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Sample records for strong lewis acid

  1. Silylium ion-catalyzed challenging Diels-Alder reactions: the danger of hidden proton catalysis with strong Lewis acids.

    Science.gov (United States)

    Schmidt, Ruth K; Müther, Kristine; Mück-Lichtenfeld, Christian; Grimme, Stefan; Oestreich, Martin

    2012-03-07

    The pronounced Lewis acidity of tricoordinate silicon cations brings about unusual reactivity in Lewis acid catalysis. The downside of catalysis with strong Lewis acids is, though, that these do have the potential to mediate the formation of protons by various mechanisms, and the thus released Brønsted acid might even outcompete the Lewis acid as the true catalyst. That is an often ignored point. One way of eliminating a hidden proton-catalyzed pathway is to add a proton scavenger. The low-temperature Diels-Alder reactions catalyzed by our ferrocene-stabilized silicon cation are such a case where the possibility of proton catalysis must be meticulously examined. Addition of the common hindered base 2,6-di-tert-butylpyridine resulted, however, in slow decomposition along with formation of the corresponding pyridinium ion. Quantitative deprotonation of the silicon cation was observed with more basic (Mes)(3)P to yield the phosphonium ion. A deuterium-labeling experiment verified that the proton is abstracted from the ferrocene backbone. A reasonable mechanism of the proton formation is proposed on the basis of quantum-chemical calculations. This is, admittedly, a particular case but suggests that the use of proton scavengers must be carefully scrutinized, as proton formation might be provoked rather than prevented. Proton-catalyzed Diels-Alder reactions are not well-documented in the literature, and a representative survey employing TfOH is included here. The outcome of these catalyses is compared with our silylium ion-catalyzed Diels-Alder reactions, thereby clearly corroborating that hidden Brønsted acid catalysis is not operating with our Lewis acid. Several simple-looking but challenging Diels-Alder reactions with exceptionally rare dienophile/enophile combinations are reported. Another indication is obtained from the chemoselectivity of the catalyses. The silylium ion-catalyzed Diels-Alder reaction is general with regard to the oxidation level of the

  2. Interactions of Verkade's Superbase with Strong Lewis Acids: From Labile Mono- and Binuclear Lewis Acid-Base Complexes to Phosphenium Cations.

    Science.gov (United States)

    Mummadi, Suresh; Kenefake, Dustin; Diaz, Rony; Unruh, Daniel K; Krempner, Clemens

    2017-09-05

    A series of mono- and binuclear Lewis acid-base complexes of the formulas N[CH 2 CH 2 N(Pr i )] 3 P→LA [LA = BH 3 (8), Ga(C 6 F 5 ) 3 (10), GaCl 3 (11)], LA←N[CH 2 CH 2 N(Pr i )] 3 P [LA = Al(C 6 F 5 ) 3 (6a), AlMe 3 (6b), AlEt 3 (6c), AlBu i 3 (6d), BF 3 (13)], and LA←N[CH 2 CH 2 N(Pr i )] 3 P→LA [Lewis acid (LA) = Al(C 6 F 5 ) 3 (7a), AlMe 3 (7b), AlEt 3 (7c), AlBu i 3 (7d), AlCl 3 (7e), BH 3 (9)] were generated from reactions of Verkade's base, N[CH 2 CH 2 N(Pr i )] 3 P (1), with various boron-, aluminum-, and gallium-containing Lewis acids, and characterized by multinuclear NMR spectroscopy. {N[CH 2 CH 2 N(Pr i )] 3 P→C 7 H 7 }[BF 4 ] (5) was synthesized via the treatment of 1 with [C 7 H 7 ][BF 4 ]. The reaction of 1 with B(C 6 F 5 ) 3 , followed by the addition of [Ph 3 C] 2 [B 12 Cl 12 ], gave rise to the rearranged borate salt [PN 4 C 9 H 17 (Pr i ) 2 ][B 12 Cl 12 ] (3), while treating 1 with [Ph 3 C] 2 [B 12 Cl 12 ] exclusively afforded {N[CH 2 CH 2 N(Pr i )] 3 PH} 2 [B 12 Cl 12 ] (4). Reactions of 1 with 2 equiv of GaCl 3 and BF 3 , respectively, afforded the novel phosphenium gallate and borate salts 12a, 12b, and 15. The solid-state structures of 1, 3-5, 6b, 7a, 7b, 7e, 8, 10, 11, 12b, 13, and 15 were determined by X-ray crystallography.

  3. Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions.

    Science.gov (United States)

    Tofan, Daniel; Gabbaï, François P

    2016-11-01

    As part of our ongoing studies of water tolerant Lewis acids, we have synthesized and investigated the properties of Sb(C 6 F 5 ) 3 (O 2 C 6 Cl 4 ), a fluorinated stiborane whose Lewis acidity approaches that of B(C 6 F 5 ) 3 . While chloroform solutions of this Lewis acid can be kept open to air or exposed to water for extended periods of time, this new Lewis acid reacts with P t Bu 3 and paraformaldehyde to form the corresponding formaldehyde adduct t Bu 3 P-CH 2 -O-Sb(C 6 F 5 ) 3 (O 2 C 6 Cl 4 ). To test if this reactivity can also be observed with systems that combine the phosphine and the stiborane within the same molecule, we have also prepared o -C 6 H 4 (PPh 2 )(SbAr 2 (O 2 C 6 Cl 4 )) (Ar = Ph, C 6 F 5 ). These yellow compounds, which possess an intramolecular P→Sb interaction, are remarkably inert to water but do, nonetheless, react with and accomodate formaldehyde into the P/Sb pocket. In the case of the fluorinated derivative o -C 6 H 4 (PPh 2 )(Sb(C 6 F 5 ) 2 (O 2 C 6 Cl 4 )), formaldehyde complexation, which occurs in water/dichloromethane biphasic mixtures, is accompanied by a colourimetric turn-off response thus highlighting the potential that this chemistry holds in the domain of molecular sensing.

  4. The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Ebbinghaus, Bartley B. [Univ. of California, Berkeley, CA (United States)

    1991-05-01

    The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cell technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF2, ThO2, YDT(0.85ThO2-0.15YO1.5), and LDT(0.85ThO2- 0.15LaO1.5) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.

  5. The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Ebbinghaus, B.B.

    1991-05-01

    The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cell technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF[sub 2], ThO[sub 2], YDT(0.85ThO[sub 2]-0.15YO[sub 1.5]), and LDT(0.85ThO[sub 2]- 0.15LaO[sub 1.5]) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.

  6. Ferrocene-based Lewis acids and Lewis pairs: Synthesis and ...

    Indian Academy of Sciences (India)

    Permanent link: http://www.ias.ac.in/article/fulltext/jcsc/125/01/0041-0049. Keywords. Ferrocene/Lewis acid; optical rotation; frustrated Lewis pairs; organoborane. Abstract. Optically active Lewis acids and Lewis pairs were synthesized and characterized by multinuclear NMR, UV/Vis spectroscopy and elemental analysis.

  7. Ferrocene-based Lewis acids and Lewis pairs: Synthesis and ...

    Indian Academy of Sciences (India)

    The design and synthesis of molecules containing non-interacting Lewis base and Lewis acid groups. [Frustrated Lewis pairs (FLP's)] have received intense attention due to their potential applications in the area of molecular catalysis.1–3. For example,. Stephen's and co-workers have demonstrated that the unquenched ...

  8. Strong Lewis acids of air-stable metallocene bis(perfluorooctanesulfonate)s as high-efficiency catalysts for carbonyl-group transformation reactions.

    Science.gov (United States)

    Qiu, Renhua; Xu, Xinhua; Peng, Lifeng; Zhao, Yalei; Li, Ningbo; Yin, Shuangfeng

    2012-05-14

    Strong Lewis acids of air-stable metallocene bis(perfluorooctanesulfonate)s [M(Cp)(2)][OSO(2)C(8)F(17)](2)⋅nH(2)O⋅THF (M = Zr (2 a⋅3 H(2)O⋅THF), M = Ti (2 b⋅2 H(2)O⋅THF)) were synthesized by the reaction of [M(Cp)(2)]Cl(2) (M = Zr (1 a), M = Ti (1 b)) with nBuLi and C(8)F(17)SO(3)H (2 equiv) or with C(8)F(17)SO(3)Ag (2 equiv). The hydrate numbers (n) of these complexes were variable, changing from 0 to 4 depending on conditions. In contrast to well-known metallocene triflates, these complexes suffered no change in open air for a year. thermogravimetry-differential scanning calorimetry (TG-DSC) analysis showed that 2 a and 2 b were thermally stable at 300 and 180 °C, respectively. These complexes exhibited unusually high solubility in polar organic solvents. Conductivity measurement showed that the complexes (2 a and 2 b) were ionic dissociation in CH(3)CN solution. X-ray analysis result confirmed 2 a⋅3 H(2)O⋅THF was a cationic organometallic Lewis acid. UV/Vis spectra showed a significant red shift due to the strong complex formation between 10-methylacridone and 2 a. Fluorescence spectra showed that the Lewis acidity of 2 a fell between those of Sc(3+) (λ(em)=474 nm) and Fe(3+) (λ(em)=478 nm). ESR spectra showed the Lewis acidity of 2 a (0.91 eV) was at the same level as that of Sc(3+) (1.00 eV) and Y(3+) (0.85 eV), while the Lewis acidity of 2 b (1.06 eV) was larger than that of Sc(3+) (1.00 eV) and Y(3+) (0.85 eV). They showed high catalytic ability in carbonyl-compound transformation reactions, such as the Mannich reaction, the Mukaiyama aldol reaction, allylation of aldehydes, the Friedel-Crafts acylation of alkyl aromatic ethers, and cyclotrimerization of ketones. Moreover, the complexes possessed good reusability. On account of their excellent catalytic efficiency, stability, and reusability, the complexes will find broad catalytic applications in organic synthesis. Copyright © 2012

  9. Quantification of Lewis acid induced Brønsted acidity of protogenic Lewis bases.

    Science.gov (United States)

    Lathem, A Paige; Heiden, Zachariah M

    2017-05-09

    Proton transfer promoted by the coordination of protogenic Lewis bases to a Lewis acid is a critical step in catalytic transformations. Although the acidification of water upon coordination to a Lewis acid has been known for decades, no attempts have been made to correlate the Brønsted acidity of the coordinated water molecule with Lewis acid strength. To probe this effect, the pK a 's (estimated error of 1.3 pK a units) in acetonitrile of ten protogenic Lewis bases coordinated to seven Lewis acids containing Lewis acidities varying 70 kcal mol -1 , were computed. To quantify Lewis acid strength, the ability to transfer a hydride (hydride donor ability) from the respective main group hydride was used. Coordination of a Lewis acid to water increased the acidity of the bound water molecule between 20 and 50 pK a units. A linear correlation exhibiting a 2.6 pK a unit change of the Lewis acid-water adduct per ten kcal mol -1 change in hydride donor ability of the respective main group hydride was obtained. For the ten protogenic Lewis bases studied, the coordinated protogenic Lewis bases were acidified between 10 and 50 pK a units. On average, a ten kcal mol -1 change in hydride donor ability of the respective main group hydride resulted in about a 2.8 pK a unit change in the Brønsted acidity of the Lewis acid-Lewis base adducts. Since attempts to computationally investigate the pK a of main group dihydrogen complexes were unsuccessful, experimental determination of the first reported pK a of a main group dihydrogen complex is described. The pK a of H 2 -B(C 6 F 5 ) 3 was determined to be 5.8 ± 0.2 in acetonitrile.

  10. Lewis acid-catalyzed depolymerization of soda lignin in supercritical ethanol/water mixtures

    NARCIS (Netherlands)

    Güvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Emiel J M

    2016-01-01

    The depolymerization of lignin model compounds and soda lignin by super Lewis acidic metal triflates has been investigated in a mixture of ethanol and water at 400 °C. The strong Lewis acids convert representative model compounds for the structure-forming linkages in lignin, namely α-O-4, 5-O-4

  11. preparation of bicyclic lactones using lewis acids catalyzed ene

    African Journals Online (AJOL)

    Administrator

    LEWIS ACIDS CATALYZED ENE-REACTION. MAKAMA, B. Y.. Department of Petroleum Chemistry, ... the Lewis acid catalysed carbonyl-ene reaction which has been widely used to access carbocycles. In 1943 ..... Alkylaluminum halide induced cyclization of unsaturated carbonyl compounds. Journal of Organic Chemistry.

  12. Lewis basicity of relevant monoanions in a non-protogenic organic solvent using a zinc(ii) Schiff-base complex as a reference Lewis acid.

    Science.gov (United States)

    Oliveri, Ivan Pietro; Di Bella, Santo

    2017-09-12

    Anions are ubiquitous species playing a primary role in chemistry, whose reactivity is essentially dominated by their Lewis basicity. However, no Lewis basicity data, in terms of Gibbs energy, are reported in the literature. We report here the first Lewis basicity of relevant monoanions through the determination of binding constants for the formation of stable 1 : 1 adducts, using a Zn II Schiff-base complex, 1, as a reference Lewis acid. Binding constants for equilibrium reactions were achieved through a nonlinear regression analysis of the binding isotherms from spectrophotometric titration data. The Lewis acidic complex 1 is a proper reference species because it forms stable adducts with both neutral and charged Lewis bases, thus allowing ranking their Lewis basicity. Binding constants indicate generally a strong Lewis basicity for all involved anions, rivalling or exceeding that of the stronger neutral bases, such as primary amines or pyridine. The cyanide anion results to be the strongest Lewis base, while the nitrate is the weaker base within the present anion series. Moreover, even the weaker base anions behave as stronger bases than the most common non-protogenic coordinating solvents.

  13. Lewis acid-Lewis base catalyzed enantioselective hetero-Diels-Alder reaction for direct access to delta-lactones.

    Science.gov (United States)

    Tiseni, Paolo S; Peters, René

    2008-05-15

    A complex formed in situ from Er(OTf)3 and a simple commercially available norephedrine ligand promotes an unprecedented [4 + 2] cycloaddition of alpha,beta-unsaturated acid chlorides with a broad range of aromatic and heteroaromatic aldehydes by a cooperative bifunctional Lewis acid-Lewis base catalytic mode of action providing valuable delta-lactone building blocks with excellent enantioselectivity.

  14. Specific acid catalysis and Lewis acid catalysis of Diels–Alder reactions in aqueous media

    NARCIS (Netherlands)

    Mubofu, Egid B.; Engberts, Jan B.F.N.

    2004-01-01

    A comparative study of specific acid catalysis and Lewis acid catalysis of Diels–Alder reactions between dienophiles (1, 4 and 6) and cyclopentadiene (2) in water and mixed aqueous media is reported. The reactions were performed in water with copper(II) nitrate as the Lewis acid catalyst whereas

  15. Specific acid catalysis and Lewis acid catalysis of Diels-Alder reactions in aqueous media

    NARCIS (Netherlands)

    Mubofu, E.B.; Engberts, J.B.F.N.

    A comparative study of specific acid catalysis and Lewis acid catalysis of Diells-Alder reactions between dienophiles (1, 4 and 6) and cyclopentadiene (2) in water and mixed aqueous media is reported. The reactions were performed in water with copper(II) nitrate as the Lewis acid catalyst whereas

  16. Lewis acidic metal catalysed organic transformations by designed ...

    Indian Academy of Sciences (India)

    ... Refresher Courses · Symposia · Live Streaming. Home; Journals; Journal of Chemical Sciences; Volume 122; Issue 3. Lewis acidic metal catalysed organic transformations by designed multi-component structures and assemblies. Afsar Ali Amit P Singh Rajeev Gupta. Perspective Articles Volume 122 Issue 3 May 2010 pp ...

  17. Lewis acidic metal catalysed organic transformations by designed ...

    Indian Academy of Sciences (India)

    Administrator

    ing metal–organic frameworks containing Lewis acidic metal ions. The emphasis has been given to un- derstand the ... frameworks (MOFs) and metal–organic coordination networks (MOCNs) offer unique opportunities.5 .... of square-grid complex 1 was postulated to be more cationic than that of Cd(NO3)2⋅4H2O and thus.

  18. Lewis acid enhanced switching of the 1,1-dicyanodihydroazulene/vinylheptafulvene photo/thermoswitch

    DEFF Research Database (Denmark)

    Parker, Christian Richard; Tortzen, Christian Gregers; Broman, Søren Lindbæk

    2011-01-01

    Mild Lewis acids enhance the rate of the thermal conversion of vinylheptafulvene (VHF) to dihydroazulene (DHA). In the absence of light, stronger Lewis acids promote the otherwise photoinduced DHA to VHF conversion....

  19. Synergy, compatibility, and innovation: merging Lewis acids with stereoselective enamine catalysis.

    Science.gov (United States)

    Gualandi, Andrea; Mengozzi, Luca; Wilson, Claire M; Cozzi, Pier Giorgio

    2014-04-01

    In recent years there has been an accelerated rate of development in the field of organocatalysis, with asymmetric organocatalysis now reaching full maturity. The invention of new organocatalytic reactions and the exploration of new concepts now appear in tandem with the application of organocatalytic techniques in the synthesis of natural products and active pharmaceutical ingredients (APIs). After a "golden rush" in organocatalysis, researchers are now starting to combine different methods, thereby taking advantage of the significant benefits of synergy. Metals are used in combination with organocatalytic processes, thus reaching complexity that is found in nature, where enzymes take advantage of the presence of certain metals to increase the arsenal of organic transformations available. In this Focus review, we illustrate the possibility of a "happy marriage" between Lewis acids and organocatalytic stereoselective processes. Questions have been raised about the combination of Lewis acids and organocatalysis owing to the presence of water and/or strong bases in these processes. Some Lewis acids have been shown to be compatible with organocatalysis and concepts relating to their use will be illustrated herein. To summarize the fruitful use of Lewis acids in stereoselective organocatalytic processes, we will draw attention to the advantages and selectivity achieved using this method.

  20. Development of Fluorous Lewis Acid-Catalyzed Reactions

    Directory of Open Access Journals (Sweden)

    Joji Nishikido

    2006-08-01

    Full Text Available Organic synthetic methodology in the 21st century aims to conform to the principles of green sustainable chemistry (GSC and we may expect that in the future, the realization of GSC will be an important objective for chemical industries. An important aim of synthetic organic chemistry is to implement waste-free and environmentally-benign industrial processes using Lewis acids as versatile as aluminum choride. A key technological objective of our work in this area has been to achieve a “catalyst recycling system that utilizes the high activity and structural features of fluorous Lewis acid catalysts”. Thus, we have developed a series of novel fluorous Lewis acid catalysts, namely the ytterbium(III, scandium(III, tin(IV or hafnium(IV bis(perfluoroalkanesulfonylamides or tris(perfluoro- alkanesulfonylmethides. Our catalysts are recyclable and effective for acylations of alcohols and aromatics, Baeyer-Villiger reactions, direct esterifications and transesterifications in a fluorous biphasic system (FBS, in supercritical carbon dioxide and on fluorous silica gel supports.

  1. Building new discrete supramolecular assemblies through the interaction of iso-tellurazole N-oxides with Lewis acids and bases.

    Science.gov (United States)

    Ho, Peter C; Jenkins, Hilary A; Britten, James F; Vargas-Baca, Ignacio

    2017-10-13

    The supramolecular macrocycles spontaneously assembled by iso-tellurazole N-oxides are stable towards Lewis bases as strong as N-heterocyclic carbenes (NHC) but readily react with Lewis acids such as BR 3 (R = Ph, F). The electron acceptor ability of the tellurium atom is greatly enhanced in the resulting O-bonded adducts, which consequently enables binding to a variety of Lewis bases that includes acetonitrile, 4-dimethylaminopyridine, 4,4'-bipyridine, triphenyl phosphine, a N-heterocyclic carbene and a second molecule of iso-tellurazole N-oxide.

  2. Lewis base activation of Lewis acids: catalytic, enantioselective vinylogous aldol addition reactions.

    Science.gov (United States)

    Denmark, Scott E; Heemstra, John R

    2007-07-20

    The generality of Lewis base catalyzed, Lewis acid mediated, enantioselective vinylogous aldol addition reactions has been investigated. The combination of silicon tetrachloride and chiral phosphoramides is a competent catalyst for highly selective additions of a variety of alpha,beta-unsaturated ketone-, 1,3-diketone-, and alpha,beta-unsaturated amide-derived dienolates to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded high enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although alpha,beta-unsaturated ketone-derived dienolate did not react with aliphatic aldehydes, alpha,beta-unsaturated amide-derived dienolates underwent addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivities achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride-chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.

  3. Lewis base mediated β-elimination and Lewis acid mediated insertion reactions of disilazido zirconium compounds.

    Science.gov (United States)

    Yan, KaKing; Duchimaza Heredia, Juan J; Ellern, Arkady; Gordon, Mark S; Sadow, Aaron D

    2013-10-09

    The reactivity of a series of disilazido zirconocene complexes is dominated by the migration of anionic groups (hydrogen, alkyl, halide, OTf) between the zirconium and silicon centers. The direction of these migrations is controlled by the addition of two-electron donors (Lewis bases) or two-electron acceptors (Lewis acids). The cationic nonclassical [Cp2ZrN(SiHMe2)2](+) ([2](+)) is prepared from Cp2Zr{N(SiHMe2)2}H (1) and B(C6F5)3 or [Ph3C][B(C6F5)4], while reactions of B(C6F5)3 and Cp2Zr{N(SiHMe2)2}R (R = Me (3), Et (5), n-C3H7 (7), CH═CHSiMe3 (9)) provide a mixture of [2](+) and [Cp2ZrN(SiHMe2)(SiRMe2)](+). The latter products are formed through B(C6F5)3 abstraction of a β-H and R group migration from Zr to the β-Si center. Related β-hydrogen abstraction and X group migration reactions are observed for Cp2Zr{N(SiHMe2)2}X (X = OTf (11), Cl (13), OMe (15), O-i-C3H7 (16)). Alternatively, addition of DMAP (DMAP = 4-(dimethylamino)pyridine) to [2](+) results in coordination to a Si center and hydrogen migration to zirconium, giving the cationic complex [Cp2Zr{N(SiHMe2)(SiMe2DMAP)}H](+) ([19](+)). Related hydrogen migration occurs from [Cp2ZrN(SiHMe2)(SiMe2OCHMe2)](+) ([18](+)) to give [Cp2Zr{N(SiMe2DMAP)(SiMe2OCHMe2)}H](+) ([22](+)), whereas X group migration is observed upon addition of DMAP to [Cp2ZrN(SiHMe2)(SiMe2X)](+) (X = OTf ([12](+)), Cl ([14](+))) to give [Cp2Zr{N(SiHMe2)(SiMe2DMAP)}X](+) (X = OTf ([26](+)), Cl ([20](+))). The species involved in these transformations are described by resonance structures that suggest β-elimination. Notably, such pathways are previously unknown in early metal amide chemistry. Finally, these migrations facilitate direct Si-H addition to carbonyls, which is proposed to occur through a pathway that previously had been reserved for later transition metal compounds.

  4. Catalytic Conversion of Glucose into 5-Hydroxymethylfurfural by Hf(OTf4 Lewis Acid in Water

    Directory of Open Access Journals (Sweden)

    Junjie Li

    2015-12-01

    Full Text Available A series of Lewis acidic metal salts were used for glucose dehydration to 5-hydroymethylfurfural (HMF in water. Effect of valence state, ionic radii of Lewis acidic cation, and the type of anions on the catalytic performance have been studied systematically. The experimental results showed that the valence state played an important role in determining catalytic activity and selectivity. It was found that a higher glucose conversion rate and HMF selectivity could be obtained over high valent Lewis acid salts, where the ionic radii of these Lewis acidic metal salts are usually relatively small. Analysis on the effect of the anions of Lewis acid salts on the catalytic activity and the selectivity suggested that a higher glucose conversion and HMF selectivity could be readily obtained with Cl−. Furthermore, the recyclability of high valence state Lewis acid salt was also studied, however, inferior catalytic performance was observed. The deactivation mechanism was speculated to be the fact that high valence state Lewis acid salt was comparatively easier to undergo hydrolysis to yield complicated metal aqua ions with less catalytic activity. The Lewis acidic activity could be recovered by introducing a stoichiometric amount of hydrochloric acid (HCl to the catalytic before the reaction.

  5. Understanding the Lewis Acidity of Co(II) Sites on a Silica Surface.

    Science.gov (United States)

    Estes, Deven P; Cook, Amanda K; Lam, Erwin; Wong, Louise; Copéret, Christophe

    2017-07-17

    Heterogeneous catalysts consisting of isolated transition-metal sites dispersed on the surface of metal oxide supports are commonly used in the chemical industry. Often their reactivity relies on the Lewis acidity of the active sites on the surface of the catalyst. A recent report from our group showed that silica-supported Co(II) sites, prepared via surface organometallic chemistry, are active in both alkene hydrogenation and alkane dehydrogenation, possibly linked to the Lewis acidity of the Co(II) sites. Here we use molecular probes and analogues to both qualitatively and quantitatively model the Lewis acidity of the surface sites. Some sites do not bind probe molecules like carbon monoxide, tetrahydrofuran, and olefins, while others exhibit a continuum of Lewis acidities. This is consistent with variations in the coordination environment of Co. These results suggest that only the most Lewis acidic sites are involved in dehydrogenation and hydrogenation, consistent with catalyst poisoning studies.

  6. Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

    Directory of Open Access Journals (Sweden)

    Tareq Irshaidat

    2014-01-01

    Full Text Available On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293 illustrated that beryllium ions are capable of significantly modulating (changing the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+, AlF2+, and Al3+ were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H, and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577 and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

  7. Lewis pair polymerization by classical and frustrated Lewis pairs: Acid, base and monomer scope and polymerization mechanism

    KAUST Repository

    Zhang, Yuetao

    2012-01-01

    Classical and frustrated Lewis pairs (LPs) of the strong Lewis acid (LA) Al(C 6F 5) 3 with several Lewis base (LB) classes have been found to exhibit exceptional activity in the Lewis pair polymerization (LPP) of conjugated polar alkenes such as methyl methacrylate (MMA) as well as renewable α-methylene-γ-butyrolactone (MBL) and γ-methyl- α-methylene-γ-butyrolactone (γ-MMBL), leading to high molecular weight polymers, often with narrow molecular weight distributions. This study has investigated a large number of LPs, consisting of 11 LAs as well as 10 achiral and 4 chiral LBs, for LPP of 12 monomers of several different types. Although some more common LAs can also be utilized for LPP, Al(C 6F 5) 3-based LPs are far more active and effective than other LA-based LPs. On the other hand, several classes of LBs, when paired with Al(C 6F 5) 3, can render highly active and effective LPP of MMA and γ-MMBL; such LBs include phosphines (e.g., P tBu 3), chiral chelating diphosphines, N-heterocyclic carbenes (NHCs), and phosphazene superbases (e.g., P 4- tBu). The P 4- tBu/Al(C 6F 5) 3 pair exhibits the highest activity of the LP series, with a remarkably high turn-over frequency of 9.6 × 10 4 h -1 (0.125 mol% catalyst, 100% MMA conversion in 30 s, M n = 2.12 × 10 5 g mol -1, PDI = 1.34). The polymers produced by LPs at RT are typically atactic (P γMMBL with ∼47% mr) or syndio-rich (PMMA with ∼70-75% rr), but highly syndiotactic PMMA with rr ∼91% can be produced by chiral or achiral LPs at -78 °C. Mechanistic studies have identified and structurally characterized zwitterionic phosphonium and imidazolium enolaluminates as the active species of the current LPP system, which are formed by the reaction of the monomer·Al(C 6F 5) 3 adduct with P tBu 3 and NHC bases, respectively. Kinetic studies have revealed that the MMA polymerization by the tBu 3P/ Al(C 6F 5) 3 pair is zero-order in monomer concentration after an initial induction period, and the polymerization

  8. From Conventional Lewis Acids to Heterogeneous Montmorillonite K10: Eco-Friendly Plant-Based Catalysts Used as Green Lewis Acids.

    Science.gov (United States)

    Hechelski, Marie; Ghinet, Alina; Louvel, Brice; Dufrénoy, Pierrick; Rigo, Benoît; Daïch, Adam; Waterlot, Christophe

    2018-04-25

    The concept of green chemistry began in the USA in the 1990s. Since the publication of the 12 principles of this concept, many reactions in organic chemistry have been developed, and chemical products have been synthesized under environmentally friendly conditions. Lewis acid mediated synthetic transformations are by far the most numerous and best studied. However, the use of certain Lewis acids may cause risks to environmental and human health. This Review discusses the evolution of Lewis acid catalyzed reactions from a homogeneous liquid phase to the solid phase to yield the expected organic molecules under green, safe conditions. In particular, recent developments and applications of biosourced catalysts from plants are highlighted. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. NH3 adsorption on the Lewis and Bronsted acid sites of MoO3 (0 1 0) surface: A cluster DFT study

    Science.gov (United States)

    Yan, Zhifeng; Fan, Junyan; Zuo, Zhijun; Li, Zhe; Zhang, Jinshan

    2014-01-01

    The adsorption of NH3 on the Lewis and Bronsted acid sites of MoO3 (0 1 0) surface has been investigated based on the density functional theory (DFT) method using the clusters models. The calculated results indicate that NH3 could strongly adsorb on both the Lewis and Bronsted acid sites in the form of NH3 species and NH4+ respectively, whereas the adsorption on the Lewis acid site is found to be more favorable energetically than that on the Bronsted acid site. For the Lewis acid site Mulliken population analysis shows a donation of lone pairs from NH3 to the surface and activation of N-H bond. The overlaps of N-s, N-p and Mo-d orbitals suggest the strong interaction between N and Mo atoms. For the Bronsted acid site N-H bond is also activated by the formation of NH4+ species. The hybridizations between H and O atoms as well as N and H atoms are the major reasons for strong chemical adsorption of NH3 and the existence of NH4+ species, which partly attributed to the presence of N-H… O hydrogen bonds. Furthermore, the formation of a second Lewis acid site at adjacent or diagonal site results in slight changes of adsorption stability, structural changes and charge redistributions, suggesting its small influence on NH3 adsorption.

  10. Organo-Lewis acid as cocatalyst for cationic homogenous metallocene Ziegler-Natta olefin polymerizations

    Energy Technology Data Exchange (ETDEWEB)

    Marks, Tobin J. (Evanston, IL); Chen, You-Xian (Chicago, IL)

    2000-01-01

    The synthesis of the organo-Lewis acid perfluorobiphenylborane (PBB) and the activation of metallocenes for the formation of a variety of highly active homogeneous Ziegler-Natta metallocene olefin polymerization, copolymerization and ring-opening polymerization catalysts is described.

  11. Stereodivergent Mannich reaction of bis(trimethylsilyl)ketene acetals with N-tert-butanesulfinyl imines by Lewis acid or Lewis base activation, a one-pot protocol to obtain chiral β-amino acids.

    Science.gov (United States)

    Cantú-Reyes, Margarita; Alvarado-Beltrán, Isabel; Ballinas-Indilí, Ricardo; Álvarez-Toledano, Cecilio; Hernández-Rodríguez, Marcos

    2017-09-20

    We report a one-pot synthesis of chiral β 2,2,3 -amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure β-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

  12. Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts.

    Science.gov (United States)

    Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G

    2015-06-22

    The catalytic performance of homogeneous Lewis acid catalysts and their interaction with Ru/C catalyst are studied in the catalytic transfer hydrogenation of furfural by using 2-propanol as a solvent and hydrogen donor. We find that Lewis acid catalysts hydrogenate the furfural to furfuryl alcohol, which is then etherified with 2-propanol. The catalytic activity is correlated with an empirical scale of Lewis acid strength and exhibits a volcano behavior. Lanthanides are the most active, with DyCl3 giving complete furfural conversion and a 97 % yield of furfuryl alcohol at 180 °C after 3 h. The combination of Lewis acid and Ru/C catalysts results in synergy for the stronger Lewis acid catalysts, with a significant increase in the furfural conversion and methyl furan yield. Optimum results are obtained by using Ru/C combined with VCl3 , AlCl3 , SnCl4 , YbCl3 , and RuCl3 . Our results indicate that the combination of Lewis acid/metal catalysts is a general strategy for performing tandem reactions in the upgrade of furans. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Polysiloxane/Polystyrene Thermo-Responsive and Self-Healing Polymer Network via Lewis Acid-Lewis Base Pair Formation

    Directory of Open Access Journals (Sweden)

    Fernando Vidal

    2018-02-01

    Full Text Available The use of thermo-reversible Lewis Pair (LP interactions in the formation of transient polymer networks is still greatly underexplored. In this work, we describe the synthesis and characterization of polydimethylsiloxane/polystyrene (PDMS/PS blends that form dynamic Lewis acid-Lewis base adducts resulting in reversible crosslinks. Linear PS containing 10 mol % of di-2-thienylboryl pendant groups randomly distributed was obtained in a two-step one-pot functionalization reaction from silyl-functionalized PS, while ditelechelic PDMS with pyridyl groups at the chain-termini was directly obtained via thiol-ene “click” chemistry from commercially available vinyl-terminated PDMS. The resulting soft gels, formed after mixing solutions containing the PDMS and PS polymers, behave at room temperature as elastomeric solid-like materials with very high viscosity (47,300 Pa·s. We applied rheological measurements to study the thermal and time dependence of the viscoelastic moduli, and also assessed the reprocessability and self-healing behavior of the dry gel.

  14. Acid-Base Pairs in Lewis Acidic Zeolites Promote Direct Aldol Reactions by Soft Enolization.

    Science.gov (United States)

    Lewis, Jennifer D; Van de Vyver, Stijn; Román-Leshkov, Yuriy

    2015-08-17

    Hf-, Sn-, and Zr-Beta zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A study of the Lewis acid-base interactions of vinylphosphonic acid-modified polybutadiene-coated zirconia.

    Science.gov (United States)

    Trammell, B C; Hillmyer, M A; Carr, P W

    2001-07-15

    Polybutadiene-coated zirconia (PBD-ZrO2) is very useful for reversed-phase separations under a wide variety of conditions. Its excellent chemical (pH = 1-13) and thermal (up to 150 degrees C) stability distinguish it from silica-based reversed phases. Just as with silica-based phases, zirconia's surface chemistry significantly influences the chromatography of certain classes of analytes. Zirconia's hard Lewis acid sites can be chromatographically problematic. Analytes such as carboxylic acids strongly interact with these sites on PBD-ZrO2 and do not elute. Addition of phosphate or other strong, hard Lewis bases to the eluent brings about elution, but the resulting peak is often tailed and broad. Typically, cationic solutes are more retained in the presence of phosphate or fluoride due to adsorption of the Lewis base additives and the concomitant development of a negative charge on the surface. This Coulombic interaction can be used to optimize selectivity, but the reversed-phase-cation-exchange retention can produce broad peaks with excessive retention. As an alternative to adding Lewis bases to the eluent, we studied the effect of permanently modifying PBD-ZrO2 by covalently attaching vinylphosphonic acid (VPA) to PBD which was predeposited in the pores of zirconia. We have investigated the chromatography of acids, bases, and small peptides on VPA-modified PBD-ZrO2 (VPA-PBD-ZrO2) and compared it to PBD-ZrO2. VPA-PBD-ZrO2 is a reversed-cation-exchange phase with properties quite different from PBD-ZrO2. The chemical stability of both phases led us to explore how low-pH (1.5-3), ultralow-pH (0), and high-pH (12) eluents effect the retention properties of these mixed-mode phases. Ultralow-pH eluents effectively separate small peptides on both phases. This approach gives lower retention, without sacrificing resolution, and much higher efficiency for small peptides than previously reported.

  16. Lewis base activation of Lewis acids: catalytic, enantioselective addition of glycolate-derived silyl ketene acetals to aldehydes.

    Science.gov (United States)

    Denmark, Scott E; Chung, Won-Jin

    2008-06-20

    A catalytic system involving silicon tetrachloride and a chiral, Lewis basic bisphosphoramide catalyst is effective for the addition of glycolate-derived silyl ketene acetals to aldehydes. It was found that the sense of diastereoselectivity could be modulated by changing the size of the substituents on the silyl ketene acetals. In general, the trimethylsilyl ketene acetals derived from methyl glycolates with a large protecting group on the alpha-oxygen provide enantiomerically enriched alpha,beta-dihydroxy esters with high syn-diastereoselectivity, whereas the tert-butyldimethylsilyl ketene acetals derived from bulky esters of alpha-methoxyacetic acid provide enantiomerically enriched alpha,beta-dihydroxy esters with high anti-diastereoselecitvity.

  17. Application of strong phosphoric acid to radiochemistry

    International Nuclear Information System (INIS)

    Terada, Kikuo

    1977-01-01

    Not only inorganic and organic compounds but also natural substrances, such as accumulations in soil, are completely decomposed and distilled by heating with strong phosphoric acid for 30 to 50 minutes. As applications of strong phosphoric acid to radiochemistry, determination of uranium and boron by use of solubilization effect of this substance, titration of uranyl ion by use of sulfuric iron (II) contained in this substance, application to tracer experiment, and determination of radioactive ruthenium in environmental samples are reviewed. Strong phosphoric acid is also applied to activation analysis, for example, determination of N in pyrographite with iodate potassium-strong phosphoric acid method, separation of Os and Ru with sulfuric cerium (IV) - strong phosphoric acid method or potassium dechromate-strong phosphoric acid method, analysis of Se, As and Sb rocks and accumulations with ammonium bromide, sodium chloride and sodium bromide-strong phosphoric acid method. (Kanao, N.)

  18. Synthesis of hydroxymethylfurfural from sucrose using brönsted-lewis acidic ionic liquid

    Directory of Open Access Journals (Sweden)

    L. Yao

    2016-08-01

    Full Text Available The synthesis of 5-hydroxymethylfurfural (HMF from sucrose was investigated in the presence of the Brönsted-Lewis acidic ionic liquids (ILs. It was concluded that IL 1-(3-sulfonic acid-propyl-3-methylimidazole chlorochrominate [HO3S-(CH23-mim]Cl-CrCl3 (molar fraction of CrCl3x = 0.55 had a good catalytic performance with 78.8% yield of HMF. The acid type of IL played a significant role in the reaction. Lewis acid site acted more effectively than its Brönsted counterpart and a synergetic effect of Brönsted and Lewis acid sites enhanced the IL catalytic performance. The reusability of IL was good.

  19. Lanthanide triflates. Effecient lewis acid catalysts in aqueous solution; Rantanoido torifurato. Suiyoekichu de kinosuru ruisu san shokubai

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, S. [Science Univ. of Tokyo (Japan). Faculty of Science

    1996-02-01

    It is a common sense in chemistry that Lewis acid is hydrolyzed quickly in water, while a new Lewis acid is discovered by which said common sense is overthrown. This new Lewis acid is lanthanide triflate (lanthanide trifluoromethanesulfonate). Such new lanthanide catalysts which have many characteristics different from the conventional Lewis acid, are paid attention as clean catalysts of next generation gentle to environment. In this paper, the details of discovery of lanthanide triflates by the present authors are introduced, and the fact that this triflates is not hydrolyzed in water though they have the same Lewis acidic properties as other Lewis acid is clarified. Further, as the examples of the synthesis reactions using lanthanide triflates as catalysts, hydroxymethylate reaction using aqueous solution of formaldehyde, Mannich reaction proceeding in aqueous solution, Friedel-Crafts reaction in organic solution and Fries rearrangement are described. 13 refs., 2 figs., 1 tab.

  20. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

    Science.gov (United States)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

    2018-01-10

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-11-14

    Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

  2. Lewis-acid catalyzed depolymerization of Protobind lignin in supercritical water and ethanol

    NARCIS (Netherlands)

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Ernie J. M.

    2016-01-01

    The use of metal acetates, metal chlorides and metal triflates as Lewis acid catalysts for the depolymerization of soda lignin under supercritical conditions was investigated. The reactions were carried out at 400 degrees C in water and ethanol. Lignin conversion in supercritical water led to

  3. Organo-Lewis acid as cocatalyst for cationic homogeneous metallocene Ziegler-Natta olefin polymerizations

    Energy Technology Data Exchange (ETDEWEB)

    Marks, T.J.; Chen, Y.X.

    2000-07-11

    The synthesis of the organo-Lewis acid perfluorobiphenylborane (PBB) and the activation of metallocenes are disclosed for the formation of a variety of highly active homogeneous Ziegler-Natta metallocene olefin polymerization, copolymerization and ring-opening polymerization catalysts is described.

  4. Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor

    NARCIS (Netherlands)

    Munirathinam, Rajesh; Ricardi, Roberto; Egberink, Richard J.M.; Huskens, Jurriaan; Holtkamp, Michael; Wormeester, Herbert; Karst, U.; Verboom, Willem

    2013-01-01

    Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR,

  5. Lewis-acid catalysis of carbon carbon bond forming reactions in water

    NARCIS (Netherlands)

    Engberts, JBFN; Feringa, BL; Keller, E; Otto, S

    1996-01-01

    In this article, we review the recent progress that has been made in the field of Lewis-acid catalysis of carbon carbon-bond-forming reactions in aqueous solution. Since water hampers the hard hard interactions between the catalyst and the reactant, it often complicates catalysis. However, once

  6. Lewis Acid-Base Properties of a Low Carbon Aluminium Killed Steel ...

    African Journals Online (AJOL)

    An important factor in achieving maximum adhesion of a particular coating system to the substrate lies in the proper preparation of the substrate prior to the application of paint. The Lewis acid-base properties of the outer metal surface play a determinant role in many of these applications, and the chemical reactions involved ...

  7. On the behaviour of biradicaloid [P(μ-NTer)]2 towards Lewis acids and bases.

    Science.gov (United States)

    Hinz, Alexander; Schulz, Axel; Villinger, Alexander

    2016-05-07

    The well-known diphosphadiazane-1,3-diyl [P(μ-NTer)]2 (Ter = 2,6-bis(2,4,6-trimethyl-phenyl)-phenyl) was treated with Lewis bases such as N-heterocyclic carbenes and Lewis acids e.g. gold(i) chloride complexes. In the reaction with the Lewis base, fragmentation of the P2N2 framework was observed, yielding a salt of the type [(NHC)2P](+)[(TerN)2P](-) in a clean reaction. The reaction of [P(μ-NTer)]2 with gold(i) chloride afforded 1 : 1 and 1 : 2 complexes. The dinuclear complex [(ClAu)2P(μ-NTer)2P] displays a bridging P atom between both gold centers, as has been observed for P based zwitterions.

  8. Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites

    Science.gov (United States)

    Bermejo-Deval, Ricardo; Assary, Rajeev S.; Nikolla, Eranda; Moliner, Manuel; Román-Leshkov, Yuriy; Hwang, Son-Jong; Palsdottir, Arna; Silverman, Dorothy; Lobo, Raul F.; Curtiss, Larry A.; Davis, Mark E.

    2012-01-01

    Isomerization of sugars is used in a variety of industrially relevant processes and in glycolysis. Here, we show that hydrophobic zeolite beta with framework tin or titanium Lewis acid centers isomerizes sugars, e.g., glucose, via reaction pathways that are analogous to those of metalloenzymes. Specifically, experimental and theoretical investigations reveal that glucose partitions into the zeolite in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center, isomerizes into the acyclic form of fructose, and finally ring closes to yield the furanose product. The zeolite catalysts provide processing advantages over metalloenzymes such as an ability to work at higher temperatures and in acidic conditions that allow for the isomerization reaction to be coupled with other important conversions. PMID:22665778

  9. Design of Lewis-acid centres in zeolitic matrices for the conversion of renewables.

    Science.gov (United States)

    Dapsens, Pierre Y; Mondelli, Cecilia; Pérez-Ramírez, Javier

    2015-10-21

    The catalytic conversion of renewable feedstocks into chemicals is pursued as a means to sustainably fulfil future societal needs. Due to the oxygen-rich nature of bio-derived substrates, isomerisation, transfer-hydrogenation and retro-aldol reactions have emerged as relevant transformations to produce commodity chemicals and polymer building blocks. In this context, porous materials containing Lewis-acid metals (e.g., Al, Ga, Sn, Ti, Zr) play an important role. Among these, tin-containing zeolites have demonstrated superior catalytic properties which have mainly been attributed to their hydrophobicity and crystallinity. This review evaluates the versatility and the scalability of bottom-up and top-down approaches to introduce Lewis-acid functionalities in zeolitic matrices. A precise characterisation is shown to be crucial to determine the structure, acidity and environment of the sites introduced. In this regard, we highlight the limitations of conventional techniques and the advantages of analytical and modelling tools recently applied to gain an improved understanding of these solids. Thereafter, property-performance relations and important aspects for the industrial amenability of new synthetic routes are exemplified through case studies. Finally, we put forward the need for gathering deeper knowledge of the site location, surface properties and stability to aid the design of next-generation Lewis-acid catalysts.

  10. New crosslinking agent as a Lewis acid for solid polymer electrolytes

    Science.gov (United States)

    Lee, Jun Young; Ko, Dong-Hyun; Lee, Yong Min; Seol, Wan-Ho; Park, Jung-Ki

    Poly(ethylene glycol) borate acrylate (PEGBA) was synthesized as a new crosslinking agent for solid polymer electrolyte (SPE) based on non-woven matrix. It has not only three crosslinkable acrylate groups for higher crosslinking density, but also Lewis acid center acting as an anion receptor. The ionic conductivity of SPE containing 15 wt.% PEGBA reached 5.5 × 10 -4 S cm -1, because the content of non-volatile plasticizer, poly(ethylene glycol) dimethyl ether (PEGDME), could be increased to 85 wt.% without leakage. In addition, its transference number and electrochemical stability were also enhanced to 0.37 and 5.2 V, respectively, due to the presence of Lewis acid center in PEGBA.

  11. Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor

    Directory of Open Access Journals (Sweden)

    Rajesh Munirathinam

    2013-08-01

    Full Text Available Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and X-ray photoelectron spectroscopy (XPS. XPS revealed the presence of one gallium per 2–3 styrene sulfonate groups of the polymer brushes. The catalytic activity of the Lewis acid-functionalized brushes in a microreactor was demonstrated for the dehydration of oximes, using cinnamaldehyde oxime as a model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3.

  12. Improved DNA Electrophoresis in Conditions Favoring Polyborates and Lewis Acid Complexation

    OpenAIRE

    Singhal, Hari; Ren, Yunzhao R.; Kern, Scott E.

    2010-01-01

    Spatial compression among the longer DNA fragments occurs during DNA electrophoresis in agarose and non-agarose gels when using certain ions in the conductive buffer, impairing the range of fragment sizes resolved well in a single gel. Substitutions using various polyhydroxyl anions supported the underlying phenomenon as the complexation of Lewis acids to DNA. We saw significant improvements using conditions (lithium borate 10 mM cations, pH 6.5) favoring the formation of borate polyanions an...

  13. The μ3 model of acids and bases: extending the Lewis theory to intermetallics.

    Science.gov (United States)

    Stacey, Timothy E; Fredrickson, Daniel C

    2012-04-02

    A central challenge in the design of new metallic materials is the elucidation of the chemical factors underlying the structures of intermetallic compounds. Analogies to molecular bonding phenomena, such as the Zintl concept, have proven very productive in approaching this goal. In this Article, we extend a foundational concept of molecular chemistry to intermetallics: the Lewis theory of acids and bases. The connection is developed through the method of moments, as applied to DFT-calibrated Hückel calculations. We begin by illustrating that the third and fourth moments (μ(3) and μ(4)) of the electronic density of states (DOS) distribution tune the properties of a pseudogap. μ(3) controls the balance of states above and below the DOS minimum, with μ(4) then determining the minimum's depth. In this way, μ(3) predicts an ideal occupancy for the DOS distribution. The μ(3)-ideal electron count is used to forge a link between the reactivity of transition metals toward intermetallic phase formation, and that of Lewis acids and bases toward adduct formation. This is accomplished through a moments-based definition of acidity which classifies systems that are electron-poor relative to the μ(3)-ideal as μ(3)-acidic, and those that are electron-rich as μ(3)-basic. The reaction of μ(3) acids and bases, whether in the formation of a Lewis acid/base adduct or an intermetallic phase, tends to neutralize the μ(3) acidity or basicity of the reactants. This μ(3)-neutralization is traced to the influence of electronegativity differences at heteroatomic contacts on the projected DOS curves of the atoms involved. The role of μ(3)-acid/base interactions in intermetallic phases is demonstrated through the examination of 23 binary phases forming between 3d metals, the stability range of the CsCl type, and structural trends within the Ti-Ni system.

  14. Efficient Lewis Acid Ionic Liquid-Catalyzed Synthesis of the Key Intermediate of Coenzyme Q10 under Microwave Irradiation

    Directory of Open Access Journals (Sweden)

    Thomas Efferth

    2010-12-01

    Full Text Available An efficient synthesis of a valuable intermediate of coenzyme Q10 by microwave-assisted Lewis acidic ionic liquid (IL-catalyzed Friedel-Crafts alkylation is reported. The acidity of six [Etpy]BF4-based ionic liquids was characterized by means of the FT-IR technique using acetonitrile as a molecular probe. The catalytic activities of these ionic liquids were correlated with their Lewis acidity. With increasing Lewis acid strength of the ionic liquids, their catalytic activity in the Friedel-Crafts reaction increased, except for [Etpy]BF4-AlCl3. The effects of the reaction system, the molar fraction of Lewis acid in the Lewis acid ILs and heating techniques were also investigated. Among the six Lewis acid ionic liquids tested [Etpy]BF4-ZnCl2 showed the best catalytic activity, with a yield of 89% after a very short reaction time (150 seconds. This procedure has the advantages of higher efficiency, better reusability of ILs, energy conservation and eco-friendliness. The method has practical value for preparation of CoQ10 on an industrial scale.

  15. Enantioselective Direct Mannich-Type Reactions Catalyzed by Frustrated Lewis Acid/Brønsted Base Complexes.

    Science.gov (United States)

    Shang, Ming; Cao, Min; Wang, Qifan; Wasa, Masayuki

    2017-10-16

    An enantioselective direct Mannich-type reaction catalyzed by a sterically frustrated Lewis acid/Brønsted base complex is disclosed. Cooperative functioning of the chiral Lewis acid and achiral Brønsted base components gives rise to in situ enolate generation from monocarbonyl compounds. Subsequent reaction with hydrogen-bond-activated aldimines delivers β-aminocarbonyl compounds with high enantiomeric purity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Lewis Acid Pairs for the Activation of Biomass-derived Oxygenates in Aqueous Media

    Energy Technology Data Exchange (ETDEWEB)

    Roman, Yuriy [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

    2015-09-14

    The objective of this project is to understand the mechanistic aspects behind the cooperative activation of oxygenates by catalytic pairs in aqueous media. Specifically, we will investigate how the reactivity of a solid Lewis acid can be modulated by pairing the active site with other catalytic sites at the molecular level, with the ultimate goal of enhancing activation of targeted functional groups. Although unusual catalytic properties have been attributed to the cooperative effects promoted by such catalytic pairs, virtually no studies exist detailing the use heterogeneous water-tolerant Lewis pairs. A main goal of this work is to devise rational pathways for the synthesis of porous heterogeneous catalysts featuring isolated Lewis pairs that are active in the transformation of biomass-derived oxygenates in the presence of bulk water. Achieving this technical goal will require closely linking advanced synthesis techniques; detailed kinetic and mechanistic investigations; strict thermodynamic arguments; and comprehensive characterization studies of both materials and reaction intermediates. For the last performance period (2014-2015), two technical aims were pursued: 1) C-C coupling using Lewis acid and base pairs in Lewis acidic zeolites. Tin-, zirconium-, and hafnium containing zeolites (e.g., Sn-, Zr-, and Hf-Beta) are versatile solid Lewis acids that selectively activate carbonyl functional groups. In this aim, we demonstrate that these zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions. 2) One-pot synthesis of MWW zeolite nanosheets for activation of bulky substrates. Through

  17. Insights into the interplay of Lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media.

    Science.gov (United States)

    Choudhary, Vinit; Mushrif, Samir H; Ho, Christopher; Anderko, Andrzej; Nikolakis, Vladimiros; Marinkovic, Nebojsa S; Frenkel, Anatoly I; Sandler, Stanley I; Vlachos, Dionisios G

    2013-03-13

    5-(Hydroxymethyl)furfural (HMF) and levulinic acid production from glucose in a cascade of reactions using a Lewis acid (CrCl3) catalyst together with a Brønsted acid (HCl) catalyst in aqueous media is investigated. It is shown that CrCl3 is an active Lewis acid catalyst in glucose isomerization to fructose, and the combined Lewis and Brønsted acid catalysts perform the isomerization and dehydration/rehydration reactions. A CrCl3 speciation model in conjunction with kinetics results indicates that the hydrolyzed Cr(III) complex [Cr(H2O)5OH](2+) is the most active Cr species in glucose isomerization and probably acts as a Lewis acid-Brønsted base bifunctional site. Extended X-ray absorption fine structure spectroscopy and Car-Parrinello molecular dynamics simulations indicate a strong interaction between the Cr cation and the glucose molecule whereby some water molecules are displaced from the first coordination sphere of Cr by the glucose to enable ring-opening and isomerization of glucose. Additionally, complex interactions between the two catalysts are revealed: Brønsted acidity retards aldose-to-ketose isomerization by decreasing the equilibrium concentration of [Cr(H2O)5OH](2+). In contrast, Lewis acidity increases the overall rate of consumption of fructose and HMF compared to Brønsted acid catalysis by promoting side reactions. Even in the absence of HCl, hydrolysis of Cr(III) decreases the solution pH, and this intrinsic Brønsted acidity drives the dehydration and rehydration reactions. Yields of 46% levulinic acid in a single phase and 59% HMF in a biphasic system have been achieved at moderate temperatures by combining CrCl3 and HCl.

  18. Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions† †Electronic supplementary information (ESI) available: Additional experimental and computational details and crystallographic data in cif format. CCDC 1483464–1483472. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc02558g Click here for additional data file. Click here for additional data file.

