally develop a tool able to answer different scientific questions relative to the evolution of the Earth atmosphere in terms of chemistry and dynamics. Based on the PALM tool able to interconnect different codes, it will be able to process different satellite data using two atmospheric models and assimilation schemes within the French Ether data base. Ether will focus on the handling and on the development of added-value services of data for which the French community is directly or indirectly involved. For these projects Ether will provide all the data needed, and will

  4. Short clinical crowns (SCC) – treatment considerations and techniques

    PubMed Central

    Rahul, G. R.; Poduval, Soorya T.; Shetty, Karunakar

    2012-01-01

    When the clinical crowns of teeth are dimensionally inadequate, esthetically and biologically acceptable restoration of these dental units is difficult. Often an acceptable restoration cannot be accomplished without first surgically increasing the length of the existing clinical crowns; therefore, successful management requires an understanding of both the dental and periodontal parameters of treatment. The complications presented by teeth with short clinical crowns demand a comprehensive treatment plan and proper sequencing of therapy to ensure a satisfactory result. Visualization of the desired result is a prerequisite of successful therapy. This review examines the periodontal and restorative factors related to restoring teeth with short clinical crowns. Modes of therapy are usually combined to meet the biologic, restorative, and esthetic requirements imposed by short clinical crowns. In this study various methods for treating short clinical crowns are reviewed, the role that restoration margin location play in the maintenance of periodontal and dental symbiosis and the effects of violation of the supracrestal gingivae by improper full-coverage restorations has also been discussed. Key words:Short clinical crown, surgical crown lengthening, forced eruption, diagnostic wax up, alveoloplasty, gingivectomy. PMID:24558561

  5. Automatic crown cover mapping to improve forest inventory

    Treesearch

    Claude Vidal; Jean-Guy Boureau; Nicolas Robert; Nicolas Py; Josiane Zerubia; Xavier Descombes; Guillaume Perrin

    2009-01-01

    To automatically analyze near infrared aerial photographs, the French National Institute for Research in Computer Science and Control developed together with the French National Forest Inventory (NFI) a method for automatic crown cover mapping. This method uses a Reverse Jump Monte Carlo Markov Chain algorithm to locate the crowns and describe those using ellipses or...

  6. Evaluation of wild Juglans species for crown gall resistance

    USDA-ARS?s Scientific Manuscript database

    Paradox, the most widely used rootstock in CA walnut production, is highly susceptible to the causal agent of crown gall (CG) Agrobacterium tumefaciens. The bacterial pathogen induces the formation of large tumors around the crown of the tree resulting in a reduction in both vigor and yield. If left...

  7. Variation in the Use of Crowns and Their Alternatives.

    ERIC Educational Resources Information Center

    Shugars, Daniel A.; And Others

    1997-01-01

    A study investigated the use and effectiveness of dental crowns and alternative treatments for posterior teeth, using data from insurance claims. Results show older patients more likely to receive crowns, with higher costs. Regional treatment differences were also found. Data raised questions about consistency of treatment recommendations among…

  8. Variation in the Use of Crowns and Their Alternatives.

    ERIC Educational Resources Information Center

    Shugars, Daniel A.; And Others

    1997-01-01

    A study investigated the use and effectiveness of dental crowns and alternative treatments for posterior teeth, using data from insurance claims. Results show older patients more likely to receive crowns, with higher costs. Regional treatment differences were also found. Data raised questions about consistency of treatment recommendations among…

  9. Models for estimation and simulation of crown and canopy cover

    Treesearch

    John D. Shaw

    2005-01-01

    Crown width measurements collected during Forest Inventory and Analysis and Forest Health Monitoring surveys are being used to develop individual tree crown width models and plot-level canopy cover models for species and forest types in the Intermountain West. Several model applications are considered in the development process, including remote sensing of plot...

  10. Management of Rhizoctonia root and crown rot of subarbeet

    USDA-ARS?s Scientific Manuscript database

    Rhizoctonia root and crown rot is caused by the fungus Rhizoctonia solani and is one of the most severe soil-borne diseases of sugarbeet in Minnesota and North Dakota. Rhizoctonia root and crown rot may reduce yield significantly, and diseased beets may cause problems in storage piles. Fields with...

  11. Using stand-level optimization to reduce crown fire hazard

    Treesearch

    David H. Graetz; John Sessions; Steven L. Garman

    2007-01-01

    This study evaluated the ability to generate prescriptions for a wide variety of stands when the goal is to reduce crown fire potential. Forest managers charged with reducing crown fire potential while providing for commodity and ecological production have been hampered by the complexity of possible management options. A program called Stand-Level Optimization with...

  12. Estimating canine tooth crown height in early Australopithecus.

    PubMed

    Plavcan, J Michael; Ward, Carol V; Paulus, Faydre L

    2009-07-01

    Canine tooth size reduction and the associated reduction in canine dimorphism is a basal hominin character that also provides important evidence for models of behavioral evolution. Two specimens of Australopithecus anamensis (KNM-KP 29287 and KNM-KP 29283) that do not preserve the canine crown, but do preserve the root or alveolus, appear to suggest that canine size variation and canine dimorphism in this species may have been greater than in other hominins. We evaluate canine root and crown dimensions in a series of extant hominoids, and estimate canine crown height in Australopithecus afarensis and A. anamensis. Our results demonstrate that it is possible to generate estimates of canine crown height from basal canine crown and root dimensions with a moderate degree of accuracy. Estimates of maxillary canine crown size for A. anamensis are slightly larger than those of A. afarensis, and are approximately the same size as canines of modern female chimpanzees. Estimated mandibular canine crown height is very similar in the two species. Variation within the A. anamensis sample of estimated canine crown heights is similar to that of modern humans, suggesting a low degree of sexual dimorphism. Inclusion of estimates for KNM-KP 29287 and KNM-KP 29283 does not substantially increase either the estimate of overall canine size or variation for A. anamensis.

  13. A local basal area adjustment for crown width prediction

    Treesearch

    Don C. Bragg

    2001-01-01

    Nonlinear crown width regressive equations were developed for 24 species common to the upper Lake States of Michigan, Minnesota, and Wisconsin. Of the species surveyed, 15 produced statistically significant (P 0.05) local basal area effect coefficients showing a reduction in crown...

  14. Short clinical crowns (SCC) - treatment considerations and techniques.

    PubMed

    Sharma, Ashu; Rahul, G R; Poduval, Soorya T; Shetty, Karunakar

    2012-10-01

    When the clinical crowns of teeth are dimensionally inadequate, esthetically and biologically acceptable restoration of these dental units is difficult. Often an acceptable restoration cannot be accomplished without first surgically increasing the length of the existing clinical crowns; therefore, successful management requires an understanding of both the dental and periodontal parameters of treatment. The complications presented by teeth with short clinical crowns demand a comprehensive treatment plan and proper sequencing of therapy to ensure a satisfactory result. Visualization of the desired result is a prerequisite of successful therapy. This review examines the periodontal and restorative factors related to restoring teeth with short clinical crowns. Modes of therapy are usually combined to meet the biologic, restorative, and esthetic requirements imposed by short clinical crowns. In this study various methods for treating short clinical crowns are reviewed, the role that restoration margin location play in the maintenance of periodontal and dental symbiosis and the effects of violation of the supracrestal gingivae by improper full-coverage restorations has also been discussed. Key words:Short clinical crown, surgical crown lengthening, forced eruption, diagnostic wax up, alveoloplasty, gingivectomy.

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

    PubMed

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

    2017-08-01

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

  16. Observation of an unusually facile fragmentation pathway of gas-phase peptide ions: a study on the gas-phase fragmentation mechanism and energetics of tryptic peptides modified with 4-sulfophenyl isothiocyanate (SPITC) and 4-chlorosulfophenyl isocyanate (SPC) and their 18-crown-6 complexes.

    PubMed

    Shin, Joong-Won; Lee, Yong Ho; Hwang, Sungu; Lee, Sang-Won

    2007-03-01

    Various peptide modifications have been explored recently to facilitate the acquisition of sequence information. N-terminal sulfonation is an interesting modification because it allows unambiguous de novo sequencing of peptides, especially in conjunction with MALDI-PSD-TOF analysis; such modified peptide ions undergo fragmentation at energies lower than those required conventionally for unmodified peptide ions. In this study, we systematically investigated the fragmentation mechanisms of N-terminal sulfonated peptide ions prepared using two different N-terminal sulfonation reagents: 4-sulfophenyl isothiocyanate (SPITC) and 4-chlorosulfophenyl isocyanate (SPC). Collision-induced dissociation (CID) of the SPC-modified peptide ions produced a set of y-series ions that were more evenly distributed relative to those observed for the SPITC-modified peptides; y(n-1) ion peaks were consistently and significantly larger than the signals of the other y-ions. We experimentally investigated the differences between the dissociation energies of the SPITC- and SPC-modified peptide ions by comparing the MS/MS spectra of the complexes formed between the crown ether 18-crown-6 (CE) and the modified peptides. Upon CID, the complexes formed between 18-crown-6 ether and the protonated amino groups of C-terminal lysine residues underwent either peptide backbone fragmentation or complex dissociation. Although the crown ether complexes of the unmodified ([M + CE + 2H]2+) and SPC-modified ([M* + CE + 2H]2+) peptides underwent predominantly noncovalent complex dissociation upon CID, the low-energy dissociations of the crown ether complexes of the SPITC-modified peptides ([M' + CE + 2H]2+) unexpectedly resulted in peptide backbone fragmentations, along with a degree of complex dissociation. We performed quantum mechanical calculations to address the energetics of fragmentations observed for the modified peptides. Copyright 2007 John Wiley & Sons, Ltd.

  17. Crown characteristics of several coniferous tree species: relations between weight of crown, branchwood and foliage and stem diameter

    Treesearch

    Theodore G Storey; Wallace L. Fons; F.M. Sauer

    1955-01-01

    Prediction of wind breakage and uprooting in tree stands requires information on weight of dry crown, branchwood, and foliage. This information has not been published. An experimental program started in 1951 has led to a number of generalized relations by which these crown characteristics can be determined with good accuracy over a wide range of tree diameters, species...

  18. Inhalation anaesthesia: from diethyl ether to xenon.

    PubMed

    Bovill, J G

    2008-01-01

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

  19. Earliest known crown-group salamanders.

    PubMed

    Gao, Ke-Qin; Shubin, Neil H

    2003-03-27

    Salamanders are a model system for studying the rates and patterns of the evolution of new anatomical structures. Recent discoveries of abundant Late Jurassic and Early Cretaceous salamanders are helping to address these issues. Here we report the discovery of well-preserved Middle Jurassic salamanders from China, which constitutes the earliest known record of crown-group urodeles (living salamanders and their closest relatives). The new specimens are from the volcanic deposits of the Jiulongshan Formation (Bathonian), Inner Mongolia, China, and represent basal members of the Cryptobranchidae, a family that includes the endangered Asian giant salamander (Andrias) and the North American hellbender (Cryptobranchus). These fossils document a Mesozoic record of the Cryptobranchidae, predating the previous record of the group by some 100 million years. This discovery provides evidence to support the hypothesis that the divergence of the Cryptobranchidae from the Hynobiidae had taken place in Asia before the Middle Jurassic period.

  20. Crystalline imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

    Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly)arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers for tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.

  1. 41. LOOKING WEST AT BUILDING NO. 519, ETHER AND ALCOHOL ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    41. LOOKING WEST AT BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, (LEFT) AND BUILDING NO. 521, ETHER VAULT, (RIGHT) IN FOREGROUND - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

  2. 37. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, NORTHWEST ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    37. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, NORTHWEST CORNER OF BUILDING. BUILDING NO. 521 (ETHER VAULT) IN BACKGROUND LEFT. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

  3. Clinical outcome of double crown-retained implant overdentures with zirconia primary crowns

    PubMed Central

    Buergers, Ralf; Ziebolz, Dirk; Roediger, Matthias

    2015-01-01

    PURPOSE This retrospective study aims at the evaluation of implant-supported overdentures (IODs) supported by ceramo-galvanic double crowns (CGDCs: zirconia primary crowns + galvano-formed secondary crown). MATERIALS AND METHODS In a private practice, 14 patients were restored with 18 IODs (mandible: 11, maxilla: 7) retained by CGDCs on 4 - 8 implants and annually evaluated for technical and/or biological failures/complications. RESULTS One of the 86 inserted implants failed during the healing period (cumulative survival rate (CSR) implants: 98.8%). During the prosthetic functional period (mean: 5.9 ± 2.2 years), 1 implant demonstrated an abutment fracture (CSR-abutments: 98.2%), and one case of peri-implantitis was detected. All IODs remained in function (CSR-denture: 100%). A total of 15 technical complications required interventions to maintain function (technical complication rate: 0.178 treatments/patients/year). CONCLUSION Considering the small sample size, the use of CGDCs for the attachment of IODs is possible without an increased risk of technical complications. However, for a final evaluation, results from a larger cohort are required. PMID:26330981

  4. Fracture strength of lithium disilicate crowns compared to polymer-infiltrated ceramic-network and zirconia reinforced lithium silicate crowns.

    PubMed

    Sieper, Kim; Wille, Sebastian; Kern, Matthias

    2017-10-01

    The aim of this study was to evaluate the fracture strength of crowns made from current CAD/CAM materials. In addition the influence of crown thickness and chewing simulation on the fracture strength was evaluated. Crowns were fabricated from lithium disilicate, zirconia reinforced lithium silicate (ZLS-ceramic) and a polymer-infiltrated ceramic-network (PICN) with an occlusal thickness of 1.0mm or 1.5mm, respectively (n=16). Crowns were cemented on composite dies. Subgroups of eight specimens were loaded with 5kg in a chewing simulator for 1,200,000 cycles with thermal cycling. Finally, all specimens were loaded until fracture in a universal testing machine. Three-way ANOVA was used to detect statistical interaction. Differences regarding the materials were tested with two-way ANOVA, following one-way ANOVA and a post-hoc Tukey's-Test. All crowns survived the chewing simulation. The material had a significant influence on the fracture resistance (p≤0.05). Lithium disilicate achieved the highest values of fracture strength in almost all groups followed by ZLS-ceramic. PICN achieved the lowest values of fracture strength. Chewing simulation increased the fracture strength of thick lithium disilicate crown significantly. Greater occlusal thickness of all crown materials resulted in higher crown fracture strength before chewing simulation. After chewing simulation occlusal thickness of lithium disilicate and PICN crowns had no significant influence on the fracture strength. All crowns revealed fracture strength above the clinically expected loading forces. Therefore the durability of the tested CAD/CAM materials seems promising also in an occlusal thickness of 1.0mm. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. High octane ethers from synthesis gas-derived alcohols

    SciTech Connect

    Klier, K.; Herman, R.G.; Johansson, M.; Feeley, O.C.

    1992-01-01

    The objective of the proposed research is to synthesize high octane ethers, primarily methyl isobutyl ether (MIBE) and methyl tertiary butyl ether (MTBE), directly from H{sub 2}/CO/CO{sub 2} coal-derived synthesis gas via alcohol mixtures that are rich in methanol and 2-methyl-1-propanol (isobutanol). The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers.

  6. High octane ethers from synthesis gas-derived alcohols

    SciTech Connect

    Klier, K.; Herman, R.G.; Johansson, M.A.; Feeley, O.C.

    1992-04-01

    The objective of the proposal research is to synthesize high octane ethers, primarily methyl isobutyl ether (MIBE) and methyl tertiary butyl ether (MTBE), directly from H{sub 2}/CO/CO{sub 2} coal-derived synthesis gas via alcohol mixtures that are rich in methanol and 2-methyl-1-propanol (isobutanol). The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers.

  7. [Restoration of composite on etched stainless steel crowns. (1)].

    PubMed

    Goto, G; Zang, Y; Hosoya, Y

    1990-01-01

    Object of investigation The retention of composite resin to etched stainless steel crowns was tested as a possible method for restoring primary anterior teeth. Method employed 1) SEM observation Stainless steel crowns (Sankin Manufacture Co.) were etched with an aqua resia to create surface roughness and undercut to retain the composite resin to the crowns. Etching times were 1, 2, 3, 5, 8, 10 and 20 minutes, then washed in a 70% alcohol solution using an ultrasonic washer and dried. A total of 96 etched samples and non etched control samples were observed through the scanning electron microscope (Hitachi 520). 2) Shear bond strength test Stainless steel crowns were etched in an aqua resia from 1 to 20 minutes, then washed and dried. Composite resin (Photo Clearfil A, Kuraray Co.) with the bonding agent was placed on the crowns and the shear bond strength was tested in 56 samples using an Autograph (DCS-500, Shimazu). Results 1) SEM observation showed that the etching surface of stainless steel crowns created surface roughness and undercut. The most desirable surface was obtained in the 3 to 5 minute etching time specimens. 2) The highest bond strength was obtained in a 3 minute etching specimen. It was 42.12 MPa, although 29.26 MPa in mean value. Conclusion Etching with an aqua resia increased the adherence of composite resin to the surface of stainless steel crowns.

  8. 40 CFR 721.3435 - Butoxy-substituted ether alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  9. 40 CFR 721.3465 - Stilbene diglycidyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Stilbene diglycidyl ether. 721.3465... Substances § 721.3465 Stilbene diglycidyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as stilbene diglycidyl ether (PMN P-96-1427) is subject...

  10. 39. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    39. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, LOOKING AT SOUTHWEST CORNER WITH BUILDING NO. 521, ETHER VAULT, AND BUILDING NO. 519-A, ETHER & ALOCOHL STORAGE TANKS, IN BACKGROUND RIGHT. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

  11. Alkyl Aryl Ether Bond Formation with PhenoFluor**

    PubMed Central

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

    2015-01-01

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

  12. Survival Predictions of Ceramic Crowns Using Statistical Fracture Mechanics.

    PubMed

    Nasrin, S; Katsube, N; Seghi, R R; Rokhlin, S I

    2017-01-01

    This work establishes a survival probability methodology for interface-initiated fatigue failures of monolithic ceramic crowns under simulated masticatory loading. A complete 3-dimensional (3D) finite element analysis model of a minimally reduced molar crown was developed using commercially available hardware and software. Estimates of material surface flaw distributions and fatigue parameters for 3 reinforced glass-ceramics (fluormica [FM], leucite [LR], and lithium disilicate [LD]) and a dense sintered yttrium-stabilized zirconia (YZ) were obtained from the literature and incorporated into the model. Utilizing the proposed fracture mechanics-based model, crown survival probability as a function of loading cycles was obtained from simulations performed on the 4 ceramic materials utilizing identical crown geometries and loading conditions. The weaker ceramic materials (FM and LR) resulted in lower survival rates than the more recently developed higher-strength ceramic materials (LD and YZ). The simulated 10-y survival rate of crowns fabricated from YZ was only slightly better than those fabricated from LD. In addition, 2 of the model crown systems (FM and LD) were expanded to determine regional-dependent failure probabilities. This analysis predicted that the LD-based crowns were more likely to fail from fractures initiating from margin areas, whereas the FM-based crowns showed a slightly higher probability of failure from fractures initiating from the occlusal table below the contact areas. These 2 predicted fracture initiation locations have some agreement with reported fractographic analyses of failed crowns. In this model, we considered the maximum tensile stress tangential to the interfacial surface, as opposed to the more universally reported maximum principal stress, because it more directly impacts crack propagation. While the accuracy of these predictions needs to be experimentally verified, the model can provide a fundamental understanding of the

  13. Clinical assessment of enamel wear caused by monolithic zirconia crowns.

    PubMed

    Stober, T; Bermejo, J L; Schwindling, F S; Schmitter, M

    2016-08-01

    The purpose of this study was to measure enamel wear caused by antagonistic monolithic zirconia crowns and to compare this with enamel wear caused by contralateral natural antagonists. Twenty monolithic zirconia full molar crowns were placed in 20 patients. Patients with high activity of the masseter muscle at night (bruxism) were excluded. For analysis of wear, vinylpolysiloxane impressions were prepared after crown incorporation and at 6-, 12-, and 24-month follow-up. Wear of the occlusal contact areas of the crowns, of their natural antagonists, and of two contralateral natural antagonists (control teeth) was measured by use of plaster replicas and a 3D laser-scanning device. Differences of wear between the zirconia crown antagonists and the control teeth were investigated by means of two-sided paired Student's t-tests and linear regression analysis. After 2 years, mean vertical loss was 46 μm for enamel opposed to zirconia, 19-26 μm for contralateral control teeth and 14 μm for zirconia crowns. Maximum vertical loss was 151 μm for enamel opposed to zirconia, 75-115 μm for control teeth and 60 μm for zirconia crowns. Statistical analysis revealed significant differences between wear of enamel by zirconia-opposed teeth and by control teeth. Gender, which significantly affected wear, was identified as a possible confounder. Monolithic zirconia crowns generated more wear of opposed enamel than did natural teeth. Because of the greater wear caused by other dental ceramics, the use of monolithic zirconia crowns may be justified.

  14. Turner syndrome isochromosome karyotype correlates with decreased dental crown width.

    PubMed

    Rizell, S; Barrenäs, M-L; Andlin-Sobocki, A; Stecksén-Blicks, C; Kjellberg, H

    2012-04-01

    The aim of this project was to study possible influences of Turner syndrome (TS) karyotype and the number of X chromosomes with intact short arm (p-arm) on dental crown width. Primary and permanent mesio-distal crown width was measured on plaster casts from 112 TS females. The influence on crown width of four karyotypes: 1. monosomy (45,X), 2. mosaic (45,X/46,XX), 3. isochromosome, and 4. other, and the number of intact X chromosomal p-arms were investigated. In comparisons between karyotypes, statistically significant differences were found for isochromosome karyotype maxillary second premolars, canines, laterals, mandibular first premolars, and canines, indicating that this karyotype was the most divergent as shown by the most reduced crown width. When each karyotype group were compared versus controls, all teeth in the isochromosome group were significantly smaller than controls (P < 0.01-0.001). The 45,X/46,XX karyotype expressed fewer and smaller differences from controls, while 45,X individuals seemed to display an intermediate tooth width compared with 45,X/46,XX and isochromosomes. No significant difference in crown width was found comparing the groups with one or two intact X chromosomal p-arms. Both primary and permanent teeth proved to have a significantly smaller crown width in the entire group of TS females compared to healthy females. We conclude that the isochromosome group deviates most from other karyotypes and controls, exhibiting the smallest dental crown width, while individuals with 45,X/46,XX mosaicism seemed to have a less affected crown width. An influence of the number of intact p-arms on crown width could not be demonstrated in this study.