    Science.gov (United States)

    Tofan, Daniel

    2016-01-01

    As part of our ongoing studies of water tolerant Lewis acids, we have synthesized and investigated the properties of Sb(C6F5)3(O2C6Cl4), a fluorinated stiborane whose Lewis acidity approaches that of B(C6F5)3. While chloroform solutions of this Lewis acid can be kept open to air or exposed to water for extended periods of time, this new Lewis acid reacts with PtBu3 and paraformaldehyde to form the corresponding formaldehyde adduct tBu3P–CH2–O–Sb(C6F5)3(O2C6Cl4). To test if this reactivity can also be observed with systems that combine the phosphine and the stiborane within the same molecule, we have also prepared o-C6H4(PPh2)(SbAr2(O2C6Cl4)) (Ar = Ph, C6F5). These yellow compounds, which possess an intramolecular P→Sb interaction, are remarkably inert to water but do, nonetheless, react with and accomodate formaldehyde into the P/Sb pocket. In the case of the fluorinated derivative o-C6H4(PPh2)(Sb(C6F5)2(O2C6Cl4)), formaldehyde complexation, which occurs in water/dichloromethane biphasic mixtures, is accompanied by a colourimetric turn-off response thus highlighting the potential that this chemistry holds in the domain of molecular sensing. PMID:28451122

  19. Lewis Acid-Base Chemistry of 7-Azaisoindigo-Based Organic Semiconductors.

    Science.gov (United States)

    Randell, Nicholas M; Fransishyn, Kyle M; Kelly, Timothy L

    2017-07-26

    Low-band-gap organic semiconductors are important in a variety of organic electronics applications, such as organic photovoltaic devices, photodetectors, and field effect transistors. Building on our previous work, which introduced 7-azaisoindigo as an electron-deficient building block for the synthesis of donor-acceptor organic semiconductors, we demonstrate how Lewis acids can be used to further tune the energies of the frontier molecular orbitals. Coordination of a Lewis acid to the pyridinic nitrogen of 7-azaisoindigo greatly diminishes the electron density in the azaisoindigo π-system, resulting in a substantial reduction in the lowest unoccupied molecular orbital (LUMO) energy. This results in a smaller highest occupied molecular orbital-LUMO gap and shifts the lowest-energy electronic transition well into the near-infrared region. Both H + and BF 3 are shown to coordinate to azaisoindigo and affect the energy of the S 0 → S 1 transition. A combination of time-dependent density functional theory and UV/vis and 1 H NMR spectroscopic titrations reveal that when two azaisoindigo groups are present and high concentrations of acid are used, both pyridinic nitrogens bind Lewis acids. Importantly, we demonstrate that this acid-base chemistry can be carried out at the solid-vapor interface by exposing thin films of aza-substituted organic semiconductors to vapor-phase BF 3 ·Et 2 O. This suggests the possibility of using the BF 3 -bound 7-azaisoindigo-based semiconductors as n-type materials in various organic electronic applications.

  20. Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Gregory R.; Bell, Alexis T. (LBNL); (UCB)

    2016-06-17

    Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH4 and increase the selectivity toward C5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becoming insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and

  1. Lewis acid catalysis and Green oxidations: sequential tandem oxidation processes induced by Mn-hyperaccumulating plants.

    Science.gov (United States)

    Escande, Vincent; Renard, Brice-Loïc; Grison, Claude

    2015-04-01

    Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.

  2. Three-Component Asymmetric Mannich Reaction Catalyzed by a Lewis Acid with Rhodium-Centered Chirality.

    Science.gov (United States)

    Feng, Lihe; Dai, Xuemei; Meggers, Eric; Gong, Lei

    2017-05-04

    A highly efficient direct asymmetric three-component Mannich reaction of an N-acylpyrazole, an aldehyde and a primary or secondary amine, was enabled by a rhodium-based Lewis-acid catalyst with metal-centered chirality. Excellent enantioselectivities were achieved for a variety of substrates at a typical catalyst loading of merely 0.5 mol % (23 examples, up to 98 % ee). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Direct Mannich-Type Reactions Promoted by Frustrated Lewis Acid/Brønsted Base Catalysts.

    Science.gov (United States)

    Chan, Jessica Z; Yao, Wenzhi; Hastings, Brian T; Lok, Charles K; Wasa, Masayuki

    2016-10-24

    Direct Mannich-type reactions that afford both α- and β-amino esters by the reaction of a broad range of carbonyl compounds and aldimines are disclosed. The transformation is promoted by a sterically frustrated Lewis acid/Brønsted base pair, which is proposed to operate cooperatively: Within the catalyst complex, an enolate is generated that then reacts with a hydrogen-bond-activated imine. Noncovalent interactions between reactants and the catalyst provide selectivity and new opportunities for future catalyst design. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Bis[N,N'-diisopropylbenzamidinato(-)]silicon(II): Lewis acid/base reactions with triorganylboranes.

    Science.gov (United States)

    Junold, Konstantin; Baus, Johannes A; Burschka, Christian; Fonseca Guerra, Célia; Bickelhaupt, F Matthias; Tacke, Reinhold

    2014-09-22

    Reaction of the donor-stabilized silylene 1 (which is three-coordinate in the solid state and four-coordinate in solution) with BEt3 and BPh3 leads to the formation of the Lewis acid/base complexes 2 and 3, respectively, which are the first five-coordinate silicon compounds with an SiB bond. These compounds were structurally characterized by crystal structure analyses and by multinuclear NMR spectroscopic studies in the solid state and in solution. Additionally, the bonding situation in 2 and 3 was analyzed by quantum chemical studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Biomimetic cyclization of epoxide precursors of indole mono-, sesqui- and diterpene alkaloids by Lewis acids.

    Science.gov (United States)

    Isaka, Tetsuya; Hasegawa, Morifumi; Toshima, Hiroaki

    2011-01-01

    Cyclization of the synthesized epoxide precursors of indole mono-, sesqui- and diterpene alkaloids was performed to elucidate the mechanism for biomimetic cationic cyclization to polycyclic structures. 3-(6,7-Epoxygeranyl)indole (11), 3-(10,11-epoxyfarnesyl)indole (2) and 3-(14,15-epoxygeranylgeranyl)indole (3) were respectively synthesized from geraniol, farnesol and geranylgeraniol in 6 or 7 steps. Four Lewis acids (MeAlCl(2), BF(3)·OEt(2), TiCl(4) and SnCl(4)) were applied for biomimetic cyclization of the synthesized epoxide precursors. The cyclization products (one product from 11, four products from 2, and three products from 3) were isolated after separation by chromatography. Their structures were determined by using NMR (COSY, HSQC, HMBC, NOESY, etc.) and HRMS analyses. The results show that biomimetic cyclization gave new polycyclic compounds similar to natural indole terpene alkaloids. We conclude that the stability of cation intermediates should determine the preference for product formation by biomimetic cyclization when using a Lewis acid.

  6. Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

    Science.gov (United States)

    Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

    2017-08-16

    Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu 2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu 2+ , and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

  7. Self-Assembled Nanocomposite Organic Polymers with Aluminum and Scandium as Heterogeneous Water-Compatible Lewis Acid Catalysts.

    Science.gov (United States)

    Miyamura, Hiroyuki; Sonoyama, Arisa; Hayrapetyan, Davit; Kobayashi, Shū

    2015-09-01

    While water-compatible Lewis acids have great potential as accessible and environmentally benign catalysts for various organic transformations, efficient immobilization of such Lewis acids while keeping high activity and without leaching of metals even under aqueous conditions is a challenging task. Self-assembled nanocomposite catalysts of organic polymers, carbon black, aluminum reductants, and scandium salts as heterogeneous water-compatible Lewis acid catalysts are described. These catalysts could be successfully applied to various C-C bond-forming reactions without leaching of metals. Scanning transmission electron microscopy analyses revealed that the nanocomposite structure of Al and Sc was fabricated in these heterogeneous catalysts. It is noted that Al species, which are usually decomposed rapidly in the presence of water, are stabilized under aqueous conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Controlled synthesis of multi-morphology Te crystals by a convenient Lewis acid/base-assisted solvothermal method

    Science.gov (United States)

    Wu, XiaoPing; Yuan, Lin; Zhou, ShaoMin; Lou, ShiYun; Wang, YongQiang; Gao, Tao; Liu, YuBiao; Shi, XiaoJing

    2012-08-01

    This paper reports on the controlled growth of multi-morphology Te crystals by a convenient Lewis acid/base-assisted solvothermal method for the first time. The morphological transformation from one-dimension (1D) nanostructures to 2D hierarchical flowerlike microarchitecture has been observed. The nanorods and nanowires with a well-defined crystallographical structure and the hierarchical flowers microarchitecture were obtained by changing the Lewis acids/bases. Lewis acids/bases were found to be crucial for the formation of the products by not only acting as the pH regulator but also as the shape controller, owing to their hydrolysis in the solvent to in situ form H+/OH- and hydrates. The results suggest that this should be an effective approach to the control the growth of t-Te crystals with interesting multiple morphologies, which are of interest for both theoretical investigations and practical applications.

  9. Controlled synthesis of multi-morphology Te crystals by a convenient Lewis acid/base-assisted solvothermal method

    International Nuclear Information System (INIS)

    Wu Xiaoping; Yuan Lin; Zhou Shaomin; Lou Shiyun; Wang Yongqiang; Gao Tao; Liu YuBiao; Shi Xiaojing

    2012-01-01

    This paper reports on the controlled growth of multi-morphology Te crystals by a convenient Lewis acid/base-assisted solvothermal method for the first time. The morphological transformation from one-dimension (1D) nanostructures to 2D hierarchical flowerlike microarchitecture has been observed. The nanorods and nanowires with a well-defined crystallographical structure and the hierarchical flowers microarchitecture were obtained by changing the Lewis acids/bases. Lewis acids/bases were found to be crucial for the formation of the products by not only acting as the pH regulator but also as the shape controller, owing to their hydrolysis in the solvent to in situ form H + /OH − and hydrates. The results suggest that this should be an effective approach to the control the growth of t-Te crystals with interesting multiple morphologies, which are of interest for both theoretical investigations and practical applications.

  10. Frustrated Lewis pairs: Design and reactivity

    Indian Academy of Sciences (India)

    Abstract. The interaction of a Lewis acid with a Lewis base results in the formation of a Lewis acid–base adduct. Understanding Lewis acids and bases is central to conceptualizing chemical interactions and constitutes a major portion of metal–ligand chemistry. Sterically encumbered/constrained Lewis pairs cannot form ...

  11. The generalized lewis acid-base titration of palladium and niobium

    Science.gov (United States)

    Cima, M.; Brewer, L.

    1988-12-01

    The high thermodynamic stability of alloys composed of platinum group metals and group IVB and VB metals has been explained by an electronic interaction analogous to the Lewis acid-base concept for nontransition elements. The analogy is further demonstrated by the titration of palladium by addition of niobium. The activity of niobium in solid palladium was measured as a function of concentration by solid-state galvanic cells and study of the ternary oxide phase diagram. The galvanic cells were of the type Pt/NbO2,Nb2O4.8/YDTJNbOy,Nbpd/Pt where the solid electrolyte is yttria-doped thoria (YDT). Ternary phase diagrams for the Pd-Nb-0 and Rh-Nb-0 systems were obtained by characterizing samples equilibrated at 1000 °C. The phase relationships found in the ternary diagrams were also used to derive thermochemical data for the alloys. Thermochemical quantities for other acid-base stabilized alloys such as Nb-Rh, Ti-Pd, and Ti-Rh were also measured. The excess partial molar ΔGxs/R of niobium at infinite dilution was determined to be -31 kilo-Kelvin at 1000 °C, and the AG°JR of formation of a mole of NbPd3.55 is —21 kilo-Kelvin. These results and those for the other systems are used to assess the importance of valence electron configuration, nuclear charge, and crystal field effects in the context of generalized Lewis acid-base theory. It is concluded that both the nuclear charge of the atom and crystal field splitting of the valence orbitals significantly affect the basicity of the platinum group metals.

  12. Improved DNA electrophoresis in conditions favoring polyborates and lewis acid complexation.

    Directory of Open Access Journals (Sweden)

    Hari Singhal

    2010-06-01

    Full Text Available Spatial compression among the longer DNA fragments occurs during DNA electrophoresis in agarose and non-agarose gels when using certain ions in the conductive buffer, impairing the range of fragment sizes resolved well in a single gel. Substitutions using various polyhydroxyl anions supported the underlying phenomenon as the complexation of Lewis acids to DNA. We saw significant improvements using conditions (lithium borate 10 mM cations, pH 6.5 favoring the formation of borate polyanions and having lower conductance and Joule heating, delayed electrolyte exhaustion, faster electrophoretic run-speed, and sharper separation of DNA bands from 100 bp to 12 kb in a single run.

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

    Science.gov (United States)

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

    2012-08-23

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

  14. Brush Polymer of Donor-Accepter Dyads via Adduct Formation between Lewis Base Polymer Donor and All Carbon Lewis Acid Acceptor

    Directory of Open Access Journals (Sweden)

    Yang Wang

    2017-09-01

    Full Text Available A synthetic method that taps into the facile Lewis base (LB→Lewis acid (LA adduct forming reaction between the semiconducting polymeric LB and all carbon LA C60 for the construction of covalently linked donor-acceptor dyads and brush polymer of dyads is reported. The polymeric LB is built on poly(3-hexylthiophene (P3HT macromers containing either an alkyl or vinyl imidazolium end group that can be readily converted into the N-heterocyclic carbene (NHC LB site, while the brush polymer architecture is conveniently constructed via radical polymerization of the macromer P3HT with the vinyl imidazolium chain end. Simply mixing of such donor polymeric LB with C60 rapidly creates linked P3HT-C60 dyads and brush polymer of dyads in which C60 is covalently linked to the NHC junction connecting the vinyl polymer main chain and the brush P3HT side chains. Thermal behaviors, electronic absorption and emission properties of the resulting P3HT-C60 dyads and brush polymer of dyads have been investigated. The results show that a change of the topology of the P3HT-C60 dyad from linear to brush architecture enhances the crystallinity and Tm of the P3HT domain and, along with other findings, they indicate that the brush polymer architecture of donor-acceptor domains provides a promising approach to improve performances of polymer-based solar cells.

  15. Lactic acid polymers: strong, degradable thermoplastics

    Energy Technology Data Exchange (ETDEWEB)

    Wehrenberg, R.H.

    1981-01-01

    Copolymers of lactic and glycolic acids are being developed by researchers at Battelle and elsewhere as renewable-resource plastics. Other uses include matrices for controlled release of drugs and pesticides as well as in prosthetic devices. In contrast to conventional plastics, lactic acid polymers are biodegradable, and after several months exposure to moisture, these materials convert back to natural harmless products. The properties of lactic acid polymers are examined.

  16. Effect of metal ions on the reactions of the cumyloxyl radical with hydrogen atom donors. Fine control on hydrogen abstraction reactivity determined by Lewis acid-base interactions.

    Science.gov (United States)

    Salamone, Michela; Mangiacapra, Livia; DiLabio, Gino A; Bietti, Massimo

    2013-01-09

    A time-resolved kinetic study on the effect of metal ions (M(n+)) on hydrogen abstraction reactions from C-H donor substrates by the cumyloxyl radical (CumO(•)) was carried out in acetonitrile. Metal salt addition was observed to increase the CumO(•) β-scission rate constant in the order Li(+) > Mg(2+) > Na(+). These effects were explained in terms of the stabilization of the β-scission transition state determined by Lewis acid-base interactions between M(n+) and the radical. When hydrogen abstraction from 1,4-cyclohexadiene was studied in the presence of LiClO(4) and Mg(ClO(4))(2), a slight increase in rate constant (k(H)) was observed indicating that interaction between M(n+) and CumO(•) can also influence, although to a limited extent, the hydrogen abstraction reactivity of alkoxyl radicals. With Lewis basic C-H donors such as THF and tertiary amines, a decrease in k(H) with increasing Lewis acidity of M(n+) was observed (k(H)(MeCN) > k(H)(Li(+)) > k(H)(Mg(2+))). This behavior was explained in terms of the stronger Lewis acid-base interaction of M(n+) with the substrate as compared to the radical. This interaction reduces the degree of overlap between the α-C-H σ* orbital and a heteroatom lone-pair, increasing the C-H BDE and destabilizing the carbon centered radical formed after abstraction. With tertiary amines, a >2-order of magnitude decrease in k(H) was measured after Mg(ClO(4))(2) addition up to a 1.5:1 amine/Mg(ClO(4))(2) ratio. At higher amine concentrations, very similar k(H) values were measured with and without Mg(ClO(4))(2). These results clearly show that with strong Lewis basic substrates variations in the nature and concentration of M(n+) can dramatically influence k(H), allowing for a fine control of the substrate hydrogen atom donor ability, thus providing a convenient method for C-H deactivation. The implications and generality of these findings are discussed.

  17. The generalized Lewis acid-base titration of palladium and niobium

    International Nuclear Information System (INIS)

    Cima, M.; Brewer, L.; California Univ., Berkeley, CA

    1988-01-01

    The high thermodynamic stability of alloys composed of platinum group metals and group IVB and VB metals has been explained by an electronic interaction analogous to the Lewis acid-base concept for nontransition elements. The analogy is further demonstrated by the titration of palladium by addition of niobium. The activity of niobium in solid palladium was measured as a function of concentration by solid-state galvanic cells and study of the ternary oxide phase diagram. The galvanic cells were of the Pt/NbO 2 , Nb 2 O 4.8 /YDT/NbO y , Nb (Pd) /Pt where the solid electrolyte is yttria-doped thoria (YDT). Ternary phase diagrams for the Pd-Nb-O and Rh-Nb-O systems were obtained by characterizing samples equilibrated at 1000 0 C. The phase relationships found in the ternary diagrams were also used to derive thermochemical data for the alloys. Thermochemical quantities for other acid-base stabilized alloys such as Nb-Rh, Ti-Pd, and Ti-Rh were also measured

  18. Frustrated Lewis Pairs

    Indian Academy of Sciences (India)

    IAS Admin

    The fundamental concept of Lewis acid–base interactions have played a substantial role in the progress of chemistry and enriched its understanding, most significantly in the evolution of coordination compounds. In the last 7 years, the chemistry of Lewis Pairs (i.e., acids and bases) has witnessed a different.

  19. Zr-SBA-15 Lewis Acid Catalyst: Activity in Meerwein Ponndorf Verley Reduction

    Directory of Open Access Journals (Sweden)

    Jose Iglesias

    2015-11-01

    Full Text Available Zr-SBA-15 Lewis acid catalyst has demonstrated an outstanding catalytic activity in the reduction of several carbonyl compounds by means of Meerwein Ponndorf Verley (MPV reaction, using several secondary alcohols, and showing a very high selectivity towards the desired products. Special focus was addressed in the catalytic activity of Zr-SBA-15 material in the production of furfuryl alcohol from furfural, which is an important reaction for the lignocellulosic biomass valorization. In this transformation, both the reaction temperature and the i-PrOH:Furfural molar ratio exert a positive influence on the rate of the MPV transformation, with the influence of the former being much higher. i-propyl-furfuryl ether, a by-product resulting from the etherification of the target product with the sacrificing alcohol, is also found together with the main product. The production of this side-product is highly influenced by the reaction temperature, so that low temperatures and high sacrificing alcohol to substrate molar ratios have to be applied to keep its production at low levels.

  20. Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

    Science.gov (United States)

    Lennon, David; Winfield, John M

    2017-01-28

    Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

  1. Polystyrene-supported pyridinium chloroaluminate ionic liquid as a new heterogeneous Lewis acid catalyst for selective synthesis of benzimidazoles

    Directory of Open Access Journals (Sweden)

    Parvanak Boroujeni Kaveh

    2013-01-01

    Full Text Available Polystyrene-supported pyridinium chloroaluminate ionic liquid was prepared from the reaction of Merrifield resin with pyridine followed by reaction with aluminium chloride. This catalyst was used as a new chemoselective Lewis acid catalyst for the exclusive synthesis of 2-substituted benzimidazoles from the reaction of aldehydes with o-phenylenediamines. The catalyst is stable (as a bench top catalyst and can be easily recovered and reused without appreciable change in its efficiency.

  2. State of the art of Lewis acid-containing zeolites: lessons from fine chemistry to new biomass transformation processes.

    Science.gov (United States)

    Moliner, Manuel

    2014-03-21

    The former synthesis of TS-1 opened new catalytic opportunities for zeolites, especially for their application as selective redox catalysts in several fine chemistry processes. Interestingly, isolated Ti species in the framework positions of hydrophobic zeolites, such as high silica zeolites, offer unique Lewis acid sites even in the presence of protic polar solvents (such as water). Following this discovery, other transition metals (such as Sn, Zr, V, Nb, among others) have been introduced in the framework positions of different hydrophobic zeolitic structures, allowing their application in new fine chemistry processes as very active and selective redox catalysts. Recently, these hydrophobic metallozeolites have been successfully applied as efficient catalysts for several biomass-transformation processes in bulk water. The acquired knowledge from the former catalytic descriptions in fine chemistry processes using hydrophobic Lewis acid-containing zeolites has been essential for their application in these novel biomass transformations. In the present review, I will describe the recent advances in the synthesis of new transition metal-containing zeolites presenting Lewis acid character, and their unique catalytic applications in both fine chemistry and novel biomass-transformations.

  3. Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts.

    Science.gov (United States)

    Bernskoetter, Wesley H; Hazari, Nilay

    2017-04-18

    alkali metal Lewis acid cocatalysts can play in promoting increased activity and catalyst stability for first row transition metal systems. We relate these effects to the nature of the elementary steps in the catalytic cycle and describe how the Lewis acids stabilize the crucial transition states. For all four transformations, we discuss in detail the currently proposed catalytic pathways, and throughout the Account we identify mechanistic similarities among catalysts for the four processes. The limitations of current catalytic systems are detailed, and suggestions are provided on the improvements that are likely required to develop catalysts that are more stable, active, and practical.

  4. Lewis Acid Promoted Hydrogenation of CO2and HCOO-by Amine Boranes: Mechanistic Insight from a Computational Approach.

    Science.gov (United States)

    Roy, Lisa; Ghosh, Boyli; Paul, Ankan

    2017-07-13

    We employ quantum chemical calculations to study the hydrogenation of carbon dioxide by amine boranes, NMe 3 BH 3 ( Me3 AB) and NH 3 BH 3 (AB) weakly bonded to a bulkier Lewis acid, Al(C 6 F 5 ) 3 (LA). Additionally, computations have also been conducted to elucidate the mechanism of hydrogenation of carbon dioxide by Me3 AB while captured between one Lewis base (P(o-tol 3 ), LB) and two Lewis acids, Al(C 6 F 5 ) 3 . In agreement with the experiments, our computational study predicts that hydride transfer to conjugated HCO 2 - , generated in the reaction of Me3 AB-LA with CO 2 , is not feasible. This is in contrast to the potential hydrogenation of bound HCO 2 H, developed in the reduction of CO 2 with AB-LA, to further reduced species like H 2 C(OH) 2 . However, the FLP-trapped CO 2 effortlessly undergoes three hydride (H - ) transfers from Me3 AB to produce a CH 3 O - derivative. DFT calculations reveal that the preference for a H - abstraction by an intrinsically anionic formate moiety is specifically dependent on the electrophilicity of the 2 e - reduced carbon center, which in particular is controlled by the electron-withdrawing capability of the associated substituents on the oxygen. These theoretical predictions are justified by frontier molecular orbitals and molecular electrostatic potential plots. The global electrophicility index, which is a balance of electron affinity and hardness, reveals that the electrophilicity of the formate species undergoing hydrogenation is twice the electrophilicity of the ones where hydrogenation is not feasible. The computed activation energies at M06-2X/6-31++G(d,p) closely predict the observed reactivity. In addition, the possibility of a dissociative channel of the frustrated Lewis pair trapped CO 2 system has been ruled out on the basis of predominantly high endergonicity. Knowledge of the underlying principle of these reactions would be helpful in recruiting appropriate Lewis acids/amine boranes for effective reduction

  5. Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions.

    Science.gov (United States)

    Li, Gao; Abroshan, Hadi; Chen, Yuxiang; Jin, Rongchao; Kim, Hyung J

    2015-11-18

    The catalytic activity of Au25(SR)18 nanoclusters (R = C2H4Ph) for the aldehyde hydrogenation reaction in the presence of a base, e.g., ammonia or pyridine, and transition-metal ions M(z+), such as Cu(+), Cu(2+), Ni(2+) and Co(2+), as a Lewis acid is studied. The addition of a Lewis acid is found to significantly promote the catalytic activity of Au25(SR)18/CeO2 in the hydrogenation of benzaldehyde and a number of its derivatives. Matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry in conjunction with UV-vis spectroscopy confirm the generation of new species, Au25-n(SR)18-n (n = 1-4), in the presence of a Lewis acid. The pathways for the speciation of Au24(SR)17 from its parent Au25(SR)18 nanocluster as well as its structure are investigated via the density functional theory (DFT) method. The adsorption of M(z+) onto a thiolate ligand "-SR-" of Au25(SR)18, followed by a stepwise detachment of "-SR-" and a gold atom bonded to "-SR-" (thus an "Au-SR" unit) is found to be the most likely mechanism for the Au24(SR)17 generation. This in turn exposes the Au13-core of Au24(SR)17 to reactants, providing an active site for the catalytic hydrogenation. DFT calculations indicate that M(z+) is also capable of adsorbing onto the Au13-core surface, producing a possible active metal site of a different kind to catalyze the aldehyde hydrogenation reaction. This study suggests, for the first time, that species with an open metal site like adducts [nanoparticle-M]((z-1)+) or fragments Au25-n(SR)18-n function as the catalysts rather than the intact Au25(SR)18.

  6. Enantioselective Alkynylation of Aromatic Aldehydes Catalyzed by a Sterically Highly Demanding Chiral-at-Rhodium Lewis Acid.

    Science.gov (United States)

    Luo, Shipeng; Zhang, Xiao; Zheng, Yu; Harms, Klaus; Zhang, Lilu; Meggers, Eric

    2017-09-01

    The enantioselective catalytic alkynylation of aromatic aldehydes is reported using a sterically highly hindered bis-cyclometalated rhodium-based Lewis acid catalyst featuring the octahedral metal as the only stereogenic center. Yields of 58-98% with 79-98% enantiomeric excess were achieved using 1-2 mol % of catalyst. This work complements previous work from our laboratory on the enantioselective alkynylation of 2-trifluoroacetyl imidazoles (Chem. - Eur. J. 2016, 22, 11977-11981) and trifluoromethyl ketones (J. Am. Chem. Soc. 2017, 139, 4322-4325) using catalysts with octahedral metal-centered chirality.

  7. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The Role of MgCl 2 as a Lewis Base in ROMgCl-MgCl 2 Electrolytes for Magnesium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Baofei [Joint Center for Energy Storage Research, Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont Illinois 60439 USA; Huang, Jinhua [Joint Center for Energy Storage Research, Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont Illinois 60439 USA; He, Meinan [Joint Center for Energy Storage Research, Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont Illinois 60439 USA; Brombosz, Scott M. [Materials Science Division, Argonne National Laboratory, Lemont Illinois 60439 USA; Vaughey, John T. [Joint Center for Energy Storage Research, Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont Illinois 60439 USA; Zhang, Lu [Joint Center for Energy Storage Research, Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont Illinois 60439 USA; Burrell, Anthony K. [Joint Center for Energy Storage Research, Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont Illinois 60439 USA; Zhang, Zhengcheng [Joint Center for Energy Storage Research, Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont Illinois 60439 USA; Liao, Chen [Joint Center for Energy Storage Research, Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont Illinois 60439 USA

    2016-02-04

    A series of strong Lewis acid-free alkoxide/siloxide-based Mg electrolytes were deliberately developed with remarkable oxidative stability up to 3.5 V (vs. Mg/Mg2+). Despite the perception of ROMgCl (R=alkyl, silyl) as a strong base, ROMgCl acts like Lewis acid, whereas the role of MgCl2 in was unambiguously demonstrated as a Lewis base through the identification of the key intermediate using single crystal X-ray crystallography. This Lewis-acid-free strategy should provide a prototype system for further investigation of Mg-ion batteries.

  9. Frustrated Lewis pairs: Design and reactivity

    Indian Academy of Sciences (India)

    trityl anion initiator mixture.7. Whereas, other Lewis acids would result in the poly- merisation of butadiene, the bulkier BPh3 failed in this case. Clearly, the bulky Lewis acids and bases behaved in a different manner compared to classical Lewis ...

  10. How strong are strong poly(sulfonic acids)? An example of the poly(2-acrylamido-2-methyl-1-propanesulfonic acid)

    Czech Academy of Sciences Publication Activity Database

    Gospodinova, Natalia; Tomšík, Elena; Omelchenko, Olga

    2016-01-01

    Roč. 74, January (2016), s. 130-135 ISSN 0014-3057 R&D Projects: GA ČR(CZ) GA15-14791S Institutional support: RVO:61389013 Keywords : polyelectrolytes * strong poly(acids) * proton conductors Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.531, year: 2016

  11. Coordination Behavior of [Cp''2Zr(η1:1-P4)] towards Different Lewis Acids.

    Science.gov (United States)

    Seitz, Andreas E; Vogel, Ulf; Eberl, Miriam; Eckhardt, Maria; Balázs, Gábor; Peresypkina, Eugenia V; Bodensteiner, Michael; Zabel, Manfred; Scheer, Manfred

    2017-08-01

    A detailed method for the preparation of [Cp'' 2 Zr(η 1:1 -P 4 )] (1) is presented. The coordination behavior of 1 towards Lewis acidic transition metal complexes of tungsten, manganese, and iron, respectively, and main group compounds (AlMe 3 , AlEt 3 ) was investigated in detail by computational and experimental studies. In doing so, a series of unprecedented complexes with different coordination modes and multiple coordination numbers of the tetraphosphabicyclo[1.1.0]butane framework were synthesized. All products, as well as the starting materials, were comprehensively characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray structural analysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Metal halide hydrates as lewis acid catalysts for the conjugated friedel-crafts reactions of indoles and activated olefins

    Energy Technology Data Exchange (ETDEWEB)

    Schwalm, Cristiane S.; Ceschi, Marco Antonio; Russowsky, Dennis, E-mail: dennis@iq.ufrgs.b [Universidade Federal do Rio Grande do Sul (IQ/UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica

    2011-07-01

    Metal halide hydrates such as SnCl{sub 2{center_dot}}2H{sub 2}O, MnCl{sub 2{center_dot}}4H{sub 2}O, SrCl{sub 2{center_dot}}6H{sub 2}O, CrCl{sub 2{center_dot}}6H{sub 2}O, CoCl{sub 2{center_dot}}6H{sub 2}O e CeCl{sub 3{center_dot}}7H{sub 2}O were investigated as mild Lewis acids catalysts for the conjugate Friedel-Crafts reaction between indoles and activated olefins. The reactions were carried out with aliphatic unsaturated ketones over a period of days at room temperature, while chalcones reacted only under reflux conditions. The reactions with nitrostyrene s were either performed in solvent or under solventless conditions. In all cases reasonable to good yields were obtained. (author)

  13. Facile and Benign Conversion of Sucrose to Fructose Using Zeolites With Balanced Brønsted and Lewis Acidity

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Tosi, Irene; Rasmussen, Kristoffer Hauberg

    2017-01-01

    Sucrose is by far the industrially most abundant simple carbohydrate with a production volume of more than 160 million metric tons from sugar cane and sugar beet per year. Many promising pathways towards bio-based organic compounds use, however, fructose as the pathway substrate. Hence, a chemoca......Sucrose is by far the industrially most abundant simple carbohydrate with a production volume of more than 160 million metric tons from sugar cane and sugar beet per year. Many promising pathways towards bio-based organic compounds use, however, fructose as the pathway substrate. Hence......, a chemocatalytic approach to convert sucrose into fructose would provide a means to channel sucrose into pathways for sugar valorization. Here, we show that a variety of heterogeneous zeolite catalysts with balanced Brønsted and Lewis acidity enable a simple route for the conversion of sucrose to more than 80...

  14. Introduction of a Simple Experiment for the Undergraduate Organic Chemistry Laboratory Demonstrating the Lewis Acid and Shape-Selective Properties of Zeolite Na-Y

    Science.gov (United States)

    Maloney, Vincent; Szczepanski, Zach

    2017-01-01

    A simple, inexpensive, discovery-based experiment for undergraduate organic laboratories has been developed that demonstrates the Lewis acid and shape-selective properties of zeolites. Calcined zeolite Na-Y promotes the electrophilic aromatic bromination of toluene with a significantly higher para/ortho ratio than observed under conventional…

  15. Synthesis of Tetrahydropyridazines by a Metal-carbene Directed Highly Enantioselective Vinylogous N-H Insertion/Lewis Acid Catalyzed Diastereoselective Mannich Addition

    Science.gov (United States)

    Xu, Xinfang; Zavalij, Peter Y.

    2012-01-01

    A versatile reaction cascade triggered by Rh(II)-catalyzed diazo decomposition followed by a vinylogous N-H insertion/Lewis acid catalyzed Mannich addition that produces highly substituted 1,2,3,6-tetrahydropyridazines in up to 97% ee with high yield and diastereocontrol has been developed. PMID:22945294

  16. Synthesis of Tetrahydropyridazines by a Metal-carbene Directed Highly Enantioselective Vinylogous N-H Insertion/Lewis Acid Catalyzed Diastereoselective Mannich Addition

    OpenAIRE

    Xu, Xinfang; Zavalij, Peter Y.; Doyle, Michael P.

    2012-01-01

    A versatile reaction cascade triggered by Rh(II)-catalyzed diazo decomposition followed by a vinylogous N-H insertion/Lewis acid catalyzed Mannich addition that produces highly substituted 1,2,3,6-tetrahydropyridazines in up to 97% ee with high yield and diastereocontrol has been developed.

  17. Dielectric loss property of strong acids doped polyaniline (PANi)

    Science.gov (United States)

    Amalia, Rianti; Hafizah, Mas Ayu Elita; Andreas, Manaf, Azwar

    2018-04-01

    In this study, strong acid doped polyaniline (PANi) has been successfully fabricated through the chemical oxidative polymerization process with various polymerization times. Nonconducting PANi resulting from the polymerization process at various polymerization times were then doped by a strong acid HClO4 to generate dielectric properties. Ammonium Persulfate (APS) as an initiator was used during Polymerization process to develop dark green precipitates which then called Emeraldine Base Polyaniline (PANi-EB). The PANi-EB was successively doped by strong acid HClO4 with dopant and PANi ratio 10:1 to enhance the electrical conductivity. The conductivity of doped PANi was evaluated by Four Point Probe. Results of evaluation showed that the conductivity values of HClO4 doped PANi were in the range 337-363 mS/cm. The dielectric properties of doped PANi were evaluated by Vector Network Analyzer (VNA) which suggested that an increase in the permittivity value in the conducting PANi. It is concluded that PANi could be a potential candidate for electromagnetic waves absorbing materials.

  18. Development of a Lewis Base Catalyzed Selenocyclization Reaction

    Science.gov (United States)

    Collins, William

    2009-01-01

    The concept of Lewis base activation of selenium Lewis acids has been effectively reduced to practice in the Lewis base catalyzed selenofunctionalization of unactivated olefins. In this reaction, the weakly acidic species, "N"-phenylselenyl succinimide, is cooperatively activated by the addition of a "soft" Lewis base donor (phosphine sulfides,…

  19. Big, strong, neutral, twisted, and chiral π acids.

    Science.gov (United States)

    Zhao, Yingjie; Huang, Guangxi; Besnard, Celine; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2015-04-13

    General synthetic access to expanded π-acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion-π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron-withdrawing substituents decreases and the high π acidity needed for strong anion-π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion-π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from -3.96 to -4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X-ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation-π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches -4.45 eV, whereas two sulfone moieties give a value of -4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion-π interactions, these conceptually innovative π-acidic surfaces are also of interest as electron transporters in conductive materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Stability range of MoC (hp2). II. Thermodynamic properties of generalized Lewis acid-base intermetallics

    International Nuclear Information System (INIS)

    Koukouvetakis, J.

    1988-01-01

    The γ-MoC phase with the hexagonal WC structure was prepared without the presence of metal stabilizers at temperatures below 1000 degree C. This phase was found to be thermodynamically stable at low temperatures and decomposed to Mo 2 C and graphite at 1400 K. Using equilibrium and thermodynamic data, the thermodynamic quantities of this phase were calculated. Oxide equilibration and solid-state galvanic cell experiments were used to study thermodynamic properties of binary Lewis acid-base stabilized transition-metal alloys. The activity of vanadium was determined in alloys of vanadium with platinum-group metals such as Rh, Pd, and Ir at 1000 degree C. The activities of titanium in titanium-iridium alloys and of niobium in Nb 3 Ir were determined at 1400 degree C. The ternary phase diagram of V-Pd-O at 1000 degree C was obtained. Based on the vanadium-palladium results, a partial titration curve of palladium by vanadium was constructed. The excess partial molar Gibbs free energy of vanadium at infinite dilution was found to be -36.4 kcal mol -1 at 1000 degree C. Results are in agreement with the predictions of Brewer's theory of transition-metal alloy acid-base behavior

  1. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

    Science.gov (United States)

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-05-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition.

  2. Organo-Lewis acids as cocatalysts in cationic metallocene polymerization catalysis. Unusual characteristics of sterically encumbered tris(perfluorobiphenyl)borane

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Y.X.; Stern, C.L.; Yang, S.; Marks, T.J. [Northwestern Univ., Evanston, IL (United States)

    1996-12-11

    Organo-Lewis acids such as methylalumoxane (MAO) and B(C{sub 6}F{sub 5} ){sub 3} (I) play pivotal roles as alkide/hydride abstractors/ cocatalysts in generating highly active, cationic olefin polymerization catalysts (II; L,L` = anionic ancillary ligands; X{sup -} = weakly coordinating anion). We communicate here the unusual cocatalytic characteristics of the new, sterically encumbered fluoroarylborane, tris(2,2`,2``-perfluorobiphenyl)-borane (PBB, III). Characteristics include substantially different abstractive and ion pair structure/reactivity relationships vis-a-vis I. PPB was synthesized as colorless microcrystals in 76% yield from C{sub 6}F{sub 5}Br. Reaction with group 4 and Th methyls proceeds cleanly to yield cationic complexes, which were characterized by standard {sup 1}H/{sup 13}C/{sup 19}F NMR spectroscopic and analytical techniques. The results illustrate the substantial and surprising differences in cationic complex ion pair structure and reactivity that can be brought about by modifications in fluoroarylborane catalyst architecture. 10 refs., 1 fig., 1 tab.

  3. Facile preparation of acid-resistant magnetite particles for removal of Sb(?) from strong acidic solution

    OpenAIRE

    Wang, Dong; Guan, Kaiwen; Bai, Zhiping; Liu, Fuqiang

    2016-01-01

    Abstract A new facile coating strategy based on the hydrophobicity of methyl groups was developed to prevent nano-sized magnetite particles from strong acid corrosion. In this method, three steps of hydrolysis led to three layers of protection shell coating Fe3O4 nanoparticles. Filled with hydrophobic methyl groups, the middle layer mainly prevented the magnetic core from strong acid corrosion. These magnetite particles managed to resist 1 M HCl solution and 2.5 M H2SO4 solution. The acid res...

  4. Lewis base additives improve the zeolite ferrierite-catalyzed synthesis of isostearic acid

    Science.gov (United States)

    Isostearic acid (IA) is of interest for industrial purposes especially in the area of biolubricants, such as cosmetics and slip additives for polyolefin and related copolymer films. This study was designed to develop a zeolitic catalysis process for IA production through isomerization of fatty aci...

  5. Key Roles of Lewis Acid-base Pairs on ZnxZryOz in Direct Ethanol/Acetone to Isobutene Conversion

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Junming; Baylon, Rebecca A.; Liu, Changjun; Mei, Donghai; Martin, Kevin J.; Venkitasubramanian, Padmesh; Wang, Yong

    2016-01-20

    The effects of surface acidity on the cascade ethanol-to-isobutene conversion were studied using ZnxZryOz catalysts. The ethanol-to-isobutene reaction was found to be limited by the secondary reaction of the key intermediate, acetone, namely the acetone-to-isobutene reaction. Although the catalysts with coexisting Brønsted acidity could catalyze the rate-limiting acetone-to-isobutene reaction, the presence of Brønsted acidity is also detrimental. First, secondary isobutene isomerization is favored, producing a mixture of butene isomers. Second, undesired polymerization and coke formation prevail, leading to rapid catalyst deactivation. Most importantly, both steady-state and kinetic reaction studies as well as FTIR analysis of adsorbed acetone-d6 and D2O unambiguously showed that a highly active and selective nature of balanced Lewis acid-base pairs was masked by the coexisting Brønsted acidity in the aldolization and self-deoxygenation of acetone to isobutene. As a result, ZnxZryOz catalysts with only Lewis acid-base pairs were discovered, on which nearly a theoretical selectivity to isobutene (~88.9%) was successfully achieved, which has never been reported before. Moreover, the absence of Brønsted acidity in such ZnxZryOz catalysts also eliminates the side isobutene isomerization and undesired polymerization/coke reactions, resulting in the production of high purity isobutene with significantly improved catalyst stability (< 2% activity loss after 200 h time-on-stream). This work not only demonstrates a balanced Lewis acid-base pair for the highly active and selective cascade ethanol-to-isobutene reaction, but also sheds light on the rational design of selective and robust acid-base catalyst for C-C coupling via aldolization reaction.

  6. Synthesis of tetrahydropyridazines by a metal-carbene-directed enantioselective vinylogous N-H insertion/Lewis acid-catalyzed diastereoselective Mannich addition.

    Science.gov (United States)

    Xu, Xinfang; Zavalij, Peter Y; Doyle, Michael P

    2012-09-24

    A versatile cascade of reactions, triggered by Rh(II)-catalyzed diazo decomposition followed by a vinylogous N-H insertion/Lewis acid catalyzed Mannich addition, that produces highly substituted 1,2,3,6-tetrahydropyridazines in up to 97 % ee with high yield and diastereocontrol has been developed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Lewis acid free high speed synthesis of nimesulide-based novel N-substituted cyclic imides

    Energy Technology Data Exchange (ETDEWEB)

    Kankanala, Kavitha; Mukkanti, Khagga [JNT University Hyderabad, Kukatpally (India); Pal, Sarbani, E-mail: sarbani277@yahoo.co [MNR Degree and PG College, Kukatpally, Hyderabad (India). Dept. of Chemistry; Reddy, Vangala Ranga [Dr. Reddy' s Laboratories Ltd. Integrated Product Development, Bachupally, Hyderabad (India)

    2010-07-01

    The first synthesis of nimesulide-based novel cyclic imides has been accomplished via the reaction of an amine prepared from nimesulide with appropriate anhydrides in the presence of sodium acetate. Using this process a variety of N-substituted cyclic imides was prepared in good yields in glacial acetic acid. Some of the compounds synthesized showed anti-inflammatory activities when tested in vivo. (author)

  8. Key Roles of Lewis Acid-Base Pairs on ZnxZryOz in Direct Ethanol/Acetone to Isobutene Conversion.

    Science.gov (United States)

    Sun, Junming; Baylon, Rebecca A L; Liu, Changjun; Mei, Donghai; Martin, Kevin J; Venkitasubramanian, Padmesh; Wang, Yong

    2016-01-20

    The effects of surface acidity on the cascade ethanol-to-isobutene conversion were studied using ZnxZryOz catalysts. The ethanol-to-isobutene reaction was found to be limited by the secondary reaction of the key intermediate, acetone, namely the acetone-to-isobutene reaction. Although the catalysts with coexisting Brønsted acidity could catalyze the rate-limiting acetone-to-isobutene reaction, the presence of Brønsted acidity is also detrimental. First, secondary isobutene isomerization is favored, producing a mixture of butene isomers. Second, undesired polymerization and coke formation prevail, leading to rapid catalyst deactivation. Most importantly, both steady-state and kinetic reaction studies as well as FTIR analysis of adsorbed acetone-d6 and D2O unambiguously showed that a highly active and selective nature of balanced Lewis acid-base pairs was masked by the coexisting Brønsted acidity in the aldolization and self-deoxygenation of acetone to isobutene. As a result, ZnxZryOz catalysts with only Lewis acid-base pairs were discovered, on which nearly a theoretical selectivity to isobutene (∼ 88.9%) was successfully achieved, which has never been reported before. Moreover, the absence of Brønsted acidity in such ZnxZryOz catalysts also eliminates the side isobutene isomerization and undesired polymerization/coke reactions, resulting in the production of high purity isobutene with significantly improved catalyst stability (catalyst for C-C coupling via aldolization reaction.

  9. A Ru-η6-arene complex as a C-based Lewis acid in the activation of hydrogen and hydrogenation catalysis.

    Science.gov (United States)

    Boone, Michael P; Stephan, Douglas W

    2013-06-12

    The PBP ligand (Ph2PC6H4)2BPh was used to prepare ((Ph2PC6H4)2B(Cl)(η(6)-Ph)RuCl (1) and subsequently [((Ph2PC6H4)2B(η(6)-Ph))RuCl][B(C6F5)4] (2). The latter species exhibited Lewis acidity on the η(6)-Ph ring, as reaction with Cy3P gave the donor-acceptor adduct [(Ph2PC6H4)2B(η(5)-C6H5-o-PCy3)RuCl][B(C6F5)4] (3). Steric frustration of this binding was seen with Mes3P, and yet the combination of 2 and Mes3P reacted with H2 to give a 2:1 mixture of 5-o and 5-p, two isomers of [(Ph2PC6H4)2B(η(5)-C6H6)RuCl] (5), along with [Mes3PH][HB(C6F5)3]. Compound 2 behaves as C-based Lewis acid and thus can also be used for catalytic hydrogenation of aldimines at room temperature via a frustrated Lewis pair mechanism.

  10. Increase in the Hydrophilicity and Lewis Acid-Base Properties of Solid Surfaces Achieved by Electric Gliding Discharge in Humid Air: Effects on Bacterial Adherence

    International Nuclear Information System (INIS)

    Kamgang, J. O.; Brisset, J.-L.; Naitali, M.; Herry, J.-M.; Bellon-Fontaine, M.-N.; Briandet, R.

    2009-01-01

    This study addressed the effects of treatment with gliding discharge plasma on the surface properties of solid materials, as well as the consequences concerning adherence of a model bacterium. As evaluated by contact angles with selected liquids, plasma treatment caused an increase in surface hydrophilicity and in the Lewis acid-base components of the surface energy of all materials tested. These modifications were more marked for low density polyethylene and stainless steel than for polytetrafluoroethylene. After treatment, the hydrophilicity of the materials remained relatively stable for at least 20 days. Moreover, analysis of the topography of the materials by atomic force microscopy revealed that the roughness of both polymers was reduced by glidarc plasma treatment. As a result of all these modifications, solid substrates were activated towards micro-organisms and the adherence of S. epidermidis, a negatively charged Lewis-base and mildly hydrophilic strain selected as the model, was increased in almost all the cases tested. (plasma technology)

  11. Effect of ferulic acid and Angelica archangelica extract on behavioral and psychological symptoms of dementia in frontotemporal lobar degeneration and dementia with Lewy bodies.

    Science.gov (United States)

    Kimura, Takemi; Hayashida, Hideki; Murata, Masako; Takamatsu, Junichi

    2011-07-01

    The behavioral and psychological symptoms of dementia place a heavy burden on caregivers. Antipsychotic drugs, though used to reduce the symptoms, frequently decrease patients' activities of daily living and reduce their quality of life. Recently, it was suggested that ferulic acid is an effective treatment for behavioral and psychological symptoms. We have also reported several patients with dementia with Lewy bodies showing good responses to ferulic acid and Angelica archangelica extract (Feru-guard). The present study investigated the efficacy of Feru-guard in the treatment of behavioral and psychological symptoms in frontotemporal lobar degeneration and dementia with Lewy bodies. We designed a prospective, open-label trial of daily Feru-guard (3.0 g/day) lasting 4 weeks in 20 patients with frontotemporal lobar degeneration or dementia with Lewy bodies. Behavioral and psychological symptoms of dementia were assessed at baseline and 4 weeks after the start of treatment, using the Neuropsychiatric Inventory. The Neuropsychiatric Inventory scores were analyzed using the Wilcoxon rank sum test. Treatment with Feru-guard led to decreased scores on the Neuropsychiatric Inventory in 19 of 20 patients and significantly decreased the score overall. The treatment also led to significantly reduced subscale scores on the Neuropsychiatric Inventory ("delusions", "hallucinations", "agitation/aggression", "anxiety", "apathy/indifference", "irritability/lability" and "aberrant behavior"). There were no adverse effects or significant changes in physical findings or laboratory data. Feru-guard may be effective and valuable for treating the behavioral and psychological symptoms of dementia in frontotemporal lobar degeneration and dementia with Lewy bodies. © 2011 Japan Geriatrics Society.

  12. Lewy Body Disease

    Science.gov (United States)

    Lewy body disease is one of the most common causes of dementia in the elderly. Dementia is the loss of mental ... to affect normal activities and relationships. Lewy body disease happens when abnormal structures, called Lewy bodies, build ...

  13. Carbon-based strong solid acid for cornstarch hydrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Nata, Iryanti Fatyasari, E-mail: yanti_tkunlam@yahoo.com [Chemical Engineering Study Program, Faculty of Engineering, Lambung Mangkurat University, Jl. A. Yani Km. 36 Banjarbaru, South Kalimantan 70714 (Indonesia); Irawan, Chairul; Mardina, Primata [Chemical Engineering Study Program, Faculty of Engineering, Lambung Mangkurat University, Jl. A. Yani Km. 36 Banjarbaru, South Kalimantan 70714 (Indonesia); Lee, Cheng-Kang, E-mail: cklee@mail.ntust.edu.tw [Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 Keelung Rd. Sec.4, Taipei 106, Taiwan (China)

    2015-10-15

    Highly sulfonated carbonaceous spheres with diameter of 100–500 nm can be generated by hydrothermal carbonization of glucose in the presence of hydroxyethylsulfonic acid and acrylic acid at 180 °C for 4 h. The acidity of the prepared carbonaceous sphere C4-SO{sub 3}H can reach 2.10 mmol/g. It was used as a solid acid catalyst for the hydrolysis of cornstarch. Total reducing sugar (TRS) concentration of 19.91 mg/mL could be obtained by hydrolyzing 20 mg/mL cornstarch at 150 °C for 6 h using C4-SO{sub 3}H as solid acid catalyst. The solid acid catalyst demonstrated good stability that only 9% decrease in TRS concentration was observed after five repeat uses. The as-prepared carbon-based solid acid catalyst can be an environmentally benign replacement for homogeneous catalyst. - Highlights: • Carbon solid acid was successfully prepared by one-step hydrothermal carbonization. • The acrylic acid as monomer was effectively reduce the diameter size of particle. • The solid acid catalyst show good catalytic performance of starch hydrolysis. • The solid acid catalyst is not significantly deteriorated after repeated use.

  14. Carbon-based strong solid acid for cornstarch hydrolysis

    International Nuclear Information System (INIS)

    Nata, Iryanti Fatyasari; Irawan, Chairul; Mardina, Primata; Lee, Cheng-Kang

    2015-01-01

    Highly sulfonated carbonaceous spheres with diameter of 100–500 nm can be generated by hydrothermal carbonization of glucose in the presence of hydroxyethylsulfonic acid and acrylic acid at 180 °C for 4 h. The acidity of the prepared carbonaceous sphere C4-SO 3 H can reach 2.10 mmol/g. It was used as a solid acid catalyst for the hydrolysis of cornstarch. Total reducing sugar (TRS) concentration of 19.91 mg/mL could be obtained by hydrolyzing 20 mg/mL cornstarch at 150 °C for 6 h using C4-SO 3 H as solid acid catalyst. The solid acid catalyst demonstrated good stability that only 9% decrease in TRS concentration was observed after five repeat uses. The as-prepared carbon-based solid acid catalyst can be an environmentally benign replacement for homogeneous catalyst. - Highlights: • Carbon solid acid was successfully prepared by one-step hydrothermal carbonization. • The acrylic acid as monomer was effectively reduce the diameter size of particle. • The solid acid catalyst show good catalytic performance of starch hydrolysis. • The solid acid catalyst is not significantly deteriorated after repeated use

  15. Carbon-based strong solid acid for cornstarch hydrolysis

    Science.gov (United States)

    Nata, Iryanti Fatyasari; Irawan, Chairul; Mardina, Primata; Lee, Cheng-Kang

    2015-10-01

    Highly sulfonated carbonaceous spheres with diameter of 100-500 nm can be generated by hydrothermal carbonization of glucose in the presence of hydroxyethylsulfonic acid and acrylic acid at 180 °C for 4 h. The acidity of the prepared carbonaceous sphere C4-SO3H can reach 2.10 mmol/g. It was used as a solid acid catalyst for the hydrolysis of cornstarch. Total reducing sugar (TRS) concentration of 19.91 mg/mL could be obtained by hydrolyzing 20 mg/mL cornstarch at 150 °C for 6 h using C4-SO3H as solid acid catalyst. The solid acid catalyst demonstrated good stability that only 9% decrease in TRS concentration was observed after five repeat uses. The as-prepared carbon-based solid acid catalyst can be an environmentally benign replacement for homogeneous catalyst.

  16. Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds.

    Science.gov (United States)

    Alkorta, Ibon; Legon, Anthony C

    2017-10-23

    It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N₂, CO, HC≡CH, CH₂=CH₂, C₃H₆, PH₃, H₂S, HCN, H₂O, H₂CO and NH₃) and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H₂O, F₂, Cl₂, Br₂, ClF, BrCl, H₃SiF, H₃GeF, F₂CO, CO₂, N₂O, NO₂F, PH₂F, AsH₂F, SO₂, SeO₂, SF₂, and SeF₂) can be represented to good approximation by means of the equation D e = c ' N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ' is a constant, conveniently chosen to have the value 1.00 kJ mol -1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1) the hydrogen bond; (2) the halogen bond; (3) the tetrel bond; (4) the pnictogen bond; and (5) the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

  17. Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds

    Directory of Open Access Journals (Sweden)

    Ibon Alkorta

    2017-10-01

    Full Text Available It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N2, CO, HC≡CH, CH2=CH2, C3H6, PH3, H2S, HCN, H2O, H2CO and NH3 and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H2O, F2, Cl2, Br2, ClF, BrCl, H3SiF, H3GeF, F2CO, CO2, N2O, NO2F, PH2F, AsH2F, SO2, SeO2, SF2, and SeF2 can be represented to good approximation by means of the equation D e = c ′ N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ′ is a constant, conveniently chosen to have the value 1.00 kJ mol−1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1 the hydrogen bond; (2 the halogen bond; (3 the tetrel bond; (4 the pnictogen bond; and (5 the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

  18. Synthesis of novel carbon/silica composites based strong acid ...

    Indian Academy of Sciences (India)

    hydrophobic acid-catalyzed reactions proceed in poor or with no catalytic activity (Nakajima et al 2009). The novel car- bon/silica composites based solid acid was synthesized for the purpose. However, the new method added the step of impregnating sucrose to the channels of SBA-15, which fur- ther added to the cost for ...

  19. A 1.9 Å Crystal Structure of the HDV Ribozyme Precleavage Suggests both Lewis Acid and General Acid Mechanisms Contribute to Phosphodiester Cleavage

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jui-Hui; Yajima, Rieko; Chadalavada, Durga M.; Chase, Elaine; Bevilacqua, Philip C.; Golden, Barbara L. (Purdue); (Penn)

    2010-11-01

    The hepatitis delta virus (HDV) ribozyme and HDV-like ribozymes are self-cleaving RNAs found throughout all kingdoms of life. These RNAs fold into a double-nested pseudoknot structure and cleave RNA, yielding 2{prime},3{prime}-cyclic phosphate and 5{prime}-hydroxyl termini. The active site nucleotide C75 has a pK{sub a} shifted >2 pH units toward neutrality and has been implicated as a general acid/base in the cleavage reaction. An active site Mg{sup 2+} ion that helps activate the 2{prime}-hydroxyl for nucleophilic attack has been characterized biochemically; however, this ion has not been visualized in any previous structures. To create a snapshot of the ribozyme in a state poised for catalysis, we have crystallized and determined the structure of the HDV ribozyme bound to an inhibitor RNA containing a deoxynucleotide at the cleavage site. This structure includes the wild-type C75 nucleotide and Mg{sup 2+} ions, both of which are required for maximal ribozyme activity. This structure suggests that the position of C75 does not change during the cleavage reaction. A partially hydrated Mg{sup 2+} ion is also found within the active site where it interacts with a newly resolved G {center_dot} U reverse wobble. Although the inhibitor exhibits crystallographic disorder, we modeled the ribozyme-substrate complex using the conformation of the inhibitor strand observed in the hammerhead ribozyme. This model suggests that the pro-RP oxygen of the scissile phosphate and the 2{prime}-hydroxyl nucleophile are inner-sphere ligands to the active site Mg{sup 2+} ion. Thus, the HDV ribozyme may use a combination of metal ion Lewis acid and nucleobase general acid strategies to effect RNA cleavage.

  20. Complexation of Nitrous Oxide by Frustrated Lewis Pairs

    NARCIS (Netherlands)

    Otten, Edwin; Neu, Rebecca C.; Stephan, Douglas W.

    2009-01-01

    Frustrated Lewis pairs comprised of a basic yet sterically encumbered phosphine with boron Lewis acids bind nitrous oxide to give intact PNNOB linkages. The synthesis, structure, and bonding of these species are described.

  1. Asymmetric catalysis in aqueous media: use of metal-chiral crown ethers as efficient chiral Lewis acid catalysts in asymmetric aldol reactions

    Directory of Open Access Journals (Sweden)

    Shu Kobayashi

    2001-01-01

    Full Text Available Metal-chiral crown ether complexes have been developed as efficient chiral Lewis acid catalysts for asymmetric aldol reactions of silyl enol ethers with aldehydes in aqueous media. While many excellent catalytic asymmetric reactions have been developed recently, most of them have to be carried out under strictly anhydrous conditions in organic solvents. This is probably due to the instability of many catalysts and/or intermediates in the presence of even a small amount of water. To address this issue, we searched for metal-crown ether complexes on the basis of our "multi-coordination" hypothesis, and found that lead(II and lanthanide(III catalysts worked well as chiral Lewis acids in aqueous media. To the best of our knowledge, these are the first examples of chiral crown-based Lewis acids that can be successfully used in catalytic asymmetric reactions. The catalysts have been characterized by X-ray diffraction, and their unique structures as chiral catalysts have been revealed. Use of water as a solvent is essential in these asymmetric catalysis, and the role of water on these reactions to explain the high reactivity and selectivity has been suggested. Another important point is that kinetic studies have shown the possibility that these types of crown ether complexes would be suitable as chiral catalysts employed in aqueous media. In addition, although the catalytic asymmetric aldol reactions are one of the most powerful carbon-carbon bond-forming methodologies and several successful examples have been reported, the use of aprotic anhydrous solvents and low reaction temperatures (-78 °C has been needed in almost all successful cases. On the other hand, the present reactions proceeded smoothly at -10-0 °C in water-alcohol solutions while retaining high levels of diastereo- and enantioselectivities.

  2. Proton-transfer and H2-elimination reactions of trimethylamine alane: role of dihydrogen bonding and Lewis acid-base interactions.

    Science.gov (United States)

    Filippov, Oleg A; Tsupreva, Victoria N; Golubinskaya, Lyudmila M; Krylova, Antonina I; Bregadze, Vladimir I; Lledos, Agusti; Epstein, Lina M; Shubina, Elena S

    2009-04-20

    Proton-transfer and H(2)-elimination reactions of aluminum hydride AlH(3)(NMe(3)) (TMAA) with XH acids were studied by means of IR and NMR spectroscopy and DFT calculations. The dihydrogen-bonded (DHB) intermediates in the interaction of the TMAA with XH acids (CH(3)OH, (i)PrOH, CF(3)CH(2)OH, adamantyl acetylene, indole, 2,3,4,5,6-pentafluoroaniline, and 2,3,5,6-tetrachloroaniline) were examined experimentally at low temperatures, and the spectroscopic characteristics, dihydrogen bond strength and structures, and the electronic and energetic characteristics of these complexes were determined by combining experimental and theoretical approaches. The possibility of two different types of DHB complexes with polydentate proton donors (typical monodentate and bidentate coordination with the formation of a symmetrical chelate structure) was shown by DFT calculations and was experimentally proven in solution. The DHB complexes are intermediates of proton-transfer and H(2)-elimination reactions. The extent of this reaction is very dependent on the acid strength and temperature. With temperature increases the elimination of H(2) was observed for OH and NH acids, yielding the reaction products with Al-O and Al-N bonds. The reaction mechanism was computationally studied. Besides the DHB pathway for proton transfer, another pathway starting from a Lewis complex was discovered. Preference for one of the pathways is related to the acid strength and the nucleophilicity of the proton donor. As a consequence of the dual Lewis acid-base nature of neutral aluminum hydride, participation of a second ROH molecule acting as a bifunctional catalyst forming a six-member cycle connecting aluminum and hydride sites notably reduces the reaction barrier. This mechanism could operate for proton transfer from weak OH acids to TMAA in the presence of an excess of proton donor.

  3. Investigation of methanol oxidation on unsupported platinum electrodes in strong alkali and strong acid

    Science.gov (United States)

    Prabhuram, J.; Manoharan, R.

    Porous unsupported electrodes are made from platinum powder prepared by a room-temperature NaBH 4 reduction method. Cyclic voltammograms (CVs) are recorded in different electrolytes of high and low pH in the presence and the absence of different concentrations of methanol. Various electrochemical processes occurring in different potential regions of the CVs are discussed. Steady-state galvanostatic polarisation measurements for the methanol oxidation reaction (MOR) on these electrodes in different electrolyte/methanol mixtures are also carried out. The MOR performance increases from a highly acidic range to a highly alkaline range. On increasing the KOH concentration above 6 M, however, the activity declines. Also, the MOR performance changes on changing the methanol concentration in a solution of a given pH. The highest MOR activity is obtained in a 6 M KOH+6 M CH 3OH mixture. It is concluded that by choosing the proper ratio of OH - ions and CH 3OH in solution, it is possible to remove completely the intermediate organic species and/or poisonous species that retard the MOR rate on the electrode surface.

  4. Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized γ-butyrolactones

    Science.gov (United States)

    Gowda, Ravikumar R.; Chen, Eugene Y.-X.

    2017-07-01

    Multivinyl-functionalized γ-butyrolactones, γ-vinyl-γ-methyl-α-methylene-γ-butyrolactone (γVMMBL) and γ-allyl-γ-methyl-α-methylene-γ-butyrolactone (γAMMBL), have been synthesized from biorenewable ethyl levulinate and effectively polymerized by Lewis pairs consisting of an organic N-heterocyclic carbene Lewis base and a strong organo-Lewis acid E(C6F5)3 (E = Al, B). This Lewis pair polymerization is quantitatively chemoselective, proceeds exclusively via polyaddition across the conjugated α-methylene double bond without participation of the γ-vinyl or γ-allyl double bond, and produces high-molecular-weight functionalized polymers with unimodal molecular-weight distributions. The Al-based Lewis pair produces a polymer with approximately 5.5 times higher molecular weight than that produced by the B-based Lewis pair. The resulting vinyl-functionalized polymers are soluble in common organic solvents and stable at room temperature, and can be thermally cured into crosslinked materials. This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

  5. New organo-Lewis acids. Tris({beta}-perfluoronaphthyl)borane (PNB) as a highly active cocatalyst for metallocene-mediated Ziegler-Natta {alpha}-olefin polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Li, L.; Marks, T.J. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry

    1998-08-31

    Tris({beta}-perfluoronaphthyl)borane (B(C{sub 10}F{sub 7}){sub 3}, PNB) is synthesized from {beta}-perfluoronaphthyllithium and BCl{sub 3} to serve as a new strong organo-Lewis acid cocatalyst. PNB efficiently activates a variety of group 4 dimethyl complexes to form highly active homogeneous Ziegler-Natta olefin polymerization catalysts. Reaction of PNB with rac-Me{sub 2}Si(Ind){sub 2}ZrMe{sub 2} and CGCMMe{sub 2} (M = Zr, Ti; CGC = Me{sub 2}Si({eta}{sup 5}-Me{sub 4}C{sub 5})({sup t}BuN)) (1:1 molar ratio) rapidly produces the base-free cationic complexes rac-Me{sub 2}Si(Ind){sub 2}ZrMe{sup +}MePNB{sup {minus}} (1) and CGCMMe{sup +}MePNB{sup {minus}} (M = Zr, 2; Ti, 3), respectively. The {mu}-methyl dinuclear cationic complex [(CGCTiMe){sub 2}({mu}-Me)]{sup +}MePNB{sup {minus}} (4) is formed when 2:1 CGCTiMe{sub 2}:PNB stoichiometry is employed. In the case of group 4 dimethyl zirconocenes, L{sub 2}ZrMe{sub 2} (L = {eta}{sup 5}-C{sub 5}H{sub 5}, Cp; {eta}{sup 5}-1,2-Me{sub 2}C{sub 5}H{sub 3}, Cp{double_prime}), reaction in a 1:1 metallocene:PNB ratio affords cationic complexes L{sub 2}ZrMe{sup +}MePNB{sup {minus}} (L = Cp, 5; Cp{double_prime}, 6), while the reaction with a 1:2 molar ratio affords dinuclear {mu}-methyl cationic complexes [(L{sub 2}ZrMe){sub 2}({mu}-Me)]{sup +}MePNB{sup {minus}} (L = Cp, 7; Cp{double_prime}, 8). In both reactions, {mu}-F dinuclear cationic complexes [(L{sub 2}ZrMe){sub 2}({mu}F)]{sup +}MePNB{sup {minus}} (L = Cp, 9; Cp{double_prime}, 10) are formed as byproducts. (C{sub 6}F{sub 5}){sub 3}BNCCH{sub 3} and PNBNCCH{sub 3} were synthesized and characterized.

  6. A novel nucleic acid analogue shows strong angiogenic activity

    Energy Technology Data Exchange (ETDEWEB)

    Tsukamoto, Ikuko, E-mail: tukamoto@med.kagawa-u.ac.jp [Department of Pharmaco-Bio-Informatics, Faculty of Medicine, Kagawa University, 1750-1 Ikenobe, Miki, Kita, Kagawa 761-0793 (Japan); Sakakibara, Norikazu; Maruyama, Tokumi [Kagawa School of Pharmaceutical Sciences, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193 (Japan); Igarashi, Junsuke; Kosaka, Hiroaki [Department of Cardiovascular Physiology, Faculty of Medicine, Kagawa University, 1750-1 Ikenobe, Miki, Kita, Kagawa 761-0793 (Japan); Kubota, Yasuo [Department of Dermatology, Faculty of Medicine, Kagawa University, 1750-1 Ikenobe, Miki, Kita, Kagawa 761-0793 (Japan); Tokuda, Masaaki [Department of Cell Physiology, Faculty of Medicine, Kagawa University, 1750-1 Ikenobe, Miki, Kita, Kagawa 761-0793 (Japan); Ashino, Hiromi [The Tokyo Metropolitan Institute of Medical Science, 1-6 Kamikitazawa2-chome, Setagaya-ku, Tokyo 156-8506 (Japan); Hattori, Kenichi; Tanaka, Shinji; Kawata, Mitsuhiro [Teikoku Seiyaku Co., Ltd., Sanbonmatsu, Higashikagawa, Kagawa 769-2695 (Japan); Konishi, Ryoji [Department of Pharmaco-Bio-Informatics, Faculty of Medicine, Kagawa University, 1750-1 Ikenobe, Miki, Kita, Kagawa 761-0793 (Japan)

    2010-09-03

    Research highlights: {yields} A novel nucleic acid analogue (2Cl-C.OXT-A, m.w. 284) showed angiogenic potency. {yields} It stimulated the tube formation, proliferation and migration of HUVEC in vitro. {yields} 2Cl-C.OXT-A induced the activation of ERK1/2 and MEK in HUVEC. {yields} Angiogenic potency in vivo was confirmed in CAM assay and rabbit cornea assay. {yields} A synthesized small angiogenic agent would have great clinical therapeutic value. -- Abstract: A novel nucleic acid analogue (2Cl-C.OXT-A) significantly stimulated tube formation of human umbilical endothelial cells (HUVEC). Its maximum potency at 100 {mu}M was stronger than that of vascular endothelial growth factor (VEGF), a positive control. At this concentration, 2Cl-C.OXT-A moderately stimulated proliferation as well as migration of HUVEC. To gain mechanistic insights how 2Cl-C.OXT-A promotes angiogenic responses in HUVEC, we performed immunoblot analyses using phospho-specific antibodies as probes. 2Cl-C.OXT-A induced robust phosphorylation/activation of MAP kinase ERK1/2 and an upstream MAP kinase kinase MEK. Conversely, a MEK inhibitor PD98059 abolished ERK1/2 activation and tube formation both enhanced by 2Cl-C.OXT-A. In contrast, MAP kinase responses elicited by 2Cl-C.OXT-A were not inhibited by SU5416, a specific inhibitor of VEGF receptor tyrosine kinase. Collectively these results suggest that 2Cl-C.OXT-A-induces angiogenic responses in HUVEC mediated by a MAP kinase cascade comprising MEK and ERK1/2, but independently of VEGF receptor tyrosine kinase. In vivo assay using chicken chorioallantoic membrane (CAM) and rabbit cornea also suggested the angiogenic potency of 2Cl-C.OXT-A.

  7. Enhanced adsorption of active brilliant red X-3B dye on chitosan molecularly imprinted polymer functionalized with Ti(IV) as Lewis acid.

    Science.gov (United States)

    Deng, Hui; Wei, Zhilai; Wang, XiaoNing

    2017-02-10

    A Ti(IV) functionalized chitosan molecularly imprinted polymer (Ti-CSMIP) was successfully prepared. Ti 4+ as Lewis acidic was used to modify chitosan MIP by producing metal hydroxyl group and protonated surface of adsorbent in aqueous solution to recognize X-3B molecule as a Lewis base. The adsorbent was characterized by FTIR, SEM, XRD, BET, elemental and zeta potential analysis. XRD illustrated Ti-CSMIP exhibited a weak anatase phase when Ti 4+ cross-linked with chitosan. Batch adsorption experiments were performed to evaluate adsorption condition, including sorption isotherm, kinetics and reusability. The maximum adsorption capacity of Ti-CSMIP for X-3B was 161.1mg/g at 293K when solution pH was in the range of 6.0-7.0. Equilibrium data was well analyzed by three-parameter isotherm model, and the kinetics of adsorption followed the pseudo-second kinetics equation. Regeneration experiments indicated a possible application as an effective sorbent for the selective removal of azo anionic dye in aqueous solutions. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Acid-, base-, and lewis-acid-catalyzed heterolysis of methoxide from an alpha-hydroxy-beta-methoxy radical: models for reactions catalyzed by coenzyme B12-dependent diol dehydratase.

    Science.gov (United States)

    Xu, Libin; Newcomb, Martin

    2005-11-11

    [Reaction: see text].A model for glycol radicals was employed in laser flash photolysis kinetic studies of catalysis of the fragmentation of a methoxy group adjacent to an alpha-hydroxy radical center. Photolysis of a phenylselenylmethylcyclopropane precursor gave a cyclopropylcarbinyl radical that rapidly ring opened to the target alpha-hydroxy-beta-methoxy radical (3). Heterolysis of the methoxy group in 3 gave an enolyl radical (4a) or an enol ether radical cation (4b), depending upon pH. Radicals 4 contain a 2,2-diphenylcyclopropane reporter group, and they rapidly opened to give UV-observable diphenylalkyl radicals as the final products. No heterolysis was observed for radical 3 under neutral conditions. In basic aqueous acetonitrile solutions, specific base catalysis of the heterolysis was observed; the pK(a) of radical 3 was determined to be 12.5 from kinetic titration plots, and the ketyl radical formed by deprotonation of 3 eliminated methoxide with a rate constant of 5 x 10(7) s(-1). In the presence of carboxylic acids in acetonitrile solutions, radical 3 eliminated methanol in a general acid-catalyzed reaction, and rate constants for protonation of the methoxy group in 3 by several acids were measured. Radical 3 also reacted by fragmentation of methoxide in Lewis-acid-catalyzed heterolysis reactions; ZnBr2, Sc(OTf)3, and BF3 were found to be efficient catalysts. Catalytic rate constants for the heterolysis reactions were in the range of 3 x 10(4) to 2 x 10(6) s(-1). The Lewis-acid-catalyzed heterolysis reactions are fast enough for kinetic competence in coenzyme B12 dependent enzyme-catalyzed reactions of glycols, and Lewis-acid-catalyzed cleavages of beta-ethers in radicals might be applied in synthetic reactions.

  9. Lewy Body Dementia Association

    Science.gov (United States)

    ... Read Story A New Mission In Life Don Kent is a licensed attorney with a brilliant career. ... Reserved Lewy Body Dementia Association, Inc. 912 Killian Hill Road S.W., Lilburn, GA 30047 © 2016 Lewy Body ...

  10. Lewy Body Dementia Diagnosis

    Science.gov (United States)

    ... provide an experienced diagnostic team skilled in Lewy body dementia. A thorough dementia diagnostic evaluation includes physical ... a good way to benefit others with Lewy body dementia. Medications Medications are one of the most ...

  11. Multicomponent Molecular Puzzles for Photofunction Design: Emission Color Variation in Lewis Acid-Base Pair Crystals Coupled with Guest-to-Host Charge Transfer Excitation.

    Science.gov (United States)

    Ono, Toshikazu; Sugimoto, Manabu; Hisaeda, Yoshio

    2015-08-05

    Simple yet ubiquitous multimolecular assembly systems with color-tunable emissions are realized by cooperative electron donor-acceptor interactions, such as the boron-nitrogen (B-N) dative bond as a Lewis acid-base pair and charge transfer (CT) interactions. These are ternary-component systems consisting of a naphthalenediimide derivative (NDI), tris(pentafluorophenyl)borane (TPFB), and aromatic molecules (guest) with an NDI:TPFB:guest ratio of 1:2:2. The crystal shows guest-dependent color-tunable emissions such as deep blue to orange when a guest molecule of benzene is replaced with other π-conjugated systems. A good correlation between the emission wavelength and ionization potential of the guest and electronic structure calculations indicated that the emission is due to the CT transition from the guest to the NDI. The present study suggests that a rational solution of multcomponent molecular puzzles would be useful for obtaining novel photofunctional solid-state systems.

  12. A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal$-$Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Jacob A. [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry; Petersen, Brenna M. [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry; Kormos, Attila [Hungarian Academy of Sciences, Budapest (Hungary); Echeverría, Elena [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Physics and Astronomy; Chen, Yu-Sheng [Univ. of Chicago, Argonne, IL (United States). ChemMatCARS, Center for Advanced Radiation Sources; Zhang, Jian [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry

    2017-02-28

    Here, we describe a new strategy to generate non-coordinating anions using zwitterionic metal–organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO2)4]$-$) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of MnIII- and FeIII-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels–Alder cycloaddition of aldehydes with dienes. Lastly, this work paves a new way to design functional MOFs for tunable chemical catalysis.

  13. Synthesis, structure and topological analysis of glycine templated highly stable cadmium sulfate framework: A New Lewis Acid catalyst

    Science.gov (United States)

    Paul, Avijit Kumar

    2018-04-01

    One new open-framework two-dimensional layer, [Cd(NH3CH2COO)(SO4)], I, has been synthesized using amino acid as templating agent. Single crystal structural analysis shows that the compound crystallizes in monoclinic cell with non-centrosymmetric space group P21, a = 4.9513(1) Å, b = 7.9763(2) Å, c = 8.0967(2) Å, β = 105.917(1)° and V = 307.504(12) Å3. The compound has connectivity between the Cd-centers and the sulfate units forming a two-dimensional layer structure. Sulfate unit is coordinated to metal center with η3, μ4 mode possessing a coordination free oxygen atom. The zwitterionic form of glycine molecule is present in the structure bridging with two metal centers through μ2-mode by carboxylate oxygens. The topological analysis reveals that the two-dimensional network is formed with a novel 4- and 6-connected binodal net of (32,42,52)(34,44,54,63) topology. Although one end of the glycine molecule is free from coordination, the structure is highly stable up to 350 °C. Strong N-H⋯ O hydrogen bonding interactions play an important role in the stabilization and formation of three-dimensional supramolecular structure. The cyanosilylation of imines using the present compounds as heterogeneous catalyst indicates good catalytic behavior. The present study illustrates the usefulness of the amino acid for the structure building in less studied sulfate based framework materials as well as designing of new heterogeneous catalysts for the broad application. The compound has also been characterized through elemental analysis, PXRD, IR, SEM and TG-DT studies.

  14. Water-stable Lewis acids. Aiming at a chemical reaction which is friendly to human being and the environment; Suichu de anteina ruisusan - hito to kankyo ni yasashii kagaku hanno wo mezashite -

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, S. [Science Univ. of Tokyo (Japan)

    1997-10-01

    A series of groups of compounds including rare earth triflates has been found which break the common knowledge of chemistry that Lewis acids are hydrolyzed in water and consequently inactivated. These compounds are stable in water and , in addition, function as a Lewis acid in water. This report describes the properties of and methods for preparing the above compounds. In particular, since the rare earth triflates have a higher solubility in water tan in organic solvents, they can be recovered merely by extraction after the completion of the reaction. Further, the reuse of the recovered compounds does not lower the catalytic activity, enabling the rare earth triflates to construct a system which can basically eliminate the need to dispose of the catalyst. This leads to realization of a chemical reaction which uses an aqueous solution and is the so called `an environmentally friendly chemical reaction.` The Mannich reaction in an aqueous solution, direct allylation of saccharides, and an alder reaction in a micelle system using a Lewis acid are described as examples of reactions using water-stable Lewis acids. 6 refs., 1 tab.

  15. Sulfur-H{sub z}(CH{sub x}){sub y}(z = 0,1) functionalized metal oxide nanostructure decorated interfaces: Evidence of Lewis base and Brönsted acid sites – Influence on chemical sensing

    Energy Technology Data Exchange (ETDEWEB)

    Laminack, William; Baker, Caitlin [Department of Physics, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Gole, James, E-mail: james.gole@physics.gatech.edu [Department of Physics, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Department of Mechanical Engineering, Georgia Tech, Atlanta, GA 30332 (United States)

    2015-06-15

    Nanostructure metal oxide decorated n-type extrinsic porous silicon (PS) semiconductor interfaces are modified through in-situ interaction with acidic ethane and butane thiols (EtSH, BuSH) and basic diethyl sulfide (Et{sub 2}S). Highly sensitive conductometric sensor evaluations and X-ray Photoelectron Spectroscopy demonstrate the effect of sulfur group functionalization modifying the acidity of the metal oxides and their interaction with NH{sub 3}. SEM micrographs demonstrate that the sulfur treated particles are less than 30 nm in size. EDAX studies confirm the chemical composition of the modified nanoparticles and suggest the surface interaction of the sulfides and thiols. The acidic thiols can form Brönsted acidic sites enhancing the acidity of the metal oxides, thus broadening the initial metal oxide acidity range. The sulfides interact to lower the Lewis acidity of nanostructured metal oxide sites. Conductometric response matrices with NH{sub 3} at room temperature, corresponding to the thiol and sulfide treated nanostructures of the metal oxides TiO{sub 2}, SnO{sub x}, Ni{sub x}O, Cu{sub x}O, and Au{sub x}O (x >> 1) are evaluated for a dominant electron transduction process forming the basis for reversible chemical sensing in the absence of chemical bond formation. Treatment with the acidic thiols enhances the metal center acidity. It is suggested that the thiols can interact to increase the Brönsted acidity of the doped metal oxide surface if they maintain SH bonds. This process may account for the shift in Lewis acidity as the Brönsted acid sites counter the decrease in Lewis acidity resulting from the interaction of S-(CH{sub x}){sub y} groups. In contrast, treatment with basic Et{sub 2}S decreases the Lewis acidity of the metal oxide sites, enhancing the basicity of the decorated interface. XPS measurements indicate a change in binding energy (BE) of the metal and oxygen centers. The observed changes in conductometric response do not represent a

  16. Titration of strong and weak acids by sequential injection analysis technique.

    Science.gov (United States)

    Maskula, S; Nyman, J; Ivaska, A

    2000-05-31

    A sequential injection analysis (SIA) titration method has been developed for acid-base titrations. Strong and weak acids in different concentration ranges have been titrated with a strong base. The method is based on sequential aspiration of an acidic sample zone and only one zone of the base into a carrier stream of distilled water. On their way to the detector, the sample and the reagent zones are partially mixed due to the dispersion and thereby the base is partially neutralised by the acid. The base zone contains the indicator. An LED-spectrophotometer is used as detector. It senses the colour of the unneutralised base and the signal is recorded as a typical SIA peak. The peak area of the unreacted base was found to be proportional to the logarithm of the acid concentration. Calibration curves with good linearity were obtained for a strong acid in the concentration ranges of 10(-4)-10(-2) and 0.1-3 M. Automatic sample dilution was implemented when sulphuric acid at concentration of 6-13 M was titrated. For a weak acid, i.e. acetic acid, a linear calibration curve was obtained in the range of 3x10(-4)-8x10(-2) M. By changing the volumes of the injected sample and the reagent, different acids as well as different concentration ranges of the acids can be titrated without any other adjustments in the SIA manifold or the titration protocol.

  17. Kinetics of Strong Acid Hydrolysis of a Bleached Kraft Pulp for Producing Cellulose Nanocrystals (CNCs)

    Science.gov (United States)

    Qianqian Wang; Xuebing Zhao; J.Y. Zhu

    2014-01-01

    Cellulose nanocrytals (CNCs) are predominantly produced using the traditional strong acid hydrolysis process. In most reported studies, the typical CNC yield is low (approximately 30%) despite process optimization. This study investigated the hydrolysis of a bleached kraft eucalyptus pulp using sulfuric acid between 50 and 64 wt % at temperatures of 35−80 °C...

  18. Treatment of infectious skin defects or ulcers with electrolyzed strong acid aqueous solution.

    Science.gov (United States)

    Sekiya, S; Ohmori, K; Harii, K

    1997-01-01

    A chronic ulcer with an infection such as methicillin-resistant Staphylococcus aureus is hard to heal. Plastic and reconstructive surgeons often encounter such chronic ulcers that are resistant to surgical or various conservative treatments. We applied conservative treatment using an electrolyzed strong acid aqueous solution and obtained satisfactory results. The lesion was washed with the solution or soaked in a bowl of the solution for approximately 20 min twice a day. Fresh electrolyzed strong acid aqueous solution is unstable and should be stored in a cool, dark site in a sealed bottle. It should be used within a week after it has been produced. Here we report on 15 cases of infectious ulcers that were treated by electrolyzed strong acid aqueous solution. Of these cases, 7 patients were healed, 3 were granulated, and in 5, infection subsided. In most cases the lesion became less reddish and less edematous. Discharge or foul odor from the lesion was decreased. Electrolyzed strong acid aqueous solution was especially effective for treating a chronic refractory ulcer combined with diabetes melitus or peripheral circulatory insufficiency. This clinically applied therapy of electrolyzed strong acid aqueous solution was found to be effective so that this new therapeutic technique for ulcer treatment can now be conveniently utilized.

  19. Carborane acids. New "strong yet gentle" acids for organic and inorganic chemistry.

    Science.gov (United States)

    Reed, Christopher A

    2005-04-07

    Icosahedral carborane anions such as CHB11Cl11- are amongst the least coordinating, most chemically inert anions known. They are also amongst the least basic, so their conjugate acids, H(carborane), are superacids (i.e. stronger than 100% H2SO4). Acidity scale measurements indicate that H(CHB11Cl11) is the strongest pure Brønsted acid presently known, surpassing triflic and fluorosulfuric acid. Nevertheless, it is also an extremely gentle acid--because its conjugate base engages in so little chemistry. Carborane acids separate protic acidity from anion nucleophilicity and destructive oxidative capacity in the conjugate base, to a degree not previously achieved. As a result, many long-sought, highly acidic, reactive cations such as protonated benzene (C6H7+), protonated C60(HC60+), tertiary carbocations (R3C+), vinyl cations (R2C=C(+)-R), silylium ions (R3Si+) and discrete hydronium ions (H3O+, H5O2+ etc.) can be readily isolated as carborane salts and characterized at room temperature by X-ray crystallography.

  20. Reduction of trace quantities of chromium(VI by strong acids

    Directory of Open Access Journals (Sweden)

    Pezzin Sérgio H

    2004-01-01

    Full Text Available The chemical behavior of Cr(VI at low concentrations (10-4 to 10-7 mol L-1 in several strong acids was studied using high specific activity 51Cr(VI as a tracer. The speciation of the products from these systems was carried out by ion exchange chromatography with stepwise elution. The results show that trace quantities of Cr(VI, monitored by means of radiochromium (51Cr, are reduced in the presence of mineral acids such as perchloric, hydrochloric, hydrofluoric, sulfuric, nitric and trifluoromethanesulfonic acids, even in the absence of conventional reducing agents, producing different measureable Cr(III species, depending on the acid anion. Detailed studies of the reduction of low concentrations of Cr(VI with nitric acid have shown that the relative rate of reduction increases as the concentration of the acid increases or as the concentration of the Cr(VI decreases.

  1. Toward understanding of the role of Lewis acidity in aldol condensation of acetone and furfural using MOF and zeolite catalysts

    Czech Academy of Sciences Publication Activity Database

    Kikhtyanin, O.; Kubička, D.; Čejka, Jiří

    2015-01-01

    Roč. 243, APR 2015 (2015), s. 158-162 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : metal organic framework * aldol condensation * acidic catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.312, year: 2015

  2. Beyond alkyl transfer: Synthesis of main group metal (Mg, Ca, Zn) silyl and tris(oxazolinyl)borato complexes and their stoichiometric and catalytic reactions with borane Lewis acids and carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Lampland, Nicole Lynn [Iowa State Univ., Ames, IA (United States)

    2015-05-09

    Recently, the fundamental knowledge of main group metal chemistry has grown. This progress is crucial for the further development of main group metal compounds in silicon chemistry and catalysis and for advancing their applications as green alternatives to many rare earth and transition metal compounds. This thesis focuses on reactivity beyond the welldocumented alkyl-transfer applications for main group metals, and it highlights examples of reactions with Lewis acids and the reduction of carbonyls.

  3. Lanthanide nitrates as Lewis acids in the one-pot synthesis of 1,2,4-oxadiazole derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Vale, Juliana A.; Faustino, Wagner M., E-mail: julianadqf@yahoo.com.br [Departamento de Quimica, Universidade Federal da Paraiba, Joao Pessoa, PB (Brazil); Zampieri, Davila de S.; Moran, Paulo J.S.; Rodrigues, Jose A.R. [Instituto de Quimica, Universidade Estadual de Campinas, SP (Brazil); Sa, Gilberto F. de [Departamento de Quimica Fundamental, CCEN, Universidade Federal de Pernambuco, Recife, PE (Brazil)

    2012-08-15

    In this work we report the use of lanthanide nitrates [Ln(NO{sub 3}){sub 3}] acting as catalyst in direct one pot synthesis of 3-benzoyl- and 3-acetyl-1,2,4-oxadiazoles derivatives from ketones, nitriles and nitric acid. This is the first example of one-pot synthesis of benzoyl- and acetyl 1,2,4-oxadiazoles derivatives preparation using acetophenones derivates with electron-donator groups. (author)

  4. Highly purified eicosapentaenoic acid as free fatty acids strongly suppresses polyps in Apc(Min/+) mice.

    Science.gov (United States)

    Fini, Lucia; Piazzi, Giulia; Ceccarelli, Claudio; Daoud, Yahya; Belluzzi, Andrea; Munarini, Alessandra; Graziani, Giulia; Fogliano, Vincenzo; Selgrad, Michael; Garcia, Melissa; Gasbarrini, Antonio; Genta, Robert M; Boland, C Richard; Ricciardiello, Luigi

    2010-12-01

    Although cyclooxygenase (COX)-2 inhibitors could represent the most effective chemopreventive tool against colorectal cancer (CRC), their use in clinical practice is hampered by cardiovascular side effects. Consumption of ω-3-polyunsaturated fatty acids (ω-3-PUFAs) is associated with a reduced risk of CRC. Therefore, in this study, we assessed the efficacy of a novel 99% pure preparation of ω-3-PUFA eicosapentaenoic acid as free fatty acids (EPA-FFA) on polyps in Apc(Min/+) mice. Apc(Min/+) and corresponding wild-type mice were fed control diet (Ctrl) or diets containing either EPA-FFA 2.5% or 5%, for 12 weeks while monitoring food intake and body weight. We found that both EPA-FFA diets protected from the cachexia observed among Apc(Min/+) animals fed Ctrl diet (P acid was replaced by EPA (P < 0.0001), leading to a significant reduction in COX-2 expression and β-catenin nuclear translocation. Moreover, in the EPA-FFA arms, we found a significant decrease in proliferation throughout the intestine together with an increase in apoptosis. Our data make 99% pure EPA-FFA an excellent candidate for CRC chemoprevention. ©2010 AACR.

  5. Tested Demonstrations: Comparison of Strong Acid and Weak Acid Titration Curves.

    Science.gov (United States)

    Gilbert, George L., Ed.

    1979-01-01

    A lecture demonstration is presented for comparing titration curves. A plot of pH vs volume of strong base is produced by connecting the external output of a pH meter to a strip recorder. Thus, pH is recorded as a function of time. (BB)

  6. Lewy body dementias

    DEFF Research Database (Denmark)

    Løkkegaard, Annemette; Korbo, Lise

    2017-01-01

    Dementia with Lewy bodies and Parkinson disease dementia share the same pathophysiology. Together they are called Lewy body dementias and are the second most common type of dementia. Lewy body dementias receive little attention, and patients are often misdiagnosed, leading to less than ideal...... management. In this article, diagnostic criteria combined with imaging and other biomarkers as well as current treatment recommendations are summarized, and some of the challenges for the future are outlined. Refinement of diagnosis and clarification of the pathogenesis are required in search for disease...

  7. Lewy Body Dementia Research

    Science.gov (United States)

    ... Caregiving topics Caregiving Briefs LEWY DIGEST multimedia LBDA tv webinars, interviews & transcripts press releases Media Kit additional ... DLB. These findings require replication in a larger series of patients (i.e. Phase III trial) but ...

  8. Dementia with Lewy Bodies

    Science.gov (United States)

    ... occurs sporadically, in people with no known family history of the disease. However, rare familial cases have occasionally been reported. × Definition Dementia with Lewy bodies (DLB) is one of ...

  9. Strong ion difference in urine: new perspectives in acid-base assessment.

    OpenAIRE

    Gattinoni, L.; Carlesso, E.; Cadringher, P.; Caironi, P.

    2006-01-01

    The plasmatic strong ion difference (SID) is the difference between positively and negatively charged strong ions. At pH 7.4, temperature 37°C and partial carbon dioxide tension 40 mmHg, the ideal value of SID is 42 mEq/l. The buffer base is the sum of negatively charged weak acids ([HCO3 -], [A-], [H2PO4 -]) and its normal value is 42 mEq/l. According to the law of electroneutrality, the amount of positive and negative charges must be equal, and therefore the SID value is equal to the buffer...

  10. Purification of di-nonyl phenyl phosphoric acid (DNPPA) for synergistic extraction of uranium from strong phosphoric acid

    International Nuclear Information System (INIS)

    Singh, D.K.; Vijayalakshmi, R.; Singh, H.; Sharma, J.N.; Ruhela, R.

    2009-01-01

    Di-nonyl phenyl phosphoric acid (DNPPA) obtained from various synthesis methods is always associated with impurities such as mono-nonyl phenyl phosphoric acid and nonyl phenol which need to be separated for its effective use in the extraction of uranium from strong phosphoric acid. Two methods of purification namely liquid-solid separation method using neodymium salt and liquid-liquid separation method using methylene glycol have been described. In the liquid solid separation method the purity of DNPPA obtained was about 95% with less than 1.0% monoester, however it heavily suffers in the recovery aspect which is of the order of 50-60%. The methylene glycol treatment method, results in high purity and recovery of the product. Purity obtained was about 95.0% diester and less than 0.5% monoester and recovery was more than 90%. Analysis of DNPPA was done by potentiometric titration method using autotitrator. (author)

  11. British strong-acid leach process targeted at refractory uranium ores

    International Nuclear Information System (INIS)

    Anon.

    1975-01-01

    The UKAEA-patented strong-acid leach process for refractory U ores is briefly outlined with emphasis on its variations from the conventional dilute-acid process and the projected economics for a processing plant using this process. The process uses 6N H 2 SO 4 with a sharply reduced leaching time over conventional processes. The solubilized U is removed by percolation and the use of only about 10 percent liquid produces less effluent. Conventional processing plant equipment can be used except at the feed preparation, acid mixing, curing, and washing stages. Ore can be processed at larger grain sizes and the milling is done in a dry rod mill. Alternatives to the percolation removal of U are listed. Other work being done by UKAEA on U recovery from ores is briefly indicated. (U.S.)

  12. Testing the nature of reaction coordinate describing interaction of H2 with carbonyl carbon, activated by Lewis acid complexation, and the Lewis basic solvent: A Born-Oppenheimer molecular dynamics study with explicit solvent

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-09-01

    Using Born-Oppenheimer molecular dynamics (BOMD), we explore the nature of interactions between H2 and the activated carbonyl carbon, C(carbonyl), of the acetone-B(C6F5)3 adduct surrounded by an explicit solvent (1,4-dioxane). BOMD simulations at finite (non-zero) temperature with an explicit solvent produced long-lasting instances of significant vibrational perturbation of the H—H bond and H2-polarization at C(carbonyl). As far as the characteristics of H2 are concerned, the dynamical transient state approximates the transition-state of the heterolytic H2-cleavage. The culprit is the concerted interactions of H2 with C(carbonyl) and a number of Lewis basic solvent molecules—i.e., the concerted C(carbonyl)⋯H2⋯solvent interactions. On one hand, the results presented herein complement the mechanistic insight gained from our recent transition-state calculations, reported separately from this article. But on the other hand, we now indicate that an idea of the sufficiency of just one simple reaction coordinate in solution-phase reactions can be too simplistic and misleading. This article goes in the footsteps of the rapidly strengthening approach of investigating molecular interactions in large molecular systems via "computational experimentation" employing, primarily, ab initio molecular dynamics describing reactants-interaction without constraints of the preordained reaction coordinate and/or foreknowledge of the sampling order parameters.

  13. Rejoinder to Lewis

    Directory of Open Access Journals (Sweden)

    Ashton Anderson

    2015-01-01

    Full Text Available In a response to our article “Political Ideology and Racial Preferences in Online Dating,” Kevin Lewis (2015 has raised concerns about various aspects of our analysis of user behavior on a national online dating site. The core of Lewis’ critique is that we do not report specifics of the sample, the website, and the analysis. Lewis also details numerous smaller points with respect to details of the analysis. The goal of this response is not to reply to every point that Lewis makes. As with any research project, our design decisions require tradeoffs, and readers should evaluate the evidence on their own. Rather, we use this space to make broader points about the general value for sociology of research using online data and how such research should be practiced.

  14. Polyaniline: Aniline oxidation with strong and weak oxidants under various acidity

    Energy Technology Data Exchange (ETDEWEB)

    Bláha, Michal, E-mail: blaha@imc.cas.cz [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Trchová, Miroslava; Bober, Patrycja; Morávková, Zuzana [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Prokeš, Jan [Charles University, Faculty of Mathematics and Physics, 180 00 Prague 8 (Czech Republic); Stejskal, Jaroslav [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic)

    2017-06-15

    Aniline was oxidized with three strong inorganic oxidants (ammonium peroxydisulfate, cerium(IV) sulfate, potassium dichromate), two weak inorganic oxidants (iron(III) chloride, silver nitrate), and one organic oxidant (p-benzoquinone) in aqueous solutions of methanesulfonic acid (MSA) of various concentration. Whereas oxidation of aniline with ammonium peroxydisulfate yielded high-molecular-weight conducting polyaniline (PANI) in the whole acidity range, the oxidation with cerium(IV) sulfate led also to a single product close to PANI with considerably lower molecular weight and lower conductivity. Potassium dichromate gave PANI only at high concentration of MSA. The use of iron(III) chloride yielded composite mixtures of PANI and low-molecular-weight aniline oligomers. The oxidation of aniline with silver nitrate led to composites of silver and an organic part, which was constituted either by aniline oligomers or conducting polyaniline or both. p-Benzoquinone as oxidant produced mainly aniline oligomers with poor conductivity and 2,5-dianilino-p-benzoquinone-like structure detected in FTIR and Raman spectra when oxidation proceeded with weak oxidants. A general model of oxidation with strong and weak oxidants was formulated. - Highlights: • Comparison of aniline oxidation with oxidants of different redox potential. • UV–vis, FTIR and Raman spectroscopies combined with size-exclusion chromatography. • The contents of polymer and oligomers were analyzed and discussed. • General model of aniline oxidation with strong and weak oxidants was formulated.

  15. An easy access to α-aryl substituted γ-ketophosphonates: Lewis acid mediated reactions of 1,3-diketones with α-hydroxyphosphonates and tandem regioselective C-C bond cleavage.

    Science.gov (United States)

    Pallikonda, Gangaram; Chakravarty, Manab; Sahoo, Manoj K

    2014-09-28

    A range of α-aryl substituted γ-ketophosphonates is synthesised by Lewis acid mediated reactions of 1,3-diketones and easily accessible, inexpensive benzylic α-hydroxyphosphonates in an operationally simple method under solvent-free conditions without exclusion of air/moisture. A regioselective C-C bond cleavage for 1,3-diketones in a tandem fashion has also been demonstrated. Synthesis of a γ-ketophosphonate with phenol functionality at the α-position (structural analogue of raspberry ketone, a natural product) has also been presented.

  16. Symptoms of Lewy Body Dementia

    Science.gov (United States)

    ... the fight against LBD! Donate Symptoms Lewy body dementia symptoms and diagnostic criteria Every person with LBD ... an umbrella term for two related clinical diagnoses, dementia with Lewy bodies and Parkinson's disease dementia. The ...

  17. Symptoms of Lewy Body Dementia

    Science.gov (United States)

    ... the fight against LBD! Donate Symptoms Lewy body dementia (LBD) has variable presentations that include cognitive difficulties ... wake cycle alterations. Cognitive impairment in Lewy body dementia (LBD) is often misdiagnosed as Alzheimer’s disease (AD). ...

  18. Extraction of uranium: comparison of stripping with ammonia vs. strong acid

    International Nuclear Information System (INIS)

    Moldovan, B.; Grinbaum, B.; Efraim, A.

    2008-01-01

    Following extraction of uranium in the first stage of solvent extraction using a tertiary amine, typically Alamine 336, the stripping of the extracted uranium is accomplished either by use of an aqueous solution of (NH 4 ) 2 SO 4 /NH 4 OH or by strong-acid stripping using 400-500 g/L H 2 SO 4 . Both processes have their merits and determine the downstream processing. The classical stripping with ammonia is followed by addition of strong base, to precipitate ammonium uranyl sulfate (NH 4 ) 2 UO 2 (SO 4 ) 2 , which yields finally the yellow cake. Conversely, stripping with H 2 SO 4 , followed by oxidation with hydrogen peroxide yields uranyl oxide as product. At the Cameco Key Lake operation, both processes were tested on a pilot scale, using a Bateman Pulsed Column (BPC). The BPC proved to be applicable to both processes. It met the process criteria both for extraction and stripping, leaving less than 1 mg/L of U 3 O 8 in the raffinate, and product solution had the required concentration of U 3 O 8 at high flux and reasonable height of transfer unit. In the Key Lake mill, each operation can be carried out in a single column. The main advantages of the strong-acid stripping over ammonia stripping are: (1) 60% higher flux in the extraction, (2) tenfold higher concentration of the uranium in the product solution, and (3) far more robust process, with no need of pH control in the stripping and no need to add acid to the extraction in order to keep the pH above the point of precipitation of iron compounds. The advantages of the ammoniacal process are easier stripping, that is, less stages needed to reach equilibrium and lower concentration of modifier needed to prevent the creation of a third phase. (authors)

  19. Transformations of griseofulvin in strong acidic conditions--crystal structures of 2'-demethylgriseofulvin and dimerized griseofulvin.

    Science.gov (United States)

    Leśniewska, Barbara; Jebors, Said; Coleman, Anthony W; Suwińska, Kinga

    2012-03-01

    The structure of griseofulvic acid, C16H15ClO6, at 100 K has orthorhombic (P2(1)2(1)2) symmetry. It is of interest with respect to biological activity. The structure displays intermolecular O-H...O, C-H...O hydrogen bonding as well as week C-H...pi and pi...pi interactions. In strong acidic conditions the griseofulvin undergoes dimerization. The structure of dimerized griseofulvin, C34H32C12O12 x C2H6O x H2O, at 100 K has monoclinic (P2(1)) symmetry. The molecule crystallized as a solvate with one ethanol and one water molecule. The dimeric molecules form intermolecular O-H...O hydrogen bonds to solvents molecules only but they interact via week C-H...O, C-H...pi, C-Cl...pi and pi...pi interactions with other dimerized molecules.

  20. Critical requirement for aspartic acid at position 82 of myelin basic protein 73-86 for recruitment of V beta 8.2+ T cells and encephalitogenicity in the Lewis rat.

    Science.gov (United States)

    Smeltz, R B; Wauben, M H; Wolf, N A; Swanborg, R H

    1999-01-15

    We synthesized single amino acid-substituted peptide analogues of guinea pig myelin basic protein (MBP) 73-86 to study the importance of aspartic acid at residue 82 (QKSQRSQDENPV), which previous reports have suggested is a critical TCR contact residue. Whereas the wild-type 73-86 peptide elicited severe experimental autoimmune encephalomyelitis (EAE) in the Lewis rat, none of the peptide analogues with substitutions at position 82 were capable of inducing EAE. The inability to cause EAE was not due to a failure to bind MHC or to elicit T cell proliferation and cytokine secretion. T cells specific for MBP73-86 did not cross-react with any of the analogues tested, further indicating the importance of this residue in T cell responses to 73-86. Analysis by flow cytometry showed that only the wild-type 73-86 peptide was capable of recruiting V beta 8.2+ T cells, which have been shown previously to be important for disease induction. Reduced expression of the V beta 8.2 TCR was also seen in Lewis rats protected from EAE by coimmunization of MBP73-86 with 73-86(82D-->A), despite an increase in cytokine production when both peptides were present during in vitro culture. The data indicate that aspartic acid 82 is a critical TCR contact residue and is required for the recruitment of V beta 8.2+ T cells and the encephalitogenic activity of MBP73-86.

  1. Lewis, Prof. Gilbert Newton

    Indian Academy of Sciences (India)

    Home; Fellowship. Fellow Profile. Elected: 1935 Honorary. Lewis, Prof. Gilbert Newton. Date of birth: 25 October 1875. Date of death: 24 March 1946. YouTube; Twitter; Facebook; Blog. Academy News. IAS Logo. 29th Mid-year meeting. Posted on 19 January 2018. The 29th Mid-year meeting of the Academy will be held ...

  2. Frustrated Lewis Pairs

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 19; Issue 11. Frustrated Lewis Pairs : Enabling via inability. Sanjoy Mukherjee ... Author Affiliations. Sanjoy Mukherjee Pakkirisamy Thilagar1. Department of Inorgainic and Physical Chemistry Indian Institute of Science Bangalore 560 012, India.

  3. Frustrated Lewis Pairs

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 19; Issue 11. Frustrated Lewis Pairs : Enabling via inability. Sanjoy Mukherjee Pakkirisamy Thilagar. General Article Volume 19 Issue 11 November 2014 pp 1017-1027. Fulltext. Click here to view fulltext PDF. Permanent link:

  4. Lewy body-demens

    DEFF Research Database (Denmark)

    Ziebell, Morten; Korbo, Lise; Hasselbalch, Steen G

    2010-01-01

    Newer estimations indicate a considerable increase in the number of elderly people with dementia and Lewy body dementia (DLB) in Denmark. Simultaneously, the prescription of antipsychotics to elderly patients remains very high in Denmark. This report reflects on the importance of keeping DLB...... to differentiate between the two diagnoses....

  5. Lewis, Prof. Gilbert Newton

    Indian Academy of Sciences (India)

    Home; Fellowship. Fellow Profile. Elected: 1935 Honorary. Lewis, Prof. Gilbert Newton. Date of birth: 25 October 1875. Date of death: 24 March 1946. YouTube; Twitter; Facebook; Blog. Academy News. IAS Logo. Theory Of Evolution. Posted on 23 January 2018. Joint Statement by the Three Science Academies of India on ...

  6. Streptomyces clavuligerus shows a strong association between TCA cycle intermediate accumulation and clavulanic acid biosynthesis.

    Science.gov (United States)

    Ramirez-Malule, Howard; Junne, Stefan; Nicolás Cruz-Bournazou, Mariano; Neubauer, Peter; Ríos-Estepa, Rigoberto

    2018-05-01

    Clavulanic acid (CA) is produced by Streptomyces clavuligerus (S. clavuligerus) as a secondary metabolite. Knowledge about the carbon flux distribution along the various routes that supply CA precursors would certainly provide insights about metabolic performance. In order to evaluate metabolic patterns and the possible accumulation of tricarboxylic acid (TCA) cycle intermediates during CA biosynthesis, batch and subsequent continuous cultures with steadily declining feed rates were performed with glycerol as the main substrate. The data were used to in silico explore the metabolic capabilities and the accumulation of metabolic intermediates in S. clavuligerus. While clavulanic acid accumulated at glycerol excess, it steadily decreased at declining dilution rates; CA synthesis stopped when glycerol became the limiting substrate. A strong association of succinate, oxaloacetate, malate, and acetate accumulation with CA production in S. clavuligerus was observed, and flux balance analysis (FBA) was used to describe the carbon flux distribution in the network. This combined experimental and numerical approach also identified bottlenecks during the synthesis of CA in a batch and subsequent continuous cultivation and demonstrated the importance of this type of methodologies for a more advanced understanding of metabolism; this potentially derives valuable insights for future successful metabolic engineering studies in S. clavuligerus.

  7. DFT Investigation of the Diastereoselectivity of the MX2and MX3Lewis-Acid-Catalyzed Mukaiyama Aldol Reaction between C,O,O-Tris(trimethylsilyl)ketene Acetal and Aldehydes.

    Science.gov (United States)

    Mohamed, Slim Hadj; Champagne, Benoît; Trabelsi, Mahmoud

    2018-03-01

    The kinetics and diastereoselectivity of the Mukaiyama aldol reaction between C,O,O-tris(trimethylsilyl)ketene acetal and aldehydes bearing alkyl, vinyl, and aromatic substituents is influenced by the nature of Lewis acid catalysts. A density functional theory investigation using the M06-2X exchange-correlation functional and the PCM scheme to account for solvent effects has been carried out to characterize the structure and energetics of the transition state when the Lewis acid is ZnBr 2 (MX 2 ) or GaCl 3 (MX 3 ) in comparison to the uncatalyzed reaction. The main observations are that (i) the pro-syn transition states are always more stable than the pro-anti ones; (ii) for MX 2 , the transition state presents a cyclic structure, whereas it is open for MX 3 , owing to steric interactions; (iii) the difference of activation free enthalpy between the pro-anti and pro-syn transition states decreases when the reaction is catalyzed, by either MX 2 or MX 3 , demonstrating a reduction of the diastereoselectivity with respect to the uncatalyzed reaction; (iv) this decrease of diastereoselectivity is larger for MX 3 - than for MX 2 -catalyzed reactions; and (v) the MX 3 -catalyzed reactions are kinetically favored by 1-2 kcal mol -1 with respect to the MX 2 ones.