  15. Crown diameters of the deciduous teeth of Taiwanese.

    PubMed

    Liu, H H; Dung, S Z; Yang, Y H

    2000-06-01

    The purposes of this study were (1) to characterize the crown diameters of the deciduous teeth of Taiwanese; (2) to compare the differences in the deciduous crown diameters between different populations. The results might provide odontometric information in making preformed stainless steel crowns of the Chinese population. Study casts of 90 children (51 boys and 39 girls) of aged 3 to 6 years were used in this study. The maximum mesiodistal crown diameter (the greatest distance between the contact points of the approximal surfaces) and the buccolingual crown diameter (the greatest distance at a right angle to the mesiodistal measurement) were obtained by using an electronic digital caliper. Significant differences between antimeres were found in the mesiodistal diameters of maxillary canine and maxillary molars (p < 0.001) as well as in the buccolingual diameters of mandibular molars (p < 0.05). Excellent correlations between the antimeres of the corresponding teeth were found (r = 0.70 to 0.96). Boys generally had larger crown diameters than girls with the exception of mesiodistal diameters of maxillary and mandibular canines, and mandibular lateral incisor, whereas the statistically significant gender difference was only found in the buccolingual diameter of mandibular second molar (p < 0.05). The higher the percentage of sexual dimorphism, the larger the gender differences. The percentage of sexual dimorphism ranged from 0.09 to 1.94 for mesiodistal diameters and 0.04 to 2.86 for buccolingual diameters. The mandibular second molar was the most dimorphic tooth. Variations in the crown diameters of the deciduous teeth existed among and within different populations. Deciduous mesiodistal crown diameters of Taiwanese were, in general, smaller than those of Australian aborigines, Taiwan Chinese aborigines, and Hong Kong Chinese, but larger than those of American whites. When considering the buccolingual crown diameters, our data were significantly smaller than those

  16. Syntheses of cis- and trans-dibenzo-30-crown-10 derivatives via regioselective routes and their complexations with paraquat and diquat.

    PubMed

    He, Chunlin; Shi, Zuming; Zhou, Qizhong; Li, Shijun; Li, Ning; Huang, Feihe

    2008-08-01

    cis-Dibenzo-30-crown-10 (cis-DB30C10) diester and trans-dibenzo-30-crown-10 (trans-DB30C10) diester were synthesized regioselectively with reasonable yields. These two isomers were further reduced to cis-dibenzo-30-crown-10 diol (1) and trans-DB30C10 diol (2), respectively. The complexations of cis- and trans-DB30C10 diols with paraquat (3) and diquat (4) were investigated by (1)H NMR, mass spectrometry, UV-vis spectroscopy, and single-crystal X-ray analysis. The reversible control of complexations of 1 x 3 and 2 x 3 by adding small molecules (KPF 6 and dibenzo-18-crown-6) was demonstrated by (1)H NMR. The addition of 2 molar equiv of KPF 6 is enough to dissociate 2 x 3 and 1 x 3 completely while the subsequent addition of 2 molar equiv of DB18C6 allows the two complexes to reform. However, 2 molar equiv of KPF6 cannot dissociate 1 x 4 and 2 x 4 completely. Because the DB30C10 cavity has a better geometry fit with paraquat 3 than with diquat 4, 4-based complexes have much higher association constants than the corresponding 3-based complexes. In the crystal structure of 1 x 4, the two hydroxymethyl groups of the crown ether 1 were joined by a "water bridge" to form a "supramolecular cryptand" while this kind of supramolecular cryptand structure was not observed in the crystal structure of 2 x 4. This is a possible reason for the increase in association constant from 2 x 4 (3.3 x 10(4) M(-1)) to 1 x 4 (5.0 x 10(4) M(-1)).

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  18. Review of glycol ether and glycol ether ester solvents used in the coating industry.

    PubMed Central

    Smith, R L

    1984-01-01

    Ethylene oxide-based glycol ether and glycol ether ester solvents have been used in the coatings industry for the past fifty years. Because of their excellent performance properties (evaporation rate, blush resistance, flow-out and leveling properties, solubility for coating resins, solvent activity, mild odor, good coupling ability, good solvent release) a complete line of ethylene oxide-based solvents of various molecular weights has been developed. These glycol ether and glycol ether ester solvents have better solvent activity for coating resin than ester or ketone solvents in their evaporation rate range. The gloss, flow and leveling, and general performance properties of many coating systems are dependent on the use of these products in the coating formula. Because of the concern about the toxicity of certain ethylene oxide-based solvents, other products are being evaluated as replacements in coating formulas. PMID:6499793

  19. POLYBROMINATED DIPHENYL ETHERS IN US SOILS

    EPA Science Inventory

    Chemical analysis of thirty-three soil samples from 15 US states reveals Polybrominated Diphenyl Ethers (PBDEs), in every sample.PBDE concentrations rangefrom 0.09 to 1200 parts per billion by mass. These data are the first analysis of soil concentrations of PBDEs in soils from a...

  20. Methyl tert-butyl ether (MTBE)

    Integrated Risk Information System (IRIS)

    Methyl tert - butyl ether ( MTBE ) ; CASRN 1634 - 04 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

  1. Orphan enzymes in ether lipid metabolism.

    PubMed

    Watschinger, Katrin; Werner, Ernst R

    2013-01-01

    Ether lipids are an emerging class of lipids which have so far not been investigated and understood in every detail. They have important roles as membrane components of e.g. lens, brain and testis, and as mediators such as platelet-activating factor. The metabolic enzymes for biosynthesis and degradation have been investigated to some extent. As most involved enzymes are integral membrane proteins they are tricky to handle in biochemical protocols. The sequence of some ether lipid metabolising enzymes has only recently been reported and other sequences still remain obscure. Defined enzymes without assigned sequence are known as orphan enzymes. One of these enzymes with uncharacterised sequence is plasmanylethanolamine desaturase, a key enzyme for the biosynthesis of one of the most abundant phospholipids in our body, the plasmalogens. This review aims to briefly summarise known functions of ether lipids, give an overview on their metabolism including the most prominent members, platelet-activating factor and the plasmalogens. A special focus is set on the description of orphan enzymes in ether lipid metabolism and on the successful strategies how four previous orphans have recently been assigned a sequence. Only one of these four was characterised by classical protein purification and sequencing, whereas the other three required alternative strategies such as bioinformatic candidate gene selection and recombinant expression or development of an inhibitor and multidimensional metabolic profiling. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  2. POLYBROMINATED DIPHENYL ETHERS IN SOUTHERN MISSISSIPPI CATFISH

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in a wide variety of consumer products. Concerns surrounding these compounds are primarily due do their ubiquitous presence in the environment as well as in human tissue, such as milk, coupled with evidence indi...

  3. Ethylene glycol monobutyl ether (EGBE) (2-Butoxyethanol)

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 08 / 006F www.epa.gov / iris TOXICOLOGICAL REVIEW OF ETHYLENE GLYCOL MONOBUTYL ETHER ( EGBE ) ( CAS No . 111 - 76 - 2 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) March 2010 U.S . Environmental Protection Agency Washington , DC DISCLAIMER Thi

  4. Dimensionally Stable Ether-Containing Polyimide Copolymers

    NASA Technical Reports Server (NTRS)

    Fay, Catharine C. (Inventor); St.Clair, Anne K. (Inventor)

    1999-01-01

    Novel polyimide copolymers containing ether linkages were prepared by the reaction of an equimolar amount of dianhydride and a combination of diamines. The polyimide copolymers described herein possess the unique features of low moisture uptake, dimensional stability, good mechanical properties, and moderate glass transition temperatures. These materials have potential application as encapsulants and interlayer dielectrics.

  5. Bis(2-chloro-1-methylethyl) ether

    Integrated Risk Information System (IRIS)

    Bis ( 2 - chloro - 1 - methylethyl ) ether ; CASRN 108 - 60 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

  6. 40 CFR 721.3380 - Anilino ether.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3380 Anilino ether. Link to an amendment published at 79 FR 34637, June 18, 2014. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as anilino...

  7. Biomonitoring Polybrominated Diphenyl Ethers in Lactating Women

    USDA-ARS?s Scientific Manuscript database

    Breast milk is a valuable biological specimen for biomonitoring lipid-soluble polybrominated diphenyl ethers (PBDEs). The goal of this project was to determine the levels of PBDEs in breast milk of lactating women from the Seacoast region of New Hampshire and to examine potential relationships betw...

  8. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES... that fits inside a patient's mouth and that is intended to deliver vaporized ether. (b) Classification... the quality system regulation in part 820 of this chapter, with the exception of § 820.180,...

  9. POLYBROMINATED DIPHENYL ETHERS IN SOUTHERN MISSISSIPPI CATFISH

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in a wide variety of consumer products. Concerns surrounding these compounds are primarily due do their ubiquitous presence in the environment as well as in human tissue, such as milk, coupled with evidence indi...

  10. Imide/arylene ether block copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

    1991-01-01

    Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

  11. Grapevine (Vitis vinifera) Crown Galls Host Distinct Microbiota.

    PubMed

    Faist, Hanna; Keller, Alexander; Hentschel, Ute; Deeken, Rosalia

    2016-09-15

    Crown gall disease of grapevine is caused by virulent Agrobacterium strains and establishes a suitable habitat for agrobacteria and, potentially, other bacteria. The microbial community associated with grapevine plants has not been investigated with respect to this disease, which frequently results in monetary losses. This study compares the endophytic microbiota of organs from grapevine plants with or without crown gall disease and the surrounding vineyard soil over the growing seasons of 1 year. Amplicon-based community profiling revealed that the dominating factor causing differences between the grapevine microbiota is the sample site, not the crown gall disease. The soil showed the highest microbial diversity, which decreased with the distance from the soil over the root and the graft union of the trunk to the cane. Only the graft union microbiota was significantly affected by crown gall disease. The bacterial community of graft unions without a crown gall hosted transient microbiota, with the three most abundant bacterial species changing from season to season. In contrast, graft unions with a crown gall had a higher species richness, which in every season was dominated by the same three bacteria (Pseudomonas sp., Enterobacteriaceae sp., and Agrobacterium vitis). For in vitro-cultivated grapevine plantlets, A. vitis infection alone was sufficient to cause crown gall disease. Our data show that microbiota in crown galls is more stable over time than microbiota in healthy graft unions and that the microbial community is not essential for crown gall disease outbreak. The characterization of bacterial populations in animal and human diseases using high-throughput deep-sequencing technologies, such as 16S amplicon sequencing, will ideally result in the identification of disease-specific microbiota. We analyzed the microbiota of the crown gall disease of grapevine, which is caused by infection with the bacterial pathogen Agrobacterium vitis. All other Agrobacterium

  12. Grapevine (Vitis vinifera) Crown Galls Host Distinct Microbiota

    PubMed Central

    Faist, Hanna; Keller, Alexander; Hentschel, Ute

    2016-01-01

    ABSTRACT Crown gall disease of grapevine is caused by virulent Agrobacterium strains and establishes a suitable habitat for agrobacteria and, potentially, other bacteria. The microbial community associated with grapevine plants has not been investigated with respect to this disease, which frequently results in monetary losses. This study compares the endophytic microbiota of organs from grapevine plants with or without crown gall disease and the surrounding vineyard soil over the growing seasons of 1 year. Amplicon-based community profiling revealed that the dominating factor causing differences between the grapevine microbiota is the sample site, not the crown gall disease. The soil showed the highest microbial diversity, which decreased with the distance from the soil over the root and the graft union of the trunk to the cane. Only the graft union microbiota was significantly affected by crown gall disease. The bacterial community of graft unions without a crown gall hosted transient microbiota, with the three most abundant bacterial species changing from season to season. In contrast, graft unions with a crown gall had a higher species richness, which in every season was dominated by the same three bacteria (Pseudomonas sp., Enterobacteriaceae sp., and Agrobacterium vitis). For in vitro-cultivated grapevine plantlets, A. vitis infection alone was sufficient to cause crown gall disease. Our data show that microbiota in crown galls is more stable over time than microbiota in healthy graft unions and that the microbial community is not essential for crown gall disease outbreak. IMPORTANCE The characterization of bacterial populations in animal and human diseases using high-throughput deep-sequencing technologies, such as 16S amplicon sequencing, will ideally result in the identification of disease-specific microbiota. We analyzed the microbiota of the crown gall disease of grapevine, which is caused by infection with the bacterial pathogen Agrobacterium vitis. All

  13. Crown lengthening procedure in the management of amelogenesis imperfecta.

    PubMed

    Kalaivani, S; Manohar, Jenish; Shakunthala, P; Sujatha, S; Rajasekaran, S A; Karthikeyan, B; Kalaiselvan, S

    2015-08-01

    Full mouth rehabilitation includes a promising treatment planning and execution thus fulfilling esthetic, occlusal, and functional parameters maintaining the harmony of the stomatognathic system. Crown lengthening procedures have become an integral component of the esthetic armamentarium and are utilized with increasing frequency to enhance the appearance of restorations placed in the esthetic zone. Crown lengthening plays a role to create healthy relationship of the gingiva and bone levels so as to gain access to more of the tooth which can be restored, if it is badly worn, decayed or fractured, below the gum line. This paper highlights the full mouth crown lengthening procedure performed on a patient with amelogenesis imperfecta.