  8. Effect of Bronsted Acids and Bases, and Lewis Acid (Sn(2+)) on the Regiochemistry of the Reaction of Amines with Trifluoromethyl-β-diketones: Reaction of 3-Aminopyrrole to Selectively Produce Regioisomeric 1H-Pyrrolo[3,2-b]pyridines.

    Science.gov (United States)

    De Rosa, Michael; Arnold, David; Hartline, Douglas; Truong, Linda; Verner, Roman; Wang, Tianwei; Westin, Christian

    2015-12-18

    Reaction of 3-aminopyrrole (as its salt) with trifluoromethyl-β-diketones gave γ-1H-pyrrolo[3,2-b]pyridines via reaction at the less reactive carbonyl group. The trifluoromethyl group increased the electrophilicity of the adjacent carbonyl group and decreased the basicity of the hydroxyl group of the CF3 amino alcohol formed. This amino alcohol was formed faster, but its subsequent dehydration to the β-enaminone was slow resulting in the preferential formation of the γ-regioisomer. Reaction of 4,4,4-trifluoro-1-phenyl-1,3-butadione with 3-aminopyrrole was carried out using a series of 6 amine buffers. Yields of the α-1H-pyrrolo[3,2-b]pyridine increased as the pKa of the amine buffer decreased. Surprisingly the yield went down at higher pKas. There was a change in mechanism as the reaction mixture became more basic. With strong amines trifluoromethyl-β-diketones were present mainly or completely as the enolate. Under reductive conditions (3-nitropyrrole/Sn/AcOH/trifluoromethyl-β-diketone) the α-1H-pyrrolo[3,2-b]pyridine was the major product as a result of Lewis acid catalysis by Sn(2+). Similar α-regiochemistry was observed when the reaction of the 3-aminopyrrole salt with trifluoromethyl-β-diketones was carried out in the presence of base and tin(II) acetate.

  9. Kinetics and Thermodynamics of Reserpine Adsorption onto Strong Acidic Cationic Exchange Fiber

    Science.gov (United States)

    Guo, Zhanjing; Liu, Xiongmin; Huang, Hongmiao

    2015-01-01

    The kinetics and thermodynamics of the adsorption process of reserpine adsorbed onto the strong acidic cationic exchange fiber (SACEF) were studied by batch adsorption experiments. The adsorption capacity strongly depended on pH values, and the optimum reserpine adsorption onto the SACEF occurred at pH = 5 of reserpine solution. With the increase of temperature and initial concentration, the adsorption capacity increased. The equilibrium was attained within 20 mins. The adsorption process could be better described by the pseudo-second-order model and the Freundlich isotherm model. The calculated activation energy Ea was 4.35 kJ/mol. And the thermodynamic parameters were: 4.97thermodynamic parameters demonstrated that the adsorption was an endothermic, spontaneous and feasible process of physisorption within the temperature range between 283 K and 323 K and the initial concentration range between 100 mg/L and 300 mg/L. All the results showed that the SACEF had a good adsorption performance for the adsorption of reserpine from alcoholic solution. PMID:26422265

  10. Synthesis and Mössbauer spectroscopy of formal tin(II) dichloride and dihydride species supported by Lewis acids and bases.

    Science.gov (United States)

    Al-Rafia, S M Ibrahim; Shynkaruk, Olena; McDonald, Sean M; Liew, Sean K; Ferguson, Michael J; McDonald, Robert; Herber, Rolfe H; Rivard, Eric

    2013-05-06

    (119)Sn Mössbauer spectroscopy was performed on a series of formal Sn(II) dichloride and dihydride adducts bound by either carbon- or phosphorus-based electron pair donors. Upon binding electron-withdrawing metal pentacarbonyl units to the tin centers in LB·SnCl2·M(CO)5 (LB = Lewis base; M = Cr or W), a significant decrease in isomer shift (IS) was noted relative to the unbound Sn(II) complexes, LB·SnCl2, consistent with removal of nonbonding s-electron density from tin upon forming Sn-M linkages (M = Cr and W). Interestingly, when the nature of the Lewis base in the series LB·SnCl2·W(CO)5 was altered, very little change in the IS values was noted, implying that the LB-Sn bonds were constructed with tin-based orbitals of large p-character (as supported by prior theoretical studies). In addition, variable temperature Mössbauer measurements were used to determine the mean displacement of the tin atoms in the solid state, a parameter that can be correlated with the degree of covalent bonding involving tin in these species.

  11. An online computer method for the potentiometric titration of mixtures of a strong and a weak acid

    NARCIS (Netherlands)

    Bos, M.

    1977-01-01

    A PDP-11 online computer method for the titration of mixtures or a strong and a weak acid is described.The method is based on multiparametric curve-fitting. One or the parameters found from the calculations is the dissociation constant of the weak acid, hence the method can be applied even when this

  12. Bactericidal Effect of Strong Acid Electrolyzed Water against Flow Enterococcus faecalis Biofilms.

    Science.gov (United States)

    Cheng, Xiaogang; Tian, Yu; Zhao, Chunmiao; Qu, Tiejun; Ma, Chi; Liu, Xiaohua; Yu, Qing

    2016-07-01

    This study evaluated the bactericidal effect of strong acid electrolyzed water (SAEW) against flow Enterococcus faecalis biofilm and its potential application as a root canal irrigant. Flow E. faecalis biofilms were generated under a constant shear flow in a microfluidic system. For comparison, static E. faecalis biofilms were generated under a static condition on coverslip surfaces. Both the flow and static E. faecalis biofilms were treated with SAEW. Sodium hypochlorite (NaOCl, 5.25%) and normal saline (0.9%) were included as the controls. Bacterial reductions were evaluated using confocal laser scanning microscopy and the cell count method. Morphological changes of bacterial cells were observed using scanning electron microscopy. The confocal laser scanning microscopic and cell count results showed that SAEW had a bactericidal effect similar to that of 5.25% NaOCl against both the flow and static E. faecalis biofilms. The scanning electron microscopic results showed that smooth, consecutive, and bright bacteria surfaces became rough, shrunken, and even lysed after treated with SAEW, similar to those in the NaOCl group. SAEW had an effective bactericidal effect against both the flow and static E. faecalis biofilms, and it might be qualified as a root canal irrigant for effective root canal disinfection. Copyright © 2016 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  13. Ion-exchange equilibrium of N-acetyl-D-neuraminic acid on a strong anionic exchanger.

    Science.gov (United States)

    Wu, Jinglan; Ke, Xu; Zhang, Xudong; Zhuang, Wei; Zhou, Jingwei; Ying, Hanjie

    2015-09-15

    N-acetyl-D-neuraminic acid (Neu5Ac) is a high value-added product widely applied in the food industry. A suitable equilibrium model is required for purification of Neu5Ac based on ion-exchange chromatography. Hence, the equilibrium uptake of Neu5Ac on a strong anion exchanger, AD-1 was investigated experimentally and theoretically. The uptake of Neu5Ac by the hydroxyl form of the resin occurred primarily by a stoichiometric exchange of Neu5Ac(-) and OH(-). The experimental data showed that the selectivity coefficient for the exchange of Neu5Ac(-) with OH(-) was a non-constant quantity. Subsequently, the Saunders' model, which took into account the dissociation reactions of Neu5Ac and the condition of electroneutrality, was used to correlate the Neu5Ac sorption isotherms at various solution pHs and Neu5Ac concentrations. The model provided an excellent fit to the binary exchange data for Cl(-)/OH(-) and Neu5Ac(-)/OH(-), and an approximate prediction of equilibrium in the ternary system Cl(-)/Neu5Ac(-)/OH(-). This basic information combined with the general mass transfer model could lay the foundation for the prediction of dynamic behavior of fixed bed separation process afterwards. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. One-pot synthesis of polyhydropyridine derivatives via Hantzsch four component condensation in water medium: Use of a recyclable Lewis acid [Ce(SO42.4H2O] catalyst

    Directory of Open Access Journals (Sweden)

    Elaheh Mosaddegh

    2012-12-01

    Full Text Available An efficient and eco-friendly method for the synthesis of polyhydroquinoline derivatives using Ce(SO42.4H2O as mild and heterogeneous Lewis acid catalyst via the Hantzsch reaction in very short reaction time is reported. A mixture of an appropriate aldehyde, dimedone, ethyl acetoacetate and malononitrile in the presence of the Ce(SO42.4H2O at reflux conditions in water based media resulted in good to excellent yields of the corresponding products. The catalyst can be used as selective for some aromatic aldehydes in the reaction conditions.DOI: http://dx.doi.org/10.4314/bcse.v26i3.16

  15. A Biography of Distinguished Scientist Gilbert Newton Lewis (by Edward S. Lewis)

    Science.gov (United States)

    Harris, Reviewed By Harold H.

    1999-11-01

    The Edward Mellen Press: Lewiston, NY, 1998. 114 pp + index. ISBN 0-7734-8284-9. $69.95. There may not be a surname better known to students of chemistry than Lewis, from the Lewis electron-dot diagrams and the Lewis theory of acids and bases. More advanced students may know of the groundbreaking textbook Thermodynamics, by Lewis and Randall. Yet few Americans know much about this remarkable U.S.-born scholar, whose contributions equal those of the greatest scientists. He is a chemist-educator of whom we should be as proud and as well informed as we are of Linus Pauling, who was part of the westward movement of science in this country that G. N. Lewis began, or of the recently deceased Glenn Seaborg, who was one of the many students of Lewis who achieved renown. Gilbert N. Lewis was born in Weymouth, Massachusetts, in 1875, but his family moved to near Lincoln, Nebraska, in 1884. He spent two years at the University of Nebraska, but then moved to Harvard when his father became an executive at Merchants Trust Company in Boston. Young Lewis (then only 17) was also said to have been disappointed with the quality of education in Nebraska, and this may have been part of the impetus for the family's move east. After earning his baccalaureate at Harvard, he taught for a year at Phillips Andover Academy before returning to Harvard to study for his doctorate, which he completed 100 years ago, in 1899, under T. W. Richards. Lewis's doctoral work was on the thermodynamics of zinc and cadmium amalgams. At that time, physical chemistry was only beginning to achieve recognition as a branch of science, and its boundaries were ill defined. Edward Lewis quotes his father as often saying, "Physical chemistry is anything interesting." Like many chemists of his time, Lewis went to Europe to complete his preparation for a career; he was in the laboratories of Ostwald in Leipzig and Nernst in Göttingen in 1900-1901. On his return to the United States, he was an instructor at Harvard

  16. Remarkable Enhancement of the Hole Mobility in Several Organic Small-Molecules, Polymers, and Small-Molecule:Polymer Blend Transistors by Simple Admixing of the Lewis Acid p-Dopant B(C6F5)3.

    Science.gov (United States)

    Panidi, Julianna; Paterson, Alexandra F; Khim, Dongyoon; Fei, Zhuping; Han, Yang; Tsetseris, Leonidas; Vourlias, George; Patsalas, Panos A; Heeney, Martin; Anthopoulos, Thomas D

    2018-01-01

    Improving the charge carrier mobility of solution-processable organic semiconductors is critical for the development of advanced organic thin-film transistors and their application in the emerging sector of printed electronics. Here, a simple method is reported for enhancing the hole mobility in a wide range of organic semiconductors, including small-molecules, polymers, and small-molecule:polymer blends, with the latter systems exhibiting the highest mobility. The method is simple and relies on admixing of the molecular Lewis acid B(C 6 F 5 ) 3 in the semiconductor formulation prior to solution deposition. Two prototypical semiconductors where B(C 6 F 5 ) 3 is shown to have a remarkable impact are the blends of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene:poly(triarylamine) (diF-TESADT:PTAA) and 2,7-dioctyl[1]-benzothieno[3,2-b][1]benzothiophene:poly(indacenodithiophene-co-benzothiadiazole) (C8-BTBT:C16-IDTBT), for which hole mobilities of 8 and 11 cm 2 V -1 s -1 , respectively, are obtained. Doping of the 6,13-bis(triisopropylsilylethynyl)pentacene:PTAA blend with B(C 6 F 5 ) 3 is also shown to increase the maximum hole mobility to 3.7 cm 2 V -1 s -1 . Analysis of the single and multicomponent materials reveals that B(C 6 F 5 ) 3 plays a dual role, first acting as an efficient p-dopant, and secondly as a microstructure modifier. Semiconductors that undergo simultaneous p-doping and dopant-induced long-range crystallization are found to consistently outperform transistors based on the pristine materials. Our work underscores Lewis acid doping as a generic strategy towards high performance printed organic microelectronics.

  17. Remarkable Enhancement of the Hole Mobility in Several Organic Small-Molecules, Polymers, and Small-Molecule:Polymer Blend Transistors by Simple Admixing of the Lewis Acid p-Dopant B(C6F5)3

    KAUST Repository

    Panidi, Julianna

    2017-10-05

    Improving the charge carrier mobility of solution-processable organic semiconductors is critical for the development of advanced organic thin-film transistors and their application in the emerging sector of printed electronics. Here, a simple method is reported for enhancing the hole mobility in a wide range of organic semiconductors, including small-molecules, polymers, and small-molecule:polymer blends, with the latter systems exhibiting the highest mobility. The method is simple and relies on admixing of the molecular Lewis acid B(C6F5)(3) in the semiconductor formulation prior to solution deposition. Two prototypical semiconductors where B(C6F5)(3) is shown to have a remarkable impact are the blends of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene:poly(triarylamine) (diF-TESADT:PTAA) and 2,7-dioctyl[1]-benzothieno[3,2-b][1]benzothiophene:poly(indacenodithiophene-co-benzothiadiazole) (C8-BTBT:C16-IDTBT), for which hole mobilities of 8 and 11 cm(2) V-1 s(-1), respectively, are obtained. Doping of the 6,13-bis(triisopropylsilylethynyl)pentacene:PTAA blend with B(C6F5)(3) is also shown to increase the maximum hole mobility to 3.7 cm(2) V-1 s(-1). Analysis of the single and multicomponent materials reveals that B(C6F5)(3) plays a dual role, first acting as an efficient p-dopant, and secondly as a microstructure modifier. Semiconductors that undergo simultaneous p-doping and dopant-induced long-range crystallization are found to consistently outperform transistors based on the pristine materials. Our work underscores Lewis acid doping as a generic strategy towards high performance printed organic microelectronics.

  18. Lewy Body Digest eNewsletter

    Science.gov (United States)

    ... latest developments in treatment and research in Lewy body dementia. February 2018 Lewy Digest Month of Courage ... 1 2 next › last » All Rights Reserved Lewy Body Dementia Association, Inc. 912 Killian Hill Road S.W., ...

  19. Lewy Body Digest eNewsletter

    Science.gov (United States)

    ... resources Join the fight against LBD! Donate Lewy Digest Click here to subscribe today to receive regular ... research in Lewy body dementia. April 2018 Lewy Digest Month of Compassion Caregiver Spotlight Research Centers of ...

  20. Selective lanthanide sorption and mechanism using novel hybrid Lewis base (N-methyl-N-phenyl-1,10-phenanthroline-2-carboxamide) ligand modified adsorbent

    International Nuclear Information System (INIS)

    Awual, Md. Rabiul; Kobayashi, Tohru; Miyazaki, Yuji; Motokawa, Ryuhei; Shiwaku, Hideaki; Suzuki, Shinichi; Okamoto, Yoshihiro; Yaita, Tsuyoshi

    2013-01-01

    Highlights: •Hybrid Lewis base adsorbent was prepared for selective lanthanide (Eu, Sm) removal. •Common ions did not interfere due to strong interactions between Eu/Sm and adsorbent. •The adsorbent has good sorption and kinetic performances for potential applications. •The adsorption is reversible and adsorbent reusable in many cycles without any deterioration. -- Abstract: This study aims to develop a highly selective Lewis base adsorbent to investigate the selective sorption and recovery of Eu(III) and Sm(III) from wastewater. The oxygen and nitrogen donor atoms containing Lewis base N-methyl-N-phenyl-1,10-phenanthroline-2-carboxamide (MePhPTA) ligand was synthesized and subsequently an adsorbent was prepared by direct immobilization onto mesoporous silica. Determined maximum adsorption capacities were 125.63 and 124.38 mg/g for Eu(III) and Sm(III), respectively. Experiments with mixed-cations solutions showed that the sequence of preferential adsorption was Eu(III) > Sm(III). The lanthanide sorption by hybrid Lewis base adsorbent (HyLBA) was not adversely affected by the presence of sodium, potassium, calcium, magnesium, chloride, sulfate and nitrate ions due to strong affinity between hard Lewis acid lanthanide and hard Lewis base adsorbent. The crystallography for the Sm-MePhPTA complex suggested that MePhPTA was strongly coordinated to Sm(III) with oxygen and nitrogen by forming a stable complex with two 5-membered rings. The data clarified that bond lengths between Sm(III) and amide oxygen (2.475 Å) were shorter than Sm-N (2.662 Å) in phenanthroline moiety indicating strong oxygen driven HyLBA. The results suggested that HyLBA has a good prospect of promising applications for separation/sorption of lanthanide ions from effluents

  1. A contribution to the problem of strong acid determination in air

    Science.gov (United States)

    Dieter Klockow; Helmut Denzinger; Gerhard R& #246; nicke; Gerhard nicke

    1976-01-01

    The main indicator for acidic substances in the atmosphere is, now as before, the pH of rainwater. Factors influencing the acidity of precipitation are discussed, using results of air monitoring stations in Germany.

  2. Reaction of aromatic azides with strong acids: formation of fused nitrogen heterocycles and arylamines

    Directory of Open Access Journals (Sweden)

    Carvalho Marcia de

    1999-01-01

    Full Text Available We describe in this paper the action of trifluoroacetic acid, trifluoromethanesulfonic acid and aluminum chloride upon ortho-substituted aryl azides to form indoles, azepines and arylamines in good yields. The protonated azides lose nitrogen to form arylnitrenium ion intermediates which undergo intramolecular aromatic N-substitution. The acid decomposition of aryl azides is compared with reported thermolyses.

  3. Isolation of a thermostable acid phytase from Aspergillus niger UFV-1 with strong proteolysis resistance

    Directory of Open Access Journals (Sweden)

    Paulo S. Monteiro

    2015-03-01

    Full Text Available An Aspergillus niger UFV-1 phytase was characterized and made available for industrial application. The enzyme was purified via ultrafiltration followed by acid precipitation, ion exchange and gel filtration chromatography. This protein exhibited a molecular mass of 161 kDa in gel filtration and 81 kDa in sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE, indicating that it may be a dimer. It presented an optimum temperature of 60 °C and optimum pH of 2.0. The KM for sodium phytate hydrolysis was 30.9 mM, while the kcat and kcat/KM were 1.46 ×105 s−1 and 4.7 × 106s−1.M−1, respectively. The purified phytase exhibited broad specificity on a range of phosphorylated compounds, presenting activity on sodium phytate, p-NPP, 2- naphthylphosphate, 1- naphthylphosphate, ATP, phenyl-phosphate, glucose-6-phosphate, calcium phytate and other substrates. Enzymatic activity was slightly inhibited by Mg2+, Cd2+, K+ and Ca2+, and it was drastically inhibited by F−. The enzyme displayed high thermostability, retaining more than 90% activity at 60 °C during 120 h and displayed a t1/2 of 94.5 h and 6.2 h at 70 °C and 80 °C, respectively. The enzyme demonstrated strong resistance toward pepsin and trypsin, and it retained more than 90% residual activity for both enzymes after 1 h treatment. Additionally, the enzyme efficiently hydrolyzed phytate in livestock feed, liberating 15.3 μmol phosphate/mL after 2.5 h of treatment.

  4. Ferrocene-based Lewis acids and Lewis pairs: Synthesis and ...

    Indian Academy of Sciences (India)

    Acta. 360 3323; c) Scheibitz M,. Bats J W, Bolte M, Lerner H-W and Wagner M 2004. Organometallics 23 940; d) Scheibitz M, Bats J W, Bolte. M and Wagner M 2003 Eur. J. Inorg. Chem. 2049; e). Ma K, Scheibitz M, Scholz S and Wagner M 2002 J. Organomet. Chem. 652 11. 11. a) Day J K, Bresner C, Coombs N D, Fallis I A, ...

  5. Simultaneous estimation of a binary mixture of a weak acid and a strong acid by volumetric titration and pH measurement

    International Nuclear Information System (INIS)

    Karmakar, Sanat; Mallika, C.; Kamachi Mudali, U.

    2012-01-01

    High level liquid waste (HLLW) generated in the aqueous reprocessing of spent nuclear fuels for the separation of uranium and plutonium by PUREX process, comprises the fission and corrosion products in 4 M nitric acid. Reduction in waste volume is accomplished by destroying the acidity of the waste solution from 4 to less than 2 M by treating it with formaldehyde and subsequent concentration by evaporation. In the denitration by HCHO, nitric acid in the waste solution is reduced to NOx and water via nitrous acid as the intermediate product: whereas formaldehyde is oxidized to formic acid which is converted to CO 2 and H 2 O subsequently. The reaction is highly exothermic and the release of all gaseous products may lead to uncontrollable process conditions. Hence, for the safe operation, it is desirable to estimate the concentration of residual formic acid as well as nitric acid in the product stream as a function of time. The acidity in the feed solution is 4 M and the concentration of HNO 3 in the product solution is in the range 1- 4 M. Since the formic acid generated during the reaction will be consumed immediately, the concentration of residual acid will be in the range 0.05-0.5 M. A simultaneous titration method based on pH measurement and volumetric analysis has been developed in the present work for the quantitative determination of the weak acid (HCOOH)with known pKa value and the strong acid (HNO 3 ) in the binary mixture

  6. Serum uric acid: A strong and independent predictor of metabolic syndrome after adjusting for body composition.

    Science.gov (United States)

    Yu, Tae Yang; Jee, Jae Hwan; Bae, Ji Cheol; Jin, Sang-Man; Baek, Jong-Ha; Lee, Moon-Kyu; Kim, Jae Hyeon

    2016-04-01

    Some observational studies have suggested that serum uric acid (SUA) levels are one of the determinants of the metabolic syndrome (MetS). However, previous studies reported combined results for men and women after adjusting for sex and few studies take body composition into consideration. Therefore, we performed this sex-specific longitudinal study to investigate how baseline SUA levels influence incident MetS, including body composition as an adjusting factor in a large number of subjects. A total of 14,442 participants (8715 men and 5727 women) participating in a medical health check-up program without diagnosed MetS at baseline were enrolled. Separate analyses were performed for men and women including body composition as a confounding factor. Cox proportional hazards models were used to quantify independent associations between SUA levels and incident MetS. During 63,940person-years of follow-up, there were 4215 (2974 men, 1241 women) incident cases of MetS between 2006 and 2012. After adjustments for age, systolic BP, diastolic BP, BMI, eGFR, smoking status, TG, LDL-C, HDL-C, fasting glucose, and proportion of fat-free mass (100-fat mass, %), the hazard ratios (HR) [95% confidence interval (CI)] for incident MetS comparing the second, the third, and the fourth quartiles to the first quartile of SUA levels were 0.862 (0.770-0.965), 1.102 (0.991-1.225), and 1.246 (1.121-1.385) in men (p for trend<0.001), and 1.045 (0.862-1.266), 1.251 (1.050-1.490), and 1.321 (1.109-1.574) in women (p for trend<0.001), respectively. As a continuous variable, in fully-adjusted models, the HRs (95% CI) for incident MetS associated with each increase of 1mg/dl of SUA levels were 1.094 (1.060-1.130) in men (p<0.001) and 1.148 (1.072-1.228) in women (p<0.001), respectively. We demonstrated that SUA levels are strong and independent predictors of MetS. This relationship remained significant after full adjustments for multiple associated confounders including body composition in both

  7. Strong Hydrogen Bonded Molecular Interactions between Atmospheric Diamines and Sulfuric Acid.

    Science.gov (United States)

    Elm, Jonas; Jen, Coty N; Kurtén, Theo; Vehkamäki, Hanna

    2016-05-26

    We investigate the molecular interaction between methyl-substituted N,N,N',N'-ethylenediamines, propane-1,3-diamine, butane-1,4-diamine, and sulfuric acid using computational methods. Molecular structure of the diamines and their dimer clusters with sulfuric acid is studied using three density functional theory methods (PW91, M06-2X, and ωB97X-D) with the 6-31++G(d,p) basis set. A high level explicitly correlated CCSD(T)-F12a/VDZ-F12 method is used to obtain accurate binding energies. The reaction Gibbs free energies are evaluated and compared with values for reactions involving ammonia and atmospherically relevant monoamines (methylamine, dimethylamine, and trimethylamine). We find that the complex formation between sulfuric acid and the studied diamines provides similar or more favorable reaction free energies than dimethylamine. Diamines that contain one or more secondary amino groups are found to stabilize sulfuric acid complexes more efficiently. Elongating the carbon backbone from ethylenediamine to propane-1,3-diamine or butane-1,4-diamine further stabilizes the complex formation with sulfuric acid by up to 4.3 kcal/mol. Dimethyl-substituted butane-1,4-diamine yields a staggering formation free energy of -19.1 kcal/mol for the clustering with sulfuric acid, indicating that such diamines could potentially be a key species in the initial step in the formation of new particles. For studying larger clusters consisting of a diamine molecule with up to four sulfuric acid molecules, we benchmark and utilize a domain local pair natural orbital coupled cluster (DLPNO-CCSD(T)) method. We find that a single diamine is capable of efficiently stabilizing sulfuric acid clusters with up to four acid molecules, whereas monoamines such as dimethylamine are capable of stabilizing at most 2-3 sulfuric acid molecules.

  8. SOLVENT EFFECTS IN THE LIQUID-PHASE HYDRATION OF CYCLOHEXENE CATALYZED BY A MACROPOROUS STRONG ACID ION-EXCHANGE RESIN

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    1992-01-01

    The liquid-phase hydration of cyclohexene, a pseudo first order reversible reaction catalyzed by a strong acid ion exchange resin, macroporous Amberlite XE 307, was investigated in solvent mixtures of water and sulfolane. A decrease by a factor of 3 and 6 is observed in the experimentally measured

  9. Experimental Observation of Strongly Bound Dimers of Sulfuric Acid: Application to Nucleation in the Atmosphere

    DEFF Research Database (Denmark)

    Petaja, Tuukka; Sipila, Mikko; Paasonen, Pauli

    2011-01-01

    Sulfuric acid is a key compound in atmospheric nucleation. Here we report on the observation of a close-to-collision-limited sulfuric acid dimer formation in atmospherically relevant laboratory conditions in the absence of measurable quantities of ammonia or organics. The observed dimer formation...... compound(s) with (a) concentration(s) high enough to prevent the dimer evaporation. Such a stabilizing compound should be abundant enough in any natural environment and would therefore not limit the formation of sulfuric acid dimers in the atmosphere....

  10. On the axisymmetric Lewis metric

    International Nuclear Information System (INIS)

    Gariel, J.; Marcilhacy, G.

    2001-03-01

    We obtain the general solution of the axisymmetric stationary vacuum spacetime of Lewis. After precising the fundamental hypothesis of Lewis, we demonstrate that the solution is related to an arbitrary harmonic function. Formally, these solutions are the same as for the corresponding cylindrically symmetric case, and can be classified in a similar way. Furthermore, the interpretation, in the cylindrically symmetric system, of the field equations as decribing the motion of a classical particle in a central force field is still valid. (author)

  11. Substrate and Lewis Acid Coordination Promote O-O Bond Cleavage of an Unreactive L2CuII2(O22-) Species to Form L2CuIII2(O)2 Cores with Enhanced Oxidative Reactivity.

    Science.gov (United States)

    Garcia-Bosch, Isaac; Cowley, Ryan E; Díaz, Daniel E; Peterson, Ryan L; Solomon, Edward I; Karlin, Kenneth D

    2017-03-01

    Copper-dependent metalloenzymes are widespread throughout metabolic pathways, coupling the reduction of O 2 with the oxidation of organic substrates. Small-molecule synthetic analogs are useful platforms to generate L/Cu/O 2 species that reproduce the structural, spectroscopic, and reactive properties of some copper-/O 2 -dependent enzymes. Landmark studies have shown that the conversion between dicopper(II)-peroxo species (L 2 Cu II 2 (O 2 2- ) either side-on peroxo, S P, or end-on trans-peroxo, T P) and dicopper(III)-bis(μ-oxo) (L 2 Cu III 2 (O 2- ) 2 : O) can be controlled through ligand design, reaction conditions (temperature, solvent, and counteranion), or substrate coordination. We recently published ( J. Am. Chem. Soc. 2012 , 134 , 8513 , DOI: 10.1021/ja300674m ) the crystal structure of an unusual S P species [(MeAN) 2 Cu II 2 (O 2 2- )] 2+ ( S P MeAN , MeAN: N-methyl-N,N-bis[3-(dimethylamino)propyl]amine) that featured an elongated O-O bond but did not lead to O-O cleavage or reactivity toward external substrates. Herein, we report that S P MeAN can be activated to generate O MeAN and perform the oxidation of external substrates by two complementary strategies: (i) coordination of substituted sodium phenolates to form the substrate-bound O MeAN -RPhO - species that leads to ortho-hydroxylation in a tyrosinase-like fashion and (ii) addition of stoichiometric amounts (1 or 2 equiv) of Lewis acids (LA's) to form an unprecedented series of O-type species (O MeAN -LA) able to oxidize C-H and O-H bonds. Spectroscopic, computational, and mechanistic studies emphasize the unique plasticity of the S P MeAN core, which combines the assembly of exogenous reagents in the primary (phenolates) and secondary (Lewis acids association to the MeAN ligand) coordination spheres with O-O cleavage. These findings are reminiscent of the strategy followed by several metalloproteins and highlight the possible implication of O-type species in copper-/dioxygen-dependent enzymes

  12. Effect of Strong Acid Functional Groups on Electrode Rise Potential in Capacitive Mixing by Double Layer Expansion

    KAUST Repository

    Hatzell, Marta C.

    2014-12-02

    © 2014 American Chemical Society. The amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10-5) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g-1) had a positive rise potential of 59 ± 4 mV in the LC solution, whereas the carbon with the highest concentration (0.36 mmol g-1) had a negative rise potential (-31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to -6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. These results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons.

  13. Comparison of three strong ion models used for quantifying the acid-base status of human plasma with special emphasis on the plasma weak acids.

    Science.gov (United States)

    Anstey, Chris M

    2005-06-01

    Currently, three strong ion models exist for the determination of plasma pH. Mathematically, they vary in their treatment of weak acids, and this study was designed to determine whether any significant differences exist in the simulated performance of these models. The models were subjected to a "metabolic" stress either in the form of variable strong ion difference and fixed weak acid effect, or vice versa, and compared over the range 25 titration curves. The results were analyzed for linearity by using ordinary least squares regression and for collinearity by using correlation. In every case, the results revealed a linear relationship between log(Pco(2)) and pH over the range 6.8 acid-base physiology and by the ease of measurement of the independent model parameters.

  14. The tricarboxylic acid cycle activity in cultured primary astrocytes is strongly accelerated by the protein tyrosine kinase inhibitor tyrphostin 23

    DEFF Research Database (Denmark)

    Hohnholt, Michaela C; Blumrich, Eva-Maria; Waagepetersen, Helle S

    2017-01-01

    Tyrphostin 23 (T23) is a well-known inhibitor of protein tyrosine kinases and has been considered as potential anti-cancer drug. T23 was recently reported to acutely stimulate the glycolytic flux in primary cultured astrocytes. To investigate whether T23 also affects the tricarboxylic acid (TCA...... production. In addition, T23-treatment strongly increased the molecular carbon labeling of the TCA cycle intermediates citrate, succinate, fumarate and malate, and significantly increased the incorporation of (13)C-labelling into the amino acids glutamate, glutamine and aspartate. These results clearly...... demonstrate that, in addition to glycolysis, also the mitochondrial TCA cycle is strongly accelerated after exposure of astrocytes to T23, suggesting that a protein tyrosine kinase may be involved in the regulation of the TCA cycle in astrocytes....

  15. Evaluation of DNA typing as a positive identification method for soft and hard tissues immersed in strong acids.

    Science.gov (United States)

    Robino, C; Pazzi, M; Di Vella, G; Martinelli, D; Mazzola, L; Ricci, U; Testi, R; Vincenti, M

    2015-11-01

    Identification of human remains can be hindered by several factors (e.g., traumatic mutilation, carbonization or decomposition). Moreover, in some criminal cases, offenders may purposely adopt various expedients to thwart the victim's identification, including the dissolution of body tissues by the use of corrosive reagents, as repeatedly reported in the past for Mafia-related murders. By means of an animal model, namely porcine samples, we evaluated standard DNA typing as a method for identifying soft (muscle) and hard (bone and teeth) tissues immersed in strong acids (hydrochloric, nitric and sulfuric acid) or in mixtures of acids (aqua regia). Samples were tested at different time intervals, ranging between 2 and 6h (soft tissues) and 2-28 days (hard tissues). It was shown that, in every type of acid, complete degradation of the DNA extracted from soft tissues preceded tissue dissolution and could be observed within 4h of immersion. Conversely, high molecular weight DNA amenable to STR analysis could be isolated from hard tissues as long as cortical bone fragments were still present (28 days for sulfuric acid, 7 days for nitric acid, 2 days for hydrochloric acid and aqua regia), or the integrity of the dental pulp chamber was preserved (7 days, in sulfuric acid only). The results indicate that DNA profiling of acid-treated body parts (in particular, cortical bone) is still feasible at advanced stages of corrosion, even when the morphological methods used in forensic anthropology and odontology can no longer be applied for identification purposes. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  16. Rational design of sterically and electronically easily tunable chiral bisimidazolines and their applications in dual Lewis acid/brønsted base catalysis for highly enantioselective nitroaldol (Henry) reactions.

    Science.gov (United States)

    Ma, Kuoyan; You, Jingsong

    2007-01-01

    A new addition to the rational design of sterically and electrically easily tunable chiral bis(imidazoline) ligands from chiral amino alcohols has been developed. Vast structural variation of chiral bis(imidazoline) ligands can be simply achieved by the choice of both the 1,2-amino alcohol and its N-1 R1 substituent. A small library of chiral bisimidazolines (1 a-h) has been constructed. The method has provided an easy and simplified route to a diverse set of air-stable and water-tolerant chiral bis(imidazoline) ligands on 10 g scales. The dual Lewis Acid/Brønsted base catalytic system generated from the (S)-1 a/Cu(OTf)2 complex and Et3N was able to catalyze Henry reactions between aldehydes and nitromethane effectively at room temperature, and also to tolerate a wide scope of aldehydes with excellent enantiomeric excesses. Not only aromatic aldehydes but also aliphatic aldehydes afforded the nitroalcohol products, with enantiomeric excesses in the 93-98% range. This dual catalytic system is among the most effective systems so far reported for the asymmetric parent Henry reactions. This work also represents the first members of the class of chiral bisimidazolines to have been demonstrated to achieve excellent enantioselectivities.

  17. Nectar sugars and amino acids in day- and night-flowering Nicotiana species are more strongly shaped by pollinators' preferences than organic acids and inorganic ions.

    Directory of Open Access Journals (Sweden)

    Kira Tiedge

    , nectar sugars and amino acids are more strongly correlated with the preferences of predominant pollinators than organic acids and inorganic ions.

  18. The Activation Mechanism of Bi3+ Ions to Rutile Flotation in a Strong Acidic Environment

    Directory of Open Access Journals (Sweden)

    Wei Xiao

    2017-07-01

    Full Text Available Lead hydroxyl compounds are known as rutile flotation of the traditional activated component, but the optimum pH range for flotation is 2–3 using styryl phosphoric acid (SPA as collector, without lead hydroxyl compounds in slurry solution. In this study, Bi3+ ions as a novel activator was investigated. The results revealed that the presence of Bi3+ ions increased the surface potential, due to the specific adsorption of hydroxyl compounds, which greatly increases the adsorption capacity of SPA on the rutile surface. Bi3+ ions increased the activation sites through the form of hydroxyl species adsorbing on the rutile surface and occupying the steric position of the original Ca2+ ions. The proton substitution reaction occurred between the hydroxyl species of Bi3+ ions (Bi(OHn+(3−n and the hydroxylated rutile surface, producing the compounds of Ti-O-Bi2+. The micro-flotation tests results suggested that Bi3+ ions could improve the flotation recovery of rutile from 61% to 90%, and from 61% to 64% for Pb2+ ions.

  19. Genetics Home Reference: dementia with Lewy bodies

    Science.gov (United States)

    ... dementia with Lewy bodies may also experience a sharp drop in blood pressure upon standing (orthostatic hypotension), ... Genetic Changes Mutations in the SNCA or SNCB gene cause dementia with Lewy bodies . GBA gene mutations ...

  20. Lewis Acid-Induced Change from Four- to Two-Electron Reduction of Dioxygen Catalyzed by Copper Complexes Using Scandium Triflate

    Science.gov (United States)

    Kakuda, Saya; Rolle, Clarence; Ohkubo, Kei; Siegler, Maxime A.; Karlin, Kenneth D.; Fukuzumi, Shunichi

    2015-01-01

    Mononuclear copper complexes, [(tmpa)CuII(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)CuII(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3), in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)CuII(O2)CuII(tmpa)]2+, the two-electron reduced product of O2 with Sc3+ is observed to be scandium peroxide ([Sc3+(O22−)]+). In the presence of three equiv of hexamethylphosphoric triamide (HMPA), [Sc3+(O22−)]+ was oxidized by [Fe(bpy)3]3+ (bpy = 2,2′-bipyridine) to the known superoxide species [(HMPA)3Sc3+(O2•−)]2+ as detected by EPR spectroscopy. A kinetic study revealed that the rate-determining step of the catalytic cycle for the two-electron reduction of O2 with 1 is electron transfer from Fc* to 1 to give a cuprous complex which is highly reactive toward O2, whereas the rate-determining step with 2 is changed to the reaction of the cuprous complex with O2 following electron transfer from ferrocene derivatives to 2. The explanation for the change in catalytic O2-reaction stoichiometry from four-electron with Brønsted acids to two-electron reduction in the presence of Sc3+ and also for the change in the rate-determining step is clarified based on a kinetics interrogation of the overall catalytic cycle as well as each step of the catalytic cycle with study of the observed effects of Sc3+ on copper-oxygen intermediates. PMID:25659416

  1. Crystal structures of three anhydrous salts of the Lewis base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU with the ring-substituted benzoic acid analogues 4-aminobenzoic acid, 3,5-dinitrobenzoic acid and 3,5-dinitrosalicylic acid

    Directory of Open Access Journals (Sweden)

    Graham Smith

    2016-03-01

    Full Text Available The anhydrous salts of the Lewis base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU with 4-aminobenzoic acid [1-aza-8-azoniabicyclo[5.4.0]undec-7-ene 4-aminobenzoate, C9H17N2+·C7H6NO2− (I], 3,5-dinitrobenzoic acid [1-aza-8-azoniabicyclo[5.4.0]undec-7-ene 3,5-dinitrobenzoate, C9H17N2+·C7H3N2O6−, (II] and 3,5-dinitrosalicylic acid (DNSA [1-aza-8-azoniabicyclo[5.4.0]undec-7-ene 2-hydroxy-3,5-dinitrobenzoate, C9H17N2+·C7H3N2O7−, (III] have been determined and their hydrogen-bonded structures are described. In both (II and (III, the DBU cations have a common disorder in three of the C atoms of the six-membered ring moieties [site-occupancy factors (SOF = 0.735 (3/0.265 (3 and 0.686 (4/0.314 (4, respectively], while in (III, there is additional rotational disorder in the DNSA anion, giving two sites (SOF = 0.72/0.28, values fixed for the phenol group. In the crystals of (I and (III, the cation–anion pairs are linked through a primary N—H...Ocarboxyl hydrogen bond [2.665 (2 and 2.869 (3 Å, respectively]. In (II, the ion pairs are linked through an asymmetric three-centre R12(4, N—H...O,O′ chelate association. In (I, structure extension is through amine N—H...Ocarboxyl hydrogen bonds between the PABA anions, giving a three-dimensional structure. The crystal structures of (II and (III are very similar, the cation–anion pairs being associated only through weak C—H...O hydrogen bonds, giving in both overall two-dimensional layered structures lying parallel to (001. No π–π ring associations are present in any of the structures.

  2. Uric Acid Is a Strong Risk Marker for Developing Hypertension From Prehypertension: A 5-Year Japanese Cohort Study.

    Science.gov (United States)

    Kuwabara, Masanari; Hisatome, Ichiro; Niwa, Koichiro; Hara, Shigeko; Roncal-Jimenez, Carlos A; Bjornstad, Petter; Nakagawa, Takahiko; Andres-Hernando, Ana; Sato, Yuka; Jensen, Thomas; Garcia, Gabriela; Rodriguez-Iturbe, Bernardo; Ohno, Minoru; Lanaspa, Miguel A; Johnson, Richard J

    2018-01-01

    Prehypertension frequently progresses to hypertension, a condition associated with high morbidity and mortality from cardiovascular diseases and stroke. However, the risk factors for developing hypertension from prehypertension remain poorly understood. We conducted a retrospective cohort study using the data from 3584 prehypertensive Japanese adults (52.1±11.0 years, 2081 men) found to be prehypertensive in 2004 and reexamined in 2009. We calculated the cumulative incidences of hypertension over 5 years, examined risk factors, and calculated odds ratios (ORs) for developing hypertension after adjustments for age, sex, body mass index, smoking and drinking habits, baseline systolic and diastolic blood pressure, pulse rate, diabetes mellitus, dyslipidemia, chronic kidney disease, and serum uric acid levels. The additional analysis evaluated whether serum uric acid (hyperuricemia) constituted an independent risk factor for developing hypertension. The cumulative incidence of hypertension from prehypertension over 5 years was 25.3%. There were no significant differences between women and men (24.4% versus 26.0%; P =0.28). The cumulative incidence of hypertension in subjects with hyperuricemia (n=726) was significantly higher than those without hyperuricemia (n=2858; 30.7% versus 24.0%; P uric acid (OR, 1.149; P uric acid is a strong risk marker for developing hypertension from prehypertension. Further studies are needed to determine whether treatment of hyperuricemia in prehypertensive subjects could impede the onset of hypertension. © 2017 American Heart Association, Inc.

  3. Strong Quantum Confinement Effects and Chiral Excitons in Bio-Inspired ZnO–Amino Acid Cocrystals

    KAUST Repository

    Muhammed, Madathumpady Abubaker Habeeb

    2018-02-20

    Elucidating the underlying principles behind band gap engineering is paramount for the successful implementation of semiconductors in photonic and optoelectronic devices. Recently it has been shown that the band gap of a wide and direct band gap semiconductor, such as ZnO, can be modified upon cocrystallization with amino acids, with the role of the biomolecules remaining unclear. Here, by probing and modeling the light-emitting properties of ZnO-amino acid cocrystals, we identify the amino acids\\' role on this band gap modulation and demonstrate their effective chirality transfer to the interband excitations in ZnO. Our 3D quantum model suggests that the strong band edge emission blue-shift in the cocrystals can be explained by a quasi-periodic distribution of amino acid potential barriers within the ZnO crystal lattice. Overall, our findings indicate that biomolecule cocrystallization can be used as a truly bio-inspired means to induce chiral quantum confinement effects in quasi-bulk semiconductors.

  4. How Do Lipids Localize in Lewy Bodies?

    NARCIS (Netherlands)

    Chaudhary, Himanshu; Subramaniam, Vinod; Claessens, Mireille

    2014-01-01

    Lewy bodies are the pathological hallmark of Parkinson's disease (PD). While fibrillar α-synuclein (αS) is the main protein component of Lewy bodies, these structures also contain lipids. To elucidate the presence of lipids in Lewy bodies, we investigated the interaction of lipids with monomeric and

  5. Metallocene electrochemistry. 3. Reduction-oxidation study of dicyclopentadienyl compounds of ruthenium and titanium in Lewis acid-base molten salts

    Energy Technology Data Exchange (ETDEWEB)

    Gale, R.J.; Job, R.

    1981-01-01

    Voltammetry at vitreous C electrodes of Ru(eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/ and Ti(eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/Cl/sub 2/ in the 0.8:1 molar ratio AlCl/sub 3/-1 butylpyridinium chloride melt reveals an irreversible oxidation (E/sub p/2/ = = +0.68 V, 100 mV s/sup -1/) and a reversible 1e reduction (E/sub 1/2/ = -0.65 V vs. SCE), respectively. These electrode potentials are comparable to those found for each species in nonaqueous, organic electrolytes. In the acidic melts (excess AlCl/sub 3/), Ru(eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/ is oxidized by multistep pathways sensitive to the melt composition, while the Ti(eta/sup 5/-C/sub 5/H/sub 5/)/sup 2 +/ dication is reduced by a reversible 1e step (E/sub 1/2/ = +0.67 V vs. SCE, 2:1 mole ratio melt) in a pC1/sup -/ dependent process. Electrochemical behavior of each of these metallocenes in neutral 1:1 molar ratio melts is complicated.

  6. Conversion of Dimethyl Ether to Branched Hydrocarbons Over Cu/BEA: the Roles of Lewis Acidic and Metallic Sites in H2 Incorporation

    Energy Technology Data Exchange (ETDEWEB)

    Hensley, Jesse E.; Schaidle, Joshua A.; Ruddy, Daniel A.; Cheah, Singfoong; Habas, Susan E.; Pan, Ming; Zhang, Guanghui; Miller, Jeffrey T.

    2017-04-26

    Conversion of biomass to fuels remains as one of the most promising approach to support our energy needs. It has been previously shown that the gasification of non-edible cellulosic biomass can be used to derive fuels like methanol and dimethyl ether (DME). However, the use of methanol and DME is limited due to the fact that they have low energy densities, poor lubricity and lower viscosity when compared to long-chain hydrocarbons. Increasing the blending percentage can also lead to undesired amounts of oxygenated molecules in the transportation fuel infrastructure, which restrict their applicability as jet or diesel fuels. Consequently, the petroleum-derived hydrocarbons remain as the main constituent of the middle-distillate based fuels. One way to increase the share of biofuels in middle-distillates is to use methanol/DME as building blocks for producing renewable, energy-dense hydrocarbons. One way to achieve this is by catalytically converting the DME and methanol to light olefins, followed by oligomerization to higher molecular weight premium alkanes, which can directly be used as kerosene/diesel fuels. Here, we report the catalytic dimerization of biomass-derived deoxygenated olefins into transportation fuel-range hydrocarbons under liquid-phase stirred-batch conditions. Specifically, the effect of operating conditions, such as reaction temperature, solvent-type, reaction duration and olefin-structure, on the conversion, selectivity and kinetics of dimerization of triptene (2,3,3-trimethyl-1-butene) were investigated. Triptene, as previously reported, is one of the major products of DME-homologation reaction over a BEA zeolite4. We show that triptene can be converted to high quality middle-distillates using a commercially available ion-exchange acid resin, Amberlyst-35 (dry) by the process of catalytic dimerization.

  7. Metal-free hydrogenation catalyzed by an air-stable borane: use of solvent as a frustrated Lewis base.

    Science.gov (United States)

    Scott, Daniel J; Fuchter, Matthew J; Ashley, Andrew E

    2014-09-15

    In recent years 'frustrated Lewis pairs' (FLPs) have been shown to be effective metal-free catalysts for the hydrogenation of many unsaturated substrates. Even so, limited functional-group tolerance restricts the range of solvents in which FLP-mediated reactions can be performed, with all FLP-mediated hydrogenations reported to date carried out in non-donor hydrocarbon or chlorinated solvents. Herein we report that the bulky Lewis acids B(C6Cl5)x(C6F5)(3-x) (x=0-3) are capable of heterolytic H2 activation in the strong-donor solvent THF, in the absence of any additional Lewis base. This allows metal-free catalytic hydrogenations to be performed in donor solvent media under mild conditions; these systems are particularly effective for the hydrogenation of weakly basic substrates, including the first examples of metal-free catalytic hydrogenation of furan heterocycles. The air-stability of the most effective borane, B(C6Cl5)(C6F5)2, makes this a practically simple reaction method. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Decision Document for the Storm Water Outfalls/Industrial Wastewater Treatment Plant, Pesticide Rinse Area, Old Fire Fighting Training Pit, Illicit PCB Dump Site, and the Battery Acid Pit Fort Lewis, Washington; FINAL

    International Nuclear Information System (INIS)

    Cantrell, Kirk J; Liikala, Terry L; Strenge, Dennis L; Taira, Randal Y

    2001-01-01

    PNNL conducted independent site evaluations for four sites at Fort Lewis, Washington, to determine their suitability for closure on behalf of the installation. These sites were recommended for ''No Further Action'' by previous investigators and included the Storm Water Outfalls/Industrial Waste Water Treatment Plant (IWTP), the Pesticide Rinse Area, the Old Fire Fighting Training Pit, and the Illicit PCB Dump Site

  9. Elucidating the Key Role of a Lewis Base Solvent in the Formation of Perovskite Films Fabricated from the Lewis Adduct Approach.

    Science.gov (United States)

    Cao, Xiaobing; Zhi, Lili; Li, Yahui; Fang, Fei; Cui, Xian; Yao, Youwei; Ci, Lijie; Ding, Kongxian; Wei, Jinquan

    2017-09-27

    High-quality perovskite films can be fabricated from Lewis acid-base adducts through molecule exchange. Substantial work is needed to fully understand the formation mechanism of the perovskite films, which helps to further improve their quality. Here, we study the formation of CH 3 NH 3 PbI 3 perovskite films by introducing some dimethylacetamide into the PbI 2 /N,N-dimethylformamide solution. We reveal that there are three key processes during the formation of perovskite films through the Lewis acid-base adduct approach: molecule intercalation of solvent into the PbI 2 lattice, molecule exchange between the solvent and CH 3 NH 3 I, and dissolution-recrystallization of the perovskite grains during annealing. The Lewis base solvents play multiple functions in the above processes. The properties of the solvent, including Lewis basicity and boiling point, play key roles in forming smooth perovskite films with large grains. We also provide some rules for choosing Lewis base additives to prepare high-quality perovskite films through the Lewis adduct approach.

  10. α,β-D-constrained nucleic acids are strong terminators of thermostable DNA polymerases in polymerase chain reaction.

    Directory of Open Access Journals (Sweden)

    Olivier Martínez

    Full Text Available (S(C5', R(P α,β-D- Constrained Nucleic Acids (CNA are dinucleotide building blocks that can feature either B-type torsional angle values or non-canonical values, depending on their 5'C and P absolute stereochemistry. These CNA are modified neither on the nucleobase nor on the sugar structure and therefore represent a new class of nucleotide with specific chemical and structural characteristics. They promote marked bending in a single stranded DNA so as to preorganize it into a loop-like structure, and they have been shown to induce rigidity within oligonucleotides. Following their synthesis, studies performed on CNA have only focused on the constraints that this family of nucleotides introduced into DNA. On the assumption that bending in a DNA template may produce a terminator structure, we investigated whether CNA could be used as a new strong terminator of polymerization in PCR. We therefore assessed the efficiency of CNA as a terminator in PCR, using triethylene glycol phosphate units as a control. Analyses were performed by denaturing gel electrophoresis and several PCR products were further analysed by sequencing. The results showed that the incorporation of only one CNA was always skipped by the polymerases tested. On the other hand, two CNA units always stopped proofreading polymerases, such as Pfu DNA polymerase, as expected for a strong replication terminator. Non-proofreading enzymes, e.g. Taq DNA polymerase, did not recognize this modification as a strong terminator although it was predominantly stopped by this structure. In conclusion, this first functional use of CNA units shows that these modified nucleotides can be used as novel polymerization terminators of proofreading polymerases. Furthermore, our results lead us to propose that CNA and their derivatives could be useful tools for investigating the behaviour of different classes of polymerases.

  11. Strong and long-lasting antinociceptive and anti-inflammatory conjugate of naturally occurring oleanolic acid and aspirin

    Directory of Open Access Journals (Sweden)

    Barbara Bednarczyk-Cwynar

    2016-07-01

    Full Text Available The conjugate 8 was obtained as a result of condensation of 3-hydroxyiminooleanolic acid morfolide (7 and aspirin in dioxane. Analgesic effect of OAO-ASA (8 for the range of doses 0.3 – 300.0 mg/kg (p.o. was performed in mice using a hot plate test. Anti-inflammatory activity was assessed on carrageenan-induced paw edema in rats for the same range of doses. The conjugate OAO-ASA (8 did not significantly change locomotor activity of mice, therefore sedative properties of the compound should be excluded. The compound 8 proved a simple, proportional, dose-dependent analgesic action and expressed strong anti-inflammatory activity showing a reversed U-shaped, dose-dependent relation with its maximum at 30.0 mg/kg. After its combined administration with morphine (MF, 5.0 mg/kg, s.c. the lowering of antinociceptive activity was found; however, the interaction with naloxone (NL, 3.0 mg/kg, s.c. did not affect the antinociceptive effect of OAO-ASA (8, therefore its opioid mechanism of action should be rather excluded. After combined administration with acetylsalicylic acid (ASA, 300.0 mg/kg, p.o. in hot-plate test, the examined compound 8 enhanced the antinociceptive activity in significant way. It also shows that rather the whole molecule is responsible for the antinociceptive and anti-inflammatory effect of the tested compound 8, however it cannot be excluded that the summarizing effect is produced by ASA released from the compound 8 and the rest of triterpene derivative. The occurrence of tolerance for triterpenic derivative 8 was not observed, since the analgesic and anti-inflammatory effects after chronic administration of the conjugate OAO-ASA (8 was on the same level as after its single treatment. It seemed that the anti-inflammatory mechanism of action of OAO-ASA (8 is not simple, even its chronic administration lowered both blood concentration of IL-6 and mRNA IL-6 expression. However, the effects of the conjugate OAO-ASA (8 on TNF-α level

  12. Capillary electrophoresis method for the analysis of organic acids and amino acids in the presence of strongly alternating concentrations of aqueous lactic acid.