  14. Crown lengthening procedure in the management of amelogenesis imperfecta

    PubMed Central

    Kalaivani, S.; Manohar, Jenish; Shakunthala, P.; Sujatha, S.; Rajasekaran, S. A.; Karthikeyan, B.; Kalaiselvan, S.

    2015-01-01

    Full mouth rehabilitation includes a promising treatment planning and execution thus fulfilling esthetic, occlusal, and functional parameters maintaining the harmony of the stomatognathic system. Crown lengthening procedures have become an integral component of the esthetic armamentarium and are utilized with increasing frequency to enhance the appearance of restorations placed in the esthetic zone. Crown lengthening plays a role to create healthy relationship of the gingiva and bone levels so as to gain access to more of the tooth which can be restored, if it is badly worn, decayed or fractured, below the gum line. This paper highlights the full mouth crown lengthening procedure performed on a patient with amelogenesis imperfecta. PMID:26538965

  15. Achieving optimal outcomes with all-zirconia crowns.

    PubMed

    Christensen, John Juel

    2014-01-01

    All-zirconia crowns are enjoying an unprecedented popularity. Dental laboratories are acquiring new equipment and adopting novel techniques, some of which require a learning curve. As a result, some crowns fabricated by computer-aided design/computer-aided manufacturing technology may come back to the dentist with unsatisfactory features. Dentists should carefully examine each crown under magnification prior to delivery to the patient. The dentist and dental laboratory should establish a close partnership with clear communication to yield the most favorable outcome for the patient.

  16. Retention force of secondary crowns to copings after temporary cementation: the effect of crown material and luting agent.

    PubMed

    Mundt, Torsten; Heinemann, Friedhelm; Golecki, Gudrun; Schwahn, Christian; Biffar, Reiner

    2010-12-01

    Tooth-implant supported restorations can be temporarily cemented if the natural abutments are protected by permanently cemented copings. This in vitro study investigated the retention forces of pure titanium crowns to milled titanium alloy copings and of cobalt-chromium crowns to copings made of electroplated gold after cementation with different luting agents. Five specimens per group were cemented with acrylic-urethane cement (inner crown surface preisolated with petroleum jelly) and provisional zinc oxide cement. The retention was measured using a universal testing machine and a dental device for crown removal. The differences between groups were compared using analysis of variance. The pull-off forces for the cobalt-chromium secondary crowns cemented on gold copings using zinc oxide cement were significantly higher (mean=144.5 N) than the other crown-cement combinations (32.2-54.4 N), which showed no significant differences in the retention force. The impulse number and magnitude of the dental device was usually low and showed no substantial differences between the crown-cement combinations. It can be concluded that the results of the clinical removal method for prostheses differ from the results of the pull-off test. The question which luting agent is the better choice for retrievable restorations remains unanswered without further clinical and laboratory studies.

  17. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOEpatents

    Crivello, J.V.

    1996-01-23

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

  18. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOEpatents

    Crivello, James V.

    1996-01-01

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

  19. Crown Recession Patterns in Three Conifer Species of the Northern Rocky Mountains

    Treesearch

    Sean M. Garber; Robert A. Monserud; Douglas A. Maguire

    2008-01-01

    Crown length is a fundamental tree dimension for characterizing growth potential, wildlife habitat, and wood quality. The relative rates of height growth and crown recession detennine the progression of crown length over time. We investigated patterns in crown recession of three co-occurring species in the northern Rocky Mountains: western white pine (Pinus...

  20. An Index of Competition Based on Relative Crown Position and Size

    Treesearch

    Dwight D. O' Neal; Allan E. Houston; Edward R. Buckner; James S. Meadows

    1995-01-01

    A new competition index, the Crown Position Index (CPI) was evaluated using a 41-year-old, well stocked, upland hardwood stand in southwestern Tennessee. CPI wss based on relative crown position and crown size as expressed by crown projections and relative heights of crop trees and their competitors. Comparisons were made among CPI, the Hegyl (1974)...

  1. Root-Crown Relations of Young Sugar Maple and Yellow Birch

    Treesearch

    Carl H. Tubbs

    1977-01-01

    Young forest-grown sugar maple and yellow birch (1 to 6 inches d.b.h.) crowns were mapped and roots excavated. Crown dimensions were compared. Sugar maple roots usually terminated within a few feet of the crown perimeter. Yellow birch roots frequently terminated well outside crown perimeters and roots of birch were more irregularly distributed than those of maple....

  2. Crown profile equations for stand-grown western hemlock trees in northwestern Oregon.

    Treesearch

    David D. Marshall; Gregory P. Johnson; David W. Hann

    2003-01-01

    Crown profile equations were developed for stand-grown western hemlock(Tsuga heterophylla (Raf.) Sarg.) in northwest Oregon. The profile model uses a segmented approach, dividing the crown into an upper and lower portion at the point of the largest crown width (LCW). The model explains about 86% of the variation in crown width when LCW is known but...

  3. Development of post-fire crown damage mortality thresholds in ponderosa pine

    Treesearch

    James F. Fowler; Carolyn Hull Sieg; Joel McMillin; Kurt K. Allen; Jose F. Negron; Linda L. Wadleigh; John A. Anhold; Ken E. Gibson

    2010-01-01

    Previous research has shown that crown scorch volume and crown consumption volume are the major predictors of post-fire mortality in ponderosa pine. In this study, we use piecewise logistic regression models of crown scorch data from 6633 trees in five wildfires from the Intermountain West to locate a mortality threshold at 88% scorch by volume for trees with no crown...

  4. 78 FR 63559 - Order of Suspension of Trading; In The Matter of Crown Alliance Capital Limited

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-10-24

    ... COMMISSION Order of Suspension of Trading; In The Matter of Crown Alliance Capital Limited October 22, 2013... information concerning the securities of Crown Alliance Capital Limited (``Crown Alliance''), quoted under the ticker symbol CACL, because of questions regarding the accuracy of assertions in Crown Alliance's...

  5. Manganese sequestration and improved high-temperature cycling of Li-ion batteries by polymeric aza-15-crown-5

    NASA Astrophysics Data System (ADS)

    Li, Zicheng; Pauric, Allen D.; Goward, Gillian R.; Fuller, Timothy J.; Ziegelbauer, Joseph M.; Balogh, Michael P.; Halalay, Ion C.

    2014-12-01

    Mn cation trapping by polymeric aza-15-crown-5 ethers is an effective means for mitigating the consequences of Mn dissolution in Li-ion batteries. Mn cations trapping was investigated in lithium manganese oxide (LMO) spinel-graphite (GR) cells containing 1 M LiPF6 in ethylene carbonate (EC):diethyl carbonate (DEC) 1:2 v/v. A commercial polyolefin separator membrane coated with poly[divinylbenzene-(vinylbenzyl-aza-15-crown-5)-vinylbenzylchloride)] effected a 39% reduction in capacity loss rate during cycling at 50 °C with 100% depth of discharge (DOD) at C/5 rate. Simultaneously, a 50-60% reduction in the Mn deposited at the negative electrode, and a 6× to 10× increase in the Mn on the coated separator were observed for cells with coated separators, over baseline cells with plain separators. X-ray absorption near-edge spectroscopy (XANES) yielded average oxidation states near +3 for Mn cations in graphite electrodes and separators from cycled cells, suggesting that Mn metal or in oxidation state +2 can only be minor fractions of the Mn existing outside the positive electrode. We discuss the implications of these results for choosing an optimal chelating agent. We also show that the cation chelating polymer reported here is compatible with existing manufacturing processes for Li-ion battery separators.

  6. Crystal and molecular structure of a series of 15-crown-5-containing styryl heterocycles and their dimethoxy substituted analogues

    SciTech Connect

    Kuz'mina, L. G. Fedorova, O. A.; Andryukhina, E. N.; Mashura, M. M.; Gromov, S. P.; Alfimov, M. V.

    2006-05-15

    A comparative study of the molecular geometry and crystal packing of crown-containing styryl heterocycles and their dimethoxy substituted analogues is performed. It is established that all the compounds exhibit an identical type of distortions of the geometry of the central styryl fragment. These are the localization of the {pi}-electron density at the ethylene bond and the bond alternation in a half of the phenyl ring due to the conjugation of lone electron pairs of the oxygen substituents with the chromophore system of the molecule. A comparative analysis of the crystal packings of the compounds reveals extended separate hydrophilic and hydrophobic regions. The hydrophilic regions are built of crown ether fragments, and the hydrophobic regions consist of {pi}-conjugated and aromatic molecular fragments. The hydrophobic regions are characterized by a wide variety of packing motifs, among which stacking packing is absent. For two compounds, the formation of sandwich dimers that are preorganized to enter into the photochemical [2 + 2]cycloaddition reaction is observed.

  7. Potentiometric stripping analysis of antimony based on carbon paste electrode modified with hexathia crown ether and rice husk.

    PubMed

    Gadhari, Nayan S; Sanghavi, Bankim J; Srivastava, Ashwini K

    2011-10-03

    An electrochemical method based on potentiometric stripping analysis (PSA) employing a hexathia 18C6 (HT18C6) and rice husk (RH) modified carbon paste electrode (HT18C6-RH-CPE) has been proposed for the subnanomolar determination of antimony. The characterization of the electrode surface has been carried out by means of scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and chronocoulometry. By employing HT18C6-RH-CPE, a 12-fold enhancement in the PSA signal (dt/dE) was observed as compared to plain carbon paste electrode (PCPE). Under the optimized conditions, dt/dE (sV(-1)) was proportional to the Sb(III) concentration in the range of 1.42×10(-8) to 6.89×10(-11)M (r=0.9944) with the detection limit (S/N=3) of 2.11×10(-11)M. The practical analytical utilities of the modified electrode were demonstrated by the determination of antimony in pharmaceutical formulations, human hair, sea water, urine and blood serum samples. The prepared modified electrode showed several advantages, such as simple preparation method, high sensitivity, very low detection limit and excellent reproducibility. Moreover, the results obtained for antimony analysis in commercial and real samples using HT18C6-RH-CPE and those obtained by inductively coupled plasma-atomic emission spectrometry (ICP-AES) are in agreement at the 95% confidence level.

  8. 6. BRIDGE LOOKING SOUTH FROM CROWN POINT STATE PARK SHOWING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    6. BRIDGE LOOKING SOUTH FROM CROWN POINT STATE PARK SHOWING SURROUNDING DEVELOPMENT FROM CONSTRUCTION OF DAM - Columbia River Bridge at Grand Coulee Dam, Spanning Columbia River at State Route 155, Coulee Dam, Okanogan County, WA

  9. Newel post and balustrade (west passage), column (seminary), crown molding ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Newel post and balustrade (west passage), column (seminary), crown molding (second floor), window sill (second floor), and baseboard (second floor). - Russian Bishop's House, 501 Lincoln Street, Sitka, Sitka Borough, AK

  10. Estimation of crown closure from AVIRIS data using regression analysis

    NASA Technical Reports Server (NTRS)

    Staenz, K.; Williams, D. J.; Truchon, M.; Fritz, R.

    1993-01-01

    Crown closure is one of the input parameters used for forest growth and yield modelling. Preliminary work by Staenz et al. indicates that imaging spectrometer data acquired with sensors such as the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) have some potential for estimating crown closure on a stand level. The objectives of this paper are: (1) to establish a relationship between AVIRIS data and the crown closure derived from aerial photography of a forested test site within the Interior Douglas Fir biogeoclimatic zone in British Columbia, Canada; (2) to investigate the impact of atmospheric effects and the forest background on the correlation between AVIRIS data and crown closure estimates; and (3) to improve this relationship using multiple regression analysis.

  11. Cost studies for commercial fuselage crown designs

    NASA Technical Reports Server (NTRS)

    Walker, T. H.; Smith, P. J.; Truslove, G.; Willden, K. S.; Metschan, S. L.; Pfahl, C. L.

    1991-01-01

    Studies were conducted to evaluate the cost and weight potential of advanced composite design concepts in the crown region of a commercial transport. Two designs from each of three design families were developed using an integrated design-build team. A range of design concepts and manufacturing processes were included to allow isolation and comparison of cost centers. Detailed manufacturing/assembly plans were developed as the basis for cost estimates. Each of the six designs was found to have advantages over the 1995 aluminum benchmark in cost and weight trade studies. Large quadrant panels and cobonded frames were found to save significant assembly labor costs. Comparisons of high- and intermediate-performance fiber systems were made for skin and stringer applications. Advanced tow placement was found to be an efficient process for skin lay up. Further analysis revealed attractive processes for stringers and frames. Optimized designs were informally developed for each design family, combining the most attractive concepts and processes within that family. A single optimized design was selected as the most promising, and the potential for further optimization was estimated. Technical issues and barriers were identified.

  12. Composite fuselage crown panel manufacturing technology

    NASA Technical Reports Server (NTRS)

    Willden, Kurtis; Metschan, S.; Grant, C.; Brown, T.

    1992-01-01

    Commercial fuselage structures contain significant challenges in attempting to save manufacturing costs with advanced composite technology. Assembly issues, material costs, and fabrication of elements with complex geometry are each expected to drive the cost of composite fuselage structures. Boeing's efforts under the NASA ACT program have pursued key technologies for low-cost, large crown panel fabrication. An intricate bond panel design and manufacturing concepts were selected based on the efforts of the Design Build Team (DBT). The manufacturing processes selected for the intricate bond design include multiple large panel fabrication with the Advanced Tow Placement (ATP) process, innovative cure tooling concepts, resin transfer molding of long fuselage frames, and utilization of low-cost material forms. The process optimization for final design/manufacturing configuration included factory simulations and hardware demonstrations. These efforts and other optimization tasks were instrumental in reducing cost by 18 percent and weight by 45 percent relative to an aluminum baseline. The qualitative and quantitative results of the manufacturing demonstrations were used to assess manufacturing risks and technology readiness.

  13. The energetic characterization of pineapple crown leaves.

    PubMed

    Braga, R M; Queiroga, T S; Calixto, G Q; Almeida, H N; Melo, D M A; Melo, M A F; Freitas, J C O; Curbelo, F D S

    2015-12-01

    Energetic characterization of biomass allows for assessing its energy potential for application in different conversion processes into energy. The objective of this study is to physicochemically characterize pineapple crown leaves (PC) for their application in energy conversion processes. PC was characterized according to ASTM E871-82, E1755-01, and E873-82 for determination of moisture, ash, and volatile matter, respectively; the fixed carbon was calculated by difference. Higher heating value was determined by ASTM E711-87 and ash chemical composition was determined by XRF. The thermogravimetric and FTIR analyses were performed to evaluate the thermal decomposition and identify the main functional groups of biomass. PC has potential for application in thermochemical processes, showing high volatile matter (89.5%), bulk density (420.8 kg/m(3)), and higher heating value (18.9 MJ/kg). The results show its energy potential justifying application of this agricultural waste into energy conversion processes, implementing sustainability in the production, and reducing the environmental liabilities caused by its disposal.

  14. Retention of Resin Composite CAM Crowns Following Different Bonding Protocols

    NASA Astrophysics Data System (ADS)

    Nejat, Amir Hossein

    Objectives: Resin composite CAM materials offer more efficient milling, however, there is a high incidence of clinical debonding when this material is used for full-coverage crowns. The aim of the present study is to evaluate the effect of different surface treat-ments and primers on the crown retention of a new resin composite CAM material. Methods: 120 molars were prepared with a 24 degree taper, 1.5mm height, and axial walls in dentin. Surface area was measured by digital microscopy and preparations were scanned with an intraoral scanner. Crowns were milled from an experimental com-posite material with 4mm occlusal height. Teeth were randomly allocated to 12 groups (n= 10) based on the possible combinations of three surface treatments (Control, Alumina air abrasion [50mum Al2O3 at 0.28MPa], Hydrofluoric acid etch [5% HF acid for 20 sec]), silane application (with or without Kerr Silane), and adhesive application (with or without Optibond XTR adhesive). Optibond XTR adhesive was applied to the tooth preparations and crowns were bonded with MaxCem Elite. Crowns were fatigued for 100,000 cycles at 100N in water. Crowns were debonded in tension in a universal testing machine at 1mm/min. Crown retention strength (maximum load/area of preparation) was analyzed using a three-way ANOVA with Tukey's post-hoc tests. Results: Surface treatment, silane and adhesive applications independently affect the retention force (p<0.05). All interactions were not statistically significant. Alumina airborne abrasion surface treatment, silane and adhesive applications all boost retention strength. Conclusions: Resin composite crowns should be alumina particle abraded and coated with silane and adhesive.

  15. Failure Probability of Three Designs of Zirconia Crowns.

    PubMed

    Ramos, Gabriela Freitas; Monteiro, Evelyn Barbosa; Bottino, Marco Antonio; Zhang, Yu; Marques de Melo, Renata

    2015-01-01

    This study used a two-parameter Weibull analysis for evaluation of the lifespan of fully or partially porcelain-/glaze-veneered zirconia crowns after fatigue test. A sample of 60 first molars were selected and prepared for full-coverage crowns with three different designs (n = 20): traditional (crowns with zirconia framework covered with feldspathic porcelain), modified (crowns partially covered with veneering porcelain), and monolithic (full-contour zirconia crowns). All specimens were treated with a glaze layer. Specimens were subjected to mechanical cycling (100 N, 3 Hz) with a piston with a hemispherical tip (Ø = 6 mm) until the specimens failed or up to 2 × 10⁶ cycles. Every 500,000 cycles, the fatigue tests were interrupted and stereomicroscopy (10×) was used to inspect the specimens for damage. The authors performed Weibull analysis of interval data to calculate the number of failures in each interval. The types and numbers of failures according to the groups were: cracking (13 traditional, 6 modified) and chipping (4 traditional) of the feldspathic porcelain, followed by delamination (1 traditional) at the veneer/core interface and debonding (2 monolithic) at the cementation interface. Weibull parameters (β, scale; η, shape), with a two-sided confidence interval of 95%, were: traditional-1.25 and 0.9 × 10⁶ cycles; modified-0.58 and 11.7 × 10⁶ cycles; and monolithic-1.05 and 16.5 × 10⁶ cycles. Traditional crowns showed greater susceptibility to fatigue, the modified group presented higher propensity to early failures, and the monolithic group showed no susceptibility to fatigue. The modified and monolithic groups presented the highest number of crowns with no failures after the fatigue test. The three crown designs presented significantly different behaviors under fatigue. The modified and monolithic groups presented less probability of failure after 2 × 10⁶ cycles.

  16. Fracture resistance of fiber-reinforced composite crown restorations.

    PubMed

    Ellakwa, Ayman; Thomas, Glyn D; Shortall, Adrian C C; Marquis, Peter M; Burke, F J Trevor

    2003-12-01

    To evaluate the laboratory fracture resistance of teeth restored with crowns constructed in one of these materials (BelleGlass HP with and without fiber reinforcement. 40 sound maxillary premolar teeth were chosen and were allocated to four groups of 10 teeth, with the mean size of any group varying by less than 2.5% from other test groups. The teeth were stored in water. Each tooth was fixed in a steel mold and subjected to a standardized crown preparation. Crowns were constructed in belleGlass HP. Group A contained no fiber reinforcement. In Group B, Construct polyethylene braided fibers were applied from the mesial margin over the coronal aspect of the die down to the distal margin, and circumferentially around the preparation, prior to crown construction as in Group A. In Group C, a bundle of experimental S-glass fiber of 9 microm diameter was applied circumferentially prior to crown construction as in Group A. In Group D, two layers of Stick net pre-impregnated woven glass fibers were adapted over the whole surface of the initial thin coping, prior to constructing crowns as in Group A. Crowns were luted with a dual cure resin cement (Nexus), with the dentin surface of the specimens having first been treated with a dentin bonding system. Each specimen was stored under water at 37 degrees C for 24 hours prior to testing, and were then subjected to compressive loading at a cross-head speed of 1 mm/minute in a Universal Testing Machine by way of a 4 mm diameter steel bar placed along the midline fissure of the upper premolar crown. The mean force required (kN) to cause fracture was as follows: Group A 2.0kN, Group B 2.4kN, Group C 2.7kN, Group D 2.3kN. ANOVA showed that there was no statistically significant difference between the groups.