    Science.gov (United States)

    Laube, Hendrik; Boden, Jana; Schneider, Roland

    2017-07-01

    During the production of bio-based bulk chemicals, such as lactic acid (LA), organic impurities have to be removed to produce a ready-to-market product. A capillary electrophoresis method for the simultaneous detection of LA and organic impurities in less than 10 min was developed. LA and organic impurities were detected using a direct UV detection method with micellar background electrolyte, which consisted of borate and sodium dodecyl sulfate. We investigated the effects of electrolyte composition and temperature on the speed, sensitivity, and robustness of the separation. A few validation parameters, such as linearity, limit of detection, and internal and external standards, were evaluated under optimized conditions. The method was applied for the detection of LA and organic impurities, including tyrosine, phenylalanine, and pyroglutamic acid, in samples from a continuous LA fermentation process from post-extraction tapioca starch and yeast extract.

  13. Catalytic performance of strong acid catalyst: Methyl modified SBA-15 loaded perfluorinated sulfonic acid obtained by the waste perfluorinated sulfonic acid ion exchange membrane

    Science.gov (United States)

    Jiang, Tingshun; Huang, Qiuyan; Li, Yingying; Fang, Minglan; Zhao, Qian

    2018-02-01

    Mesoporous molecular sieve (SBA-15) was modified using the trimethylchlorosilane as functional agent and the silylation SBA-15 mesoporous material was prepared in this work. The alcohol solution of perfluorinated sulfonic acid dissolved from the waste perfluorinated sulfonic acid ion exchange membrane (PFSIEM) was loaded onto the resulting mesoporous material by the impregnation method and their physicochemical properties were characterized by FT-IR, N2-physisorption, XRD, TG-DSC and TEM. The catalytic activities of these synthesized solid acid catalysts were evaluated by alkylation of phenol with tert-butyl alcohol. The influence of reaction temperature, weight hour space velocity (WHSV) and reaction time on the phenol conversion and product selectivity were assessed by means of a series of experiments. The results showed that with the increase of the active component of the catalyst, these catalysts still remained good mesoporous structure, but the mesoporous ordering decreased to some extent. These catalysts exhibited good catalytic performance for the alkylation of phenol with tert-butanol. The maximum phenol conversion of 89.3% with 70.9% selectivity to 4-t-butyl phenol (4-TBP) was achieved at 120 °C and the WHSV is 4 h-1. The methyl group was loaded on the surface of the catalyst by trimethylchlorosilane. This is beneficial to retard the deactivation of the catalyst. In this work, the alkylation of phenol with tert-butyl alcohol were carried out using the methyl modified SBA-15 mesoporous materials loaded perfluorinated sulfonic acid as catalysts. The results show that the resulting catalyst exhibited high catalytic activity.

  14. The pH of very dilute solutions of strong acids – a calculation for a medical or biomedical class involving the application of simple numerical skills

    OpenAIRE

    Peter Michael Barling

    2012-01-01

    This paper presents the solution to a calculationof the pH of a very dilute solution of a strong acid orbase, taking into account the effect of the hydroniumor hydroxyl ions generated from the ionisation of thestrong acid or base on the ionisation of water, as asecond very weak acid. To be solved successfully, thiscalculation involves the concepts of conservation ofcharge, pH and the application of the general solutionto a quadratic equation. Such an exercise involves theapplication of skills...

  15. Comparison of the Electrochemical Behavior of Ti and Nanostructured Ti-Coated AISI 304 Stainless Steel in Strongly Acidic Solutions

    Science.gov (United States)

    Attarzadeh, Farid Reza; Elmkhah, Hassan; Fattah-Alhosseini, Arash

    2017-02-01

    In this study, the electrochemical behaviors of pure titanium (Ti) and nanostructured (NS) Ti-coated AISI 304 stainless steel (SS) in strongly acidic solutions of H2SO4 were investigated and compared. A type of physical vapor deposition method, cathodic arc evaporation, was applied to deposit NS Ti on 304 SS. Scanning electron microscope and X-ray diffraction were used to characterize surface coating morphology. Potentiodynamic polarization, electrochemical impedance spectroscopy, and Mott-Schottky (M-S) analysis were used to evaluate the passive behavior of the samples. Electrochemical measurements revealed that the passive behavior of NS Ti coating was better than that of pure Ti in 0.1 and 0.01 M H2SO4 solutions. M-S analysis indicated that the passive films behaved as n-type semiconductors in H2SO4 solutions and the deposition method did not affect the semiconducting type of passive films formed on the coated samples. In addition, this analysis showed that the NS Ti coating had lower donor densities. Finally, all electrochemical tests showed that the passive behavior of the Ti-coated samples was superior, mainly due to the formation of thicker, yet less defective passive films.

  16. A strategy for the preparation of thioantimonates based on the concept of weak acids and corresponding strong bases.

    Science.gov (United States)

    Anderer, Carolin; Delwa de Alarcón, Natalie; Näther, Christian; Bensch, Wolfgang

    2014-12-15

    By following a new synthetic approach, which is based on the in situ formation of a basic medium by the reaction between the strong base Sb(V)S4 (3-) and the weak acid H2 O, it was possible to prepare three layered thioantimonate(III) compounds of composition [TM(2,2'-bipyridine)3 ][Sb6 S10 ] (TM=Ni, Fe) and [Ni(4,4'-dimethyl-2,2'-bipyridine)3 ][Sb6 S10 ] under hydrothermal conditions featuring two different thioantimonate(III) network topologies. The antimony source, Na3 SbS4 ⋅ 9 H2 O, undergoes several decomposition reactions and produces the Sb(III) S3 species, which condenses to generate the layered anion. The application of transition-metal complexes avoids crystallization of dense phases. The reactions are very fast compared to conventional hydrothermal/solvothermal syntheses and are much less sensitive to changes of the reaction parameters. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Fullerene–Carbene Lewis Acid–Base Adducts

    KAUST Repository

    Li, Huaping

    2011-08-17

    The reaction between a bulky N-heterocylic carbene (NHC) and C60 leads to the formation of a thermally stable zwitterionic Lewis acid-base adduct that is connected via a C-C single bond. Low-energy absorption bands with weak oscillator strengths similar to those of n-doped fullerenes were observed for the product, consistent with a net transfer of electron density to the C60 core. Corroborating information was obtained using UV photoelectron spectroscopy, which revealed that the adduct has an ionization potential ∼1.5 eV lower than that of C60. Density functional theory calculations showed that the C-C bond is polarized, with a total charge of +0.84e located on the NHC framework and -0.84e delocalized on the C 60 cage. The combination of reactivity, characterization, and theoretical studies demonstrates that fullerenes can behave as Lewis acids that react with C-based Lewis bases and that the overall process describes n-doping via C-C bond formation. © 2011 American Chemical Society.

  18. Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide

    OpenAIRE

    Rochette, Étienne; Courtemanche, Marc-André; Pulis, Alexander; Bi, Wenhua; Fontaine, Frédéric-Georges

    2015-01-01

    The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6‑tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robus...

  19. Assessing College Students' Understanding of Acid Base Chemistry Concepts

    Science.gov (United States)

    Wan, Yanjun Jean

    2014-01-01

    Typically most college curricula include three acid base models: Arrhenius', Bronsted-Lowry's, and Lewis'. Although Lewis' acid base model is generally thought to be the most sophisticated among these three models, and can be further applied in reaction mechanisms, most general chemistry curricula either do not include Lewis' acid base model, or…

  20. Quantitative physicochemical analysis of acid-base balance and clinical utility of anion gap and strong ion gap in 806 neonatal calves with diarrhea.

    Science.gov (United States)

    Trefz, F M; Constable, P D; Lorenz, I

    2015-01-01

    Acid-base abnormalities in neonatal diarrheic calves can be assessed by using the Henderson-Hasselbalch equation or the simplified strong ion approach which use the anion gap (AG) or the strong ion gap (SIG) to quantify the concentration of unmeasured strong anions such as D-lactate. To determine and compare the clinical utility of AG and SIG in quantifying the unmeasured strong anion charge in neonatal diarrheic calves, and to examine the associations between biochemical findings and acid-base variables by using the simplified strong ion approach. We hypothesized that the SIG provides a more accurate prediction of unmeasured strong anions than the AG. Eight hundred and six neonatal diarrheic calves admitted to a veterinary teaching hospital. Retrospective study utilizing clinicopathologic findings extracted from medical records. Hyperphosphatemia was an important predictor of venous blood pH. Serum inorganic phosphorus and plasma D-lactate concentrations accounted for 58% of the variation in venous blood pH and 77% of the variation in AG and SIG. Plasma D- and total lactate concentrations were slightly better correlated with SIG (rs = -0.69; -0.78) than to AG (rs = 0.63; 0.74). Strong ion gap is slightly better at quantifying the unmeasured strong anion concentration in neonatal diarrheic calves than AG. Phosphorus concentrations should be included as part of the calculation of Atot when applying the simplified strong ion approach to acid-base balance to critically ill animals with hyperphosphatemia. Copyright © 2015 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

  1. SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .3. EFFECT OF SULFOLANE ON THE EQUILIBRIUM CONVERSION

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    The liquid-phase hydration of cyclohexene, a pseudo-first-order reversible reaction catalyzed by a strong acid ion-exchange resin, was investigated in solvent mixtures of water and sulfolane. Macroporous Amberlite XE 307 was used because of its superior catalytic activity. Chemical equilibrium

  2. Fast Hydrazone Reactants: Electronic and Acid/Base Effects Strongly Influence Rate at Biological pH

    OpenAIRE

    Kool, Eric T.; Park, Do-Hyoung; Crisalli, Pete

    2013-01-01

    Kinetics studies with structurally varied aldehydes and ketones in aqueous buffer at pH 7.4 reveal that carbonyl compounds with neighboring acid/base groups form hydrazones at accelerated rates. Similarly, tests of a hydrazine with a neighboring carboxylic acid group show that it also reacts at an accelerated rate. Rate constants for the fastest carbonyl/hydrazine combinations are 2–20 M−1sec−1, which is faster than recent strain-promoted cycloaddition reactions.

  3. Slovene critics on Sinclair Lewis's novels

    Directory of Open Access Journals (Sweden)

    Vanja Avsenak

    2010-12-01

    Full Text Available The purpose of this article is to present the reception of Sinclair Lewis's novels by Slovene critics. Initially, the article focuses on the life and workof Sinclair Lewis, giving special emphasis to social influences that made the author a representative figure in the literary and social world. Thus his works are nowadays to be understood primarily as fiction, but on the other hand also as sociological documents of a social and political situation of the period between the two world wars. Generally, the effect they produce is one of a critical discussion of the nation of the United States. When speaking of the social relevance that Lewis's novels have, it is obvious that his works are the portrayals of Americans and their deficiencies. At the time of their publication Lewis's novels received unfavourable criticism on accountof his overly open pro-European attitude and Slovene critics of the period before World War II emphasise this in much detail. It was precisely this anti-American propaganda in the novels themselves and sincerity on the part of the novelist that won the European critics as well as the readers whenit came to appreciating his works. However, Lewis's view of the Americans, as presented throughout his works, only enhanced his literary credibility as a modern writer. That is why the articles by Slovene critics that appeared after the Second World War, and even more significantly after Lewis's death, almost minutely reflect a more favourable attitude to Sinclair Lewis, which was also the case with foreign literary criticism of the post-war period. Critics still discuss the qualities and flaws of Lewis's novels, but being more lenient they no longer profess that the novels lack in artistic value. They remain, however, primarily relevant as social documents of the pre- and post-war era, which fully presented the American middle-class mentality in America and elsewhere. For this reason, the Nobel Prize for Literature awarded to

  4. Lipid oxidation in fish oil enriched mayonnaise : Calcium disodium ethylenediaminetetraacetate, but not gallic acid, strongly inhibited oxidative deterioration

    DEFF Research Database (Denmark)

    Jacobsen, Charlotte; Hartvigsen, Karsten; Thomsen, Mikael Holm

    2001-01-01

    The antioxidative effects of gallic acid, EDTA, and extra emulsifier Panodan DATEM TR in mayonnaise enriched with 16% fish oil were investigated. EDTA reduced the formation of free radicals, lipid hydroperoxides, volatiles, and fishy and rancid off-flavors. The antioxidative effect of EDTA...... was attributed to its ability to chelate free metal ions and iron from egg yolk located at the oil-water interface. Gallic acid reduced the levels of both free radicals and lipid hydroperoxides but promoted slightly the oxidative flavor deterioration in mayonnaise and influenced the profile of volatiles. Gallic...... acid may therefore promote the decomposition of lipid hydroperoxides to volatile oxidation products. Addition of extra emulsifier reduced the lipid hydroperoxide levels but did not influence the level of free radicals or the oxidative flavor deterioration in mayonnaisse; however, it appeared to alter...

  5. Dissociation of strong acid revisited: X-ray photoelectron spectroscopy and molecular dynamics simulations of HNO3 in water

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

    2011-08-04

    Molecular-level insight into the dissociation of nitric acid in water is obtained from photoelectron X-ray spectroscopy and first-principles molecular dynamics (MD) simulations. Our combined studies reveal surprisingly abrupt changes in solvation configurations of undissociated nitric acid at approximately 4 M concentration. Experimentally, this is inferred from N1s binding energy shifts of HNO3(aq) as a function of concentration, and is associated with variations in the local electronic structure of the nitrogen atom. It also shows up as a discontinuity in the degree of dissociation as a function of concentration, determined here from the N1s photoelectron signal intensity, which can be separately quantified for undissociated HNO3(aq) and dissociated NO3-(aq). Intermolecular interactions within the nitric acid solution are discussed on the basis of MD simulations, which reveal that molecular HNO3 interacts remarkably weakly with solvating water molecules at low concentration; around 4 M there is a turnover to a more structured solvation shell, accompanied by an increase in hydrogen bonding between HNO3 and water. We suggest that the driving force behind the more structured solvent configuration of HNO3 is the overlap of nitric acid solvent shells that sets in around 4 M concentration. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  6. Dissolved organic carbon and nitrogen mineralization strongly affect co2 emissions following lime application to acidic soil

    International Nuclear Information System (INIS)

    Shaaban, M.; Peng, Q.; Lin, S.; Wu, Y.

    2014-01-01

    Emission of greenhouse gases from agricultural soils has main contribution to the climatic change and global warming. Dynamics of dissolved organic carbon (DOC) and nitrogen mineralization can affect CO/sub 2/ emission from soils. Influence of DOC and nitrogen mineralization on CO/sub 2/ emissions following lime application to acidic soil was investigated in current study. Laboratory experiment was conducted under aerobic conditions with 25% moisture contents (66% water-filled pore space) at 25 degree C in the dark conditions. Different treatments of lime were applied to acidic soil as follows: CK (control), L (low rate of lime: 0.2g lime / 100 g soil) and H (high rate of lime: 0.5g lime /100g soil). CO/sub 2/ emissions were measured by gas chromatography and dissolved organic carbon, NH4 +-N, NO/sub 3/ --N and soil pH were measured during incubation study. Addition of lime to acidic soil significantly increased the concentration of DOC and N mineralization rate. Higher concentrations of DOC and N mineralization, consequently, increased the CO/sub 2/ emissions from lime treated soils. Cumulative CO/sub 2/ emission was 75% and 71% higher from L and H treatments as compared to CK. The results of current study suggest that DOC and N mineralization are critical in controlling gaseous emissions of CO/sub 2/ from acidic soils following lime application. (author)

  7. Aging rather than stress strongly influences amino acid metabolisms in the brain and genital organs of female mice.

    Science.gov (United States)

    Kodaira, Momoko; Nagasawa, Mao; Yamaguchi, Takeshi; Ikeda, Hiromi; Minaminaka, Kimie; Chowdhury, Vishwajit S; Yasuo, Shinobu; Furuse, Mitsuhiro

    2017-03-01

    Aging and stress affect quality of life, and proper nourishment is one of means of preventing this effect. Today, there is a focus on the amount of protein consumed by elderly people; however, changes in the amino acid metabolism of individuals have not been fully considered. In addition, the difference between average life span and healthy life years is larger in females than it is in males. To prolong the healthy life years of females, in the present study we evaluated the influence of stress and aging on metabolism and emotional behavior by comparing young and middle-aged female mice. After 28 consecutive days of immobilization stress, behavioral tests were conducted and tissue sampling was performed. The results showed that the body weight of middle-aged mice was severely lowered by stress, but emotional behaviors were hardly influenced by either aging or stress. Aging influenced changes in amino acid metabolism in the brain and increased various amino acid levels in the uterus and ovary. In conclusion, we found that aged mice were more susceptible to stress in terms of body-weight reduction, and that amino acid metabolisms in the brain and genital organs were largely influenced by aging rather than by stress. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  8. Reaction of Hydrogen Sulfide with Disulfide and Sulfenic Acid to Form the Strongly Nucleophilic Persulfide*♦

    Science.gov (United States)

    Cuevasanta, Ernesto; Lange, Mike; Bonanata, Jenner; Coitiño, E. Laura; Ferrer-Sueta, Gerardo; Filipovic, Milos R.; Alvarez, Beatriz

    2015-01-01

    Hydrogen sulfide (H2S) is increasingly recognized to modulate physiological processes in mammals through mechanisms that are currently under scrutiny. H2S is not able to react with reduced thiols (RSH). However, H2S, more precisely HS−, is able to react with oxidized thiol derivatives. We performed a systematic study of the reactivity of HS− toward symmetric low molecular weight disulfides (RSSR) and mixed albumin (HSA) disulfides. Correlations with thiol acidity and computational modeling showed that the reaction occurs through a concerted mechanism. Comparison with analogous reactions of thiolates indicated that the intrinsic reactivity of HS− is 1 order of magnitude lower than that of thiolates. In addition, H2S is able to react with sulfenic acids (RSOH). The rate constant of the reaction of H2S with the sulfenic acid formed in HSA was determined. Both reactions of H2S with disulfides and sulfenic acids yield persulfides (RSSH), recently identified post-translational modifications. The formation of this derivative in HSA was determined, and the rate constants of its reactions with a reporter disulfide and with peroxynitrite revealed that persulfides are better nucleophiles than thiols, which is consistent with the α effect. Experiments with cells in culture showed that treatment with hydrogen peroxide enhanced the formation of persulfides. Biological implications are discussed. Our results give light on the mechanisms of persulfide formation and provide quantitative evidence for the high nucleophilicity of these novel derivatives, setting the stage for understanding the contribution of the reactions of H2S with oxidized thiol derivatives to H2S effector processes. PMID:26269587

  9. Elusive silane-alane complex [Si-H⋅⋅⋅Al]: isolation, characterization, and multifaceted frustrated Lewis pair type catalysis.

    Science.gov (United States)

    Chen, Jiawei; Chen, Eugene Y-X

    2015-06-01

    The super acidity of the unsolvated Al(C6F5)3 enabled isolation of the elusive silane-alane complex [Si-H⋅⋅⋅Al], which was structurally characterized by spectroscopic and X-ray diffraction methods. The Janus-like nature of this adduct, coupled with strong silane activation, effects multifaceted frustrated-Lewis-pair-type catalysis. When compared with the silane-borane system, the silane-alane system offers unique features or clear advantages in the four types of catalytic transformations examined in this study, including: ligand redistribution of tertiary silanes into secondary and quaternary silanes, polymerization of conjugated polar alkenes, hydrosilylation of unactivated alkenes, and hydrodefluorination of fluoroalkanes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Effects of strong inter-hydrogen bond dynamical couplings in the polarized IR spectra of adipic acid crystals

    Energy Technology Data Exchange (ETDEWEB)

    Flakus, Henryk T., E-mail: flakus@ich.us.edu.pl [Institute of Chemistry, University of Silesia, 9 Szkolna Street, Pl-40-006 Katowice (Poland); Tyl, Aleksandra; Jablonska, Magdalena [Institute of Chemistry, University of Silesia, 9 Szkolna Street, Pl-40-006 Katowice (Poland)

    2009-10-16

    This paper presents the results of the re-investigation of polarized IR spectra of adipic acid and of its d{sub 2}, d{sub 8} and d{sub 10} deuterium derivative crystals. The spectra were measured at 77 K by a transmission method using polarized light for two different crystalline faces. Theoretical analysis concerned linear dichroic effects and H/D isotopic effects observed in the spectra of the hydrogen and deuterium bonds in adipic acid crystals at the frequency ranges of the {nu}{sub O-H} and the {nu}{sub O-D} bands. The two-branch fine structure pattern of the {nu}{sub O-H} and {nu}{sub O-D} bands and the basic linear dichroic effects characterizing them were ascribed to the vibronic mechanism of vibrational dipole selection rule breaking for IR transitions in centrosymmetric hydrogen bond dimers. It was proved that for isotopically diluted crystalline samples of adipic acid, a non-random distribution of protons and deuterons occurs in the dimers (H/D isotopic 'self-organization' effect). This effect results from the dynamical co-operative interactions involving the dimeric hydrogen bonds.

  11. Effects of strong inter-hydrogen bond dynamical couplings in the polarized IR spectra of adipic acid crystals

    Science.gov (United States)

    Flakus, Henryk T.; Tyl, Aleksandra; Jablońska, Magdalena

    2009-10-01

    This paper presents the results of the re-investigation of polarized IR spectra of adipic acid and of its d2, d8 and d10 deuterium derivative crystals. The spectra were measured at 77 K by a transmission method using polarized light for two different crystalline faces. Theoretical analysis concerned linear dichroic effects and H/D isotopic effects observed in the spectra of the hydrogen and deuterium bonds in adipic acid crystals at the frequency ranges of the νO-H and the νO-D bands. The two-branch fine structure pattern of the νO-H and νO-D bands and the basic linear dichroic effects characterizing them were ascribed to the vibronic mechanism of vibrational dipole selection rule breaking for IR transitions in centrosymmetric hydrogen bond dimers. It was proved that for isotopically diluted crystalline samples of adipic acid, a non-random distribution of protons and deuterons occurs in the dimers (H/D isotopic " self-organization" effect). This effect results from the dynamical co-operative interactions involving the dimeric hydrogen bonds.

  12. Conversion of corn stalk into furfural using a novel heterogeneous strong acid catalyst in γ-valerolactone.

    Science.gov (United States)

    Xu, Zhiping; Li, Wenzhi; Du, Zhijie; Wu, Hao; Jameel, Hasan; Chang, Hou-Min; Ma, Longlong

    2015-12-01

    A novel solid acid catalyst was prepared by the copolymerization of p-toluenesulfonic acid and paraformaldehyde and then characterized by FT-IR, TG/DTG, HRTEM and N2-BET. Furfural was successfully produced by the dehydration of xylose and xylan using the novel catalyst in γ-valerolactone. This investigation focused on effects of various reaction conditions including solvent, acid catalyst, reaction temperature, residence time, water concentration, xylose loading and catalyst dosage on the dehydration of xylose to furfural. It was found that the solid catalyst displayed extremely high activity for furfural production. 80.4% furfural yield with 98.8% xylose conversion was achieved at 170°C for 10 min. The catalyst could be recycled at least five times without significant loss of activity. Furthermore, 83.5% furfural yield and 19.5% HMF yield were obtained from raw corn stalk under more severe conditions (190°C for 100 min). Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Evaluation of different approaches to quantify strong organic acidity and acid-base buffering of organic-rich surface waters in Sweden.

    Science.gov (United States)

    Köhler, Stephan; Hruska, Jakub; Jönsson, Jörgen; Lövgren, Lars; Lofts, Stephen

    2002-11-01

    The role of organic acids in buffering pH in surface waters has been studied using a small brownwater stream (26mg L(-1) TOC) draining a forested catchment in Northern Sweden. Under the conditions of elevated pressure of CO2 stream field pH was changed between 3.5 and 6.1 during the acidification and alkalinization experiment. Acid-base characteristics of the natural organic matter were also determined using a high precision potentiometric method for a concentrated sample from the same stream. We compared the predictions from the Windermere Humic Aqueous Model (WHAM Model V), a model derived from the potentiometric titration (diprotic/monoprotic acid model) and a previously derived triprotic acid model which only uses alkalinity and TOC as input variables. The predicted buffering characteristics of all three models are very similar in the pH range 4.5-7 which suggests that during routine analysis alkalinity and TOC are sufficient to give a good estimate of organic acid anion charge contribution in a large range of surface waters. A slightly adjusted version of WHAM V successfully describes the organic charge contribution in a large number of sampled surface water lakes, which were previously used to calibrate the triprotic model.

  14. Olefin-borane "van der Waals complexes": intermediates in frustrated Lewis pair addition reactions.

    Science.gov (United States)

    Zhao, Xiaoxi; Stephan, Douglas W

    2011-08-17

    The nature of the borane-olefin interactions that take place prior to frustrated Lewis pair addition reactions has been probed employing a Lewis acidic borane tethered to a vinyl group through an alkyl chain. (1)H{(19)F} HOESY spectral data obtained at -50 °C demonstrated the spatial proximity of the boryl and vinyl groups and computational data support the initial formation of a van der Waals borane-olefin complex. Such species serve as intermediates undergoing facile addition reactions with phosphine bases to afford cyclic zwitterionic products.

  15. Hippocampal α-Synuclein in Dementia with Lewy Bodies Contributes to Memory Impairment and Is Consistent with Spread of Pathology.

    Science.gov (United States)

    Adamowicz, David H; Roy, Subhojit; Salmon, David P; Galasko, Douglas R; Hansen, Lawrence A; Masliah, Eliezer; Gage, Fred H

    2017-02-15

    Despite considerable research to uncover them, the anatomic and neuropathologic correlates of memory impairment in dementia with Lewy bodies (DLB) remain unclear. While some studies have implicated Lewy bodies in the neocortex, others have pointed to α-synuclein pathology in the hippocampus. We systematically examined hippocampal Lewy pathology and its distribution in hippocampal subfields in 95 clinically and neuropathologically characterized human cases of DLB, finding that α-synuclein pathology was highest in two hippocampal-related subregions: the CA2 subfield and the entorhinal cortex (EC). While the EC had numerous classic somatic Lewy bodies, CA2 contained mainly Lewy neurites in presumed axon terminals, suggesting the involvement of the EC → CA2 circuitry in the pathogenesis of DLB symptoms. Clinicopathological correlations with measures of verbal and visual memory supported a role for EC Lewy pathology, but not CA2, in causing these memory deficits. Lewy pathology in CA1-the main output region for CA2-correlated best with results from memory testing despite a milder pathology. This result indicates that CA1 may be more functionally relevant than CA2 in the context of memory impairment in DLB. These correlations remained significant after controlling for several factors, including concurrent Alzheimer's pathology (neuritic plaques and neurofibrillary tangles) and the interval between time of testing and time of death. Our data suggest that although hippocampal Lewy pathology in DLB is predominant in CA2 and EC, memory performance correlates most strongly with CA1 burden. SIGNIFICANCE STATEMENT This study provides a detailed neuropathologic analysis of hippocampal Lewy pathology in human patients with autopsy-confirmed dementia with Lewy bodies. The approach-informed by regional molecular markers, concurrent Alzheimer's pathology analysis, and relevant clinical data-helps tease out the relative contribution of Lewy pathology to memory dysfunction in the

  16. The Critical Reception of Lewis Nordan

    DEFF Research Database (Denmark)

    Bjerre, Thomas Ærvold

    2010-01-01

    The essay covers the critical reception of Mississippi-writer Lewis Nordan from his debut in 1983 to the boost in scholarly attention in the new millennium. The essay covers newspaper reviews but pays particular attention to the many academic essays that have placed Nordan as a writer in the sout......The essay covers the critical reception of Mississippi-writer Lewis Nordan from his debut in 1983 to the boost in scholarly attention in the new millennium. The essay covers newspaper reviews but pays particular attention to the many academic essays that have placed Nordan as a writer...

  17. Methanetrisulfonic Acid: A Highly Efficient Strongly Acidic Catalyst for Wagner-Meerwein Rearrangement, Friedel-Crafts Alkylation and Acylation Reactions. Examples from Vitamin E Synthesis

    Directory of Open Access Journals (Sweden)

    Francesco Pace

    2009-04-01

    Full Text Available Methanetrisulfonic acid had been prepared for the first time over 140 years ago, but it was used only scarcely in chemical transformations. In the course of our activities dealing with key-steps of industrial syntheses of vitamins, e.g. economically important vitamin E (acetate, we found that methanetrisulfonic acid is an extremely effective catalyst in a variety of reactions. Examples of its applications are Wagner-Meerwein rearrangements, Friedel-Crafts alkylations and ring closures, as well as acylation reactions. Use of this catalyst in truly catalytic amounts (0.04-1.0 mol% resulted in highly selective transformations and yields over 95%. (Remark by the authors: We are describing only one example each for the various types of reactions. Therefore, it would be more appropriate to write (here and in the Introduction and in the Conclusion sections: “Wagner-Meerwein rearrangement, Friedel-Crafts alkylation and ring closure, as well as acylation reactions”

  18. Playing around in Lewis Carroll's "Alice" Books

    Science.gov (United States)

    Susina, Jan

    2010-01-01

    Mathematician Charles Dodgson's love of play and his need for rules came together in his use of popular games as part of the structure of the two famous children's books, "Alice in Wonderland" and "Through the Looking-Glass," he wrote under the pseudonym Lewis Carroll. The author of this article looks at the interplay between…

  19. Frustrated Lewis pairs: Design and reactivity

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 2. Frustrated Lewis pairs: Design and reactivity. Sanjoy Mukherjee Pakkirisamy Thilagar. Volume 127 Issue 2 ... main group as well as transition metal chemistry. The design strategies adopted for FLP systems and their unique reactivity are discussed here.

  20. Frustrated Lewis pairs-assisted tritium labeling

    Czech Academy of Sciences Publication Activity Database

    Marek, Aleš; Široká, Sabina; Elbert, Tomáš

    2016-01-01

    Roč. 14, č. 5 (2016), s. 219 ISSN 2336-7202. [Sjezd českých a slovenských chemických společností /68./. 04.09.2016-07.09.2016, Praha] Institutional support: RVO:61388963 Keywords : frustrated Lewis pairs * one-pot synthesis * tritium -labeling Subject RIV: CC - Organic Chemistry

  1. One hundred years of Lewis Chemical Bond!

    Indian Academy of Sciences (India)

    2016-09-20

    Sep 20, 2016 ... Having understood the stable electronic configuration of the rare gases, Lewis suggested that H and F atom can both attain such configuration, if they were to share one electron with each other. He developed a cubic model of atoms with each surrounded by 8 electrons after forming electron pair bonds.

  2. Mitochondrial oxidative stress alters a pathway in Caenorhabditis elegans strongly resembling that of bile acid biosynthesis and secretion in vertebrates.

    Directory of Open Access Journals (Sweden)

    Ju-Ling Liu

    Full Text Available Mammalian bile acids (BAs are oxidized metabolites of cholesterol whose amphiphilic properties serve in lipid and cholesterol uptake. BAs also act as hormone-like substances that regulate metabolism. The Caenorhabditis elegans clk-1 mutants sustain elevated mitochondrial oxidative stress and display a slow defecation phenotype that is sensitive to the level of dietary cholesterol. We found that: 1 The defecation phenotype of clk-1 mutants is suppressed by mutations in tat-2 identified in a previous unbiased screen for suppressors of clk-1. TAT-2 is homologous to ATP8B1, a flippase required for normal BA secretion in mammals. 2 The phenotype is suppressed by cholestyramine, a resin that binds BAs. 3 The phenotype is suppressed by the knock-down of C. elegans homologues of BA-biosynthetic enzymes. 4 The phenotype is enhanced by treatment with BAs. 5 Lipid extracts from C. elegans contain an activity that mimics the effect of BAs on clk-1, and the activity is more abundant in clk-1 extracts. 6 clk-1 and clk-1;tat-2 double mutants show altered cholesterol content. 7 The clk-1 phenotype is enhanced by high dietary cholesterol and this requires TAT-2. 8 Suppression of clk-1 by tat-2 is rescued by BAs, and this requires dietary cholesterol. 9 The clk-1 phenotype, including the level of activity in lipid extracts, is suppressed by antioxidants and enhanced by depletion of mitochondrial superoxide dismutases. These observations suggest that C. elegans synthesizes and secretes molecules with properties and functions resembling those of BAs. These molecules act in cholesterol uptake, and their level of synthesis is up-regulated by mitochondrial oxidative stress. Future investigations should reveal whether these molecules are in fact BAs, which would suggest the unexplored possibility that the elevated oxidative stress that characterizes the metabolic syndrome might participate in disease processes by affecting the regulation of metabolism by BAs.

  3. Graphene-oxide-supported Pt nanoparticles with high activity and stability for hydrazine electro-oxidation in a strong acidic solution

    Science.gov (United States)

    Kim, Ji Dang; Choi, Myong Yong; Choi, Hyun Chul

    2017-10-01

    Graphene-oxide-supported Pt (GO-Pt) nanoparticles were prepared by performing diimide-activated amidation and used in an electrocatalyst for hydrazine electro-oxidation in 0.5 M H2SO4 solution. The physico-chemical properties of the GO-Pt nanoparticles were characterized with various techniques, which revealed that highly dispersed Pt nanoparticles with an average size of 2.6 nm were densely deposited on the amidated GO due to their strong adhesion. Cyclic voltammograms were obtained and demonstrate that the GO-Pt catalyst exhibits significantly improved catalytic activity and long-term stability in hydrazine electro-oxidation in a strong acidic solution when compared to commercial Pt/C and Pt metal electrodes. These enhanced electrochemical properties are attributed to the large electrochemically active surface area that results from the smaller size and excellent dispersion of the Pt nanoparticles on amidated GO.

  4. Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide.

    Science.gov (United States)

    Rochette, Étienne; Courtemanche, Marc-André; Pulis, Alexander P; Bi, Wenhua; Fontaine, Frédéric-Georges

    2015-06-29

    The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6‑tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robust, showing little sign of degradation after heating at 80 °C in benzene with 10 equiv. of formic acid for 24 h. The robustness of the system could be exploited in the design of metal-free catalysts for the hydrogenation of carbon dioxide.

  5. Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Étienne Rochette

    2015-06-01

    Full Text Available The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP having a 2,2,6,6‑tetramethylpiperidine (TMP as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robust, showing little sign of degradation after heating at 80 °C in benzene with 10 equiv. of formic acid for 24 h. The robustness of the system could be exploited in the design of metal-free catalysts for the hydrogenation of carbon dioxide.

  6. Calculation of the total plasma concentration of nonvolatile weak acids and the effective dissociation constant of nonvolatile buffers in plasma for use in the strong ion approach to acid-base balance in cats.

    Science.gov (United States)

    McCullough, Sheila M; Constable, Peter D

    2003-08-01

    To determine values for the total concentration of nonvolatile weak acids (Atot) and effective dissociation constant of nonvolatile weak acids (Ka) in plasma of cats. Convenience plasma samples of 5 male and 5 female healthy adult cats. Cats were sedated, and 20 mL of blood was obtained from the jugular vein. Plasma was tonometered at 37 degrees C to systematically vary PCO2 from 8 to 156 mm Hg, thereby altering plasma pH from 6.90 to 7.97. Plasma pH, PCO2, and concentrations of quantitatively important strong cations (Na+, K+, and Ca2+), strong anions (Cl-, lactate), and buffer ions (total protein, albumin, and phosphate) were determined. Strong ion difference was estimated from the measured strong ion concentrations and nonlinear regression used to calculate Atot and Ka from the measured pH and PCO2 and estimated strong ion difference. Mean (+/- SD) values were as follows: Atot = 24.3 +/- 4.6 mmol/L (equivalent to 0.35 mmol/g of protein or 0.76 mmol/g of albumin); Ka = 0.67 +/- 0.40 x 10(-7); and the negative logarithm (base 10) of Ka (pKa) = 7.17. At 37 degrees C, pH of 7.35, and a partial pressure of CO2 (PCO2) of 30 mm Hg, the calculated venous strong ion difference was 30 mEq/L. These results indicate that at a plasma pH of 7.35, a 1 mEq/L decrease in strong ion difference will decrease pH by 0.020, a 1 mm Hg decrease in PCO2 will increase plasma pH by 0.011, and a 1 g/dL decrease in albumin concentration will increase plasma pH by 0.093.

  7. A comparison of prognostic significance of strong ion gap (SIG) with other acid-base markers in the critically ill: a cohort study.

    Science.gov (United States)

    Ho, Kwok M; Lan, Norris S H; Williams, Teresa A; Harahsheh, Yusra; Chapman, Andrew R; Dobb, Geoffrey J; Magder, Sheldon

    2016-01-01

    This cohort study compared the prognostic significance of strong ion gap (SIG) with other acid-base markers in the critically ill. The relationships between SIG, lactate, anion gap (AG), anion gap albumin-corrected (AG-corrected), base excess or strong ion difference-effective (SIDe), all obtained within the first hour of intensive care unit (ICU) admission, and the hospital mortality of 6878 patients were analysed. The prognostic significance of each acid-base marker, both alone and in combination with the Admission Mortality Prediction Model (MPM0 III) predicted mortality, were assessed by the area under the receiver operating characteristic curve (AUROC). Of the 6878 patients included in the study, 924 patients (13.4 %) died after ICU admission. Except for plasma chloride concentrations, all acid-base markers were significantly different between the survivors and non-survivors. SIG (with lactate: AUROC 0.631, confidence interval [CI] 0.611-0.652; without lactate: AUROC 0.521, 95 % CI 0.500-0.542) only had a modest ability to predict hospital mortality, and this was no better than using lactate concentration alone (AUROC 0.701, 95 % 0.682-0.721). Adding AG-corrected or SIG to a combination of lactate and MPM0 III predicted risks also did not substantially improve the latter's ability to differentiate between survivors and non-survivors. Arterial lactate concentrations explained about 11 % of the variability in the observed mortality, and it was more important than SIG (0.6 %) and SIDe (0.9 %) in predicting hospital mortality after adjusting for MPM0 III predicted risks. Lactate remained as the strongest predictor for mortality in a sensitivity multivariate analysis, allowing for non-linearity of all acid-base markers. The prognostic significance of SIG was modest and inferior to arterial lactate concentration for the critically ill. Lactate concentration should always be considered regardless whether physiological, base excess or physical-chemical approach

  8. Fermi resonance and strong anharmonic effects in the absorption spectra of the ν-OH ( ν-OD) vibration of solid H- and D-benzoic acid

    Science.gov (United States)

    Yaremko, A. M.; Ratajczak, H.; Barnes, A. J.; Baran, J.; Durlak, P.; Latajka, Z.

    2009-10-01

    The vibrational spectra of polycrystalline benzoic acid (BA) and its deuterated derivative were studied over the wide frequency region 4000-10 cm -1 by IR and Raman methods. A theoretical analysis of the hydrogen bond frequency region and calculations at the B3LYP/6-311++G(2d, 2p) level for the benzoic acid cyclic dimer in the gas phase were made. In order to study the dynamics of proton transfer two formalisms were applied: Car-Parrinello Molecular Dynamics (CPMD) and Path Integrals Molecular Dynamics (PIMD). It was shown that the experimentally observed very broad ν-OH band absorption is the result of complex anharmonic interaction: Fermi resonance between the OH-stretching and bending vibrations and strong interaction of the ν-OH stretching with the low frequency phonons. The theoretical analysis in the framework of such an approach gave a good correlation with experiment. From the CPMD calculations it was confirmed that the O-H⋯O bridge is not rigid, with the O⋯O distance being described by a large amplitude motion. For the benzoic acid dimer we observed stepwise (asynchronous) proton transfer.

  9. In-situ methylation of strongly polar organic acids in natural waters supported by ion-pairing agents for headspace GC-MSD analysis

    Energy Technology Data Exchange (ETDEWEB)

    Neitzel, P.L.; Walther, W. [Dresden University of Technology, Institute for Groundwater Managemant, Dresden (Germany); Nestler, W. [Institute for Technology and Economics, Department of Civil Engineering and Architecture, Dresden (Germany)

    1998-06-01

    Strongly polar organic substances like halogenated acetic acids have been analyzed in surface water and groundwater in the catchment area of the upper Elbe river in Saxony since 1992. Coming directly from anthropogenic sources like industry, agriculture and indirectly by rainfall, their concentrations can increase up to 100 {mu}g/L in the aquatic environment of this catchment area. A new static headspace GC-MSD method without a manual pre-concentration step is presented to analyze the chlorinated acetic acids relevant to the Elbe river as their volatile methyl esters. Using an ion-pairing agent as modifier for the in-situ methylation of the analytes by dimethylsulfate, a minimal detection limit of 1 {mu}g/L can be achieved. Problems like the thermal degradation of chlorinated acetic acids to halogenated hydrocarbons and changing reaction yields during the headspace methylation, could be effectively reduced. The method has been successfully applied to monitoring bank infiltrate, surface water, groundwater and water works pumped raw water according to health provision principles. (orig.) With 3 figs., 2 tabs., 29 refs.

  10. Identification and quantification of the caproic acid-producing bacterium Clostridium kluyveri in the fermentation of pit mud used for Chinese strong-aroma type liquor production.

    Science.gov (United States)

    Hu, Xiao-Long; Du, Hai; Xu, Yan

    2015-12-02

    Chinese strong-aroma type liquor (CSAL) is a popular distilled alcoholic beverage in China. It is produced by a complex fermentation process that is conducted in pits in the ground. Ethyl caproate is a key flavor compound in CSAL and is thought to originate from caproic acid produced by Clostridia inhabiting the fermentation pit mud. However, the particular species of Clostridium associated with this production are poorly understood and problematic to quantify by culturing. In this study, a total of 28 closest relatives including 15 Clostridia and 8 Bacilli species in pit muds from three CSAL distilleries, were detected by culture-dependent and -independent methods. Among them, Clostridium kluyveri was identified as the main producer of caproic acid. One representative strain C. kluyveri N6 could produce caproic, butyric and octanoic acids and their corresponding ethyl esters, contributing significantly to CSAL flavor. A real time quantitative PCR assay of C. kluyveri in pit muds developed showed that a concentration of 1.79×10(7) 16S rRNA gene copies/g pit mud in LZ-old pit was approximately six times higher than that in HLM and YH pits and sixty times higher than that in LZ-new pit respectively. This method can be used to improve the management of pit mud microbiology and its impact on CSAL quality. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Ermakov–Lewis invariants and Reid systems

    International Nuclear Information System (INIS)

    Mancas, Stefan C.; Rosu, Haret C.

    2014-01-01

    Reid's mth-order generalized Ermakov systems of nonlinear coupling constant α are equivalent to an integrable Emden–Fowler equation. The standard Ermakov–Lewis invariant is discussed from this perspective, and a closed formula for the invariant is obtained for the higher-order Reid systems (m≥3). We also discuss the parametric solutions of these systems of equations through the integration of the Emden–Fowler equation and present an example of a dynamical system for which the invariant is equivalent to the total energy. - Highlights: • Reid systems of order m are connected to Emden–Fowler equations. • General expressions for the Ermakov–Lewis invariants both for m=2 and m≥3 are obtained. • Parametric solutions of the Emden–Fowler equations related to Reid systems are obtained

  12. Capgras' syndrome in dementia with Lewy bodies.

    Science.gov (United States)

    Marantz, Andrew G; Verghese, Joe

    2002-01-01

    We report the occurrence of Capgras' syndrome, or the delusion of doubles, in a patient with dementia with Lewy bodies. The patient believed that several similar-looking impostors had replaced his wife of over 50 years. Uncharacteristically, he adopted a friendly attitude with these impostors. This unusual convivial reaction to the impostors may result from differential involvement of the dual visual pathways processing facial recognition and emotional responses to faces. The delusion resolved spontaneously, coincident with worsening of the dementia. In a retrospective chart review of 18 autopsy-confirmed cases of dementia with Lewy bodies, delusions were reported in 5 subjects (27.8%), of whom 1 had misidentification delusions much like Capgras' syndrome.

  13. C. S. Lewis: The Romantic Rationalist

    Directory of Open Access Journals (Sweden)

    Vasiliu Daniela

    2014-12-01

    Full Text Available The paper “C. S. Lewis: The Romantic Rationalist” presents the way C. S. Lewis gives an account in his first fictional (allegorical book, The Pilgrim’s Regress, of how he discovered Christianity on the converging paths of romanticism and rationalism. The outstanding scholar and author whose intellectual and spiritual development has turned him into one of the most influential Christian writers of the twentieth century became an atheist in his teens and after a long journey through different philosophical convictions he converted to Christianity in his early thirties, a change that affected his entire work. His love of literature was essential in discovering both the rational and the imaginative appeal of Christianity, which led him into a vision of the reality of the world and of life that satisfied the longing of his heart and the hunger of his imagination.

  14. Ermakov–Lewis invariants and Reid systems

    Energy Technology Data Exchange (ETDEWEB)

    Mancas, Stefan C., E-mail: stefan.mancas@erau.edu [Department of Mathematics, Embry-Riddle Aeronautical University, Daytona Beach, FL 32114-3900 (United States); Rosu, Haret C., E-mail: hcr@ipicyt.edu.mx [IPICyT, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la presa San José 2055, Col. Lomas 4a Sección, 78216 San Luis Potosí, S.L.P. (Mexico)

    2014-06-13

    Reid's mth-order generalized Ermakov systems of nonlinear coupling constant α are equivalent to an integrable Emden–Fowler equation. The standard Ermakov–Lewis invariant is discussed from this perspective, and a closed formula for the invariant is obtained for the higher-order Reid systems (m≥3). We also discuss the parametric solutions of these systems of equations through the integration of the Emden–Fowler equation and present an example of a dynamical system for which the invariant is equivalent to the total energy. - Highlights: • Reid systems of order m are connected to Emden–Fowler equations. • General expressions for the Ermakov–Lewis invariants both for m=2 and m≥3 are obtained. • Parametric solutions of the Emden–Fowler equations related to Reid systems are obtained.

  15. Rendezvous, un juego de Lewis Carroll

    Directory of Open Access Journals (Sweden)

    José Manuel Sánchez Muñoz

    2011-10-01

    Full Text Available Todos en mayor o menor medida asociamos el nombre de Lewis Carrolla la literatura, sobre todo a la de temática infantil, con títulos a sus espaldas como Alicia en el País de las Maravillas, Alicia a través del espejo, o La Caza del Snark. Pero además de literato, Lewis Carrol fue un hombre con bastantes inquietudes en torno a la matemática, la lógica y el pensamiento filosófico. Pero no todo el mundo es conocedor de su faceta como creativo en el campo de los juegos. Rendezvous es una de sus más sorprendentes invenciones,un juego de inteligencia para todos los públicos, cuyas directrices hacen de él un entretenimiento bastante original.

  16. Maudlin's challenge refuted: A reply to Lewis

    Science.gov (United States)

    Kastner, Ruth E.

    2014-08-01

    Lewis has recently argued that Maudlin's contingent absorber experiment remains a significant problem for the Transactional Interpretation (TI). He argues that the only straightforward way to resolve the challenge is by describing the absorbers as offer waves, and asserts that this is a previously unnoticed aspect of the challenge for TI. This argument is refuted in two basic ways: (i) it is noted that the Maudlin experiment cannot be meaningfully recast with absorbers described by quantum states; instead the author replaces it with an ordinary which-way experiment; and (ii) the extant rebuttals to the Maudlin challenge in its original form are not in fact subject to the alleged flaws that Lewis ascribes to them. This paper further seeks to clarify the issues raised in Lewis' presentation concerning the distinction between quantum systems and macroscopic objects in TI. It is noted that the latest, possibilist version of TI (PTI) has no ambiguity concerning macroscopic absorbers. In particular, macroscopic objects are not subject to indeterminate trajectories, since they are continually undergoing collapse. It is concluded that the Maudlin challenge poses no significant problem for the transactional interpretation.

  17. Evaluation of acid-base disorders in dogs and cats presenting to an emergency room. Part 2: comparison of anion gap, strong ion gap, and semiquantitative analysis.

    Science.gov (United States)

    Hopper, Kate; Epstein, Steven E; Kass, Philip H; Mellema, Matthew S

    2014-01-01

    To compare the diagnostic performance of the anion gap (AG) with 2 physicochemical approaches to identify unmeasured anions. Prospective cohort study. University teaching hospital. Eighty-four dogs and 14 cats presenting to a university teaching hospital emergency room. All dogs and cats in which venous blood samples for acid-base, lactate, and serum biochemical analysis were all collected within 60 minutes of each other, over a 5-month enrollment period. Unmeasured anions were quantified using each of three approaches: the anion gap (AG), strong ion gap (SIG), and a semiquantitative approach (XA). An increased AG metabolic acidosis was evident in 34/98 of cases. The Stewart approach identified an increased SIG acidosis in 49/98 of cases. There was a strong correlation between SIG and AG (r = 0.89; P anions in 68/98 of cases. There was a moderate correlation between AG and XA (r = 0.68; P anions occurred commonly in this sample of small animal emergency room patients and physiochemical approaches identified more animals with unmeasured anions than the traditional AG calculation. Further studies are needed to determine if the results of the physicochemical approach improves clinical management and warrants the associated increases in cost and complexity. © Veterinary Emergency and Critical Care Society 2014.

  18. Vibrational tug-of-war: The pKA dependence of the broad vibrational features of strongly hydrogen-bonded carboxylic acids

    Science.gov (United States)

    Van Hoozen, Brian L.; Petersen, Poul B.

    2018-04-01

    Medium and strong hydrogen bonds give rise to broad vibrational features frequently spanning several hundred wavenumbers and oftentimes exhibiting unusual substructures. These broad vibrational features can be modeled from first principles, in a reduced dimensional calculation, that adiabatically separates low-frequency modes, which modulate the hydrogen bond length, from high-frequency OH stretch and bend modes that contribute to the vibrational structure. Previously this method was used to investigate the origin of an unusual vibrational feature frequently found in the spectra of dimers between carboxylic acids and nitrogen-containing aromatic bases that spans over 900 cm-1 and contains two broad peaks. It was found that the width of this feature largely originates from low-frequency modes modulating the hydrogen bond length and that the structure results from Fermi resonance interactions. In this report, we examine how these features change with the relative acid and base strength of the components as reflected by their aqueous pKA values. Dimers with large pKA differences are found to have features that can extend to frequencies below 1000 cm-1. The relationships between mean OH/NH frequency, aqueous pKA, and O-N distance are examined in order to obtain a more rigorous understanding of the origin and shape of the vibrational features. The mean OH/NH frequencies are found to correlate well with O-N distances. The lowest OH stretch frequencies are found in dimer geometries with O-N distances between 2.5 and 2.6 Å. At larger O-N distances, the hydrogen bonding interaction is not as strong, resulting in higher OH stretch frequencies. When the O-N distance is smaller than 2.5 Å, the limited space between the O and N determines the OH stretch frequency, which gives rise to frequencies that decrease with O-N distances. These two effects place a lower limit on the OH stretch frequency which is calculated to be near 700 cm-1. Understanding how the vibrational features

  19. Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation

    OpenAIRE

    Sumerin, Victor

    2011-01-01

    Organocatalysis, the use of organic molecules as catalysts, is attracting increasing attention as one of the most modern and rapidly growing areas of organic chemistry, with countless research groups in both academia and the pharmaceutical industry around the world working on this subject. The literature review of this thesis mainly focuses on metal-free systems for hydrogen activation and organocatalytic reduction. Since these research topics are relatively new, the literature review al...

  20. Clinicopathological Correlates of Lewy Body Disease: Fundamental Issues

    Directory of Open Access Journals (Sweden)

    Tae-Beom Ahn

    2010-05-01

    Full Text Available Lewy body pathology (LBP is the pathological hallmark of Lewy body diseases, such as Parkinson’s disease and Lewy body dementia. Recent studies have shed new light on the role of LBP, the interactions of LBP with concomitant pathologies, and the propagation of LBP from the olfactory bulb and enteric nervous system to the central nervous system. The intrinsic difficulty with identifying clinicopathological correlates could be overcome by improving our understanding of the pathological evolution of LBP.

  1. Asymmetric allylation of α-ketoester-derived N-benzoylhydrazones promoted by chiral sulfoxides/N-oxides Lewis bases: highly enantioselective synthesis of quaternary α-substituted α-allyl-α-amino acids.

    Science.gov (United States)

    Reyes-Rangel, Gloria; Bandala, Yamir; García-Flores, Fred; Juaristi, Eusebio

    2013-09-01

    Chiral sulfoxides/N-oxides (R)-1 and (R,R)-2 are effective chiral promoters in the enantioselective allylation of α-keto ester N-benzoylhydrazone derivatives 3a-g to generate the corresponding N-benzoylhydrazine derivatives 4a-g, with enantiomeric excesses as high as 98%. Representative hydrazine derivatives 4a-b were subsequently treated with SmI2, and the resulting amino esters 5a-b with LiOH to obtain quaternary α-substituted α-allyl α-amino acids 6a-b, whose absolute configuration was assigned as (S), with fundament on chemical correlation and electronic circular dichroism (ECD) data. © 2013 Wiley Periodicals, Inc.