  17. Variation in Crown Light Utilization Characteristics among Tropical Canopy Trees

    PubMed Central

    KITAJIMA, KAORU; MULKEY, STEPHEN S.; WRIGHT, S. JOSEPH

    2004-01-01

    • Background and Aims Light extinction through crowns of canopy trees determines light availability at lower levels within forests. The goal of this paper is the exploration of foliage distribution and light extinction in crowns of five canopy tree species in relation to their shoot architecture, leaf traits (mean leaf angle, life span, photosynthetic characteristics) and successional status (from pioneers to persistent). • Methods Light extinction was examined at three hierarchical levels of foliage organization, the whole crown, the outermost canopy and the individual shoots, in a tropical moist forest with direct canopy access with a tower crane. Photon flux density and cumulative leaf area index (LAI) were measured at intervals of 0·25–1 m along multiple vertical transects through three to five mature tree crowns of each species to estimate light extinction coefficients (K). • Results Cecropia longipes, a pioneer species with the shortest leaf life span, had crown LAI <0·5. Among the remaining four species, crown LAI ranged from 2 to 8, and species with orthotropic terminal shoots exhibited lower light extinction coefficients (0·35) than those with plagiotropic shoots (0·53–0·80). Within each type, later successional species exhibited greater maximum LAI and total light extinction. A dense layer of leaves at the outermost crown of a late successional species resulted in an average light extinction of 61 % within 0·5 m from the surface. In late successional species, leaf position within individual shoots does not predict the light availability at the individual leaf surface, which may explain their slow decline of photosynthetic capacity with leaf age and weak differentiation of sun and shade leaves. • Conclusion Later-successional tree crowns, especially those with orthotropic branches, exhibit lower light extinction coefficients, but greater total LAI and total light extinction, which contribute to their efficient use of light and competitive

  18. Variation in crown light utilization characteristics among tropical canopy trees.

    PubMed

    Kitajima, Kaoru; Mulkey, Stephen S; Wright, S Joseph

    2005-02-01

    Light extinction through crowns of canopy trees determines light availability at lower levels within forests. The goal of this paper is the exploration of foliage distribution and light extinction in crowns of five canopy tree species in relation to their shoot architecture, leaf traits (mean leaf angle, life span, photosynthetic characteristics) and successional status (from pioneers to persistent). Light extinction was examined at three hierarchical levels of foliage organization, the whole crown, the outermost canopy and the individual shoots, in a tropical moist forest with direct canopy access with a tower crane. Photon flux density and cumulative leaf area index (LAI) were measured at intervals of 0.25-1 m along multiple vertical transects through three to five mature tree crowns of each species to estimate light extinction coefficients (K). Cecropia longipes, a pioneer species with the shortest leaf life span, had crown LAI <0.5. Among the remaining four species, crown LAI ranged from 2 to 8, and species with orthotropic terminal shoots exhibited lower light extinction coefficients (0.35) than those with plagiotropic shoots (0.53-0.80). Within each type, later successional species exhibited greater maximum LAI and total light extinction. A dense layer of leaves at the outermost crown of a late successional species resulted in an average light extinction of 61% within 0.5 m from the surface. In late successional species, leaf position within individual shoots does not predict the light availability at the individual leaf surface, which may explain their slow decline of photosynthetic capacity with leaf age and weak differentiation of sun and shade leaves. Later-successional tree crowns, especially those with orthotropic branches, exhibit lower light extinction coefficients, but greater total LAI and total light extinction, which contribute to their efficient use of light and competitive dominance.

  19. Indications and complications of crown halo vest placement: A review.

    PubMed

    Lee, Dennis; Adeoye, Adeola L; Dahdaleh, Nader S

    2017-06-01

    Crown halo vest placement remains an option for the treatment of a variety of upper and subaxial cervical spinal fractures. While the device remains a useful non-operative option for the treatment of these injuries, it has been associated with a variety of complications. This manuscript represents an up to date narrative review of the indications, complications, and complication avoidance for the placement of crown halo vests. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Comparison of dental crown height in bite impressions.

    PubMed

    Kane, J F; Stack, A; Dickerson, J; Schmidt, S

    1985-01-01

    A wax bite impression can serve as a reliable identification of missing and unknown children, particularly in the absence of caries and restorations. Dental crown heights in bite impressions made from noncontoured and contoured wax wafers were compared in ten patients, ranging in age from three to eight years. The contoured wax wafer produced significantly greater crown heights in the casts which were fabricated from it. The differences were most pronounced in the anterior teeth; but generally true for all the teeth.

  1. Failure probability of three designs of zirconia crowns

    PubMed Central

    Ramos, G. Freitas; Monteiro, E. Barbosa Carmona; Bottino, M.A.; Zhang, Y.; de Melo, R. Marques

    2015-01-01

    Objectives This study utilized a 2-parameter Weibull analysis for evaluation of lifetime of fully or partially porcelain-/glaze-veneered zirconia crowns after fatigue test. Methods Sixty first molars were selected and prepared for full-coverage crowns with three different designs(n = 20): Traditional –crowns with zirconia framework covered with feldspathic porcelain; Modified– crowns partially covered with veneering porcelain; and Monolithic–full-contour zirconia crowns. All specimens were treated with a glaze layer. Specimens were subjected to mechanical cycling (100N, 3Hz) with a piston with hemispherical tip (Ø=6 mm) until the specimens failed or up to 2×106 cycles. Every 500,000 cycles intervals, the fatigue tests were interrupted, and stereomicroscopy (10 X) was used to inspect the specimens for damage. We performed Weibull analysis of interval data to calculate the number of failures in each interval. Results The types and number of failures according to the groups were: cracking (Traditional-13, Modified-6) and chipping (Traditional-4) of the feldspathic porcelain, followed by delamination (Traditional-1) at the veneer/core interface and debonding (Monollithic-2) at the cementation interface. Weibull parameters (beta, scale; and eta, shape), with a two-sided confidence interval of 95%, were: Traditional – 1.25 and 0.9 × 106cycles; Modified– 0.58 and 11.7 × 106 cycles; and Monolithic – 1.05 and 16.5 × 106 cycles. Traditional crowns showed greater susceptibility to fatigue, the Modified group presented higher propensity to early failures, and the Monolithic group showed no susceptibility to fatigue. The Modified and Monolithic groups presented the highest number of crowns with no failures after the fatigue test. Conclusions The three crown designs presented significantly different behaviors under fatigue. The Modified and the Monolithic groups presented less probability to failure after 2×106cycles. PMID:26509988

  2. Inhibition of diethyl ether degradation in Rhodococcus sp. strain DEE5151 by glutaraldehyde and ethyl vinyl ether.

    PubMed

    Kim, Yong-Hak; Engesser, Karl-Heinrich

    2005-02-15

    Alkyl ether-degrading Rhodococcus sp. strain DEE5151, isolated from activated sewage sludge, has an activity for the oxidation of a variety of alkyl ethers, aralkyl ethers and dibenzyl ether. The whole cell activity for diethyl ether oxidation was effectively inhibited by 2,3-dihydrofurane, ethyl vinyl ether and glutaraldehyde. Glutaraldehyde of less than 30 microM inhibited the activity by a competitive manner with the inhibition constant, K(I) of 7.07+/-1.36 microM. The inhibition type became mixed at higher glutaraldehyde concentrations >30 microM, probably due to the inactivation of the cell activity by the Schiff-base formation. Structurally analogous ethyl vinyl ether inhibited the diethyl ether oxidation activity in a mixed manner with decreasing the apparent maximum oxidation rate, v(max)(app), and increasing the apparent Michaelis-Menten constant, K(M)(app). The mixed type inhibition by ethyl vinyl ether seemed to be introduced not only by the structure similarity with diethyl ether, but also by the reactivity of the vinyl ether with cellular components in the whole cell system.

  3. Ab initio investigation of the structure and alkali metal cation selectivity of 18-crown-6

    SciTech Connect

    Glendening, E.D.; Feller, D.; Thompson, M.A. )

    1994-11-16

    We present an ab inito, quantum mechanical study of 18-crown-6 (18c6) and its interaction with the alkali metal cations Li[sup +], Na[sup +], K[sup +], Rb[sup +], and Cs[sup +]. Geometries, binding energies, and binding enthalpies are evaluated at the restricted Hartree-Fock (RHF) level using standard basis sets (3-21G and 6-31 + G*) and relativistic effective core potentials. Electron correlation effects are determined at the MP2 level, and wave function analysis is performed by the natural bond orbital (NBO) and associated methods. The affinity of 18c6 for the alkali metal cations is quite strong (50-100 kcal mol[sup [minus]1], depending on cation type), arising largely from the electrostatic (ionic) interaction of the cation with the nucleophilic ether backbone. Charge transfer (covalent bonding) contributions are somewhat less important, only 20-50% as strong as the electrostatic interaction. Agreement of the calculated binding enthalpies and experimentally determined quantities is rather poor. For example, the binding energy for K[sup +]/18c6 (-71.5 kcal mol[sup [minus]1]) is about 30 kcal mol[sup [minus]1] stronger than that determined by experiment, and it is not clear how to reconcile this difference. Our calculations clearly show that solvation effects strongly influence cation selectivity. 48 refs., 12 figs., 5 tabs.

  4. Development of Conductometric Sensor Based on 25,27-Di-(5-thio-octyloxy)calix[4]arene-crown-6 for Determination of Ammonium

    NASA Astrophysics Data System (ADS)

    Saiapina, O. Y.; Kharchenko, S. G.; Vishnevskii, S. G.; Pyeshkova, V. M.; Kalchenko, V. I.; Dzyadevych, S. V.

    2016-02-01

    The conductometric sensor based on 25,27-di-(5-thio-octyloxy)calix[4]arene-crown-6 was developed for the quantitative analysis of ammonium. The calixarene was immobilized on the surface of the planar interdigitated electrodes by attachment of its dialkyl sulfide groups to the surface of the gold electrodes. The intrinsic ability of the calixarene to capture ammonium was studied in the conductometric measuring mode and by the electrochemical impedance spectroscopy. The developed sensor showed high selectivity to ammonium in the presence of mono-, di-, and trivalent cations. Selective and highly sensitive detection of ammonium resulted from the complexation between the ammonium ions and a crown-ether fragment of the upper rim of the 25,27-di-(5-thio-octyloxy)calix[4]arene-crown-6 macrocycle. The developed sensor had high signal repeatability. Its sensitivity was found to be satisfactory for the forthcoming sensor application in the water-sample analysis; the linear range was 0.01-1.5 mM and limit of detection 10 μM.

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

    DTIC Science & Technology

    2014-12-01

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

  6. Ether bridge formation in loline alkaloid biosynthesis

    PubMed Central

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

    2014-01-01

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

  7. Thrust measurement of dimethyl ether arcjet thruster

    NASA Astrophysics Data System (ADS)

    Kakami, Akira; Beppu, Shinji; Maiguma, Muneyuki; Tachibana, Takeshi

    2011-04-01

    The present paper describes thrust measurement results for an arcjet thruster using Dimethyl ether (DME) as the propellant. DME is an ether compound and can be stored as a liquid due to its relatively low freezing point and preferable vapor pressure. The thruster successfully produced high-voltage mode at DME mass flow rates above 30 mg/s, whereas it yielded low-voltage mode below 30 mg/s. Thrust measurements yielded a thrust of 0.15 N and a specific impulse of 270 s at a mass flow rate of 60 mg/s with a discharge power of 1300 W. The DME arcjet thruster was comparable to a conventional one for thrust and discharge power.

  8. Composite crown-form crowns for severely decayed primary molars: a technique for restoring function and esthetics.

    PubMed

    Ram, D; Peretz, B

    2000-01-01

    Current developments in esthetic dentistry center around new techniques and materials that improve the ability of the clinician to provide esthetic services. This article describes a step-by-step method of placing composite crown-form crowns on severely decayed primary mandibular molars. The described technique allows for restoring, as close as possible, form and function lost to caries in an esthetic mode in cases of severely decayed primary molars that would have required stainless steel crowns had they been treated traditionally. Disadvantages of this treatment mode are that dryness may not be prevented in the proximal margins, especially where subgingival carious involvement is encountered and the margin areas may be contaminated with gingival fluid or blood. Although no long-term follow-up has been reported for the technique, when strong opposition by the parent or child to the stainless steel crown is encountered, and a desire for esthetic restoration is strongly expressed, the composite crown-form crowns may be considered as an alternative.