  2. Ablative Material Testing at Lewis Rocket Lab

    Science.gov (United States)

    1997-01-01

    The increasing demand for a low-cost, reliable way to launch commercial payloads to low- Earth orbit has led to the need for inexpensive, expendable propulsion systems for new launch vehicles. This, in turn, has renewed interest in less complex, uncooled rocket engines that have combustion chambers and exhaust nozzles fabricated from ablative materials. A number of aerospace propulsion system manufacturers have utilized NASA Lewis Research Center's test facilities with a high degree of success to evaluate candidate materials for application to new propulsion devices.

  3. Structure of Al-Lewis Site in Beta Zeolite Active in Meerwein-Ponndorf-Verley Reduction of Ketone to Alcohol

    Czech Academy of Sciences Publication Activity Database

    Bortnovsky, O.; Sobalík, Zdeněk; Wichterlová, Blanka; Bastl, Zdeněk

    2002-01-01

    Roč. 210, - (2002), s. 171-182 ISSN 0021-9517 R&D Projects: GA AV ČR IBS4040015 Institutional research plan: CEZ:AV0Z4040901 Keywords : Meerwein-Ponndorf-Verley reduction * beta zeolite * Lewis acid Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.118, year: 2002

  4. CATALYTIC PROPERTIES AND ACIDITY OF MODIFIED MCM-41 ...

    African Journals Online (AJOL)

    Adsorption of pyridine and IR spectroscopy indicated various types of Lewis and Brönsted acid sites. The density distribution of acid sites was determined by TPD. Both Lewis and Brönsted acid sites were found to be active in the heptane isomerisation. The presence of aluminium (low Si/Al) combined to the ionic exchange ...

  5. High night temperature strongly impacts TCA cycle, amino acid and polyamine biosynthetic pathways in rice in a sensitivity-dependent manner.

    Science.gov (United States)

    Glaubitz, Ulrike; Erban, Alexander; Kopka, Joachim; Hincha, Dirk K; Zuther, Ellen

    2015-10-01

    Global climate change combined with asymmetric warming can have detrimental effects on the yield of crop plants such as rice (Oryza sativa L.). Little is known about metabolic responses of rice to high night temperature (HNT) conditions. Twelve cultivars with different HNT sensitivity were used to investigate metabolic changes in the vegetative stage under HNT compared to control conditions. Central metabolism, especially TCA cycle and amino acid biosynthesis, were strongly affected particularly in sensitive cultivars. Levels of several metabolites were correlated with HNT sensitivity. Furthermore, pool sizes of some metabolites negatively correlated with HNT sensitivity under control conditions, indicating metabolic pre-adaptation in tolerant cultivars. The polyamines putrescine, spermidine and spermine showed increased abundance in sensitive cultivars under HNT conditions. Correlations between the content of polyamines and 75 other metabolites indicated metabolic shifts from correlations with sugar-phosphates and 1-kestose under control to correlations with sugars and amino and organic acids under HNT conditions. Increased expression levels of ADC2 and ODC1, genes encoding enzymes catalysing the first committed steps of putrescine biosynthesis, were restricted to sensitive cultivars under HNT. Additionally, transcript levels of eight polyamine biosynthesis genes were correlated with HNT sensitivity. Responses to HNT in the vegetative stage result in distinct differences between differently responding cultivars with a dysregulation of central metabolism and an increase of polyamine biosynthesis restricted to sensitive cultivars under HNT conditions and a pre-adaptation of tolerant cultivars already under control conditions with higher levels of potentially protective compatible solutes. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  6. Unprecedented access to strong and ductile poly(lactic acid) by introducing In Situ Nanofibrillar Poly(butylene succinate) for green packaging.

    Science.gov (United States)

    Xie, Lan; Xu, Huan; Niu, Ben; Ji, Xu; Chen, Jun; Li, Zhong-Ming; Hsiao, Benjamin S; Zhong, Gan-Ji

    2014-11-10

    The notion of toughening poly(lactic acid) (PLA) by adding flexible biopolymers has generated enormous interest but has yielded few desirable advances, mainly blocked by the sacrifice of strength and stiffness due to uncontrollable phase morphology and poor interfacial interactions. Here the phase control methodology, that is, intense extrusion compounding followed by "slit die extrusion-hot stretching-quenching" technique, was proposed to construct well-aligned, stiff poly(butylene succinate) (PBS) nanofibrils in the PLA matrix for the first time. We show that generating nanosized discrete droplets of PBS phase during extrusion compounding is key to enable the development of in situ nanofibrillar PBS assisted by the shearing/stretching field. The size of PBS nanofibrils strongly dependent on the PBS content, showing an increased average diameter from 83 to 116 and 236 nm for the composites containing 10, 20, and 40 wt % nanofibrils, respectively. More importantly, hybrid shish-kebab superstructure anchoring ordered PLA kebabs were induced by the PBS nanofibrils serving as the central shish, conferring the creation of tenacious interfacial crystalline ligaments. The exceptional combination of strength, modulus, and ductility for the composites loaded 40 wt % PBS nanofibrils were demonstrated, outperforming pure PLA with the increments of 31, 51, and 72% in strength, modulus, and elongation at break (56.4 MPa, 1702 MPa, and 92.4%), respectively. The high strength, modulus, and ductility are unprecedented for PLA and are in great potential need for packaging applications.

  7. Ion exchange removal of chromium (iii) from tannery wastes by using a strong acid cation exchange resin amberlite ir-120 h+ and its hybrids

    International Nuclear Information System (INIS)

    Ahmad, T.

    2014-01-01

    A strong acid cation exchange resin Amberlite IR-120 H+ and its hybrids with Mn(OH)/sub 2/, Cu(OH)/sub 2/ and Fe(OH)/sub 3/ are used for the removal of chromium (III) from spent tannery bath. The experimental data give good fits with the Langmuir sorption model. The thermodynamic parameters entropy (delta S), enthalpy (delta H) and free energy (delta G) changes are computed, which reveal that the chromium removal from tannery wastes by ion exchangers is an endothermic, physical sorption and entropically driven process. The rate of sorption is found to increase with the increase of resin dosage, stirring speed and temperature. Different kinetic models such as film diffusion, particle diffusion and Lagergren pseudo first order are used to evaluate the mechanism of the process. It is found that the hybrid ion exchange resins have better removal capacity as compared to the parent ion exchanger. The increase in the removal capacity is found to be in the order of the corresponding PZC values of the hybrid ion exchangers. Further, it is suggested that the higher exchange capacity is the result of Donnan effect and specific adsorption of chromium by the oxides / hydroxides present inside the matrix of the organic cation exchanger. (author)

  8. The Organization of Narrative Discourse in Lewy Body Spectrum Disorder

    Science.gov (United States)

    Ash, Sharon; McMillan, Corey; Gross, Rachel G.; Cook, Philip; Morgan, Brianna; Boller, Ashley; Dreyfuss, Michael; Siderowf, Andrew; Grossman, Murray

    2011-01-01

    Narrative discourse is an essential component of day-to-day communication, but little is known about narrative in Lewy body spectrum disorder (LBSD), including Parkinson's disease (PD), Parkinson's disease with dementia (PDD), and dementia with Lewy bodies (DLB). We performed a detailed analysis of a semi-structured speech sample in 32 non-aphasic…

  9. Thoughts on Teaching: John L. Lewis, Jesus, and President Bush.

    Science.gov (United States)

    Starnes, Bobby Ann

    2004-01-01

    Bobby Ann Starnes, the author of this article, grew up with portraits of two important people displayed prominently in her home, Jesus, and John L. Lewis. Lewis, a giant among American leaders in the first half of the twentieth century, sent hundreds of organizers to help create some of the nation's leading labor unions, including the United…

  10. LEWIS BINFORD AND HIS MORAL MAJORITY (Lewis Binford y su mayoría moral

    Directory of Open Access Journals (Sweden)

    Alice Beck Kehoe

    2011-06-01

    Full Text Available This essay looks at the late Lewis Binford’s career from the standpoint of sociology of science. His thinking and manner reflect his socialization in Virginia Baptist subculture. As convinced of his authority on science as Jerry Falwell was of his authority on Biblical morality, Lewis Binford and his third wife Sally Rosen Binford excited a group of 1960s students to follow Lewis in an outmoded version of science (hypothetico-deductive and in trusting statistics. The “frames of reference” he laboriously constructed are naïve on environmental interpretation and, because he expressed contempt for “political” aspects of archaeology, fail to take into account effects of colonialism. His work is often scientistic, in the “modern” mode that historian Dorothy Ross describes as characteristic of twentieth-century American social sciences. ESPAÑOL: En este ensayo se analiza la etapa final de la carrera de Lewis Binford desde el punto de vista de la sociología de la ciencia. Su pensamiento refleja su socialización en el seno de la subcultura de la Virginia baptista. Tan convencido de su autoridad en la ciencia como Jerry Falwell lo fuera sobre la moralidad bíblica, Lewis Binford y su tercera esposa Sally Rosen Binford animaron a un grupo estudiantes de los sesenta a seguir a Lewis a través de una versión anticuada de la ciencia (hipotético-deductiva y a confiar en la estadística. Los “marcos de referencia” que laboriosamente construyó son ingenuos en la interpretación del medio ambiente y, como expresó el desprecio por los aspectos “políticos” de la arqueología, no tienen en cuenta los efectos del colonialismo. Su trabajo es a menudo cientificista, en el sentido “moderno” que la historiadora Dorothy Ross describe como una característica de las ciencias sociales norteamericanas del siglo XX.

  11. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    Science.gov (United States)

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. NASA Lewis Meshed VSAT Workshop meeting summary

    Science.gov (United States)

    Ivancic, William

    1993-11-01

    NASA Lewis Research Center's Space Electronics Division (SED) hosted a workshop to address specific topics related to future meshed very small-aperture terminal (VSAT) satellite communications networks. The ideas generated by this workshop will help to identify potential markets and focus technology development within the commercial satellite communications industry and NASA. The workshop resulted in recommendations concerning these principal points of interest: the window of opportunity for a meshed VSAT system; system availability; ground terminal antenna sizes; recommended multifrequency for time division multiple access (TDMA) uplink; a packet switch design concept for narrowband; and fault tolerance design concepts. This report presents a summary of group presentations and discussion associated with the technological, economic, and operational issues of meshed VSAT architectures that utilize processing satellites.

  13. [Clinical Neuropsychology of Dementia with Lewy Bodies].

    Science.gov (United States)

    Nagahama, Yasuhiro

    2016-02-01

    Dementia with Lewy bodies (DLB) shows lesser memory impairment and more severe visuospatial disability than Alzheimer disease (AD). Although deficits in both consolidation and retrieval underlie the memory impairment, retrieval deficit is predominant in DLB. Visuospatial dysfunctions in DLB are related to the impairments in both ventral and dorsal streams of higher visual information processing, and lower visual processing in V1/V2 may also be impaired. Attention and executive functions are more widely disturbed in DLB than in AD. Imitation of finger gestures is impaired more frequently in DLB than in other mild dementia, and provides additional information for diagnosis of mild dementia, especially for DLB. Pareidolia, which lies between hallucination and visual misperception, is found frequently in DLB, but its mechanism is still under investigation.

  14. The development of Lewis Henry Morgan's evolutionism.

    Science.gov (United States)

    Kuper, A

    1985-01-01

    Lewis Henry Morgan never used the term evolution in any of his major sociological works. If he may be labeled an evolutionist, the specificity of his views must be taken into account. The main "evolutionist" issue that concerned him was that of the unity or diversity of the human species. This was an urgent political and theological issue in the America of his day, and it impinged also on research on the American Indians. Morgan's first major study was designed to demonstrate the unity of origin of the American aborigines and their "Asian" origins. His methods were derived from the tradition of Indo-European philology. It was virtually as an afterthought that he added a social evolutionary component to what he conceived of as an exercise in philology. Later he came under the direct influence of the English evolutionists, and this was crucial for the conception of Ancient Society.

  15. Lewy Body Dementias: Dementia With Lewy Bodies and Parkinson Disease Dementia

    Science.gov (United States)

    Gomperts, Stephen N.

    2016-01-01

    ABSTRACT Purpose of Review: This article provides an overview of the clinical features, neuropathologic findings, diagnostic criteria, and management of dementia with Lewy bodies (DLB) and Parkinson disease dementia (PDD), together known as the Lewy body dementias. Recent Findings: DLB and PDD are common, clinically similar syndromes that share characteristic neuropathologic changes, including deposition of α-synuclein in Lewy bodies and neurites and loss of tegmental dopamine cell populations and basal forebrain cholinergic populations, often with a variable degree of coexisting Alzheimer pathology. The clinical constellations of DLB and PDD include progressive cognitive impairment associated with parkinsonism, visual hallucinations, and fluctuations of attention and wakefulness. Current clinical diagnostic criteria emphasize these features and also weigh evidence for dopamine cell loss measured with single-photon emission computed tomography (SPECT) imaging and for rapid eye movement (REM) sleep behavior disorder, a risk factor for the synucleinopathies. The timing of dementia relative to parkinsonism is the major clinical distinction between DLB and PDD, with dementia arising in the setting of well-established idiopathic Parkinson disease (after at least 1 year of motor symptoms) denoting PDD, while earlier cognitive impairment relative to parkinsonism denotes DLB. The distinction between these syndromes continues to be an active research question. Treatment for these illnesses remains symptomatic and relies on both pharmacologic and nonpharmacologic strategies. Summary: DLB and PDD are important and common dementia syndromes that overlap in their clinical features, neuropathology, and management. They are believed to exist on a spectrum of Lewy body disease, and some controversy persists in their differentiation. Given the need to optimize cognition, extrapyramidal function, and psychiatric health, management can be complex and should be systematic. PMID

  16. Serum uric acid is more strongly associated with impaired fasting glucose in women than in men from a community-dwelling population.

    Directory of Open Access Journals (Sweden)

    Ryuichi Kawamoto

    Full Text Available Serum uric acid (SUA levels are associated with metabolic syndrome (MetS and its components such as glucose intolerance and type 2 diabetes. It is unknown whether there are gender-specific differences regarding the relationship between SUA levels, impaired fasting glucose (IFG and newly detected diabetes. We recruited 1,209 men aged 60±15 (range, 19-89 years and 1,636 women aged 63±12 (range, 19-89 years during their annual health examination from a single community. We investigated the association between SUA levels and six categories according to fasting plasma glucose (FPG level {normal fasting glucose (NFG, <100 mg/dL; high NFG-WHO, 100 to 109 mg/dL; IFG-WHO, 110 to 125 mg/dL; IFG-ADA, 100 to 125 mg/dL; newly detected diabetes, ≥126 mg/dL; known diabetes} SUA levels were more strongly associated with the different FPG categories in women compared with men. In women, the associations remained significant for IFG-WHO (OR, 1.23, 95% CI, 1.00-1.50 and newly detected diabetes (OR, 1.33, 95% CI, 1.03-1.72 following multivariate adjustment. However, in men all the associations were not significant. Thus, there was a significant interaction between gender and SUA level for newly detected diabetes (P = 0.005. SUA levels are associated with different categories of impaired fasting glucose in participants from community-dwelling persons, particularly in women.

  17. Strong linkage of polar cod (Boreogadus saida) to sea ice algae-produced carbon: Evidence from stomach content, fatty acid and stable isotope analyses

    Science.gov (United States)

    Kohlbach, Doreen; Schaafsma, Fokje L.; Graeve, Martin; Lebreton, Benoit; Lange, Benjamin Allen; David, Carmen; Vortkamp, Martina; Flores, Hauke

    2017-03-01

    The polar cod (Boreogadus saida) is considered an ecological key species, because it reaches high stock biomasses and constitutes an important carbon source for seabirds and marine mammals in high-Arctic ecosystems. Young polar cod (1-2 years) are often associated with the underside of sea ice. To evaluate the impact of changing Arctic sea ice habitats on polar cod, we examined the diet composition and quantified the contribution of ice algae-produced carbon (αIce) to the carbon budget of polar cod. Young polar cod were sampled in the ice-water interface layer in the central Arctic Ocean during late summer 2012. Diets and carbon sources of these fish were examined using 4 approaches: (1) stomach content analysis, (2) fatty acid (FA) analysis, (3) bulk nitrogen and carbon stable isotope analysis (BSIA) and (4) compound-specific stable isotope analysis (CSIA) of FAs. The ice-associated (sympagic) amphipod Apherusa glacialis dominated the stomach contents by mass, indicating a high importance of sympagic fauna in young polar cod diets. The biomass of food measured in stomachs implied constant feeding at daily rates of ∼1.2% body mass per fish, indicating the potential for positive growth. FA profiles of polar cod indicated that diatoms were the primary carbon source, indirectly obtained via amphipods and copepods. The αIce using bulk isotope data from muscle was estimated to be >90%. In comparison, αIce based on CSIA ranged from 34 to 65%, with the highest estimates from muscle and the lowest from liver tissue. Overall, our results indicate a strong dependency of polar cod on ice-algae produced carbon. This suggests that young polar cod may be particularly vulnerable to changes in the distribution and structure of sea ice habitats. Due to the ecological key role of polar cod, changes at the base of the sea ice-associated food web are likely to affect the higher trophic levels of high-Arctic ecosystems.

  18. Synthesis of Trisubstituted Imidazoles Using Lewis and Bronsted Acid Catalysts

    OpenAIRE

    Hekmatshoar, Rahim; HEKMATSHOAR, Rahim; JAHANBAKHSHI, Hajar; MOUSAVIZADEH, Farnoosh; RAHNAMAFAR, Reyhane

    2010-01-01

    An efficient and one-pot method for the preparation of trisubstituted imidazoles by condensation of benzil, different aldehydes and ammonium acetate in the presence of  a catalytic amount of NiSO4.7H2O or H3BO3 under different conditions is reported.                    Key Words: Trisubstituted imidazoles, Multi-component &a...

  19. Lewis acid adducts of [PCl2N]3.

    Science.gov (United States)

    Heston, Amy J; Panzner, Matthew J; Youngs, Wiley J; Tessier, Claire A

    2005-09-19

    Reaction of aluminum trichloride or gallium trichloride with the extremely weak base hexachlorotriphosphazene gives adducts in which the group 13 element is bound to a phosphazene nitrogen atom. In solution, the adducts exhibit fluxional behavior. The phosphazene ring of the adducts is distorted into a slight chair conformation.

  20. Lewis acidic metal catalysed organic transformations by designed ...

    Indian Academy of Sciences (India)

    Administrator

    exclusive use of SiO4/AlO4 building blocks. Second, the desirable chemical modification within the inte- rior of the material has limitations. Such chemical modifications are important for expanding and enhancing the catalytic performance of the resultant material. Third, the catalytic applications of zeolites are restricted to ...

  1. Influence of the acid and basic properties of rhenium oxide supported on alumina catalyst on the catalytic performance in olefin metathesis; Influence des proprietes acido-basiques de l`oxyde de rhenium supporte sur les performances catalytiques en metathese des olefines

    Energy Technology Data Exchange (ETDEWEB)

    Nahama, F.

    1996-11-30

    The aim of this work is to study the influence of the acid-basic properties of rhenium oxide supported on alumina catalyst on the catalytic performance in olefin metathesis. The literature data indicate that the environment of the active site does possess acid properties. However, the nature of the acid sites is still matter of debate. Concerning the Re O{sub x} - Al{sub 2}O{sub 3} interactions, we have shown that perrhenate ions are electrostatically absorbed on alumina. The uptake of rhenium is favoured at acidic pH (below 4), and the absorbed rhenium is in equilibrium with rhenium in solution. The results of rhenium extraction by water strongly suggest that the surface compounds of the calcined Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} materials is aluminium perrhenate. Characterization of surface acidity of the catalyst by infrared spectroscopy reveals that the initiation of the metathesis reaction is governed essentially by Lewis acidity. This strongly supports the role of Lewis acidity, which is exalted by the increase of the rhenium content and the calcination temperature. Finally, we point out by ammonia adsorption-thermodesorption a band at 1320 cm{sup -1} characteristic of the Lewis acidity of aluminium perrhenate. This result is a second indication of the presence of aluminium perrhenate on the Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} catalyst surface. (author)

  2. Non-Directed Allylic C–H Acetoxylation in the Presence of Lewis Basic Heterocycles

    Science.gov (United States)

    Malik, Hasnain A.; Taylor, Buck L. H.; Kerrigan, John R.; Grob, Jonathan E.; Houk, K. N.; Du Bois, J.; Hamann, Lawrence G.; Patterson, Andrew W.

    2015-01-01

    We outline a strategy to enable non-directed Pd(II)-catalyzed C–H functionalization in the presence of Lewis basic heterocycles. In a high-throughput screen of two Pd-catalyzed C–H acetoxylation reactions, addition of a variety of N-containing heterocycles is found to cause low product conversion. A pyridine-containing test substrate is selected as representative of heterocyclic scaffolds that are hypothesized to cause catalyst arrest. We pursue two approaches in parallel that allow product conversion in this representative system: Lewis acids are found to be effective in situ blocking groups for the Lewis basic site, and a pre-formed pyridine N-oxide is shown to enable high yield of allylic C–H acetoxylation. Computational studies with density functional theory (M06) of binding affinities of selected heterocycles to Pd(OAc)2 provide an inverse correlation of the computed heterocycle–Pd(OAc)2 binding affinities with the experimental conversions to products. Additionally, 1H NMR binding studies provide experimental support for theoretical calculations. PMID:25685311

  3. The Lewis Pair Polymerization of Lactones Using Metal Halides and N-Heterocyclic Olefins: Theoretical Insights

    Directory of Open Access Journals (Sweden)

    Jan Meisner

    2018-02-01

    Full Text Available Lewis pair polymerization employing N-Heterocyclic olefins (NHOs and simple metal halides as co-catalysts has emerged as a useful tool to polymerize diverse lactones. To elucidate some of the mechanistic aspects that remain unclear to date and to better understand the impact of the metal species, computational methods have been applied. Several key aspects have been considered: (1 the formation of NHO-metal halide adducts has been evaluated for eight different NHOs and three different Lewis acids, (2 the coordination of four lactones to MgCl2 was studied and (3 the deprotonation of an initiator (butanol was investigated in the presence and absence of metal halide for one specific Lewis pair. It was found that the propensity for adduct formation can be influenced, perhaps even designed, by varying both organic and metallic components. Apart from the NHO backbone, the substituents on the exocyclic, olefinic carbon have emerged as interesting tuning site. The tendency to form adducts is ZnCl2 > MgCl2 > LiCl. If lactones coordinate to MgCl2, the most likely binding mode is via the carbonyl oxygen. A chelating coordination cannot be ruled out and seems to gain importance upon increasing ring-size of the lactone. For a representative NHO, it is demonstrated that in a metal-free setting an initiating alcohol cannot be deprotonated, while in the presence of MgCl2 the same process is exothermic with a low barrier.

  4. Isospecific Propylene Polymerization Behavior of Lewis Base Functionalized Unbridged Zirconocences under Bulk Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Seung Woong; Kim, Hwa Kyu; Kim, Seong Kyun; Do, Young Kyu [KAIST, Daejeon (Korea, Republic of); Kim, Tae Won; Lee, Min Hyung [Univ. of Ulsan, Ulsan (Korea, Republic of)

    2014-01-15

    Isospecific propylene polymerization behavior of meta- and para-Lewis base (E) functionalized unbridged zirconocenes ([1-(E{sub n}-Ph)-3,4-Me{sub 2}C{sub 5}H{sub 2}]{sub 2}ZrCl{sub 2}, E = NMe{sub 2}, OMe; n = 1 or 2) was investigated under bulk conditions. Catalytic activity of the zirconocenes, and molecular weight and isotacticity of polypropylenes are found to be dependent on the position and number of the Lewis base functional groups in the zirconocenes. All the crude polypropylenes possess a broad molecular weight distribution and multi-melting transitions, indicating an involvement of multi-catalytic active species in the polymerization. The highest [mmmm] value of an isotactic portion of the polypropylenes reached 89%, which is higher than that (85%) from the well-known C{sub 2}-symmetric EBIZr (rac-Et(Ind){sub 2}ZrCl{sub 2}) catalyst. These results support that the in situ generated, rigid rac-like cation-anion pair through the Lewis acid-base interactions between the functional groups of zirconocenes and methylaluminoxane anion is effective in the formation of isotactic polypropylene under bulk propylene polymerization conditions.

  5. Proton dynamics in the strong chelate hydrogen bond of crystalline picolinic acid N-oxide. A new computational approach and infrared, raman and INS study.

    Science.gov (United States)

    Stare, Jernej; Panek, Jarosław; Eckert, Juergen; Grdadolnik, Joze; Mavri, Janez; Hadzi, Dusan

    2008-02-21

    Infrared, Raman and INS spectra of picolinic acid N-oxide (PANO) were recorded and examined for the location of the hydronic modes, particularly O-H stretching and COH bending. PANO is representative of strong chelate hydrogen bonds (H-bonds) with its short O...O distance (2.425 A). H-bonding is possibly well-characterized by diffraction, NMR and NQR data and calculated potential energy functions. The analysis of the spectra is assisted by DFT frequency calculations both in the gas phase and in the solid state. The Car-Parrinello quantum mechanical solid-state method is also used for the proton dynamics simulation; it shows the hydron to be located about 99% of time in the energy minimum near the carboxylic oxygen; jumps to the N-O acceptor are rare. The infrared spectrum excels by an extended absorption (Zundel's continuum) interrupted by numerous Evans transmissions. The model proton potential functions on which the theories of continuum formation are based do not correspond to the experimental and computed characteristics of the hydrogen bond in PANO, therefore a novel approach has been developed; it is based on crystal dynamics driven hydronium potential fluctuation. The envelope of one hundred 0 --> 1 OH stretching transitions generated by molecular dynamics simulation exhibits a maximum at 1400 cm-1 and a minor hump at approximately 1600 cm-1. These positions square well with ones predicted for the COH bending and OH stretching frequencies derived from various one- and two-dimensional model potentials. The coincidences with experimental features have to be considered with caution because the CPMD transition envelope is based solely on the OH stretching coordinate while the observed infrared bands correspond to heavily mixed modes as was previously shown by the normal coordinate analysis of the IR spectrum of argon matrix isolated PANO, the present CPMD frequency calculation and the empirical analysis of spectra. The experimental infrared spectra show some

  6. Polysomnographic findings in dementia with Lewy bodies.

    Science.gov (United States)

    Pao, Winnie C; Boeve, Bradley F; Ferman, Tanis J; Lin, Sioung-Chi; Smith, Glenn E; Knopman, David S; Graff-Radford, Neill R; Petersen, Ronald C; Parisi, Joseph E; Dickson, Dennis W; Silber, Michael H

    2013-01-01

    The clinical features of dementia with Lewy bodies (DLB) during wakefulness are well known. Other than rapid eye movement (REM) sleep behavior disorder, only limited data exists on other sleep disturbances and disorders in DLB. We sought to characterize the polysomnographic (PSG) findings in a series of DLB patients with sleep-related complaints. Retrospective study of patients with DLB who underwent clinical PSG at Mayo Clinic, Rochester or Mayo Clinic, Jacksonville over an almost 11-year span for evaluation of dream enactment behavior, excessive nocturnal movements, sleep apnea, hypersomnolence, or insomnia. The following variables were analyzed: respiratory disturbance index (RDI) in disordered breathing events/hour, periodic limb movement arousal index, arousals for no apparent reason (AFNAR), total arousal index, presence of REM sleep without atonia, and percent sleep efficiency. Data on 78 patients (71 male, 7 female) were analyzed. The mean age was 71±8 years. Seventy-five (96%) patients had histories of recurrent dream enactment during sleep with 83% showing confirmation of REM sleep without atonia±dream enactment during PSG. Mean RDI=11.9±5.8, periodic limb movement arousal index =5.9±8.5, arousals for no apparent reason index=10.7±12.0, and total arousal index=26.6±17.4. Sleep efficiency was <80% in 72% of the sample, <70% in 49%, and <60% in 24%. In patients who did not show evidence of significant disordered breathing (23 with RDI<5), 62% of arousals were AFNARs. In those patients who had significant disordered breathing (55 with RDI≥5), 36% of arousals were AFNARs. Six patients underwent evaluations with PSG plus multiple sleep latency test. Two patients had mean initial sleep latencies of <5 minutes, and both had RDI<5. No patient had any sleep onset REM periods. Nineteen patients have undergone neuropathologic examination, and 18 have had limbic-predominant or neocortical-predominant Lewy body pathology. One had progressive supranuclear palsy

  7. Metal Catalysis with Nanostructured Metals Supported Inside Strongly Acidic Cross-linked Polymer Frameworks: Influence of Reduction Conditions of AuIII-containing Resins on Metal Nanoclusters Formation in Macroreticular and Gel-Type Materials

    Czech Academy of Sciences Publication Activity Database

    Calore, L.; Cavinato, g.; Canton, P.; Peruzzo, L.; Banavali, R.; Jeřábek, Karel; Corain, B.

    2012-01-01

    Roč. 391, AUG 30 (2012), s. 114-120 ISSN 0020-1693 Institutional support: RVO:67985858 Keywords : strongly acidic cross-linked polymer * frameworks * gold(0) nanoclusters Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.687, year: 2012

  8. Lewis Dahl and the genetics of salt-induced hypertension

    OpenAIRE

    Bashyam, Hema

    2007-01-01

    In the 1960s, Lewis Dahl bred two strains of rats that differed in their susceptibility to developing salt-induced hypertension. These animal models proved that hypertension induced by a high-salt diet is influenced by genetic background.

  9. Is It Lewy Body Dementia or Something Else?

    Science.gov (United States)

    ... Caregiving topics Caregiving Briefs LEWY DIGEST multimedia LBDA tv webinars, interviews & transcripts press releases Media Kit additional ... the brain. Vascular dementia is caused by a series of small strokes that deprive the brain of ...

  10. Stability on local unconditional structure and the Gordon-Lewis ...

    African Journals Online (AJOL)

    Abstract. Click on the link to view the abstract. Keywords: local unconditional structure; Gordon-Lewis property and tensor products of Banach spaces. Quaestiones Mathematicae 31(2008), 141–150 ...

  11. I-Metaiodobenzylguanidine Myocardial Scintigraphy in Lewy Body-Related Disorders: A Literature Review

    Directory of Open Access Journals (Sweden)

    Eun Joo Chung

    2015-05-01

    Full Text Available Lewy body-related disorders are characterized by the presence of Lewy bodies and Lewy neurites, which have abnormal aggregations of α-synuclein in the nigral and extranigral areas, including in the heart. 123I-metaiodobenzylguanidine (MIBG scintigraphy is a well-known tool to evaluate cardiac sympathetic denervation in the Lewy body-related disorders. MIBG scintigraphy showed low uptake of MIBG in the Lewy body-related disorders, including Parkinson’s disease, dementia with Lewy bodies, pure autonomic failure and rapid eye movement sleep behavior disorder. This review summarizes previous results on the diagnostic applications of MIBG scintigraphy in Lewy body-related disorders.

  12. A second look at Duckworth - Lewis in Twenty20 Cricket

    OpenAIRE

    Perera, G. Harsha P.

    2011-01-01

    This project investigates the suitability of the Duckworth-Lewis method as an approach to resetting targets in interrupted Twenty20 cricket matches. Whereas the Duckworth-Lewis method has been adopted in both international Twenty20 matches and in the Indian Premier League, there has been growing objections to its use. In this project, we develop methodology for the estimation of a resource table designed for Twenty20 cricket. The approach differs from previous analyses in the literature by co...

  13. LEWY BODY DEMENTIA: CAREGIVER BURDEN AND UNMET NEEDS

    OpenAIRE

    Galvin, James E.; Duda, John E.; Kaufer, Daniel I.; Lippa, Carol F.; Taylor, Angela; Zarit, Steven H.

    2010-01-01

    Lewy body dementia (LBD) is a common cause of dementia but to date, little is known about caregiver burden. The Lewy Body Dementia Association (www.LBDA.org) conducted a web-based survey of 962 caregivers (mean age 56y; 88% women). The most common initial symptoms were cognitive (48%), motor (39%), or both (13%). Caregivers expressed concerns about fear of future (77%), feeling stressed (54%), loss of social life (52%) and uncertainty about what to do next (50%). Caregivers reported moderate ...

  14. Tribute to Erwin Felix Lewy-Bertaut

    International Nuclear Information System (INIS)

    2006-01-01

    Erwin Lewy (alias Felix Bertaut) was born in 1913 in Germany, he emigrated to France where he undertook graduate studies in chemistry. Then, he joined the powder central laboratory where he learnt how to use international tables for structure determination. His thesis work was the X-ray study of the statistical distribution of the size of iron grains. The method Bertaut developed is still a reference in powder granulometry. Bertaut was also interested in the nascent neutron diffraction method and he flew to the United-States to improve his knowledge on this topic. Felix Bertaut created the neutron diffraction laboratory in the atomic research center in Grenoble and later he headed the CNRS' crystallography laboratory till 1982. Felix Bertaut and his laboratories became internationally renowned in crystallography, neutron diffraction and magnetism. He favored the scientific cooperation between France and Germany that led to the creation of the Laue-Langevin Institute (ILL). The ILL became European and was a key partner for building the European Synchrotron Facility (ESRF) in Grenoble. Bertaut was elected as a full member of the French Academy of Sciences in 1979, he died in 2003. (A.C.)

  15. Aluminium Diphosphamethanides: Hidden Frustrated Lewis Pairs.

    Science.gov (United States)

    Styra, Steffen; Radius, Michael; Moos, Eric; Bihlmeier, Angela; Breher, Frank

    2016-07-04

    The synthesis and characterisation of two aluminium diphosphamethanide complexes, [Al(tBu)2 {κ(2) P,P'-Mes*PCHPMes*}] (3) and [Al(C6 F5 )2 {κ(2) P,P'-Mes*PCHPMes*}] (4), and the silylated analogue, Mes*PCHP(SiMe3 )Mes* (5), are reported. The aluminium complexes feature four-membered PCPAl core structures consisting of diphosphaallyl ligands. The silylated phosphine 5 was found to be a valuable precursor for the synthesis of 4 as it cleanly reacts with the diaryl aluminium chloride [(C6 F5 )2 AlCl]2 . The aluminium complex 3 reacts with molecular dihydrogen at room temperature under formation of the acyclic σ(2) λ(3) ,σ(3) λ(3) -diphosphine Mes*PCHP(H)Mes* and the corresponding dialkyl aluminium hydride [tBu2 AlH]3 . Thus, 3 belongs to the family of so-called hidden frustrated Lewis pairs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. False memories in Lewy-body disease.

    Science.gov (United States)

    Algarabel, Salvador; Pitarque, Alfonso; Sales, Alicia; Meléndez, Juan Carlos; Escudero, Joaquín

    2015-12-01

    Recently, de Boysson, Belleville, Phillips et al. (2011) found that patients with Lewy-body disease (LBD) showed significantly lower rates of false memories than healthy controls, using the Deese-Roediger-McDermott (DRM) experimental procedure. Given that this result could be explained by the practically null rate of true recognition in the LBD group (0.09), we decided to replicate the study by de Boysson et al. (2011), but including a new condition that would maximize the true recognition rate (and analyze its effect on the rate of false memories). Specifically, in a DRM experiment, we manipulated (within subjects) two study and recognition conditions: in the "immediate" condition, both the LBD patients and the control group of healthy older people received a different recognition test after each study list (containing twelve words associated with a non-presented critical word), while in the "delayed" condition (similar to the one in de Boysson et al., 2011), the participants received the entire series of study lists and then took only one recognition test. The results showed that, in both samples, the "immediate" condition produced higher corrected rates of both true and false recognition than the "delayed" condition, although they were both lower in the LBD patients, which shows that these patients are capable of encoding and recognizing the general similitude underlying information (gist memory) in the right conditions. © 2015 Scandinavian Psychological Associations and John Wiley & Sons Ltd.

  17. Lewis Research Center R and D Facilities

    Science.gov (United States)

    1991-01-01

    The NASA Lewis Research Center (LeRC) defines and develops advanced technology for high priority national needs. The work of the Center is directed toward new propulsion, power, and communications technologies for application to aeronautics and space, so that U.S. leadership in these areas is ensured. The end product is knowledge, usually in a report, that is made fully available to potential users--the aircraft engine industry, the energy industry, the automotive industry, the space industry, and other NASA centers. In addition to offices and laboratories for almost every kind of physical research in such fields as fluid mechanics, physics, materials, fuels, combustion, thermodynamics, lubrication, heat transfer, and electronics, LeRC has a variety of engineering test cells for experiments with components such as compressors, pumps, conductors, turbines, nozzles, and controls. A number of large facilities can simulate the operating environment for a complete system: altitude chambers for aircraft engines; large supersonic wind tunnels for advanced airframes and propulsion systems; space simulation chambers for electric rockets or spacecraft; and a 420-foot-deep zero-gravity facility for microgravity experiments. Some problems are amenable to detection and solution only in the complete system and at essentially full scale. By combining basic research in pertinent disciplines and generic technologies with applied research on components and complete systems, LeRC has become one of the most productive centers in its field in the world. This brochure describes a number of the facilities that provide LeRC with its exceptional capabilities.

  18. Interphase transfer kinetics of uranium using the drop method, Lewis cell, and Kenics mixer

    International Nuclear Information System (INIS)

    Horner, D.E.; Mailen, J.C.; Thiel, S.W.; Scott, T.C.; Yates, R.G.

    1979-05-01

    The rate constants for the interphase transfer of uranium between 3.5 M HNO 3 and tributyl phosphate (TBP) - normal hydrocarbon diluent solutions have been measured using the single drop method, Lewis cell method, and a Kenics mixer - centrifugal separator. Rate constants obtained by all methods were the same within experimental error. The variables studied that affect the rate constants include the TBP concentration, the acidity and total neutral nitrate concentrations of the aqueous phase, and temperature. Results of these tests indicate that the rate controlling mechanism is chemical reaction at the interface

  19. Did Immanuel Kant have dementia with Lewy bodies and REM behavior disorder?

    Science.gov (United States)

    Miranda, Marcelo; Slachevsky, Andrea; Garcia-Borreguero, Diego

    2010-06-01

    Immanuel Kant, one of the most brilliant minds of the XVIII century and of western philosophy, suffered from dementia in his late years. Based on the analysis of testimonies of his close friends, in this report we describe his neurological disorder which, after 8years of evolution, led to his death. His cognitive decline was strongly associated with a parasomnia compatible with a severe rapid eye movement (REM) behavior disorder (RBD) and dementia with Lewy bodies. Copyright 2010 Elsevier B.V. All rights reserved.

  20. Capgras syndrome in Dementia with Lewy Bodies.

    Science.gov (United States)

    Thaipisuttikul, Papan; Lobach, Iryna; Zweig, Yael; Gurnani, Ashita; Galvin, James E

    2013-05-01

    Capgras syndrome is characterized by the recurrent, transient belief that a person has been replaced by an identical imposter. We reviewed clinical characteristics of Dementia with Lewy Bodies (DLB) patients with Capgras syndrome compared to those without Capgras. We identified 55 consecutive DLB patients (11 cases with Capgras syndrome (DLB-C) and 44 cases without evidence of Capgras (DLB). Semi-structured interviews with the patient and an informant, neurological exams, and neuropsychological testing were performed. Caregivers were assessed for caregiver burden and depression. Primary comparisons were made between DLB-C and DLB. Exploratory analyses using stepwise logistic regression and bootstrap analyses were performed to determine clinical features associated with Capgras. DLB-C patients experienced more visual hallucinations and self-reported anxiety, had higher scores on the Neuropsychiatric Inventory, and were less likely to be treated with cholinesterase inhibitors at time of initial evaluation. Extrapyramidal symptoms and depression were not associated with Capgras. Caregivers of DLB-C patients had higher caregiver burden. DLB-C was associated with self-reported anxiety (OR = 10.9; 95% CI = 2.6-47.6). In a bootstrap analysis, clinical findings that were predictors of Capgras included visual hallucinations (log(OR) = 18.3; 95% CI = 17.9-19.3) and anxiety (log(OR) = 2.9; 95% CI = 0.31-20.2). Our study suggests that Capgras syndrome is common in DLB and usually occurs in the presence of anxiety and visual hallucinations, suggesting related etiopathogenesis. Early appreciation of Capgras syndrome may afford the opportunity to alleviate caregiver burden and improve patient and caregiver outcomes.

  1. Zeolite-catalysed preparation of alpha-hydroxy carboxylic acids and esters thereof

    OpenAIRE

    Taarning, Esben; Shunmugavel, Saravanamurugan; Holm, Martin Spangsberg

    2010-01-01

    A process for the production of lactic acid and 2-hydroxy-3-butenoic acid or esters thereof by conversion of glucose, fructose, sucrose, xylose and glycolaldehyde dissolved in a solvent in presence of a solid Lewis acidic catalyst.

  2. A new oxidimetric reagent-potassium dichromate in a strong phosphoric acid medium-VIII Potentiometric titration of molybdenum(VI) and vanadium(V).

    Science.gov (United States)

    Muralikrishna, U; Rao, G G

    1968-01-01

    A new titrimetric method is described for the determination of molybdenum(VI) involving prior reduction to Mo(V) with an excess of Fe(II) in a concentrated phosphoric acid solution, followed by titration with dichromate. The titration can be done at room temperature and without protective atmosphere. Uranium interferes, but vanadium may be determined simultaneously.

  3. Effects of non-unity Lewis number of gas-phase species in turbulent nonpremixed sooting flames

    KAUST Repository

    Attili, Antonio

    2016-02-13

    Turbulence statistics from two three-dimensional direct numerical simulations of planar n-heptane/air turbulent jets are compared to assess the effect of the gas-phase species diffusion model on flame dynamics and soot formation. The Reynolds number based on the initial jet width and velocity is around 15, 000, corresponding to a Taylor scale Reynolds number in the range 100 ≤ Reλ ≤ 150. In one simulation, multicomponent transport based on a mixture-averaged approach is employed, while in the other the gas-phase species Lewis numbers are set equal to unity. The statistics of temperature and major species obtained with the mixture-averaged formulation are very similar to those in the unity Lewis number case. In both cases, the statistics of temperature are captured with remarkable accuracy by a laminar flamelet model with unity Lewis numbers. On the contrary, a flamelet with a mixture-averaged diffusion model, which corresponds to the model used in the multi-component diffusion three-dimensional DNS, produces significant differences with respect to the DNS results. The total mass of soot precursors decreases by 20-30% with the unity Lewis number approximation, and their distribution is more homogeneous in space and time. Due to the non-linearity of the soot growth rate with respect to the precursors\\' concentration, the soot mass yield decreases by a factor of two. Being strongly affected by coagulation, soot number density is not altered significantly if the unity Lewis number model is used rather than the mixture-averaged diffusion. The dominant role of turbulent transport over differential diffusion effects is expected to become more pronounced for higher Reynolds numbers. © 2016 The Combustion Institute.

  4. Zeolite-catalysed preparation of alpha-hydroxy carboxylic acids and esters thereof

    DEFF Research Database (Denmark)

    2010-01-01

    A process for the production of lactic acid and 2-hydroxy-3-butenoic acid or esters thereof by conversion of glucose, fructose, sucrose, xylose and glycolaldehyde dissolved in a solvent in presence of a solid Lewis acidic catalyst.......A process for the production of lactic acid and 2-hydroxy-3-butenoic acid or esters thereof by conversion of glucose, fructose, sucrose, xylose and glycolaldehyde dissolved in a solvent in presence of a solid Lewis acidic catalyst....

  5. Habitat selection and reproductive success of Lewis's Woodpecker (Melanerpes lewis at its northern limit.

    Directory of Open Access Journals (Sweden)

    Xiang Zhu

    Full Text Available Lewis's Woodpecker (Melanerpes lewis has experienced population declines in both Canada and the United States and in 2010 was assigned a national listing of threatened in Canada. We conducted a two-year study (2004-2005 of this species at its northern range limit, the South Okanagan Valley in British Columbia, Canada. Our main objective was to determine whether the habitat features that influenced nest-site selection also predicted nest success, or whether other factors (e.g. cavity dimensions, clutch initiation date or time of season were more important. Nest tree decay class, density of suitable cavities and total basal area of large trees were the best predictors of nest-site selection, but these factors were unrelated to nesting success. Estimates of demographic parameters (mean ± SE included daily nest survival rate (0.988±0.003, years combined, nest success (0.52±0.08, clutch size (5.00±0.14 eggs, female fledglings per successful nest (1.31±0.11, and annual productivity (0.68±0.12 female fledglings per nest per year. Although higher nest survival was associated with both early and late initiated clutches, early-initiated clutches allowed birds to gain the highest annual productivity as early clutches were larger. Nests in deep cavities with small entrances experienced lower predation risk especially during the peak period of nest predation. We concluded that nest-site selection can be predicted by a number of easily measured habitat variables, whereas nest success depended on complicated ecological interactions among nest predators, breeding behaviors, and cavity features. Thus, habitat-based conservation strategies should also consider ecological factors that may not be well predicted by habitat.

  6. [Clinical and neuropathological characteristics of dementia with Lewy bodies].

    Science.gov (United States)

    Bencze, János; Simon, Viktória; Bereczki, Erika; Majer, Réka; Varkoly, Gréta; Murnyák, Balázs; Kálmán, János; Hortobágyi, Tibor

    2017-04-01

    Dementia with Lewy bodies (DLB) is the second most common neurodegenerative dementia. The accurate diagnosis is often possible only by neuropathological examination. The morphologic hallmarks are the presence of α-synuclein-rich Lewy bodies and Lewy neurites, identical to those seen in Parkinson's disease (PD) and Parkinson's disease dementia (PDD). Neurotransmitter deficits, synaptic and ubiquitin-proteasome system (UPS) dysfunction play major role in the pathomechanism. Characteristic symptoms are cognitive fluctuation, parkinsonism and visual hallucinations. Due to the often atypical clinical presentation novel imaging techniques and biomarkers could help the early diagnosis. Although curative treatment is not available, therapies can improve quality of life. Clinicopathological studies are important in exploring pathomechanisms, ensuring accurate diagnosis and identifying therapeutic targets. Orv Hetil. 2017; 158(17): 643-652.

  7. Lewy and his inclusion bodies: Discovery and rejection

    Directory of Open Access Journals (Sweden)

    Eliasz Engelhardt

    Full Text Available ABSTRACT Fritz Jacob Heinrich Lewy described the pathology of Paralysis agitans [Parkinson disease] and was the first to identify eosinophilic inclusion bodies in neurons of certain brain nuclei, later known as Lewy bodies, the pathological signature of the Lewy body diseases. In 1912, he published his seminal study, followed soon after by an update paper, and 10 years later, in 1923, by his voluminous book, where he exhaustively described the subject. The publication provided extensive information on the pathology of Paralysis agitans, and the entirely novel finding of eosinophilic inclusion bodies, which would become widely recognized and debated in the future. His discovery was acknowledged by important researchers who even named the structure after him. However, after his last publication on the issue, inexplicably, he never mentioned his histopathological discovery again. Despite several hypotheses, the reasons that led him to neglect (reject the structure which he so preeminently described have remained elusive.

  8. Utilization of NASA Lewis mobile terminals for the Hermes satellite

    Science.gov (United States)

    Edelman, E. A.; Fiala, J. L.; Rizzolla, L.

    1977-01-01

    The high power of the Hermes satellite enables two-way television and voice communication with small ground terminals. The Portable Earth Terminal (PET) and the Transportable Earth Terminal (TET) were developed and built by NASA-Lewis to provide communications capability to short-term users. The NASA-Lewis mobile terminals are described in terms of vehicles and onboard equipment, as well as operation aspects, including use in the field. The section on demonstrations divides the uses into categories of medicine, education, technology and government. Applications of special interest within each category are briefly described.

  9. A thermodynamic and kinetic study of the heterolytic activation of hydrogen by frustrated borane-amine Lewis pairs.

    Science.gov (United States)

    Karkamkar, Abhi; Parab, Kshitij; Camaioni, Donald M; Neiner, Doinita; Cho, Herman; Nielsen, Thomas K; Autrey, Tom

    2013-01-21

    Calorimetry is used to measure the reaction enthalpies of hydrogen (H(2)) activation by 2,6-lutidine (Lut), 2,2,6,6-tetramethylpiperidine (TMP), N-methyl-2,2,6,6-tetramethylpiperidine (MeTMP), and tri-tert-butylphosphine (TBP) with tris(pentafluorophenyl)borane (BCF). At 6.6 bar H(2) the conversion of the Lewis acid Lewis base pair to the corresponding ionic pair in bromobenzene at 294 K was quantitative in under 60 min. Integration of the heat release from the reaction of the Frustrated Lewis Pair (FLP) with H(2) as a function of time yields a relative rate of hydrogenation in addition to the enthalpy of hydrogenation. The half-lives of hydrogenation range from 230 s with TMP, ΔH(H2) = -31.5(0.2) kcal mol(-1), to 1400 s with Lut, ΔH(H2) = -23.4(0.4) kcal mol(-1). The (11)B nuclear magnetic resonance (NMR) spectrum of B(C(6)F(5))(3) in bromobenzene exhibits three distinct traits depending on the sterics of the Lewis base; (1) in the presence of pyridine, only the dative bond adduct pyridine-B(C(6)F(5))(3) is observed; (2) in the presence of TMP and MeTMP, only the free B(C(6)F(5))(3) is observed; and (3) in the presence of Lut, both the free B(C(6)F(5))(3) and the Lut-B(C(6)F(5))(3) adduct appear in equilibrium. A measure of the change in K(eq) of Lut + B(C(6)F(5))(3) ⇔ Lut-B(C(6)F(5))(3) as a function of temperature provides thermodynamic properties of the Lewis acid Lewis base adduct, ΔH = -17.9(1.0) kcal mol(-1) and a ΔS = -49.2(2.5) cal mol(-1) K, suggesting the Lut-B(C(6)F(5))(3) adduct is more stable in bromobenzene than in toluene.

  10. A new oxidimetric reagent: potassium dichromate in a strong phosphoric acid medium-VI Potentiometric titration of vanadium(III) alone and in mixture with vanadium(IV).

    Science.gov (United States)

    Rao, G G; Rao, P K

    1966-09-01

    Vanadium(III) can be titrated at room temperature with potassium dichromate in an 8-12M phosphoric acid medium. Two potential breaks are observed in 12M phosphoric add with 0.2N potassium dichromate, the first corresponding to the oxidation of vanadium(III) to vanadium(IV) and the second to the oxidation of vanadium(IV) to vanadium(V). In titrations with 0.05N dichromate only the first break in potential is clearly observed. The method has been extended to the titration of mixtures of vanadium(III) and vanadium(IV). Conditions have also been found for the visual titration of vanadium(III) using ferroln or barium diphenylamine sulphonate as indicator.

  11. 32 CFR 552.168 - Fort Lewis Area Access Office.

    Science.gov (United States)

    2010-07-01

    ... of this subpart. (d) A wallet-sized permit (HFL Form 653) and a vehicle pass (HFL Form 652) will be... 552.168 National Defense Department of Defense (Continued) DEPARTMENT OF THE ARMY MILITARY..., Yakima Training Center, and Camp Bonneville § 552.168 Fort Lewis Area Access Office. (a) DPTM Range...

  12. Who Needs Lewis Structures to Get VSEPR Geometries?

    Science.gov (United States)

    Lindmark, Alan F.

    2010-01-01

    Teaching the VSEPR (valence shell electron-pair repulsion) model can be a tedious process. Traditionally, Lewis structures are drawn and the number of "electron clouds" (groups) around the central atom are counted and related to the standard VSEPR table of possible geometries. A simpler method to deduce the VSEPR structure without first drawing…

  13. Lewis Latimer: African American Inventor, Poet and Activist.

    Science.gov (United States)

    Judd, Michael

    1998-01-01

    Details a lesson plan that examines the life and career of Lewis Latimer. Latimer, the self-taught son of fugitive slaves, rose to a prominent position in Thomas Edison's Electric Company and pioneered many innovations in the early electric industry. Includes a biographical sketch of Latimer, photographs, and illustrations. (MJP)

  14. Development of a metastatic fluorescent Lewis Lung carcinoma mouse model

    DEFF Research Database (Denmark)

    Rask, Lene; Fregil, Marianne; Høgdall, Estrid

    2013-01-01

    ) and spleen tyrosine kinase (SYK). A modest decrease in Drosha and Dicer mRNA levels was accompanied by significant downregulation of ten microRNAs, including miR-9 and miR-203, in the lung metastatic Lewis Lung carcinoma cell culture. Thus, a tool for cancer metastasis studies has been established...

  15. Telling Lewis Hine's Story: Russell Freedman's "Kids at Work."

    Science.gov (United States)

    Zarnowski, Myra

    In "Kids at Work," Russell Freedman explores the world of child labor during the years 1908-1918 when Lewis Hine, "teacher-crusader," worked as an investigative photographer for the National Child Labor Committee (NCLC). Hine's writing and the photos he gathered from across the country revealed a "shocking reality that…

  16. Effect of external Lewis base concentration on the polymerisation ...

    African Journals Online (AJOL)

    Effect of external Lewis base concentration on the polymerisation parameter of styrene using high activity Zieglar-Natta catalyst. PT Tait, Yayani Babayo, FI Abdulrahman. Abstract. No Abstract. Nigerian Journal of Chemical Research Vol. 2 1997: 5-10. Full Text: EMAIL FREE FULL TEXT EMAIL FREE FULL TEXT

  17. Q & A with Ed Tech Leaders: Interview with Brian Lewis

    Science.gov (United States)

    Shaughnessy, Michael F.; Fulgham, Susan M.

    2013-01-01

    Brian Lewis, International Society for Technology in Education (ISTE) chief executive officer, is an education advocate and leader specializing in management and governance, policy, corporate communications, branding, and marketing. He provides leadership to ISTE's Washington, DC, and Eugene, Oregon, offices and directs organizational…

  18. Modified NASA-Lewis Chemical Equilibrium Code for MHD applications

    Energy Technology Data Exchange (ETDEWEB)

    Sacks, R. A.; Geyer, H. K.; Grammel, S. J.; Doss, E. D.

    1979-12-01

    A substantially modified version of the NASA-Lewis Chemical Equilibrium Code has recently been developed. The modifications were designed to extend the power and convenience of the Code as a tool for performing combustor analysis for MHD systems studies. This report describes the effect of the programming details from a user point of view, but does not describe the Code in detail.

  19. Modified NASA-Lewis chemical equilibrium code for MHD applications

    Science.gov (United States)

    Sacks, R. A.; Geyer, H. K.; Grammel, S. J.; Doss, E. D.

    1979-01-01

    A substantially modified version of the NASA-Lewis Chemical Equilibrium Code was recently developed. The modifications were designed to extend the power and convenience of the Code as a tool for performing combustor analysis for MHD systems studies. The effect of the programming details is described from a user point of view.

  20. Daniel Day-Lewis - veri peab voolama / Kristiina Davidjants

    Index Scriptorium Estoniae

    Davidjants, Kristiina, 1974-

    2008-01-01

    Iiri-juudi näitleja Daniel Day-Lewis, kes võitis oma rolliga P.T. Andersoni filmis "Veri hakkab voolama" parima meespeaosatäitja Oscari. Tema põhjalikust tööst rollidega läbi tema filmiloomingu

  1. Early and presenting symptoms of dementia with lewy bodies

    NARCIS (Netherlands)

    Auning, Eirik; Rongve, Arvid; Fladby, Tormod; Booij, Jan; Hortobágyi, Tibor; Siepel, Françoise J.; Ballard, Clive; Aarsland, Dag

    2011-01-01

    To explore the presenting and early symptoms of dementia with Lewy bodies (DLB). Patients with mild dementia fulfilling diagnostic criteria for DLB (n = 61) and Alzheimer's disease (AD) (n = 109) were recruited from outpatient dementia clinics in western Norway. At diagnosis, caregivers were asked

  2. Californian Genius: Lewis Terman's Gifted Child in Regional Perspective

    Science.gov (United States)

    Beauvais, Clémentine

    2016-01-01

    This article pays attention to the regional embeddedness of early research on giftedness, looking principally at the works of Lewis Terman and his peers, between the 1910s and 1930s. The rhetoric, ideology, and aesthetics of giftedness in those early works were, I argue, stamped by the context and imaginary of Progressive-Era California and shaped…

  3. Metabolic connectomics targeting brain pathology in dementia with Lewy bodies.

    Science.gov (United States)

    Caminiti, Silvia P; Tettamanti, Marco; Sala, Arianna; Presotto, Luca; Iannaccone, Sandro; Cappa, Stefano F; Magnani, Giuseppe; Perani, Daniela

    2017-04-01

    Dementia with Lewy bodies is characterized by α-synuclein accumulation and degeneration of dopaminergic and cholinergic pathways. To gain an overview of brain systems affected by neurodegeneration, we characterized the [18F]FDG-PET metabolic connectivity in 42 dementia with Lewy bodies patients, as compared to 42 healthy controls, using sparse inverse covariance estimation method and graph theory. We performed whole-brain and anatomically driven analyses, targeting cholinergic and dopaminergic pathways, and the α-synuclein spreading. The first revealed substantial alterations in connectivity indexes, brain modularity, and hubs configuration. Namely, decreases in local metabolic connectivity within occipital cortex, thalamus, and cerebellum, and increases within frontal, temporal, parietal, and basal ganglia regions. There were also long-range disconnections among these brain regions, all supporting a disruption of the functional hierarchy characterizing the normal brain. The anatomically driven analysis revealed alterations within brain structures early affected by α-synuclein pathology, supporting Braak's early pathological staging in dementia with Lewy bodies. The dopaminergic striato-cortical pathway was severely affected, as well as the cholinergic networks, with an extensive decrease in connectivity in Ch1-Ch2, Ch5-Ch6 networks, and the lateral Ch4 capsular network significantly towards the occipital cortex. These altered patterns of metabolic connectivity unveil a new in vivo scenario for dementia with Lewy bodies underlying pathology in terms of changes in whole-brain metabolic connectivity, spreading of α-synuclein, and neurotransmission impairment.

  4. Frustrated Lewis pairs-assisted reduction of carbonyl compounds

    Czech Academy of Sciences Publication Activity Database

    Marek, Aleš; Pedersen, M. H. F.

    2015-01-01

    Roč. 71, č. 6 (2015), s. 917-921 ISSN 0040-4020 Institutional support: RVO:61388963 Keywords : frustrated Lewis pairs * hydrogen activation * benzyl alcohol * tritium labeling * labeled compounds Subject RIV: CC - Organic Chemistry Impact factor: 2.645, year: 2015

  5. Frustrated Lewis pairs-assisted reduction of carbonyl compounds

    DEFF Research Database (Denmark)

    Marek, Ales; Pedersen, Martin Holst Friborg

    2015-01-01

    An alternative and robust method for the reduction of carbonyl groups by frustrated Lewis pairs (FLPs) is reported in this paper. With its very mild reaction conditions, good to excellent yields, absolute regioselectivity and the non-metallic character of the reagent, it provides an excellent too...

  6. File list: DNS.Lng.10.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available DNS.Lng.10.AllAg.Carcinoma,_Lewis_Lung mm9 DNase-seq Lung Carcinoma, Lewis Lung htt...p://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/DNS.Lng.10.AllAg.Carcinoma,_Lewis_Lung.bed ...

  7. File list: DNS.Lng.50.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available DNS.Lng.50.AllAg.Carcinoma,_Lewis_Lung mm9 DNase-seq Lung Carcinoma, Lewis Lung htt...p://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/DNS.Lng.50.AllAg.Carcinoma,_Lewis_Lung.bed ...

  8. File list: Unc.Lng.20.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Unc.Lng.20.AllAg.Carcinoma,_Lewis_Lung mm9 Unclassified Lung Carcinoma, Lewis Lung ...http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Unc.Lng.20.AllAg.Carcinoma,_Lewis_Lung.bed ...

  9. File list: Oth.Lng.05.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.Lng.05.AllAg.Carcinoma,_Lewis_Lung mm9 TFs and others Lung Carcinoma, Lewis Lun...g http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.Lng.05.AllAg.Carcinoma,_Lewis_Lung.bed ...

  10. File list: His.Lng.05.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

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  11. File list: Pol.Lng.50.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

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  12. File list: Pol.Lng.05.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

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  13. File list: Pol.Lng.10.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

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  14. File list: DNS.Lng.20.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

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  15. Nine supramolecular assemblies from 5,7-dimethyl-1,8-naphthyridine-2-amine and carboxylic acids by strong classical H-bonds and other noncovalent associations

    Science.gov (United States)

    Ding, Aihua; Jin, Shouwen; Jin, Shide; Guo, Ming; Liu, Hui; Guo, Jianzhong; Wang, Daqi

    2017-12-01

    This article demonstrates 5,7-dimethyl-1,8-naphthyridine-2-amine based organic salt formation in nine crystalline solids 1-9, in which the carboxylates have been integrated. Addition of equivalents of the COOH to the solution of 5,7-dimethyl-1,8-naphthyridine-2-amine generates the singly protonated cationic species which direct the carboxylates. The nine compounds crystallize as their organic salts with the COOH proton transferred to the aromatic N of the 5,7-dimethyl-1,8-naphthyridine-2-amine. All salts have been characterized by IR, mp, EA and XRD technique. The major driving force in 1-9 is the classical H-bonds from 5,7-dimethyl-1,8-naphthyridine-2-amine and the acids, here the Nsbnd H⋯O H-bonds were found in all salts. Other extensive non-covalent interactions also exhibit great functions in space association of the molecular counterparts in relevant crystals. Except 4, all salts had the CHsbnd O, or CH3sbnd O interactions or both. Except 9, the common R22 (8) graph set has been observed in all salts due to the H-bonds and the non-covalent associations. For the synergistic interactions of the classical H-bonds and the various non-covalent associations, the salts displayed 1D-3D structures.

  16. Solid-state NMR as a spectroscopic tool for characterizing phosphane-borane frustrated lewis pairs.

    Science.gov (United States)

    Wiegand, Thomas; Eckert, Hellmut; Grimme, Stefan

    2013-01-01

    Frustrated Lewis pair (FLP) chemistry has provided a new strategy for small molecule binding and/or catalytic activation. It is based on the cooperative reaction behavior of Lewis acid and Lewis base centers that are in close proximity to each other (e.g., within the same molecule) but cannot form a direct bond because of geometrical constraints. The most prominent FLPs are based on intramolecular phosphane-borane adducts, whose catalytic properties can be tailored over wide ranges of reactivity and selectivity. For the structural and chemical design of such systems, a fundamental understanding needs to be developed on how structure, dynamics and covalent interactions between the Lewis centers influence the reactivity profile. Advanced solid-state nuclear magnetic resonance (NMR) spectroscopic techniques afford new opportunities for addressing this challenge. Following a general introduction into the fundamentals of NMR spectroscopy, this review discusses the different types of internal interactions - magnetic shielding, nuclear electric quadrupolar coupling, indirect spin-spin interactions, and "through-space" dipole-dipole couplings - influencing NMR spectra in the solid state. As discussed in detail, each type of interaction bears specific informational content with regard to structural issues in FLP chemistry. One of the most attractive features of solid-state NMR is the possibility of tailoring the effective Hamiltonian by manipulations in either physical space or spin space. Using such "decoupling" or "recoupling" techniques certain types of interactions can be selectively turned off for spectral simplification or turned on for selective evaluation. The present review summarizes the most important selective averaging techniques that have found applications in the characterization of FLPs. In a second step the interaction parameters need to be connected with structure and bonding information. As illustrated in this chapter, ab initio calculations using density

  17. Tribute to Erwin Felix Lewy-Bertaut; Hommage a Erwin Felix Lewy-Bertaut

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2006-07-01

    Erwin Lewy (alias Felix Bertaut) was born in 1913 in Germany, he emigrated to France where he undertook graduate studies in chemistry. Then, he joined the powder central laboratory where he learnt how to use international tables for structure determination. His thesis work was the X-ray study of the statistical distribution of the size of iron grains. The method Bertaut developed is still a reference in powder granulometry. Bertaut was also interested in the nascent neutron diffraction method and he flew to the United-States to improve his knowledge on this topic. Felix Bertaut created the neutron diffraction laboratory in the atomic research center in Grenoble and later he headed the CNRS' crystallography laboratory till 1982. Felix Bertaut and his laboratories became internationally renowned in crystallography, neutron diffraction and magnetism. He favored the scientific cooperation between France and Germany that led to the creation of the Laue-Langevin Institute (ILL). The ILL became European and was a key partner for building the European Synchrotron Facility (ESRF) in Grenoble. Bertaut was elected as a full member of the French Academy of Sciences in 1979, he died in 2003. (A.C.)

  18. Comentarios sobre dos ensayos de sir Arthur Lewis

    Directory of Open Access Journals (Sweden)

    Currie Lauchlin

    1999-06-01

    Full Text Available

    Es un texto inédito del Profesor Lauchlin Currie, escrito en 1980 cuando todavía ocupaba su oficina en el Departamento Nacional de Planeación, En lo esencial, se trata de una crítica de algunos argumentos expuestos por Lewis en su breve libro
    The Evolution of the International Economic Order, publicado en inglés en 1978 y dos años más tarde en castellano por el Colegio de México. El problema central de este libro es el de por qué algunos países son ricos y otros son pobres. La respuesta de Lewis no dejó satisfecho al profesor Currie. A lo largo de este comentario, se observa un contrapunteo entre dos enfoques teóricos de la economía del desarrollo: la de Lewis -inicialmente expuesta en su celebre artículo sobre el desarrollo económico con oferta ilimitada de trabajo-que enfatiza la necesidad de generar un excedente agrícola como punto de partida del proceso; y la de Currie, que señala la posibilidad del crecimiento desequlibrado liderado por la actividad económica urbana, específicamente por el sector de la construcción. Aunque el profesor Currie destaca sus diferencias con Lewis, las conclusiones de ambos autores tienden a converger en torno de un punto que se resume en una frase del ensayo de Lewis, no citada en el comentario: "El motor del crecimiento debe ser el cambio tecnológico, y el comercio internacional debe servir como lubricante y no como combustible". Como bien señala el profesor Currie en su análisis, a la larga es irrelevante cuál sea el sector donde se presente ese cambio tecnológico.

  19. A novel polymyxin derivative that lacks the fatty acid tail and carries only three positive charges has strong synergism with agents excluded by the intact outer membrane.

    Science.gov (United States)

    Vaara, Martti; Siikanen, Osmo; Apajalahti, Juha; Fox, John; Frimodt-Møller, Niels; He, Hui; Poudyal, Anima; Li, Jian; Nation, Roger L; Vaara, Timo

    2010-08-01

    Polymyxins are cationic lipopeptides (five cationic charges) and the last resort for the treatment of serious Gram-negative infections caused by multiresistant strains. NAB741 has a cyclic peptide portion identical to that of polymyxin B but carries in the linear peptide portion a threonyl-D-serinyl residue (no cationic charges) instead of the diaminobutyryl-threonyl-diaminobutyryl residue (two cationic charges). At the N terminus of the peptide, NAB741 carries an acetyl group instead of a mixture of methyl octanoyl and methyl heptanoyl residues. NAB741 sensitized Escherichia coli, Klebsiella pneumoniae, Enterobacter cloacae, and Acinetobacter baumannii to antibiotics against which the intact outer membrane is an effective permeability barrier. When tested by using Etest strips on plates containing increasing concentrations of NAB741, the fractional inhibition concentration index (FICI) of the combination of NAB741 with rifampin ranged from acid, and vancomycin for E. coli strains and E. cloacae by factors ranging from 8 to 200. A sister peptide, NAB752, carrying a threonyl-aminobutyryl residue as the linear peptide portion, was inactive. Furthermore, NAB741 sensitized E. coli to the bactericidal activity of fresh guinea pig serum. The renal clearance of NAB741 was approximately 400-fold, 16-fold, and 8-fold higher than those measured for colistin, NAB7061, and NAB739, respectively.

  20. Serum expression of HA and LN in lewis rat models of autoimmune myocarditis

    International Nuclear Information System (INIS)

    Han Li'na; Li Tieling; Zhang Yajing; Yang Tingshu; Ding Yu; Guo Shuli; Zhao Xiaoning

    2011-01-01

    Objective: To study the clinical significance of dynamic changes of serum expressions of hyaluronic acid (HA) and laminin (LN) in Lewis rat models of experimental autoimmune myocarditis (EAM). Methods: Fifty Lewis rat models of experimental autoimmune myocarditis (EAM) were established with injection of recombinant cardiac C protein with complete freund adjuvant into two foot-pads plus intraperitoneal injection of pertussis toxin. At 1w, 2w, 4w, 6w and 8w, 10 models were sacrificed each time;cardiac tissues were examined with HE stain for myocardial inflammatory score and examined with picrosirius red stain for myocardial fibrosis score, also, serum HA and LN expressions were determined with RIA. These examinations were performed in 10 undisturbed animals as controls. Results: The myocardial inflammatory scores of the models at 1w were about the same as those in the controls, but the scores rapidly increased from 2w on to 4w then fell gradually. The myocardial fibrosis scores of the models at 1wk were also not much different from those in controls. The fibrosis scores increased rapidly at 4w and maintained at high level up to 8w. The changes of serum expressions of HA and LN roughly paralleled those of myocardial fibrosis scores i. e. rapidly increased at 4w up to 8w. Conclusion: Serum expressions of HA and LN could faithfully reflect the degree of myocardial fibrosis in rat models of EAM. HA and LN were useful markers of myocardial fibrois and were of prognostic importance. (authors)

  1. Lewis-Langmuir Atomic Charge: Method and Applications

    Science.gov (United States)

    Heo, Hoon

    1995-01-01

    Unlike other physical properties atomic charge is not a well defined quantity in quantum mechanics but a very important property frequently used by chemists. Since there is no experimental measurement of this quantity there have been many different theoretical methods proposed to calculate the values. However, despite that some of the methods produce reasonable predictions which are compatible with chemists' expectation, they are either too sensitive to a choice of basis set or other parameters in the schemes employed. Most importantly, they are generally dependent on large computational efforts and in addition those not familiar with their theoretical formulation may not understand what they are doing. In this thesis a new simple atomic charge calculation method is introduced which partitions the electrons by the ratio of participating atoms' electronegativities. Because the partitioning is a ratio, it is rather insensitive to the specific electronegativity scale. The method requires only knowledge of the Lewis dot structures and the calculation is obtained by solving a set of linear equations which can be often executed even by hand. In spite of its simple form and very high speed, it gives comparable results to the most complicated quantum mechanical calculation. Introducing classical bond orders obtained from simple HMO pi-electron consideration, the method accounts for the delocalization of pi-electrons in conjugated/aromatic compounds. Atomic charges in large inorganic crystals can also be easily obtained by applying the Brown-O'Keeffe bond length-bond order relationship for complex solids. The method is likewise applicable to ionic systems and the test calculations on ammonium cations and oxide anions give good agreement with other quantum mechanical calculations. The simplicity of the method makes possible applications to biomolecules with hundreds of atoms. It can also easily handle the zwitter ionic form of amino acids and various nucleotides. Recently

  2. Lactic Acid Bacteria Inducing a Weak Interleukin-12 and Tumor Necrosis Alpha Response in Human Dendritic Cells Inhibit Strongly Stimulating Lactic Acid Bacteria but Act Synergistically with Gram-Negative Bacteria

    DEFF Research Database (Denmark)

    Zeuthen, Louise Hjerrild; Christensen, Hanne Risager; Frøkiær, Hanne

    2006-01-01

    The development and maintenance of immune homeostasis indispensably depend on signals from the gut flora. Lactic acid bacteria (LAB), which are gram-positive (G+) organisms, are plausible significant players and have received much attention. Gram-negative (G-) commensals, such as members...

  3. Computational Design of Cobalt Catalysts for Hydrogenation of Carbon Dioxide and Dehydrogenation of Formic Acid.

    Science.gov (United States)

    Ge, Hongyu; Jing, Yuanyuan; Yang, Xinzheng

    2016-12-05

    A series of cobalt complexes with acylmethylpyridinol and aliphatic PNP pincer ligands are proposed based on the active site structure of [Fe]-hydrogenase. Density functional theory calculations indicate that the total free energy barriers of the hydrogenation of CO 2 and dehydrogenation of formic acid catalyzed by these Co complexes are as low as 23.1 kcal/mol in water. The acylmethylpyridinol ligand plays a significant role in the cleavage of H 2 by forming a strong Co-H δ- ···H δ+ -O dihydrogen bond in a fashion of frustrated Lewis pairs.

  4. A study of the Lewis blood group system in the Singapore population.

    Science.gov (United States)

    Mohan, T C; Koo, W H; Ng, H W

    1989-07-01

    The purpose of this retrospective study is to delineate: a) The ethnic group specific distribution patterns of the various Lewis phenotypes in our population in Singapore. b) The occurrence rates of the various anti-Lewis antibodies in our population. The approximate frequencies of the Lewis A-B-, Lewis A-B+ and Lewis A + B- phenotypes in the blood-donor population were estimated to be about 10%, 48% and 42% respectively. It was evident that frequency of the Lewis A-B- phenotype was highest among the Malays, being almost 3 times more frequent than it was among the Chinese (P less than 0.01). The anti-Lewis antibodies were noted to be the commonest irregular antibodies seen in our blood donor population, with an occurrence rate of about 127 per 100,000. Likewise, from 1982 to 1987, the anti-Lewis antibodies were also noted to be the most frequently encountered antibodies in our patient population, accounting for nearly 60% of all cases. Although the Malays comprised only about 15% of the Singaporean population, they accounted for as much as 42.9% of all patients with anti-Lewis antibodies. Similarly, out of all 76 blood donors in 1987 with anti-Lewis antibodies, 50% were found to be Malays although they comprised only 14.28% of the donor population. It was also interesting to note that a sizeable proportion of all patients with anti-Lewis antibodies were pregnant women with or without obstetric complications.

  5. Controlled and Efficient Polymerization of Conjugated Polar Alkenes by Lewis Pairs Based on Sterically Hindered Aryloxide-Substituted Alkylaluminum

    Directory of Open Access Journals (Sweden)

    Xiaojun Wang

    2018-02-01

    Full Text Available Reported herein is the development of an effective strategy for controlled and efficient Lewis pair polymerization of conjugated polar alkenes, including methyl methacrylate (MMA, n-butyl methacrylate (nBuMA, and γ-methyl-α-methylene-γ-butyrolactone (γMMBL, by the utilization of sterically encumbered Al(BHT2Me (BHT: 2,6-di-tert-butyl-4-methylphenol as a Lewis acid that shuts down intramolecular backbiting termination. In combination with a selected N-heterocyclic carbene (NHC as a Lewis base, the polymerization of MMA exhibited activity up to 3000 h−1 TOF and an acceptable initiation efficiency of 60.6%, producing polymers with high molecular weight (Mn up to 130 kg/mol and extremely narrow dispersity (Đ = 1.06~1.13. This controlled polymerization with a living characteristic has been evidenced by chain-extension experiments and chain-end analysis, and enabled the synthesis of well-defined diblock copolymers.

  6. A highly selective route to linear alpha olefins from biomass-derived lactones and unsaturated acids.

    Science.gov (United States)

    Wang, Dong; Hakim, Sikander H; Alonso, David Martin; Dumesic, James A

    2013-08-14

    This work demonstrates the use of Lewis-acid catalysts, such as gamma-alumina and tungstated alumina, for selective production of linear alpha olefins by decarboxylation of lactones and unsaturated carboxylic acids.

  7. The organization of narrative discourse in Lewy body spectrum disorder.

    Science.gov (United States)

    Ash, Sharon; McMillan, Corey; Gross, Rachel G; Cook, Philip; Morgan, Brianna; Boller, Ashley; Dreyfuss, Michael; Siderowf, Andrew; Grossman, Murray

    2011-10-01

    Narrative discourse is an essential component of day-to-day communication, but little is known about narrative in Lewy body spectrum disorder (LBSD), including Parkinson's disease (PD), Parkinson's disease with dementia (PDD), and dementia with Lewy bodies (DLB). We performed a detailed analysis of a semi-structured speech sample in 32 non-aphasic patients with LBSD, and we related their narrative impairments to gray matter (GM) atrophy using voxel-based morphometry. We found that patients with PDD and DLB have significant difficulty organizing their narrative speech. This was correlated with deficits on measures of executive functioning and speech fluency. Regression analyses associated this deficit with reduced cortical volume in inferior frontal and anterior cingulate regions. These findings are consistent with a model of narrative discourse that includes executive as well as language components and with an impairment of the organizational component of narrative discourse in patients with PDD and DLB. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. The Organization of Narrative Discourse in Lewy Body Spectrum Disorder

    Science.gov (United States)

    Ash, Sharon; McMillan, Corey; Gross, Rachel G.; Cook, Philip; Morgan, Brianna; Boller, Ashley; Dreyfuss, Michael; Siderowf, Andrew; Grossman, Murray

    2011-01-01

    Narrative discourse is an essential component of day-to-day communication, but little is known about narrative in Lewy Body spectrum disorder (LBSD), including Parkinson's disease (PD), Parkinson's disease with dementia (PDD), and dementia with Lewy bodies (DLB). We performed a detailed analysis of a semi-structured speech sample in 32 non-aphasic patients with LBSD, and we related their narrative impairments to gray matter (GM) atrophy using voxel-based morphometry. We found that patients with PDD and DLB have significant difficulty organizing their narrative speech. This was correlated with deficits on measures of executive functioning and speech fluency. Regression analyses associated this deficit with reduced cortical volume in inferior frontal and anterior cingulate regions. These findings are consistent with a model of narrative discourse that includes executive as well as language components and with an impairment of the organizational component of narrative discourse in patients with PDD and DLB. PMID:21689852

  9. TRANSPOSICION DIDACTICA DEL MODELO CIENTIFICO DE LEWIS-LANGMUIR

    Directory of Open Access Journals (Sweden)

    Janneth Isabel Herreño Chaves

    2010-04-01

    Full Text Available Este artículo presenta las conclusiones obtenidas en un proyecto de investigación, en el que se auscultó la transposición didáctica que hacen del modelo de Lewis-Langmuir, diez de los textos para la enseñanza de la química más empleados por algunos profesores universitarios y de educación secundaria. Para el análisis se tuvo en cuenta lo histórico, lo epistemológico y lo didáctico. Los resultados muestran que en estos textos no hay referencia a la historia de la construcción del modelo y solo se reducen a la utilización didáctica de las fórmulas de Lewis. Tampoco aluden al papel cumplido por I. Langmuir en la divulgación de dicho modelo.

  10. Glucagon-like peptide-1 analog, Liraglutide, delays onset of experimental autoimmune encephalitis in Lewis rats

    DEFF Research Database (Denmark)

    Della Valle, Brian William; Brix, Gitte S.; Brock, Birgitte

    2016-01-01

    Introduction: Recent findings indicate that metabolic disturbances are involved in multiple sclerosis (MS) pathology and influence the susceptibility to treatment, directing attention toward anti-diabetic drugs such as metformin and pioglitazone. Liraglutide, a drug of the glucagon-like peptide-1......, that liraglutide treatment delays onset of EAE in Lewis rats and is associated with improved protective capacity against oxidative stress. These data suggest GLP-1 receptor agonists should be investigated further as a potential therapy for MS...... by blinded observers. Animals were killed at peak disease severity (day 11) or if exceeding humane endpoint (clinical score ≥4). Protein levels of manganese superoxide dismutase (MnSOD), amyloid precursor protein (APP), and glial fibrillary acidic protein (GFAP) were determined. Results: Liraglutide...

  11. Lewis Y Antigen as a Target for Breast Cancer Therapy

    Science.gov (United States)

    1998-09-01

    M. A., Savio, A. and De , G. J. 1996. Potential role of molecular mimicry between Helicobacter pylori lipopolysaccharide and host Lewis blood group...and Helicobacter pylori [27] and some human neoplasms, including certain breast, ovarian and prostate cancers [28]. Vaccinations with LeY-containing...expression) on tumor cells; (2) their function as differentiation antigens; and (3) their role in cell adhesion and motility underlying their metastatic

  12. Uniportal video-assisted thoracic surgery Ivor Lewis esophagectomy.

    Science.gov (United States)

    Dmitrii, Sekhniaidze; Malik, Agasiev

    2016-01-01

    Esophageal cancer is one of the most debilitating diseases, and treatment of patients with this medical condition is considered to be one of the most complicated problems in clinical oncology. The up-to-date tendency of bringing minimally-invasive surgeries into more widespread use makes it necessary to invent new techniques to solve some or other tasks including those accompanying esophageal diseases. This article shows our innovation minimally-invasive technique of Ivor Lewis esophagectomy.

  13. Lewis F. Richardson and the analysis of war

    Energy Technology Data Exchange (ETDEWEB)

    Craig, P.P.; Levine, M.D.

    1983-01-01

    The authors show that since about 1970 the strategic nuclear weaponry of the US and the USSR have been following the classic exponential growth pattern first discussed by Lewis Fry Richardson, the founder of mathematical analysis of war. They also present data suggesting a correlation between war deaths and two-generation, half century long waves (Kondratieff cycles) in human systems. 14 references, 9 figures.

  14. Solid acid catalysis from fundamentals to applications

    CERN Document Server

    Hattori, Hideshi

    2014-01-01

    IntroductionTypes of solid acid catalystsAdvantages of solid acid catalysts Historical overviews of solid acid catalystsFuture outlookSolid Acids CatalysisDefinition of acid and base -Brnsted acid and Lewis acid-Acid sites on surfacesAcid strengthRole of acid sites in catalysisBifunctional catalysisPore size effect on catalysis -shape selectivity-Characterization of Solid Acid Catalysts Indicator methodTemperature programmed desorption (TPD) of ammoniaCalorimetry of adsorption of basic moleculesInfrare

  15. Effect of supplementing grain amaranth diets with amino acids ...

    African Journals Online (AJOL)

    James Bond

    145 impeding availability of its essential amino acids. Reduced availability of essential amino acids at the digestive stage would further be expected to adversely affect the concentration of amino acids in plasma. According to Hewitt & Lewis (1972a; b) plasma amino acid concentrations are a sensitive index of changes.

  16. Gilbert Newton Lewis: his influence on physical-organic chemists at Berkeley

    International Nuclear Information System (INIS)

    Calvin, M.

    1982-03-01

    A review is presented of the historical contributions of Gilbert N. Lewis to science and a discussion of the influence of Lewis on the research of the members of the physical-organic staff at Berkeley, including Melvin Calvin, during the twenties, thirties and forties. Some specific examples are discussed. Also, the effect of Lewis, his science and administrative concepts in the creation of excellence in a department of chemistry are reviewed

  17. Gilbert Newton Lewis: his influence on physical-organic chemists at Berkeley

    Energy Technology Data Exchange (ETDEWEB)

    Calvin, M.

    1982-03-01

    A review is presented of the historical contributions of Gilbert N. Lewis to science and a discussion of the influence of Lewis on the research of the members of the physical-organic staff at Berkeley, including Melvin Calvin, during the twenties, thirties and forties. Some specific examples are discussed. Also, the effect of Lewis, his science and administrative concepts in the creation of excellence in a department of chemistry are reviewed.

  18. Testing strong interaction theories

    International Nuclear Information System (INIS)

    Ellis, J.

    1979-01-01

    The author discusses possible tests of the current theories of the strong interaction, in particular, quantum chromodynamics. High energy e + e - interactions should provide an excellent means of studying the strong force. (W.D.L.)

  19. Into the Unknown: The Logistics Preparation of the Lewis and Clark Expedition

    National Research Council Canada - National Science Library

    Carr, Donald

    2003-01-01

    .... This starting point ignores the important logistics planning, preparation and training that commenced with Lewis's appointment as personal secretary to President Thomas Jefferson in the spring of 1801...

  20. Visual Perceptual Organization Ability in Autopsy-Verified Dementia with Lewy Bodies and Alzheimer's Disease.

    Science.gov (United States)

    Mitolo, Micaela; Hamilton, Joanne M; Landy, Kelly M; Hansen, Lawrence A; Galasko, Douglas; Pazzaglia, Francesca; Salmon, David P

    2016-07-01

    Prominent impairment of visuospatial processing is a feature of dementia with Lewy bodies (DLB), and diagnosis of this impairment may help clinically distinguish DLB from Alzheimer's disease (AD). The current study compared autopsy-confirmed DLB and AD patients on the Hooper Visual Organization Test (VOT), a test that requires perceptual and mental reorganization of parts of an object into an identifiable whole. The VOT may be particularly sensitive to DLB since it involves integration of visual information processed in separate dorsal and ventral visual "streams". Demographically similar DLB (n=28), AD (n=115), and normal control (NC; n=85) participants were compared on the VOT and additional neuropsychological tests. Patient groups did not differ in dementia severity at time of VOT testing. High and Low AD-Braak stage DLB subgroups were compared to examine the influence of concomitant AD pathology on VOT performance. Both patient groups were impaired compared to NC participants. VOT scores of DLB patients were significantly lower than those of AD patients. The diagnostic sensitivity and specificity of the VOT for patients versus controls was good, but marginal for DLB versus AD. High-Braak and low-Braak DLB patients did not differ on the VOT, but High-Braak DLB performed worse than Low-Braak DLB on tests of episodic memory and language. Visual perceptual organization ability is more impaired in DLB than AD but not strongly diagnostic. The disproportionate severity of this visual perceptual deficit in DLB is not related to degree of concomitant AD pathology, which suggests that it might primarily reflect Lewy body pathology. (JINS, 2016, 22, 609-619).

  1. Creativity and Autism Spectrum Conditions: a Hypothesis on Lewis Carroll

    Directory of Open Access Journals (Sweden)

    Stefano Calabrese

    2017-06-01

    Full Text Available The hypothesis formulated by Simon Baron-Cohen and his collaborators on the onset of autistic syndromes and their link with an excess of the so-called S brain is reflected in the work of Lewis Carroll, a formal logic and mathematics professor deeply inclined to visual and spatial descriptions, interested in affordances and systemic circuits, and devoid of empathic tendencies in creating his characters. In the future, this finding may serve as a test for predicting autism spectrum disorders and support the elaboration of narrative artefact for therapeutic purposes in relation to people with autism.

  2. NASA Lewis and Ohio Company Hit Hole in One

    Science.gov (United States)

    1998-01-01

    Ben Hogan Company's Golf Ball Division, which is based in Elyria, Ohio, had developed concepts and prototypes for new golf balls but was unable to determine exact performance characteristics. Specifically, the company's R&D department wanted to measure the spin rates of experimental golf balls. After the Golf Ball Division requested assistance, researchers and technicians from the NASA Lewis Research Center went to Elyria and conducted several days worth of tests. Ben Hogan is using the test results to improve the spin characteristics of a new ball it plans to introduce to the market.

  3. Telecommuting (Work-At-Home) at NASA Lewis Research Center

    Science.gov (United States)

    Srinidhi, Saragur M.

    1994-01-01

    This report presents a study in evaluating the viability of providing a work-at-home (telecommuting) program for Lewis Research Center's corporate employees using Integrated Services Digital Network (ISDN). Case studies have been presented for a range of applications from casual data access to interactive access. The network performance of telemedia applications were studied against future requirements for such level of remote connectivity. Many of the popular ISDN devices were characterized for network and service functionality. A set of recommendations to develop a telecommuting policy have been proposed.

  4. NASA Lewis advanced IPV nickel-hydrogen technology

    Science.gov (United States)

    Smithrick, John J.; Britton, Doris L.

    1993-01-01

    Individual pressure vessel (IPV) nickel-hydrogen technology was advanced at NASA Lewis and under Lewis contracts. Some of the advancements are as follows: to use 26 percent potassium hydroxide electrolyte to improve cycle life and performance, to modify the state of the art cell design to eliminate identified failure modes and further improve cycle life, and to develop a lightweight nickel electrode to reduce battery mass, hence reduce launch and/or increase satellite payload. A breakthrough in the LEO cycle life of individual pressure vessel nickel-hydrogen battery cells was reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 accelerated LEO cycles at 80 percent DOD compared to 3,500 cycles for cells containing 31 percent KOH. Results of the boiler plate cell tests have been validated at NWSC, Crane, Indiana. Forty-eight ampere-hour flight cells containing 26 and 31 percent KOH have undergone real time LEO cycle life testing at an 80 percent DOD, 10 C. The three cells containing 26 percent KOH failed on the average at cycle 19,500. The three cells containing 31 percent KOH failed on the average at cycle 6,400. Validation testing of NASA Lewis 125 Ah advanced design IPV nickel-hydrogen flight cells is also being conducted at NWSC, Crane, Indiana under a NASA Lewis contract. This consists of characterization, storage, and cycle life testing. There was no capacity degradation after 52 days of storage with the cells in the discharged state, on open circuit, 0 C, and a hydrogen pressure of 14.5 psia. The catalyzed wall wick cells have been cycled for over 22,694 cycles with no cell failures in the continuing test. All three of the non-catalyzed wall wick cells failed (cycles 9,588; 13,900; and 20,575). Cycle life test results of the Fibrex nickel electrode has demonstrated the feasibility of an improved nickel electrode giving a higher specific energy nickel-hydrogen cell. A nickel-hydrogen boiler plate cell using an 80

  5. Feminine Hypostases in Epic Fantasy: Tolkien, Lewis, Rowling

    Directory of Open Access Journals (Sweden)

    Măcineanu Laura

    2015-12-01

    Full Text Available The paper identifies the types of female figures present in the works of three well-known fantasy writers, J.R.R. Tolkien, C.S. Lewis and J.K. Rowling, discussing the ways in which these characters are presented, their relationship with other characters, and their role in the economy of the novel, which is more important than may appear from a first reading. It also tries to explain the reasons that prompted the above-mentioned authors to choose these female hypostases.

  6. NASA Lewis H2-O2 MHD program

    Science.gov (United States)

    Smith, M.; Nichols, L. D.; Seikel, G. R.

    1974-01-01

    Performance and power costs of H2-O2 combustion powered steam-MHD central power systems are estimated. Hydrogen gas is assumed to be transmitted by pipe from a remote coal gasifier into the city and converted to electricity in a steam MHD plant having an integral gaseous oxygen plant. These steam MHD systems appear to offer an attractive alternative to both in-city clean fueled conventional steam power plants and to remote coal fired power plants with underground electric transmission into the city. Status and plans are outlined for an experimental evaluation of H2-O2 combustion-driven MHD power generators at NASA Lewis Research Center.

  7. Integration of Chemical and Biological Catalysis: Production of Furylglycolic Acid from Glucose via Cortalcerone

    Science.gov (United States)

    Thomas J. Schwartz; Samuel M. Goodman; Christian M. Osmundsen; Esben Taarning; Michael D. Mozuch; Jill Gaskell; Daniel Cullen; Philip J. Kersten; James A. Dumesic

    2013-01-01

    Furylglycolic acid (FA), a pseudoaromatic hydroxy-acid suitable for copolymerization with lactic acid, can be produced from glucose via enzymatically derived cortalcerone using a combination of Brønsted and Lewis acid catalysts. Cortalcerone is first converted to furylglyoxal hydrate (FH) over a Brønsted acid site (HCl or Al-containing betazeolite), and FH is...

  8. Nest-site selection and nest survival of Lewis's woodpecker in aspen riparian woodlands

    Science.gov (United States)

    Karen R. Newlon; Victoria A. Saab

    2011-01-01

    Riparian woodlands of aspen (Populus tremuloides) provide valuable breeding habitat for several cavity-nesting birds. Although anecdotal information for this habitat is available for Lewis's Woodpecker (Melanerpes lewis), no study has previously examined the importance of aspen woodlands to this species' breeding biology. From 2002 to 2004, we monitored 76...

  9. LewiSpace: An Exploratory Study with a Machine Learning Model in an Educational Game

    Science.gov (United States)

    Ghali, Ramla; Ouellet, Sébastien; Frasson, Claude

    2016-01-01

    The use of educational games as a tool for providing learners with a playful and educational aspect is widespread. In this paper, we present an educational game that we developed to teach a chemistry lesson, namely drawing a Lewis diagram. Our game is a 3D environment known as LewiSpace and aims at balancing between playful and educational…

  10. Enthalpy Costs of Making and Breaking Bonds: A Game of Generating Molecules with Proper Lewis Structures

    Science.gov (United States)

    Bell, Peter T.; Adkins, Alyssa D.; Gamble, Rex J.; Schultz, Linda D.

    2009-01-01

    "Enthalpy Costs" is a simple card game created to assist students in developing proper Lewis structure drawing skills. Score keeping is accomplished by tracking the enthalpy changes associated with bond-making and bond-breaking processes during formation of molecules represented by proper Lewis structures. Playing the game requires the student to…

  11. Loss of EEG Network Efficiency Is Related to Cognitive Impairment in Dementia With Lewy Bodies

    NARCIS (Netherlands)

    van Dellen, E.; de Waal, H.; van der Flier, W.M.; Lemstra, A.W.; Slooter, A.J.C.; Smits, L.L.; van Straaten, E.C.W.; Stam, C.J.; Scheltens, P.

    2015-01-01

    Objective: The aim of this study was to test whether disturbed EEG resting-state functional connectivity and network organization are a potential neurophysiological substrate of cognitive impairment in dementia with Lewy bodies. Methods: EEG recordings were obtained in dementia with Lewy bodies

  12. An Integrated Perspective of Humanism and Supernaturalism for Education: C. S. Lewis's Version of Education

    Science.gov (United States)

    Lee, Seung Chun

    2013-01-01

    This paper explores some theoretical reflections on the connection between C. S. Lewis's thoughts on the purpose and process of education and his understanding of supernatural human nature which has been relatively little explored. An introduction about Lewis's career as a college teacher blends into the background of this paper. It is followed by…

  13. Estimating forest structure parameters within Fort Lewis Military Reservation using airborne laser scanner (LIDAR) data.

    Science.gov (United States)

    Hans-Erik Andersen; Jeffrey R. Foster; Stephen E. Reutebuch

    2003-01-01

    Three-dimensional (3-D) forest structure information is critical to support a variety of ecosystem management objectives on the Fort Lewis Military Reservation, including habitat assessment, ecological restoration, fire management, and commercial timber harvest. In particular, the Forestry Program at Fort Lewis requires measurements of shrub, understory, and overstory...

  14. Catalytic Deprotection of Acetals In Strongly Basic Solution Usinga Self-Assembled Supramolecular 'Nanozyme'

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

    2007-07-26

    Acetals are among the most commonly used protecting groups for aldehydes and ketones in organic synthesis due to their ease of installation and resistance to cleavage in neutral or basic solution.[1] The common methods for hydrolyzing acetals almost always involve the use of either Broensted acid or Lewis acid catalysts.[2] Usually aqueous acids or organic solutions acidified with organic or inorganic acids have been used for reconversion of the acetal functionality to the corresponding carbonyl group; however, recently a number of reports have documented a variety of strategies for acetal cleavage under mild conditions. These include the use of Lewis acids such as bismuth(III)[3] or cerium(IV),[4, 5] functionalized silica gel, such as silica sulfuric acid[6] or silica-supported pyridinium p-toluene sulfonate,[7] or the use of silicon-based reagents such as TESOTf-2,6-Lutidine.[8] Despite these mild reagents, all of the above conditions require either added acid or overall acidic media. Marko and co-workers recently reported the first example of acetal deprotection under mildly basic conditions using catalytic cerium ammonium nitrate at pH 8 in a water-acetonitrile solution.[5] Also recently, Rao and co-workers described a purely aqueous system at neutral pH for the deprotection of acetals using {beta}-cyclodextrin as the catalyst.[9] Herein, we report the hydrolysis of acetals in strongly basic aqueous solution using a self-assembled supramolecular host as the catalyst. During the last decade, we have used metal-ligand interactions for the formation of well-defined supramolecular assemblies with the stoichiometry M{sub 4}L{sub 6}6 (M = Ga{sup III} (1 refers to K{sub 12}[Ga{sub 4}L{sub 6}]), Al{sup III}, In{sup III}, Fe{sup III}, Ti{sup IV}, or Ge{sup IV}, L = N,N{prime}-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) (Figure 1).[10] The metal ions occupy the vertices of the tetrahedron and the bisbidentate catecholamide ligands span the edges. The strong

  15. Incorporating spectroscopic on-line monitoring as a method of detection for a Lewis cell setup.

    Science.gov (United States)

    Heller, Forrest D; Casella, Amanda J; Lumetta, Gregg J; Nash, Kenneth L; Sinkov, Sergey I; Bryan, Samuel A

    2017-07-07

    A Lewis cell was designed and constructed for investigating solvent extraction systems by spectrophotometrically monitoring both the organic and aqueous phases in real time. This new Lewis cell was tested and shown to perform well compared to other previously reported Lewis cell designs. The advantage of the new design is that the spectroscopic measurement allows determination of not only metal ion concentrations, but also information regarding chemical speciation - information not available with previous Lewis cell designs. For convenience, the new Lewis cell design was dubbed COSMOFLEX (COntinuous Spectroscopic MOnitoring of Forrest's Liquid-liquid EXtraction cell). After construction performance testing was done for establishing the ideal stir speed range, UV-Vis measured concentration and D value determination. Each one of these tests was satisfactorily passed.

  16. Exercise for Individuals with Lewy Body Dementia: A Systematic Review.

    Directory of Open Access Journals (Sweden)

    Michael Inskip

    Full Text Available Individuals with Lewy body Dementia (LBD, which encompasses both Parkinson disease dementia (PDD and Dementia with Lewy Bodies (DLB experience functional decline through Parkinsonism and sedentariness exacerbated by motor, psychiatric and cognitive symptoms. Exercise may improve functional outcomes in Parkinson's disease (PD, and Alzheimer's disease (AD. However, the multi-domain nature of the LBD cluster of symptoms (physical, cognitive, psychiatric, autonomic results in vulnerable individuals often being excluded from exercise studies evaluating physical function in PD or cognitive function in dementia to avoid confounding results. This review evaluated existing literature reporting the effects of exercise interventions or physical activity (PA exposure on cluster symptoms in LBD.A high-sensitivity search was executed across 19 databases. Full-length articles of any language and quality, published or unpublished, that analysed effects of isolated exercise/physical activity on indicative Dementia with Lewy Bodies or PD-dementia cohorts were evaluated for outcomes inclusive of physical, cognitive, psychiatric, physiological and quality of life measures. The protocol for this review (Reg. #: CRD42015019002 is accessible at http://www.crd.york.ac.uk/PROSPERO/.111,485 articles were initially retrieved; 288 full articles were reviewed and 89.6% subsequently deemed ineligible due to exclusion of participants with co-existence of dementia and Parkinsonism. Five studies (1 uncontrolled trial, 1 randomized controlled trial and 3 case reports evaluating 16 participants were included. Interventions were diverse and outcome homogeneity was low. Habitual gait speed outcomes were measured in 13 participants and increased (0.18m/s, 95% CI -0.02, 0.38m/s, exceeding moderate important change (0.14m/s for PD cohorts. Other outcomes appeared to improve modestly in most participants.Scarce research investigating exercise in LBD exists. This review confirms

  17. Ransom, Religion, and Red Giants: C.S. Lewis and Fred Hoyle

    Science.gov (United States)

    Larsen, Kristine

    2010-01-01

    Famed fantasy writer C.S. Lewis (1898-1963) was known to friends as a well-read astronomy aficionado. However, this medieval scholar and Christian apologist embraced a pre-Copernican universe (with its astrological overtones) in his Chronicles of Narnia series and defended the beauty and relevance of the geocentric model in his final academic work, "The Discarded Image". In the "Ransom Trilogy” ("Out of the Silent Planet", "Perelandra", and "That Hideous Strength") philologist Ransom (loosely based on Lewis's close friend J.R.R. Tolkien) travels to Lewis's visions of Mars and Venus, where he interacts with intelligent extraterrestrials, battles with evil scientists, and aids in the continuation of extraterrestrial Christian values. In the final book, Ransom is joined by a handful of colleagues in open warfare against the satanic N.I.C.E. (National Institute for Coordinated Experiments). Geneticist and evolutionary biologist J.B.S. Haldane criticized Lewis for his scientifically inaccurate descriptions of the planets, and his disdain for the scientific establishment. Lewis responded to the criticism in essays of his own. Another of Lewis's favorite scientific targets was atheist Fred Hoyle, whom he openly criticized for anti-Christian statements in Hoyle's BBC radio series. Writer and Lewis friend Dorothy L. Sayers voiced her own criticism of Hoyle. In a letter, Lewis dismissed Hoyle as "not a great philosopher (and none of my scientific colleagues think much of him as a scientist.” Given Lewis's lack of respect for Hoyle, and use of creative license in describing the planets, and the flat-earth, "geocentric” Narnia, it is surprising that Lewis very carefully includes an astronomically correct description of red giants in two novels in the Narnia series ("The Magician's Nephew" and "The Last Battle"). This inclusion is even more curious given that Fred Hoyle is well-known as one of the pioneers in the field of stellar death and the properties of red giants.

  18. File list: NoD.Lng.05.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available NoD.Lng.05.AllAg.Carcinoma,_Lewis_Lung mm9 No description Lung Carcinoma, Lewis Lun...g http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/NoD.Lng.05.AllAg.Carcinoma,_Lewis_Lung.bed ...

  19. File list: InP.Lng.50.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available InP.Lng.50.AllAg.Carcinoma,_Lewis_Lung mm9 Input control Lung Carcinoma, Lewis Lung... http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/InP.Lng.50.AllAg.Carcinoma,_Lewis_Lung.bed ...

  20. File list: NoD.Lng.10.AllAg.Carcinoma,_Lewis_Lung [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available NoD.Lng.10.AllAg.Carcinoma,_Lewis_Lung mm9 No description Lung Carcinoma, Lewis Lun...g http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/NoD.Lng.10.AllAg.Carcinoma,_Lewis_Lung.bed ...

  1. Disease-modifying therapeutic directions for Lewy-Body Dementias

    Directory of Open Access Journals (Sweden)

    Qiang eZhang

    2015-08-01

    Full Text Available Dementia with Lewy bodies (DLB is the second leading cause of dementia following Alzheimer's disease (AD and accounts for up to 25% of all dementia. DLB is distinct from AD in that it involves extensive neuropsychiatric symptoms as well as motor symptoms, leads to enormous societal costs in terms of direct medical care and is associated with high financial and caregiver costs. Although there are no disease-modifying therapies for DLB, we review several new therapeutic directions in treating DLB. We discuss progress in strategies to decrease the level of alpha-synuclein, to prevent the cell to cell transmission of misfolded alpha-synuclein, and the potential of brain stimulation in DLB.

  2. Transport Coefficients for the NASA Lewis Chemical Equilibrium Program

    Science.gov (United States)

    Svehla, Roger A.

    1995-01-01

    The new transport property data that will be used in the NASA Lewis Research Center's Chemical Equilibrium and Applications Program (CEA) is presented. It complements a previous publication that documented the thermodynamic and transport property data then in use. Sources of the data and a brief description of the method by which the data were obtained are given. Coefficients to calculate the viscosity, thermal conductivity, and binary interactions are given for either one, or usually, two temperature intervals, typically 300 to 1000 K and 1000 to 5000 K. The form of the transport equation is the same as used previously. The number of species was reduced from the previous database. Many species for which the data were estimated were eliminated from the database. Some ionneutral interactions were added.

  3. Time perception in patients with dementia with Lewy bodies.

    Science.gov (United States)

    Lesimple, Blandine; Dieudonné, Bénédicte; Campillo-Gimenez, Boris; Verny, Marc; Giannopulu, Irini

    2016-06-01

    Disturbances of time perception could explain some behavioral disorders in patients with dementia with Lewy bodies (DLB), and the aim of this preliminary study was to evaluate time perception in these patients. 7 patients with DLB (mean age = 82±6,8 years) were compared to 7 cognitively normal subjects (m = 81.2±6,8 years) for spatiotemporal orientation, verbal estimation, semantic knowledge, rhythm perception and verbal time estimation. The scores on the semantic scale of temporality were statistically different between the two groups, and patients made more rhythm errors than the control sample. Moreover, a significant improvement between the first and second assessment on verbal time estimation was found in the control subjetcs but not in the patients. Time perception seems to be disturbed in patients with DLB, but more studies are required to understand this result with the behavioural disorders.

  4. Computational model of visual hallucination in dementia with Lewy bodies.

    Science.gov (United States)

    Tsukada, Hiromichi; Fujii, Hiroshi; Aihara, Kazuyuki; Tsuda, Ichiro

    2015-02-01

    Patients with dementia with Lewy bodies (DLB) frequently experience visual hallucination (VH), which has been aptly described as people seeing things that are not there. The distinctive character of VH in DLB necessitates a new theory of visual cognition. We have conducted a series of studies with the aim to understand the mechanism of this dysfunction of the cognitive system. We have proposed that if we view the disease from the internal mechanism of neurocognitive processes, and if also take into consideration recent experimental data on conduction abnormality, at least some of the symptoms can be understood within the framework of network (or disconnection) syndromes. This paper describes the problem from a computational aspect and tries to determine whether conduction disturbances in a computational model can in fact produce a "computational" hallucination under appropriate assumptions. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. A comparison of two instructional methods for drawing Lewis Structures

    Science.gov (United States)

    Terhune, Kari

    Two instructional methods for teaching Lewis structures were compared -- the Direct Octet Rule Method (DORM) and the Commonly Accepted Method (CAM). The DORM gives the number of bonds and the number of nonbonding electrons immediately, while the CAM involves moving electron pairs from nonbonding to bonding electrons, if necessary. The research question was as follows: Will high school chemistry students draw more accurate Lewis structures using the DORM or the CAM? Students in Regular Chemistry 1 (N = 23), Honors Chemistry 1 (N = 51) and Chemistry 2 (N = 15) at an urban high school were the study participants. An identical pretest and posttest was given before and after instruction. Students were given instruction with either the DORM (N = 45), the treatment method, or the CAM (N = 44), the control for two days. After the posttest, 15 students were interviewed, using a semistructured interview process. The pretest/posttest consisted of 23 numerical response questions and 2 to 6 free response questions that were graded using a rubric. A two-way ANOVA showed a significant interaction effect between the groups and the methods, F (1, 70) = 10.960, p = 0.001. Post hoc comparisons using the Bonferroni pairwise comparison showed that Reg Chem 1 students demonstrated larger gain scores when they had been taught the CAM (Mean difference = 3.275, SE = 1.324, p learning the DORM (Mean difference = 1.931, SE = 0.848, p working memory, and better metacognitive skills. Regular Chemistry 1 students performed better with the CAM, perhaps because it is more visual. Teachers may want to use the CAM or a direct-pairing method to introduce the topic and use the DORM in advanced classes when a correct structure is needed quickly.

  6. Strongly Correlated Topological Insulators

    Science.gov (United States)

    2016-02-03

    Strongly Correlated Topological Insulators In the past year, the grant was used for work in the field of topological phases, with emphasis on finding...surface of topological insulators. In the past 3 years, we have started a new direction, that of fractional topological insulators. These are materials...in which a topologically nontrivial quasi-flat band is fractionally filled and then subject to strong interactions. The views, opinions and/or

  7. Strong Cosmic Censorship

    Science.gov (United States)

    Isenberg, James

    2017-01-01

    The Hawking-Penrose theorems tell us that solutions of Einstein's equations are generally singular, in the sense of the incompleteness of causal geodesics (the paths of physical observers). These singularities might be marked by the blowup of curvature and therefore crushing tidal forces, or by the breakdown of physical determinism. Penrose has conjectured (in his `Strong Cosmic Censorship Conjecture`) that it is generically unbounded curvature that causes singularities, rather than causal breakdown. The verification that ``AVTD behavior'' (marked by the domination of time derivatives over space derivatives) is generically present in a family of solutions has proven to be a useful tool for studying model versions of Strong Cosmic Censorship in that family. I discuss some of the history of Strong Cosmic Censorship, and then discuss what is known about AVTD behavior and Strong Cosmic Censorship in families of solutions defined by varying degrees of isometry, and discuss recent results which we believe will extend this knowledge and provide new support for Strong Cosmic Censorship. I also comment on some of the recent work on ``Weak Null Singularities'', and how this relates to Strong Cosmic Censorship.