  9. Crown depth as a result of evolutionary games: decreasing solar angle should lead to shallower, not deeper crowns.

    PubMed

    Vermeulen, Peter Johannes

    2014-06-01

    There is a general notion in the literature that, with increasing latitude, trees have deeper crowns as a result of a lower solar elevation angle. However, these predictions are based on models that did not include the effects of competition for light between individuals. Here, I argue that there should be selection for trees to increase the height of the crown base, as this decreases shading by neighbouring trees, leading to an evolutionarily stable strategy (ESS). Because the level of between-tree shading increases with decreasing solar angle, the predicted ESS will shift to higher crown base height. This argument is supported by a simulation model to check for the effects of crown shape and the change of light intensity that occurs with changing solar angle on model outcomes. So, the lower solar angle at higher latitudes would tend to select for shallower, and not deeper, crowns. This casts doubt on the common belief that a decreasing solar angle increases crown depth. More importantly, it shows that different assumptions about what should be optimized can lead to different predictions, not just for absolute trait values, but for the direction of selection itself. © 2014 The Author. New Phytologist © 2014 New Phytologist Trust.

  10. Rhodium-Catalyzed Dehydrogenative Silylation of Acetophenone Derivatives: Formation of Silyl Enol Ethers versus Silyl Ethers.

    PubMed

    Garcés, Karin; Lalrempuia, Ralte; Polo, Víctor; Fernández-Alvarez, Francisco J; García-Orduña, Pilar; Lahoz, Fernando J; Pérez-Torrente, Jesús J; Oro, Luis A

    2016-10-04

    A series of rhodium-NSiN complexes (NSiN=bis (pyridine-2-yloxy)methylsilyl fac-coordinated) is reported, including the solid-state structures of [Rh(H)(Cl)(NSiN)(PCy3 )] (Cy=cyclohexane) and [Rh(H)(CF3 SO3 )(NSiN)(coe)] (coe=cis-cyclooctene). The [Rh(H)(CF3 SO3 )(NSiN)(coe)]-catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3 SO3 )(NSiN)(coe)] with HSiMe3 and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si-H bond by a metal-ligand cooperative mechanism as the rate-determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2 and the corresponding silyl enol ether.

  11. Promoting environmentally sound management of polybrominated diphenyl ethers in Asia.

    PubMed

    Li, Jinhui; Zhao, Nana; Liu, Xue; Wu, Xiaoyang

    2014-06-01

    Polybrominated diphenyl ethers with persistent organic pollutant properties are required to be controlled by the Stockholm Convention. Recently, polybrominated diphenyl ether contamination has become widespread in Asia, mainly because of the disposal and recycling processes of polybrominated diphenyl ether-containing wastes. The management status, production, usage, import/export, treatment, and disposal, as well as implementation deficiencies for the environmentally sound management of polybrominated diphenyl ethers and polybrominated diphenyl ether-containing materials in ten Asian countries were investigated and assessed in this study. This information could help the participating countries implement the Stockholm Convention and could promote the regional environmentally sound management of polybrominated diphenyl ether-containing articles and products. The results obtained were as follows. (1) Most of the countries studied lacked environmental policies and regulations, or even standards of polybrominated diphenyl ether pollution management and emission control actions. Accurate data on the consumption and importation of polybrominated diphenyl ether-containing materials, however, were not available for all the participating countries. In addition, there were no special treatment or disposal systems for polybrominated diphenyl ether-containing materials, or emission-cutting measures for the treatment of waste in these countries, owing to the lack of sufficient funding or technologies. (2) The improper dismantling of e-waste is a major source of polybrominated diphenyl ether emissions in these countries. (3) Proper e-waste management could result in a breakthrough in the environmentally sound management of this major polybrominated diphenyl ether-containing material flow, and could significantly reduce polybrominated diphenyl ether emissions. Finally, based on the study results, this article puts forward some recommendations for improving the environmentally

  12. Nikola Tesla, the Ether and his Telautomaton

    NASA Astrophysics Data System (ADS)

    Milar, Kendall

    2014-03-01

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

  13. Biodegradation of glycol ethers in soil

    SciTech Connect

    Gonsior, S.J.; West, R.J.

    1995-08-01

    Because of the widespread use of glycol ethers in applications ranging from consumer products to use as chemical intermediates, there is a need to better understand the fate of these compounds in the environment. Soil biodegradation studies were conducted for three propylene glycol ethers: 1-methoxy-2-propanol, 1-phenoxy-2-propanol, and 1-methoxy-2-propanol acetate. The test compounds were labeled with carbon-14 at either the methoxy or phenoxy substituents. Biodegradation of the three compounds was observed in two sandy loam soils. The time required for disappearance of 50% of the test compounds ranged from < 1 d at 0.2 ppm (w/w) to <7 d at 107 ppm. Degradation rates were slower in a sandy soil, reflecting the lower concentration of microorganisms present. No significant accumulation of intermediate products was observed, and ultimate yields of {sup 14}CO{sub 2} were in the range of 40 to 65% of the initial concentration. Results indicated that the glycol ethers were degraded in a variety of soils under aerobic conditions.

  14. 3D statistical failure analysis of monolithic dental ceramic crowns.

    PubMed

    Nasrin, Sadia; Katsube, Noriko; Seghi, Robert R; Rokhlin, Stanislav I

    2016-07-05

    For adhesively retained ceramic crown of various types, it has been clinically observed that the most catastrophic failures initiate from the cement interface as a result of radial crack formation as opposed to Hertzian contact stresses originating on the occlusal surface. In this work, a 3D failure prognosis model is developed for interface initiated failures of monolithic ceramic crowns. The surface flaw distribution parameters determined by biaxial flexural tests on ceramic plates and point-to-point variations of multi-axial stress state at the intaglio surface are obtained by finite element stress analysis. They are combined on the basis of fracture mechanics based statistical failure probability model to predict failure probability of a monolithic crown subjected to single-cycle indentation load. The proposed method is verified by prior 2D axisymmetric model and experimental data. Under conditions where the crowns are completely bonded to the tooth substrate, both high flexural stress and high interfacial shear stress are shown to occur in the wall region where the crown thickness is relatively thin while high interfacial normal tensile stress distribution is observed at the margin region. Significant impact of reduced cement modulus on these stress states is shown. While the analyses are limited to single-cycle load-to-failure tests, high interfacial normal tensile stress or high interfacial shear stress may contribute to degradation of the cement bond between ceramic and dentin. In addition, the crown failure probability is shown to be controlled by high flexural stress concentrations over a small area, and the proposed method might be of some value to detect initial crown design errors.

  15. Retention of esthetic veneers on primary stainless steel crowns.

    PubMed

    Baker, L H; Moon, P; Mourino, A P

    1996-01-01

    The purpose of this study was to ascertain the amount of shearing force necessary to fracture, dislodge or deform the esthetic veneer facings of four commercially available veneered primary incisor stainless steel crowns. The four types tested were: Cheng Crowns, [Peter Cheng Orthodontic Laboratory]; Whiter Biter Crown II, [White Bite Inc.]; Kinder Krowns, [Mayclin Dental Studio, Inc]; and NuSmile Primary Crowns, [Orthodontic Technologies, Inc]. The crowns (#4 right central incisor) from each manufacturer were obtained with the facings attached. The crowns were soaked for ninety days and thermocycled at 4 degrees C and 55 degrees C for 500 45-second cycles. The crowns were cemented to standardized chromium cobalt metal dies. Each die was placed in to a custom holder on the Instron Universal testing machine. A force was applied at the incisal edge of the veneer at 148 degrees, (the primary interincisal angle), with a crosshead speed of 0.05 inches/minute until the veneer either fractured, dislodged or deformed. The mean force (Ibs) required +/- SD to produce failure, in descending order, was as follows: Cheng (107.8 +/- 17.3); NuSmile (100.2 +/- 18.2); KinderKrown (91.3 +/- 27.4)d Whiter Biter (81.5 +/- 21.7). To test the hypothesis of no difference among the four manufacturers, an analysis of variance was performed using PROC GLM. The resultant F statistic was 2.79 (p < 0.0543), indicating a marginally statistically significant difference in the response variable "pressure" among the four groups. A posthoc test was then performed to ascertain where these differences occurred. These results, using Turkey's studentized range test for pairwise comparisons, suggested that the only difference was between the Cheng and Whiter Biter manufacturers.

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

    PubMed

    Raia, Courtenay Grean

    2007-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Connell, John W.

    1991-01-01

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

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

    PubMed

    Morikawa, Atsushi

    2016-02-16

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

  19. Open-grown crown radius of eleven bottomland hardwood species: Prediction and use in assessing stocking

    SciTech Connect

    Goelz, J.C.G.

    1996-08-01

    Equations were prepared to predict crown radius for eleven species of open-grown bottomland hardwood trees. Crown radius was predicted as a function of diameter at breast height (dbh) and as a function of dbh, total height, and crown ratio. Equations were prepared for individual species and species groups. Pecan has the largest crowns over a broad range of dbh. Eastern cottonwood has the smallest crowns for most levels of dbh. Sweetgum has relatively small crowns for trees of small dbh, but crown radius is comparable to most species at the largest dbh. The crown radius predictions may be used to calculate crown competition factor. B-lines of stocking may be calculated that represent a stand of one species as well as a mixed-species stand of any particular species proportion.

  20. Investigation of distortions around the cervical area of teeth restored with two kinds of crown materials.

    PubMed

    Suzuki, Chikako; Miura, Hiroyuki; Okada, Daizo; Komada, Wataru; Miyasaka, Munenaga; Yamamoto, Masahiro; Masuoka, David

    2009-03-01

    The purpose of this study was to identify crown materials to decrease the stress concentrated at the cervical area of endodontically treated teeth. To this end, 14 extracted human mandibular premolars were divided into two groups for this study: complete cast crowns versus polymer-based crown and bridge material crowns. Both complete cast crowns (MC) and polymer-based crown and bridge material crowns (HC) were cemented with a glycidyl methacrylate-based resin cement (RC) to composite resin cores with glass fiber posts. Static loading was applied and distortion was measured with four pieces of strain gages attached to the marginal area. Findings showed that there was a large difference in distortion between crown and root in MC. On the other hand, distortions at the cervical area of crown and root were similar in HC.

  1. Modeling the spatial distribution of forest crown biomass and effects on fire behavior with FUEL3D and WFDS

    Treesearch

    Russell A. Parsons; William Mell; Peter McCauley

    2010-01-01

    Crown fire poses challenges to fire managers and can endanger fire fighters. Understanding of how fire interacts with tree crowns is essential to informed decisions about crown fire. Current operational crown fire predictions in the United States assume homogeneous crown fuels. While a new class of research fire models, which model fire behavior with computational...

  2. Digital modeling technology for full dental crown tooth preparation.

    PubMed

    Dai, Ning; Zhong, Yicheng; Liu, Hao; Yuan, Fusong; Sun, Yuchun

    2016-04-01

    A dental defect is one of the most common oral diseases, and it often requires a full crown restoration. In this clinical operation, the dentist must manually prepare the affected tooth for the full crown so that it has a convergence angle between 4° and 10°, no undercuts, and uniform and even shoulder widths and depths using a high speed diamond bur in the patient׳s mouth within one hour, which is a difficult task that requires visual-manual operation. The quality of the tooth preparation has an important effect on the success rate of the subsequent prosthodontic treatment. This study involved research into digital modeling technology for full dental crown tooth preparation. First, the margin line of the tooth preparation was designed using a semi-automatic interactive process. Second, the inserting direction was automatically computed. Then, the characteristic parameters and the constraints on the tooth preparation were defined for the model. Next, the shoulder and axial surface of the tooth preparation were formed using parametric modeling. Finally, the implicit surface of a radial basis function was used to construct the tooth preparation׳s occlusal surface. The experimental results verified that the method of digital modeling for full crown preparation proposed in this study can quickly and accurately implement personalized designs of various parameters, such as the shoulder width and the convergence angle; it provides a digital design tool for full crown preparation.

  3. Effect of cements on fracture resistance of monolithic zirconia crowns

    PubMed Central

    Nakamura, Keisuke; Mouhat, Mathieu; Nergård, John Magnus; Lægreid, Solveig Jenssen; Kanno, Taro; Milleding, Percy; Örtengren, Ulf

    2016-01-01

    Abstract Objectives The present study investigated the effect of cements on fracture resistance of monolithic zirconia crowns in relation to their compressive strength. Materials and methods Four different cements were tested: zinc phosphate cement (ZPC), glass-ionomer cement (GIC), self-adhesive resin-based cement (SRC) and resin-based cement (RC). RC was used in both dual cure mode (RC-D) and chemical cure mode (RC-C). First, the compressive strength of each cement was tested according to a standard (ISO 9917-1:2004). Second, load-to-failure test was performed to analyze the crown fracture resistance. CAD/CAM-produced monolithic zirconia crowns with a minimal thickness of 0.5 mm were prepared and cemented to dies with each cement. The crown–die samples were loaded until fracture. Results The compressive strength of SRC, RC-D and RC-C was significantly higher than those of ZPC and GIC (p < 0.05). However, there was no significant difference in the fracture load of the crown between the groups. Conclusion The values achieved in the load-to-failure test suggest that monolithic zirconia crowns with a minimal thickness of 0.5 mm may have good resistance against fracture regardless of types of cements. PMID:27335900

  4. Biology and control of the raspberry crown borer (Lepidoptera: Sesiidae).

    PubMed

    McKern, Jacquelyn A; Johnson, Donn T; Lewis, Barbara A

    2007-04-01

    This study explored the biology of raspberry crown borer, Pennisetia marginata (Harris) (Lepidoptera: Sesiidae), in Arkansas and the optimum timing for insecticide and nematode applications. The duration of P. marginata's life cycle was observed to be 1 yr in Arkansas. Insecticide trials revealed that bifenthrin, chlorpyrifos, imidacloprid, metaflumizone, and metofluthrin efficacy were comparable with that of azinphosmethyl, the only labeled insecticide for P. marginata in brambles until 2005. Applications on 23 October 2003 for plots treated with bifenthrin, chlorpyrifos, and azinphosmethyl resulted in >88% reduction in larvae per crown. Applications on 3 November 2004 of metaflumizone, metofluthrin, and bifenthrin resulted in >89% reduction in larvae per crown. Applications on 7 April 2005 for metofluthrin, imidacloprid, bifenthrin, metaflumizone, and benzoylphenyl urea resulted in >64% reduction in the number of larvae per crown. Applications on 6 May 2004 did not reduce larval numbers. The optimum timing for treatments was found to be between October and early April, before the larvae tunneled into the crowns of plants. Applying bifenthrin with as little as 468 liters water/ha (50 gal/acre) was found to be as effective against larvae as higher volumes of spray. Nematode applications were less successful than insecticides. Nematode applications of Steinernemafeltiae, Steinernema carpocapsae, and Heterorhabditis bacteriophora reduced larvae counts per plant by 46, 53, and 33%, respectively.

  5. Experimental investigation of the abrasive crown dynamics in orbital atherectomy.

    PubMed

    Zheng, Yihao; Belmont, Barry; Shih, Albert J

    2016-07-01

    Orbital atherectomy is a catheter-based minimally invasive procedure to modify the plaque within atherosclerotic arteries using a diamond abrasive crown. This study was designed to investigate the crown motion and its corresponding contact force with the vessel. To this end, a transparent arterial tissue-mimicking phantom made of polyvinyl chloride was developed, a high-speed camera and image processing technique were utilized to visualize and quantitatively analyze the crown motion in the vessel phantom, and a piezoelectric dynamometer measured the forces on the phantom during the procedure. Observed under typical orbital atherectomy rotational speeds of 60,000, 90,000, and 120,000rpm in a 4.8mm caliber vessel phantom, the crown motion was a combination of high-frequency rotation at 1000, 1500, and 1660.4-1866.1Hz and low-frequency orbiting at 18, 38, and 40Hz, respectively. The measured forces were also composed of these high and low frequencies, matching well with the rotation of the eccentric crown and the associated orbital motion. The average peak force ranged from 0.1 to 0.4N at different rotational speeds.

  6. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

  7. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

  8. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  9. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

  10. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

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

    NASA Technical Reports Server (NTRS)

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

    2002-01-01

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

  12. IRIS Toxicological Review of Ethyl Tertiary Butyl Ether (Etbe) ...

    EPA Pesticide Factsheets

    EPA is conducting a peer review and public comment of the scientific basis supporting the human health hazard and dose-response assessment of ethyl tertiary butyl ether (ETBE) that when finalized will appear on the Integrated Risk Information System (IRIS) database. The draft Toxicological Review of Ethyl Tertiary Butyl Ether provides scientific support and rationale for the hazard and dose-response assessment pertaining to chronic exposure to ethyl tertiary butyl ether.

  13. Glycol ether/siloxane polymer penetrating and lubricating composition

    SciTech Connect

    MacIntosh, D.H.

    1981-02-03

    A penetrating and lubricating composition consists of a silicone lubricant dissolved in a glycol ether carrier having a very low surface tension. The glycol ether gives the composition the ability to penetrate into the cracks between two seized or corroded elements and dissolve any rust or corrosion present. The glycol ether then volitalizes leaving a coating of silicone on the parts to serve as a lubricant and prevent further corrosion.

  14. Divinyl ether synthase gene, and protein and uses thereof

    DOEpatents

    Howe, Gregg A.; Itoh, Aya

    2006-12-26

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  15. Divinyl ether synthase gene and protein, and uses thereof

    DOEpatents

    Howe, Gregg A [East Lansing, MI; Itoh, Aya [Tsuruoka, JP

    2011-09-13

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  16. Ether Cleavage Re-Investigated: Elucidating the Mechanism of BBr3-Facilitated Demethylation of Aryl Methyl Ethers

    PubMed Central

    Kosak, Talon M; Conrad, Heidi A; Korich, Andrew L; Lord, Richard L

    2015-01-01

    One of the most well-known, highly utilized reagents for ether cleavage is boron tribromide (BBr3), and this reagent is frequently employed in a 1:1 stoichiometric ratio with ethers. Density functional theory calculations predict a new mechanistic pathway involving charged intermediates for ether cleavage in aryl methyl ethers. Moreover, these calculations predict that one equivalent of BBr3 can cleave up to three equivalents of anisole, producing triphenoxyborane [B(OPh)3] prior to hydrolysis. These predictions were validated by gas chromatography analysis of reactions where the BBr3:anisole ratio was varied. Not only do we confirm that sub-stoichiometric equivalents may be used for ether demethylation, but the findings also support our newly proposed three cycle mechanism for cleavage of aryl methyl ethers. PMID:26693209

  17. Museum security and the Thomas Crown Affair.

    SciTech Connect

    Michaud, E. C.

    2010-01-01

    Over the years, I've daydreamed about stealing a Vermeer, a Picasso, or Rembrandt. It tickles me, as much as watching the reboot of The Thomas Crown Affair. Why is it, do you suppose, so much fun to think about stealing a world renowned piece off the wall of a major metropolitan museum? Is it the romantic thoughts of getting away with it, walking past infrared detectors, and pressure sensors ala Indiana Jones with the sack of sand to remove the idol without triggering the security system? Is it the idea of snatching items with such fantastic prices, where the romance of possessing an item of such value is less intoxicating than selling it to a private collector for it to never be seen again? I suspect others share my daydreams as they watch theater or hear of a brazen daylight heist at museums around the world, or from private collections. Though when reality sets in, the mind of the security professional kicks in. How could one do it, why would one do it, what should you do once it's done? The main issue a thief confronts when acquiring unique goods is how to process or fence them. They become very difficult to sell because they are one-of-a-kind, easy to identify, and could lead to the people involved with the theft. The whole issue of museum security takes up an ironic twist when one considers the secretive British street artist 'Banksy'. Banksy has made a name for himself by brazenly putting up interesting pieces of art in broad daylight (though many critics don't consider his work to be art) on building walls, rooftops, or even museums. I bring him up for a interesting take on what may become a trend in museum security. In March of 2005, Banksy snuck a piece of his called 'Vandalized Oil Painting' into the Brooklyn Museum's Great Historical Painting Wing, plus 3 other pieces into major museums in New York. Within several days, 2 paintings had been torn down, but 2 stayed up much longer. In his home country of the UK, a unauthorized piece he created and placed

  18. Chipping resistance of graded zirconia ceramics for dental crowns.

    PubMed

    Zhang, Y; Chai, H; Lee, J J-W; Lawn, B R

    2012-03-01

    A serious drawback of veneering porcelains is a pronounced susceptibility to chipping. Glass-infiltrated dense zirconia structures can now be produced with esthetic quality, making them an attractive alternative. In this study, we examined the hypothesis that such infiltrated structures are much more chip-resistant than conventional porcelains, and at least as chip-resistant as non-infiltrated zirconia. A sharp indenter was used to produce chips in flat and anatomically correct glass-infiltrated zirconia crown materials, and critical loads were measured as a function of distance from the specimen edge (flat) or side wall (crown). Control data were obtained on zirconia specimens without infiltration and on crowns veneered with porcelains. The results confirmed that the resistance to chipping in graded zirconia is more than 4 times higher than that of porcelain-veneered zirconia and is at least as high as that of non-veneered zirconia.

  19. Crown angulation and inclination of Northern Thais with good occlusion.

    PubMed

    Jotikasthira, Dhirawat; Sheffield, Peter; Kalha, Anmol; Syed, Zameer

    2010-01-01

    When patients of differing ethnicities are treated with one bracket system, negative consequences for the occlusion can result. This study investigated the crown angulation and inclination on study casts of 60 Northern Thais (30 males and 30 females) with a good occlusion. In all study casts, each tooth (except the third molars) was evaluated with the orthodontic Torque Angulation Device (TAD) twice on the right side; this was also performed twice on the left side. The mean of the two evaluations was used for the statistical analysis. The means of the males and females were compared with the independent Student t test. The results were that the crown angulation of the mandibular first and second molars was significantly higher in females (P<.01) and that the crown inclination of all teeth did not differ between the two sexes.

  20. Consequences of crown shortening canine teeth in Greenland sled dogs.

    PubMed

    Kortegaard, H E; Anthony Knudsen, T; Dahl, S; Agger, J F G; Eriksen, T

    2015-04-01

    To evaluate the consequences of crown shortening, focusing on the prevalence of pulp exposure and periapical pathology in Greenland sled dogs that had had their canine crowns shortened at an early age. Five cadaver heads and 54 sled dogs underwent an oral examination for dental fractures and pulp exposure of canines. All canines were radiographed and evaluated for periapical pathology. The prevalence of canine pulp exposure in 12 (5 heads and 7 dogs) crown shortened dogs was 91 · 7%, and 21 · 3% in 47 not-crown shortened dogs. A significant (P < 0 · 001) risk of pulp exposure of the canines in the crown shortened group compared to the not-crown shortened group was seen with a relative risk of 4 · 3 on a dog basis and a relative risk of 12 · 2 on a tooth basis. In dogs with pulp exposure of canines (n = 51) the prevalence of periapical pathology was 82 · 4%, but only 0 · 8% in dogs without pulp exposure (n = 133) resulting in a significant (relative risk, 109 · 5; P < 0 · 001) risk of periapical pathology in teeth with pulp exposure compared to teeth without pulp exposure. The high risk of periapical pathology observed in teeth with pulp exposure confirms that these teeth should not be neglected in affected dogs. © 2015 British Small Animal Veterinary Association.