  8. Probing substituent effects on the activation of H(2) by phosphorus and boron frustrated Lewis pairs.

    Science.gov (United States)

    Neu, Rebecca C; Ouyang, Eva Y; Geier, Stephen J; Zhao, Xiaoxi; Ramos, Alberto; Stephan, Douglas W

    2010-05-14

    The impact of substituent changes on phosphorus and boron-containing frustrated Lewis pairs (FLPs) has been examined. The phosphites (RO)(3)P R = Me, Ph form classical Lewis acid-base adducts of the formula (RO)(3)PB(C(6)F(5))(3) R = Me ; R = Ph , whereas P(O-2,4-(t)Bu(2)C(6)H(3))(3) and P(O-2,6-Me(2)C(6)H(3))(3) generate FLPs. Nonetheless, these latter combinations do not react with H(2). The more basic phosphinite tBu(2)POR, R = tBu reacts with B(C(6)F(5))(3) to give (tBu(2)(H)PO)B(C(6)F(5))(3). The related species tBu(2)POR, R = Ph ; 2,6-Me(2)C(6)H(3) showed no reaction with B(C(6)F(5))(3) but the FLPs react under H(2) (4 atm) to give [tBu(2)P(OR)H][HB(C(6)F(5))(3)] R = Ph and 2,6-Me(2)C(6)H(3). Similarly, tBu(2)PCl in combination with B(C(6)F(5))(3), generates an FLP that upon addition of H(2), gives [tBu(2)PH(2)][ClB(C(6)F(5))(3)] albeit in low yield. The diborane 1,4-(C(6)F(5))(2)B(C(6)F(4))B(C(6)F(5))(2) in combination with either tBu(3)P or (C(6)H(2)Me(3))(3)P generates FLPs that react with H(2) to give [R(3)PH](2)[1,4-(C(6)F(5))(2)HB(C(6)F(4))BH(C(6)F(5))(2)] (R = tBu , C(6)H(2)Me(3)). Similarly PhB(C(6)F(5))(2) and tBu(3)P react with H(2) giving [tBu(3)PH][HBPh(C(6)F(5))(2)] . The combination of B(OC(6)F(5))(3) and PtBu(3) also generate an FLP which reacts with H(2) to give [HPtBu(3)][B(OC(6)F(5))(4)] , the product of substituent redistribution. The boronic esters, (C(6)H(4)O(2))BC(6)F(5), (C(6)H(3)FO(2))BC(6)F(5) and (C(6)F(4)O(2))BC(6)F(5), and the borate esters B(OC(6)H(3)(CF(3))(2))(3), B(OC(6)H(2)F(3))(3) and B(OC(6)H(4)CF(3))(3) were prepared and shown to generate FLPs with tBu(3)P or (C(6)H(2)Me(3))(3)P. Nonetheless, no reaction with H(2) was observed for . Collectively these data suggest that there is a threshold of combined Lewis acidity and basicity that is required to effect the splitting of H(2).

  9. Monocyte chemotactic protein-1 deficiency attenuates and high-fat diet exacerbates bone loss in mice with Lewis lung carcinoma.

    Science.gov (United States)

    Yan, Lin; Nielsen, Forrest H; Sundaram, Sneha; Cao, Jay

    2017-04-04

    Bone loss occurs in obesity and cancer-associated complications including wasting. This study determined whether a high-fat diet and a deficiency in monocyte chemotactic protein-1 (MCP-1) altered bone structural defects in male C57BL/6 mice with Lewis lung carcinoma (LLC) metastases in lungs. Compared to non-tumor-bearing mice, LLC reduced bone volume fraction, connectivity density, trabecular number, trabecular thickness and bone mineral density and increased trabecular separation in femurs. Similar changes occurred in vertebrae. The high-fat diet compared to the AIN93G diet exacerbated LLC-induced detrimental structural changes; the exacerbation was greater in femurs than in vertebrae. Mice deficient in MCP-1 compared to wild-type mice exhibited increases in bone volume fraction, connectivity density, trabecular number and decreases in trabecular separation in both femurs and vertebrae, and increases in trabecular thickness and bone mineral density and a decrease in structure model index in vertebrae. Lewis lung carcinoma significantly decreased osteocalcin but increased tartrate-resistant acid phosphatase 5b (TRAP 5b) in plasma. In LLC-bearing mice, the high-fat diet increased and MCP-1 deficiency decreased plasma TRAP 5b; neither the high-fat diet nor MCP-1 deficiency resulted in significant changes in plasma concentration of osteocalcin. In conclusion, pulmonary metastasis of LLC is accompanied by detrimental bone structural changes; MCP-1 deficiency attenuates and high-fat diet exacerbates the metastasis-associated bone wasting.

  10. Highly Efficient One-Pot Synthesis of COS-Based Block Copolymers by Using Organic Lewis Pairs.

    Science.gov (United States)

    Yang, Jia-Liang; Cao, Xiao-Han; Zhang, Cheng-Jian; Wu, Hai-Lin; Zhang, Xing-Hong

    2018-01-31

    A one-pot synthesis of block copolymer with regioregular poly(monothiocarbonate) block is described via metal-free catalysis. Lewis bases such as guanidine, quaternary onium salts, and Lewis acid triethyl borane (TEB) were equivalently combined and used as the catalysts. By using polyethylene glycol (PEG) as the macromolecular chain transfer agent (CTA), narrow polydispersity block copolymers were obtained from the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO). The block copolymers had a poly(monothiocarbonate) block with perfect alternating degree and regioregularity. Unexpectedly, the addition of CTA to COS/PO copolymerization system could dramatically improve the turnover frequency (TOF) of PO (up to 240 h -1 ), higher than that of the copolymerization without CTA. In addition, the conversion of CTA could be up to 100% in most cases, as revealed by ¹H NMR spectra. Of consequence, the number-average molecular weights ( M n s) of the resultant block copolymers could be regulated by varying the feed ratio of CTA to PO. Oxygen-sulfur exchange reaction (O/S ER), which can generate randomly distributed thiocarbonate and carbonate units, was effectively suppressed in all of the cases in the presence of CTA, even at 80 °C. This work presents a versatile method for synthesizing sulfur-containing block copolymers through a metal-free route, providing an array of new block copolymers.

  11. Strong Arcwise Connectedness

    OpenAIRE

    Espinoza, Benjamin; Gartside, Paul; Kovan-Bakan, Merve; Mamatelashvili, Ana

    2012-01-01

    A space is `n-strong arc connected' (n-sac) if for any n points in the space there is an arc in the space visiting them in order. A space is omega-strong arc connected (omega-sac) if it is n-sac for all n. We study these properties in finite graphs, regular continua, and rational continua. There are no 4-sac graphs, but there are 3-sac graphs and graphs which are 2-sac but not 3-sac. For every n there is an n-sac regular continuum, but no regular continuum is omega-sac. There is an omega-sac ...

  12. Abortion: Strong's counterexamples fail

    DEFF Research Database (Denmark)

    Di Nucci, Ezio

    2009-01-01

    This paper shows that the counterexamples proposed by Strong in 2008 in the Journal of Medical Ethics to Marquis's argument against abortion fail. Strong's basic idea is that there are cases--for example, terminally ill patients--where killing an adult human being is prima facie seriously morally......'s scenarios have some valuable future or admitted that killing them is not seriously morally wrong. Finally, if "valuable future" is interpreted as referring to objective standards, one ends up with implausible and unpalatable moral claims....

  13. A note on generalization of the Lewis invariant and the Ermakov systems

    Science.gov (United States)

    Simic, Srboljub S.

    2000-08-01

    In this paper we examine several possible generalizations of the well known Lewis invariant and the Ermakov systems. The analysis relies on the application of the theorem of Emmy Noether. The problem of constructing Lewis-type invariants is reduced to a problem of solving a single partial differential equation - the so-called potential equation. Within this approach, the role of the auxiliary equation is clarified by an analysis of linear systems. Generalization of the Ermakov-type procedure for derivation of the Lewis invariant is also discussed. Moreover, different forms of general solution of the problem will be provided, which extend the range of possible applications of the analysis.

  14. Preclinical Polymodal Hallucinations for 13 Years before Dementia with Lewy Bodies

    Directory of Open Access Journals (Sweden)

    Carlo Abbate

    2014-01-01

    Full Text Available Objective. We describe a case of dementia with Lewy bodies (DLB that presented long-lasting preclinical complex polymodal hallucinations. Background. Few studies have deeply investigated the characteristics of hallucinations in DLB, especially in the preclinical phase. Moreover, the clinical phenotype of mild cognitive impairment-(MCI- DLB is poorly understood. Methods. The patient was followed for 4 years and a selective phenomenological and cognitive study was performed at the predementia stage. Results. The phenomenological study showed the presence of hypnagogic and hypnopompic hallucinations that allowed us to make a differential diagnosis between DLB and Charles Bonnet syndrome (CBS. The neuropsychological evaluation showed a multiple domain without amnesia MCI subtype with prefrontal dysexecutive, visuoperceptual, and visuospatial impairments and simultanagnosia, which has not previously been reported in MCI-DLB. Conclusions. This study extends the prognostic value of hallucinations for DLB to the preclinical phases. It supports and refines the MCI-DLB concept and identifies simultanagnosia as a possible early cognitive marker. Finally, it confirms an association between hallucinations and visuoperceptual impairments at an intermediate stage of the disease course and strongly supports the hypothesis that hallucinations in the earliest stages of DLB may reflect a narcolepsy-like REM-sleep disorder.

  15. Preclinical Polymodal Hallucinations for 13 Years before Dementia with Lewy Bodies

    Science.gov (United States)

    Abbate, Carlo; Trimarchi, Pietro Davide; Inglese, Silvia; Viti, Niccolò; Cantatore, Alessandra; De Agostini, Lisa; Pirri, Federico; Marino, Lorenza; Bagarolo, Renzo

    2014-01-01

    Objective. We describe a case of dementia with Lewy bodies (DLB) that presented long-lasting preclinical complex polymodal hallucinations. Background. Few studies have deeply investigated the characteristics of hallucinations in DLB, especially in the preclinical phase. Moreover, the clinical phenotype of mild cognitive impairment-(MCI-) DLB is poorly understood. Methods. The patient was followed for 4 years and a selective phenomenological and cognitive study was performed at the predementia stage. Results. The phenomenological study showed the presence of hypnagogic and hypnopompic hallucinations that allowed us to make a differential diagnosis between DLB and Charles Bonnet syndrome (CBS). The neuropsychological evaluation showed a multiple domain without amnesia MCI subtype with prefrontal dysexecutive, visuoperceptual, and visuospatial impairments and simultanagnosia, which has not previously been reported in MCI-DLB. Conclusions. This study extends the prognostic value of hallucinations for DLB to the preclinical phases. It supports and refines the MCI-DLB concept and identifies simultanagnosia as a possible early cognitive marker. Finally, it confirms an association between hallucinations and visuoperceptual impairments at an intermediate stage of the disease course and strongly supports the hypothesis that hallucinations in the earliest stages of DLB may reflect a narcolepsy-like REM-sleep disorder. PMID:24868122

  16. A strong comeback

    International Nuclear Information System (INIS)

    Marier, D.

    1992-01-01

    This article presents the results of a financial rankings survey which show a strong economic activity in the independent energy industry. The topics of the article include advisor turnover, overseas banks, and the increase in public offerings. The article identifies the top project finance investors for new projects and restructurings and rankings for lenders

  17. Expanded solubility parameter approach. I: Naphthalene and benzoic acid in individual solvents.

    Science.gov (United States)

    Beerbower, A; Wu, P L; Martin, A

    1984-02-01

    An expanded solubility parameter system was tested in conjunction with the extended Hansen solubility approach and the UNIFAC method to calculate the solubilities of naphthalene and benzoic acid in polar and nonpolar solvents. The expanded parameter system is characterized by delta d for the dispersion force, delta p for dipolar forces, a basic or electron-donor parameter, delta b, and an acidic or electron-acceptor parameter delta a. The correlation between the calculated and observed solubilities of benzoic acid was increased by use of the four-parameter system. An indicator variable was required to bring the solubilities into line in strongly dipolar solvents such as N,N-dimethylformamide. For naphthalene, use of the four-parameter approach proved not to be an improvement over the three-parameter extended Hansen solubility approach. The UNIFAC method was not successful in calculating solubilities of benzoic acid in the 40 polar and nonpolar solvents. A triangular plot of the three Hansen parameters for benzoic acid, p-hydroxybenzoic acid, and methyl p-hydroxybenzoate illustrated the contributions of dispersion, dipolar, and Lewis acid-base (hydrogen bonding) interaction forces among the three benzoic acid compounds and the various classes of solvents. A multiple regression procedure for calculating the four partial solubility parameters of drug solutes was developed.

  18. Students' Understandings of Acid Strength: How Meaningful Is Reliability When Measuring Alternative Conceptions

    Science.gov (United States)

    Bretz, Stacey Lowery; McClary, LaKeisha

    2015-01-01

    Most organic chemistry reactions occur by a mechanism that includes acid-base chemistry, so it is important that students develop and learn to use correct conceptions of acids and acid strength. Recent studies have described undergraduate organic chemistry students' cognitive resources related to the Brønsted-Lowry acid model and the Lewis acid…

  19. Expression of glycogenes in differentiating human NT2N neurons. Downregulation of fucosyltransferase 9 leads to decreased Lewis(x) levels and impaired neurite outgrowth.

    Science.gov (United States)

    Gouveia, Ricardo; Schaffer, Lana; Papp, Suzanne; Grammel, Nicolas; Kandzia, Sebastian; Head, Steven R; Kleene, Ralf; Schachner, Melitta; Conradt, Harald S; Costa, Júlia

    2012-12-01

    Several glycan structures are functionally relevant in biological events associated with differentiation and regeneration which occur in the central nervous system. Here we have analysed the glycogene expression and glycosylation patterns during human NT2N neuron differentiation. We have further studied the impact of downregulating fucosyltransferase 9 (FUT9) on neurite outgrowth. The expression of glycogenes in human NT2N neurons differentiating from teratocarcinoma NTERA-2/cl.D1 cells has been analysed using the GlycoV4 GeneChip expression microarray. Changes in glycosylation have been monitored by immunoblot, immunofluorescence microscopy, HPLC and MALDI-TOF MS. Peptide mass fingerprinting and immunoprecipitation have been used for protein identification. FUT9 was downregulated using silencing RNA. One hundred twelve mRNA transcripts showed statistically significant up-regulation, including the genes coding for proteins involved in the synthesis of the Lewis(x) motif (FUT9), polysialic acid (ST8SIA2 and ST8SIA4) and HNK-1 (B3GAT2). Accordingly, increased levels of the corresponding carbohydrate epitopes have been observed. The Lewis(x) structure was found in a carrier glycoprotein that was identified as the CRA-a isoform of human neural cell adhesion molecule 1. Downregulation of FUT9 caused significant decreases in the levels of Lewis(x), as well as GAP-43, a marker of neurite outgrowth. Concomitantly, a reduction in neurite formation and outgrowth has been observed that was reversed by FUT9 overexpression. These results provided information about the regulation of glycogenes during neuron differentiation and they showed that the Lewis(x) motif plays a functional role in neurite outgrowth from human neurons. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Selective carbon dioxide sorption by a new breathing three-dimensional Zn-MOF with Lewis basic nitrogen-rich channels.

    Science.gov (United States)

    Kim, Hyun-Chul; Huh, Seong; Lee, Do Nam; Kim, Youngmee

    2018-04-03

    Lewis basic heteroatoms orderly located inside the well-defined channels of metal-organic frameworks (MOFs) are potentially ideal active sites for selective gas sorption and catalysis. To develop functional MOFs with Lewis basic sites inside channels, a new C2h-symmetric dicarboxylate-based bridging ligand, 3,3'-(pyrazine-2,5-diyl)dibenzoic acid (3,3'-PDBA), was prepared by a Suzuki coupling reaction. Subsequently, two new Zn-MOFs containing the C2h-symmetric 3,3'-PDBA bridging ligand and two different bis(pyridyl)-based pillars, 1,2-bis(4-pyridyl)ethane (bpa) or 1,2-bis(4-pyridyl)ethylene (bpe), were prepared through a thermal reaction in N,N-dimethylformamide (DMF). The resulting two Zn-MOFs of the general formula of three-dimensional (3D) [Zn2(μ4-3,3'-PDBA)2(μ2-bpa)]3·(DMF)5(H2O)13 (1) or 3D-like 2D [Zn2(μ4-3,3'-PDBA)2(μ2-bpe)]·(H2O) (2) displayed primitive cubic pcu net and 2D sql net, respectively. Both Zn-MOFs 1 and 2 contain uncoordinated Lewis basic pyrazinyl nitrogen atoms in the frameworks. The solvent-free 1 with flexible bpa linkers only showed a potential porosity of 15.9% by PLATON analysis. Zn-MOF 1 with openly accessible Lewis basic sites exhibited selective sorption of CO2 over N2, H2, and CH4 at low temperature. The adsorption and desorption isotherms for CO2 sorption at 196 K showed phenomenal hysteretic behaviour indicative of a breathing process through an adsorbate-discriminatory gate-opening process toward CO2 at a low gas pressure.

  1. Antitumor and other effects of 24R,25-dihydroxycholecalciferol in Lewis lung carcinoma causing abnormal calcium metabolism in tumor-bearing mice.

    Science.gov (United States)

    Maeda, Y; Yamato, H; Hirai, T; Kobori, N; Fujii, T; Kobayashi, Y; Saitoh, K; Inoguchi, E; Hakozaki, M; Iijima, H

    1988-01-01

    Lewis lung carcinoma was found to cause hypercalcemia in tumor-bearing mice. 24R,25(OH)2D3 (K-DR, prepared by Kureha Chemical Ind.) significantly prolonged the survival time of mice with Lewis lung carcinoma. K-DR exhibited an antimetastatic effect on Lewis lung carcinoma, and also had an analgesic effect in mice with Lewis lung carcinoma.

  2. Strong Electroweak Symmetry Breaking

    CERN Document Server

    Grinstein, Benjamin

    2011-01-01

    Models of spontaneous breaking of electroweak symmetry by a strong interaction do not have fine tuning/hierarchy problem. They are conceptually elegant and use the only mechanism of spontaneous breaking of a gauge symmetry that is known to occur in nature. The simplest model, minimal technicolor with extended technicolor interactions, is appealing because one can calculate by scaling up from QCD. But it is ruled out on many counts: inappropriately low quark and lepton masses (or excessive FCNC), bad electroweak data fits, light scalar and vector states, etc. However, nature may not choose the minimal model and then we are stuck: except possibly through lattice simulations, we are unable to compute and test the models. In the LHC era it therefore makes sense to abandon specific models (of strong EW breaking) and concentrate on generic features that may indicate discovery. The Technicolor Straw Man is not a model but a parametrized search strategy inspired by a remarkable generic feature of walking technicolor,...

  3. Reduced frequency of blood group Lewis a-b- in female Type 1 diabetes patients

    DEFF Research Database (Denmark)

    Kharagjitsingh, A.V.; Prinsen, K.; Lemkes, H.H.

    2008-01-01

    population. RESULTS: T1D patients had a lower frequency (4.1%) of Lewis(a(-)b(-)) blood group compared with simultaneously tested healthy control subjects (10.0%) and the historical control group (11.1%, P = 0.02). Male T1D patients showed a Lewis(a(-)b(-)) frequency of 8.0%, which was similar to both......AIMS: To examine a disputed association between the Lewis(a(-)b(-)) phenotype and Type 1 diabetes (T1D). METHODS: Lewis red blood cell phenotyping was performed for 97 T1D White patients and 100 control subjects using monoclonal antibodies. Two historical cohorts were also included as a control...

  4. Lewis Phenotype in Women With Preterm Labor and Premature Rupture of the Membranes

    Directory of Open Access Journals (Sweden)

    William F. O'Brien

    1995-01-01

    Full Text Available Objective: The purpose of this study was to evaluate the possible association between Lewis phenotype status in pregnant women and preterm labor (PTL or preterm rupture of the membranes (PROM.

  5. Highlighting High Performance: Adam Joseph Lewis Center for Environmental Studies, Oberlin College, Oberlin, Ohio

    Energy Technology Data Exchange (ETDEWEB)

    None

    2002-11-01

    Oberlin College’s Adam Joseph Lewis Center for Environmental Studies is a high-performance building featuring an expansive photovoltaic system and a closed-loop groundwater heat pump system. Designers incorporated energy-efficient components and materials

  6. 2005 Puget Sound LiDAR Consortium (PSLC) Topographic LiDAR: Lewis County

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Terrapoint collected Light Detection and Ranging (LiDAR) data for the Lewis County project of 2005. The project site covered approximately 223 square miles, divided...

  7. Involvement of the Cerebellum in Parkinson Disease and Dementia with Lewy Bodies

    NARCIS (Netherlands)

    Seidel, Kay; Bouzrou, Mohamed; Heidemann, Nina; Kruger, Rejko; Schöls, Ludger; den Dunnen, Wilfred F. A.; Korf, Horst-Werner; Rüb, Udo

    Brains from patients with Parkinson disease or dementia with Lewy bodies show aggregation of alpha-synuclein in precerebellar brainstem structures. Furthermore, patients exhibit resting tremor, unstable gait, and impaired balance, which may be associated with cerebellar dysfunction. Therefore, we

  8. Lewis Research Center studies of multiple large wind turbine generators on a utility network

    Science.gov (United States)

    Gilbert, L. J.; Triezenberg, D. M.

    1979-01-01

    A NASA-Lewis program to study the anticipated performance of a wind turbine generator farm on an electric utility network is surveyed. The paper describes the approach of the Lewis Wind Energy Project Office to developing analysis capabilities in the area of wind turbine generator-utility network computer simulations. Attention is given to areas such as, the Lewis Purdue hybrid simulation, an independent stability study, DOE multiunit plant study, and the WEST simulator. Also covered are the Lewis mod-2 simulation including analog simulation of a two wind turbine system and comparison with Boeing simulation results, and gust response of a two machine model. Finally future work to be done is noted and it is concluded that the study shows little interaction between the generators and between the generators and the bus.

  9. 2009 Puget Sound LiDAR Consortium (PSLC) Topographic LiDAR: Lewis County, Washington

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Watershed Sciences, Inc. (WSI) collected Light Detection and Ranging (LiDAR) data for the Lewis County survey area for the Puget Sound LiDAR Consortium. This data...

  10. Barack Obama, John Lewis, and the Legacy of the Civil Rights Struggle

    Directory of Open Access Journals (Sweden)

    Glenn T. Eskew

    2012-01-01

    Full Text Available The watershed election in 2008 of Barack Obama as the first President of the United States to have African ancestry resulted from the life work of such civil rights activists as U.S. Congressman John Lewis. Born on a sharecropper’s farm in 1940, the African American Lewis grew up in segregated Alabama. As a college student in Nashville, he joined the sit-in protests and volunteered for the original Freedom Ride in 1961. He was elected chairman of the Student Nonviolent Coordinating Committee, becoming the youngest speaker at the March on Washington in 1963. The radical shift to Black ultimately forced Lewis out of SNCC. Consequently Lewis capitalized on the Voting Rights Act of 1965, turned his attentions to voter registration campaigns, and continued working within the system. In 1986 he won election to the U.S. House of Representatives to represent Atlanta’s Fifth Congressional District, a seat he continues to hold today.

  11. Plasmons in strong superconductors

    International Nuclear Information System (INIS)

    Baldo, M.; Ducoin, C.

    2011-01-01

    We present a study of the possible plasmon excitations that can occur in systems where strong superconductivity is present. In these systems the plasmon energy is comparable to or smaller than the pairing gap. As a prototype of these systems we consider the proton component of Neutron Star matter just below the crust when electron screening is not taken into account. For the realistic case we consider in detail the different aspects of the elementary excitations when the proton, electron components are considered within the Random-Phase Approximation generalized to the superfluid case, while the influence of the neutron component is considered only at qualitative level. Electron screening plays a major role in modifying the proton spectrum and spectral function. At the same time the electron plasmon is strongly modified and damped by the indirect coupling with the superfluid proton component, even at moderately low values of the gap. The excitation spectrum shows the interplay of the different components and their relevance for each excitation modes. The results are relevant for neutrino physics and thermodynamical processes in neutron stars. If electron screening is neglected, the spectral properties of the proton component show some resemblance with the physical situation in high-T c superconductors, and we briefly discuss similarities and differences in this connection. In a general prospect, the results of the study emphasize the role of Coulomb interaction in strong superconductors.

  12. Functional connectivity in cortical regions in dementia with Lewy bodies and Alzheimer's disease.

    Science.gov (United States)

    Kenny, Eva R; Blamire, Andrew M; Firbank, Michael J; O'Brien, John T

    2012-02-01

    Using resting-state functional magnetic resonance imaging, spontaneous low-frequency fluctuations in the blood oxygenation level-dependent signal were measured to investigate connectivity between key brain regions hypothesized to be differentially affected in dementia with Lewy bodies compared with Alzheimer's disease and healthy controls. These included connections of the hippocampus, because of its role in learning, and parietal and occipital areas involved in memory, attention and visual processing. Connectivity was investigated in 47 subjects aged 60 years and over: 15 subjects with dementia with Lewy bodies, 16 subjects with Alzheimer's disease and 16 control subjects. Subjects were scanned using a 3 Tesla magnetic resonance imaging system. The mean blood oxygenation level-dependent signal time series was extracted from seed regions in the hippocampus, posterior cingulate cortex, precuneus and primary visual cortex and correlated with all other brain voxels to determine functional connectivity. Both subjects with dementia with Lewy bodies and Alzheimer's disease showed greater connectivity than control subjects. Compared with controls, the dementia with Lewy bodies group had greater connectivity between the right posterior cingulate cortex and other brain areas. In dementia with Lewy bodies, there were no significant differences in hippocampal connectivity compared with controls, but in Alzheimer's disease left hippocampal connectivity was greater compared with controls. There were no significant differences between groups for precuneus or primary visual cortex connectivity. No seed regions showed significantly less connectivity in subjects with dementia with Lewy bodies or Alzheimer's disease compared with controls. We found greater connectivity with the posterior cingulate in dementia with Lewy bodies and with the hippocampus in Alzheimer's disease. Consistent with the known relative preservation of memory in dementia with Lewy bodies compared with Alzheimer

  13. Clinical and imaging correlates of amyloid deposition in dementia with Lewy bodies.

    Science.gov (United States)

    Donaghy, Paul C; Firbank, Michael J; Thomas, Alan J; Lloyd, Jim; Petrides, George; Barnett, Nicola; Olsen, Kirsty; O'Brien, John T

    2018-04-19

    Amyloid deposition is common in dementia with Lewy bodies, but its pathophysiological significance is unclear. The objective of this study was to investigate the relationship between amyloid deposition and clinical profile, gray matter volume, and brain perfusion in dementia with Lewy bodies. Dementia with Lewy bodies (n = 37), Alzheimer's disease (n = 20), and controls (n = 20) underwent a thorough clinical assessment, 3T MRI, and early- and late-phase 18 F-Florbetapir PET-CT to assess cortical perfusion and amyloid deposition, respectively. Amyloid scans were visually categorized as positive or negative. Image analysis was carried out using statistical parametric mapping (SPM) 8. There were no significant differences between amyloid-positive and amyloid-negative dementia with Lewy bodies cases in age (P = .78), overall cognitive impairment (P = .83), level of functional impairment (P = .80), or any other clinical or cognitive scale. There were also no significant differences in hippocampal or gray matter volumes. However, amyloid-positive dementia with Lewy bodies cases had lower medial temporal lobe perfusion (P = .03) than amyloid-negative cases, although a combination of medial temporal lobe perfusion, hippocampal volume, and cognitive measures was unable to accurately predict amyloid status in dementia with Lewy bodies. Amyloid deposition was not associated with differences in clinical or neuropsychological profiles in dementia with Lewy bodies, but was associated with imaging evidence of medial temporal lobe dysfunction. The presence of amyloid in dementia with Lewy bodies cannot be identified on the basis of clinical and other imaging features and will require direct assessment via PET imaging or CSF. © 2018 The Authors. Movement Disorders published by Wiley Periodicals, Inc. on behalf of International Parkinson and Movement Disorder Society. © 2018 The Authors. Movement Disorders published by Wiley Periodicals, Inc. on behalf

  14. An Engineering Approach to Management of Occupational and Community Noise Exposure at NASA Lewis Research Center

    Science.gov (United States)

    Cooper, Beth A.

    1997-01-01

    Workplace and environmental noise issues at NASA Lewis Research Center are effectively managed via a three-part program that addresses hearing conservation, community noise control, and noise control engineering. The Lewis Research Center Noise Exposure Management Program seeks to limit employee noise exposure and maintain community acceptance for critical research while actively pursuing engineered controls for noise generated by more than 100 separate research facilities and the associated services required for their operation.

  15. Lactadherin is a candidate oviduct Lewis X trisaccharide receptor on porcine spermatozoa.

    Science.gov (United States)

    Silva, E; Frost, D; Li, L; Bovin, N; Miller, D J

    2017-05-01

    A recent study has demonstrated that porcine spermatozoa recognize with high affinity carbohydrate structures containing Lewis X motifs. Sperm adhesion to Lewis X is proposed to mediate sperm binding to the oviduct epithelium to form a reservoir. The objective of this study was to identify Lewis X-binding proteins from porcine spermatozoa as candidate receptors for oviduct glycans. To identify low-abundance proteins typically masked by proteins originating from seminal fluid, Lewis X candidate receptors were enriched from cauda epididymal boar spermatozoa. Plasma membrane preparations from cauda epididymal spermatozoa were subjected to RP-HPLC and glycan blotting assays to isolate and detect proteins that bind Lewis X. Following bottom-up LC-MS/MS analysis, among the two bands that bound sulfated Lewis X, ADAM5, which spermatozoa, was confidently identified. ADAM family members have been established as contributors to sperm entry into the oviduct. A second sulfated Lewis X-binding protein identified was the peripheral membrane protein lactadherin (also known as P47, SED1 and MFG-E8 in different species). The interaction between Lewis X and lactadherin was functionally important because competitive inhibition by soluble recombinant lactadherin reduced sperm binding to the oviduct epithelium. Furthermore, far-western blotting demonstrated that purified lactadherin could bind oviduct cells. In summary, these findings reveal that, in addition to the previously reported glycan affinity of accessory gland proteins that adhere to spermatozoa, multiple proteins intrinsic to spermatozoa have affinity for a specific oviduct glycan. Further, in addition to binding to the zona pellucida, lactadherin is now implicated in binding to oviduct glycans to promote formation of the sperm reservoir. © 2017 American Society of Andrology and European Academy of Andrology.

  16. Cerebral Microbleeds in Patients with Dementia with Lewy Bodies and Parkinson Disease Dementia.

    Science.gov (United States)

    Kim, S W; Chung, S J; Oh, Y-S; Yoon, J H; Sunwoo, M K; Hong, J Y; Kim, J-S; Lee, P H

    2015-09-01

    The burden of amyloid β is greater in patients with dementia with Lewy bodies than in those with Parkinson disease dementia, and an increased amyloid β load is closely related to a higher incidence of cerebral microbleeds. Here, we investigated the prevalence and topography of cerebral microbleeds in patients with dementia with Lewy bodies and those with Parkinson disease dementia to examine whether cerebral microbleeds are more prevalent in patients with dementia with Lewy bodies than in those with Parkinson disease dementia. The study population consisted of 42 patients with dementia with Lewy bodies, 88 patients with Parkinson disease dementia, and 35 controls who underwent brain MR imaging with gradient recalled-echo. Cerebral microbleeds were classified as deep, lobar, or infratentorial. The frequency of cerebral microbleeds was significantly greater in patients with dementia with Lewy bodies (45.2%) than in those with Parkinson disease dementia (26.1%) or in healthy controls (17.1%; P = .017). Lobar cerebral microbleeds were observed more frequently in the dementia with Lewy bodies group (40.5%) than in the Parkinson disease dementia (17%; P = .004) or healthy control (8.6%; P = .001) group, whereas the frequencies of deep and infratentorial cerebral microbleeds did not differ among the 3 groups. Logistic regression analyses revealed that, compared with the healthy control group, the dementia with Lewy bodies group was significantly associated with the presence of lobar cerebral microbleeds after adjusting for age, sex, nonlobar cerebral microbleeds, white matter hyperintensities, and other vascular risk factors (odds ratio, 4.39 [95% CI, 1.27-15.25]). However, compared with the healthy control group, the Parkinson disease dementia group was not significantly associated with lobar cerebral microbleeds. This study showed that patients with dementia with Lewy bodies had a greater burden of cerebral microbleeds and exhibited a lobar predominance of cerebral

  17. Visual Hallucinations in PD and Lewy Body Dementias: Old and New Hypotheses

    Directory of Open Access Journals (Sweden)

    M. Onofrj

    2013-01-01

    Full Text Available Visual Hallucinations (VH are a common non-motor symptom of Parkinson’s Disease (PD and the Lewy body dementias (LBD of Parkinson's disease with dementia (PDD and Dementia with Lewy Bodies (DLB. The origin of VH in PD and LBD is debated: earlier studies considered a number of different possible mechanisms underlying VH including visual disorders, Rapid Eye Movement (REM Sleep Intrusions, dysfunctions of top down or bottom up visual pathways, and neurotransmitter imbalance.

  18. Lewis Swift celebrated comet hunter and the people's astronomer

    CERN Document Server

    Kronk, Gary W

    2017-01-01

    This biography covers the life of Lewis Swift (1820-1913), who discovered 13 comets and nearly 1,200 other deep sky objects. All 13 comets found by Swift now bear his name, including three periodic comets with periods of 6 years (11P/Tempel-Swift-LINEAR), 9 years (64P/Swift-Gehrels), and 133 years (109P/Swift-Tuttle). Swift's enthusiasm and success as an amateur astronomer helped make him famous in the United States. With the help of others, Swift was able to buy a 16-inch refractor, the third largest telescope in the United States at the time. Hulbert Harrington Warner built "Warner Observatory" to house this telescope. As a prolific writer and lecturer, Swift's stories appeared in newspapers and magazines, while his lectures showed that he was able to explain anything in a way that everyone could understand.  When Warner went broke during the "Panic of 1893," Swift was forced to leave his home. Almost two dozen invitations arrived from around the United States asking him to bring his telescope to their ci...

  19. Clinical and neuroimage findings of dementia with lewy bodies

    International Nuclear Information System (INIS)

    Kang, Do Young; Park, Kyung Won; Kim, Jae Woo

    2002-01-01

    Dementia with lewy bodies (DLB) is the second common degenerative dementia and has several characteristics including fluctuating cognition, visual hallucination and Parkinsonism. We investigated clinical manifestations and neuroimaging findings in DLB patients. Ten probable DLB patients were included in this study. Brain MRI, Tc-99m HMPAO brain perfusion SPECT and I-123 IPT SPECT were performed. All patients were men and mean age of onset was 64.2 years (range from 54 to 80). All had fluctuating cognition and Parkinsonism, and 8 had visual hallucination. Dementia preceded Parkinsonism in 3 patients. Fluctuation of K-MMSE ranges from 3 to 8 points. Rest tremor was seen in 5 patients. Brain MRI showed cortical atrophy in all patients. Tc-99m brain perfusion SPECT showed hypoperfusion in occipital area as well as fronto-temporo-parietal areas. I-123 IPT SPECT revealed reduced uptake comparable to Parkinson's disease in the striatum. DLB should be first considered as one of possible diagnosis in patients showing dementia in the early stage of Parkinsonism. Hypoperfusion in the occipital area was thought to be a characteristic finding in DLB and to be helpful in differentiating DLB from other degenerative dementias

  20. Cognitive impairment in Parkinson's disease and dementia with Lewy bodies.

    Science.gov (United States)

    Aarsland, Dag

    2016-01-01

    Parkinson's disease (PD) and dementia with Lewy bodies (DLB) share clinical and pathological similarities. The defining features are motor parkinsonism and cognitive impairment, often accompanied by visual hallucinations, fluctuating consciousness, autonomic and sleep disturbances, and a number of other non-motor symptoms. Mild cognitive impairment (MCI) can be identified in 15% of PD patients at time of diagnosis, and may even precede motor symptoms. MCI usually progresses further, and dementia is a common endpoint. Cognitive impairment is usually the initial symptom of DLB, and the disease course is severe. A variety of biomarkers can assist in the diagnosis and prognosis of PD and DLB, including structural and functional imaging, cerebrospinal fluid, and EEG. Compared to the many treatments available for motor symptoms, relatively few systematic studies exist to guide the treatment of cognitive impairment in PD, and even less in DLB. However, there is good evidence for cholinesterase inhibitors in both DLB and PD with dementia, and some indications that memantine is helpful. Emerging evidence suggest that physical exercise and cognitive training are also effective, as are some reports of various brain stimulation techniques. Disease-modifying agents that delay the rate of cognitive decline in PD and DLB are urgently needed. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Fort Lewis electric energy baseline and efficiency resource assessment

    Energy Technology Data Exchange (ETDEWEB)

    Secrest, T.J.; Currie, J.W.; DeSteese, J.G.; Dirks, J.A.; Marseille, T.J.; Parker, G.B.; Richman, E.E.; Shankle, S.A.

    1991-10-01

    In support of the US DOE Federal Energy Management Program, the Pacific Northwest Laboratory is developing a fuel-neutral approach for identifying, evaluating, and acquiring all cost-effective energy projects at federal installations. Fort Lewis, a US Army installation near Tacoma, Washington, was selected as the pilot site for developing this approach. This site was chosen in conjunction with the interests of the Bonneville Power Administration to develop programs for its federal sector customers and the Army Forces Command to develop an in-house program to upgrade the energy efficiency of its installations. This report documents the electricity assessment portion of the approach, providing an estimate of the electricity use baseline and efficiency improvement potential for major sectors and end uses at the Fort. Although the assessment did not identify all possible efficiency improvement opportunities, it is estimated that electricity use can be reduced by at least 20% cost-effectively at the $0.045/kWh marginal cost of electricity in the Pacific Northwest. 12 refs., 3 figs., 7 tabs.

  2. Clinical and neuroimage findings of dementia with lewy bodies

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Do Young; Park, Kyung Won; Kim, Jae Woo [Dong-A University College of Medicine, Busan (Korea, Republic of)

    2002-07-01

    Dementia with lewy bodies (DLB) is the second common degenerative dementia and has several characteristics including fluctuating cognition, visual hallucination and Parkinsonism. We investigated clinical manifestations and neuroimaging findings in DLB patients. Ten probable DLB patients were included in this study. Brain MRI, Tc-99m HMPAO brain perfusion SPECT and I-123 IPT SPECT were performed. All patients were men and mean age of onset was 64.2 years (range from 54 to 80). All had fluctuating cognition and Parkinsonism, and 8 had visual hallucination. Dementia preceded Parkinsonism in 3 patients. Fluctuation of K-MMSE ranges from 3 to 8 points. Rest tremor was seen in 5 patients. Brain MRI showed cortical atrophy in all patients. Tc-99m brain perfusion SPECT showed hypoperfusion in occipital area as well as fronto-temporo-parietal areas. I-123 IPT SPECT revealed reduced uptake comparable to Parkinson's disease in the striatum. DLB should be first considered as one of possible diagnosis in patients showing dementia in the early stage of Parkinsonism. Hypoperfusion in the occipital area was thought to be a characteristic finding in DLB and to be helpful in differentiating DLB from other degenerative dementias.

  3. Streamline segment statistics of premixed flames with nonunity Lewis numbers

    Science.gov (United States)

    Chakraborty, Nilanjan; Wang, Lipo; Klein, Markus

    2014-03-01

    The interaction of flame and surrounding fluid motion is of central importance in the fundamental understanding of turbulent combustion. It is demonstrated here that this interaction can be represented using streamline segment analysis, which was previously applied in nonreactive turbulence. The present work focuses on the effects of the global Lewis number (Le) on streamline segment statistics in premixed flames in the thin-reaction-zones regime. A direct numerical simulation database of freely propagating thin-reaction-zones regime flames with Le ranging from 0.34 to 1.2 is used to demonstrate that Le has significant influences on the characteristic features of the streamline segment, such as the curve length, the difference in the velocity magnitude at two extremal points, and their correlations with the local flame curvature. The strengthenings of the dilatation rate, flame normal acceleration, and flame-generated turbulence with decreasing Le are principally responsible for these observed effects. An expression for the probability density function (pdf) of the streamline segment length, originally developed for nonreacting turbulent flows, captures the qualitative behavior for turbulent premixed flames in the thin-reaction-zones regime for a wide range of Le values. The joint pdfs between the streamline length and the difference in the velocity magnitude at two extremal points for both unweighted and density-weighted velocity vectors are analyzed and compared. Detailed explanations are provided for the observed differences in the topological behaviors of the streamline segment in response to the global Le.

  4. Lewis Carroll, a educação e o ensino de geometria na Inglaterra vitoriana - Lewis Carroll, education and the teaching of geometry in victorian England

    Directory of Open Access Journals (Sweden)

    Rafael Montoito

    2015-04-01

    Full Text Available Parte da pesquisa motivada pela tradução para o português do livro Euclides e seus rivais modernos, publicado por Lewis Carroll em 1879, este artigo se inscreve numa série de estudos que visam a um exame hermenêutico dessa obra. São discutidos temas relacionados com a educação, a educação matemática e o ensino de geometria na Inglaterra vitoriana.Palavras-chave: Lewis Carroll, Euclides e seus rivais modernos, história da educação, educação matemática, geometria. LEWIS CARROLL, EDUCATION AND THE TEACHING OF GEOMETRY IN VICTORIAN ENGLANDAbstractResearch partly motivated by Lewis Carrroll's Euclid and his modern rivals (1879 portuguese translation, this paper presents some hermeneutical remarks taken as necessary to understand the context in which such book was produced. The paper focuses particularly on education, in general, and on the teaching of mathematics and geometry in victorian England.Key-words: Lewis Carroll, Euclid and his modern rivals, history of education, mathematics education, geometry. LEWIS CARROLL, LA EDUCACIÓN Y EL ENSINO DE GEOMETRÍA EN LA INGLATERRA VICTORIANAResumenParte de la investigación motivada por la traducción al portugués del libro Euclides y sus enemigos modernos, publicado por Lewis Carroll en 1879, este artículo se inscribe en una serie de estudios que tienen por objetivo hacer un examen hermenéutico de la obra. Son aquí discutidos temas relacionados como la educación, la educación matemática y la enseñanza de geometría en la Inglaterra victoriana.Palabras-clave: Lewis Carroll, Euclides y sus enemigos modernos, historia de la educación, educación matemática, geometría. LEWIS CARROLL, L’ÉDUCATION ET L’ENSEIGMENT DE GÉOMÉTRIE EN L’ANGLETERRE VICTORIENNERésuméFaisant partie de la recherche motivée par la traduction en portugais du livre Euclide et ses rivaux modernes, publié par Lewis Carrol en 1879 , cet article s’inscrit dans une série d’études dont le but

  5. Strong-coupling approximations

    International Nuclear Information System (INIS)

    Abbott, R.B.

    1984-03-01

    Standard path-integral techniques such as instanton calculations give good answers for weak-coupling problems, but become unreliable for strong-coupling. Here we consider a method of replacing the original potential by a suitably chosen harmonic oscillator potential. Physically this is motivated by the fact that potential barriers below the level of the ground-state energy of a quantum-mechanical system have little effect. Numerically, results are good, both for quantum-mechanical problems and for massive phi 4 field theory in 1 + 1 dimensions. 9 references, 6 figures

  6. Strong interaction and QFD

    International Nuclear Information System (INIS)

    Ebata, T.

    1981-01-01

    With an assumed weak multiplet structure for bosonic hadrons, which is consistent with the ΔI = 1/2 rule, it is shown that the strong interaction effective hamiltonian is compatible with the weak SU(2) x U(1) gauge transformation. Especially the rho-meson transforms as a triplet under SU(2)sub(w), and this is the origin of the rho-photon analogy. It is also shown that the existence of the non-vanishing Cabibbo angle is a necessary condition for the absence of the exotic hadrons. (orig.)

  7. Strong Coupling Holography

    CERN Document Server

    Dvali, Gia

    2009-01-01

    We show that whenever a 4-dimensional theory with N particle species emerges as a consistent low energy description of a 3-brane embedded in an asymptotically-flat (4+d)-dimensional space, the holographic scale of high-dimensional gravity sets the strong coupling scale of the 4D theory. This connection persists in the limit in which gravity can be consistently decoupled. We demonstrate this effect for orbifold planes, as well as for the solitonic branes and string theoretic D-branes. In all cases the emergence of a 4D strong coupling scale from bulk holography is a persistent phenomenon. The effect turns out to be insensitive even to such extreme deformations of the brane action that seemingly shield 4D theory from the bulk gravity effects. A well understood example of such deformation is given by large 4D Einstein term in the 3-brane action, which is known to suppress the strength of 5D gravity at short distances and change the 5D Newton's law into the four-dimensional one. Nevertheless, we observe that the ...

  8. Carboxylic acid terminated, solution exfoliated graphite by organic ...

    Indian Academy of Sciences (India)

    under mild conditions using succinic anhydride as acylating agent and anhydrous aluminum chloride as Lewis acid. Such reaction renders towards the carboxylic acid terminated graphite nanosheets (SEGn–FC) that usually requires harsh reaction conditions. The product thus obtained was characterized using various ...

  9. Demência com corpos de Lewy: uma revisão para o psiquiatra Dementia with Lewy bodies: a review for psychiatrists

    Directory of Open Access Journals (Sweden)

    Almir Tavares

    2003-01-01

    Full Text Available A demência com corpos de Lewy (DCL tornou-se hoje uma entidade nosológica distinta, considerada por muitos autores a segunda causa principal de demência degenerativa, atrás apenas da doença de Alzheimer. Sua neuropatologia é caracterizada pela presença de corpos de Lewy tanto em regiões corticais como em áreas subcorticais do encéfalo. As principais manifestações clínicas incluem: declínio cognitivo progressivo, alucinações visuais recorrentes, flutuação no estado cognitivo e sinais parkinsonianos. Observa-se maior sensibilidade a efeitos indesejáveis de medicamentos neurolépticos e a resposta a medicações inibidoras da acetilcolinesterase é geralmente boa.Lewy body dementia became today a distinct nosological entity, considered by many authors the second cause of degenerative dementia, after Alzheimer's disease. Its neuropathology is caracterized by the presence of Lewy bodies both in cortical and subcortical areas of the brain. The main clinical manifestations are: progressive cognitive impairment, recurrent visual hallucinations, fluctuating cognitive status and parkinsonian signs. There is greater sensitivity to side effects of neuroleptic drugs and the response to cholinesterase inhibitors is generally good.

  10. The determination of acid-base properties of polymer surfaces by XPS: Present status and future prospects

    International Nuclear Information System (INIS)

    Chehimi, M.M.; Delamar, M.; Shahidzadeh-Ahmadi, N.; Arefi-Khonsari, F.; Amouroux, J.; Watts, J.F.

    1996-01-01

    The use of the molecular probe technique in conjunction with X-ray photoelectron spectroscopy (XPS) for the assessment of acid-base properties of polymer surfaces is reviewed. The method is based on the determination of the concentration and chemical shifts of Lewis acids (bases) sorbed in polymers of basic (acidic) character. In the case of chloroform (Lewis acid) sorbed in polymers of Lewis basic character, C12p binding energy is linearly correlated with ΔH AB , the heat of acid-base complex formation chloroform-polymer. This relationship has been used to determine the acid-base properties of poly(phenylene oxide), a homopolymer, and ammonia plasma-treated polypropylene. This work shows that XPS can now indeed be used to quantitatively assess the acid-base properties of modified polymer surfaces and perhaps be extended to map acid-base properties of polymer surfaces at the micron or submicron scale. copyright 1996 American Institute of Physics

  11. LIGO: The strong belief

    CERN Multimedia

    Antonella Del Rosso

    2016-01-01

    Twenty years of designing, building and testing a number of innovative technologies, with the strong belief that the endeavour would lead to a historic breakthrough. The Bulletin publishes an abstract of the Courier’s interview with Barry Barish, one of the founding fathers of LIGO.   The plots show the signals of gravitational waves detected by the twin LIGO observatories at Livingston, Louisiana, and Hanford, Washington. (Image: Caltech/MIT/LIGO Lab) On 11 February, the Laser Interferometer Gravitational-Wave Observatory (LIGO) and Virgo collaborations published a historic paper in which they showed a gravitational signal emitted by the merger of two black holes. These results come after 20 years of hard work by a large collaboration of scientists operating the two LIGO observatories in the US. Barry Barish, Linde Professor of Physics, Emeritus at the California Institute of Technology and former Director of the Global Design Effort for the Internat...

  12. Expression of hPNAS-4 Radiosensitizes Lewis Lung Cancer

    International Nuclear Information System (INIS)

    Zeng Hui; Yuan Zhu; Zhu Hong; Li Lei; Shi Huashan; Wang Zi; Fan Yu; Deng Qian; Zeng Jianshuang; He Yinbo; Xiao Jianghong; Li Zhiping

    2012-01-01

    Purpose: This study aimed to transfer the hPNAS-4 gene, a novel apoptosis-related human gene, into Lewis lung cancer (LL2) and observe its radiosensitive effect on radiation therapy in vitro and in vivo. Methods and Materials: The hPNAS-4 gene was transfected into LL2 cells, and its expression was detected via western blot. Colony formation assay and flow cytometry were used to detect the growth and apoptosis of cells treated with irradiation/PNAS-4 in vitro. The hPNAS-4 gene was transferred into LL2-bearing mice through tail vein injection of the liposome/gene complex. The tumor volumes were recorded after radiation therapy. Proliferating cell nuclear antigen (PCNA) immunohistochemistry staining and terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling (TUNEL) assay were performed to detect the tumor cell growth and apoptosis in vivo. Results: The hPNAS-4 gene was successfully transferred into LL2 cells and tumor tissue, and its overexpressions were confirmed via western blot analysis. Compared with the control, empty plasmid, hPNAS-4, radiation, and empty plasmid plus radiation groups, the hPNAS-4 plus radiation group more significantly inhibited growth and enhanced apoptosis of LL2 cells in vitro and in vivo (P<.05). Conclusions: The hPNAS-4 gene was successfully transferred into LL2 cells and tumor tissue and was expressed in both LL2 cell and tumor tissue. The hPNAS-4 gene therapy significantly enhanced growth inhibition and apoptosis of LL2 tumor cells by radiation therapy in vitro and in vivo. Therefore, it may be a potential radiosensitive treatment of radiation therapy for lung cancer.

  13. Lewis M. Rutherfurd and the First Photograph of Solar Granulation

    Science.gov (United States)

    Harvey, J. W.; Briggs, John W.; Prosser, Sian

    2017-08-01

    A major astronomical controversy of the mid-19th century was discordant descriptions of the small scale structure of the solar surface. Visual observers contradicted each other by describing the surface as consisting of “corrugations”, “willow leaves”, “rice grains”, “cumuli”, “thatch”, “granules”, etc. Early photographs of the solar surface were not good enough to settle the controversy. The French astronomer Jules Janssen is credited with the first 1876 photographs that clearly showed what we now call solar granulation (1876, CRAS 82, 1363). Upon seeing these images, New Yorker Lewis M. Rutherfurd (1878, MNRAS 38, 410) praised the high quality of Janssen’s images but asserted that he had also photographed granulation as early as 1871 using collodion wet plates. He sent copies of his best photograph to the Royal Astronomical Society to support his assertion. Curious about his claim, Briggs and Harvey set up Rutherfurd’s 13-inch achromatic refractor on Kitt Peak and found that it easily showed well-resolved solar granulation, so his claim might well have been justified. But without his plates we could not confirm the claim. For 140 years the copies of Rutherfurd’s best solar photograph remained in the archives of the Royal Astronomical Society and were recently discovered by Prosser (RAS Photographs A3/001B and A3/002). By coincidence a few days later, Briggs found the original August 11, 1871 plate. Despite poor condition these photographs show solar granulation. There are at least two other possible early claimants (Reade; Vogel) but their plates are almost certainly lost. Rutherfurd was a master of astronomical instrumentation and photography. He was reticent about his work, letting results speak for themselves, so it is satisfying to find that he was justified in making his claim of priority.

  14. Structure of framework aluminum Lewis sites and perturbed aluminum atoms in zeolites as determined by 27Al{1H} REDOR (3Q) MAS NMR spectroscopy and DFT/molecular mechanics

    Czech Academy of Sciences Publication Activity Database

    Brus, Jiří; Kobera, Libor; Schoefberger, W.; Urbanová, Martina; Klein, Petr; Sazama, Petr; Tabor, Edyta; Sklenák, Štěpán; Fishchuk, A. V.; Dědeček, Jiří

    2015-01-01

    Roč. 54, č. 2 (2015), s. 541-545 ISSN 1433-7851 R&D Projects: GA ČR(CZ) GA14-10251S; GA ČR(CZ) GA13-24155S Institutional support: RVO:61389013 ; RVO:61388955 Keywords : aluminum * density functional calculations * Lewis acids Subject RIV: JN - Civil Engineering; CI - Industrial Chemistry, Chemical Engineering (UFCH-W) Impact factor: 11.709, year: 2015

  15. A new oxidimetric reagent: potassium dichromate in a strong phosphoric acid medium--VII. Photometric titration of vanadium(IV) and of cerium(III) alone and in mixtures with iroN(II).

    Science.gov (United States)

    Rao, G G; Rao, P K

    1967-01-01

    Vanadium(IV) can be accurately titrated with potassium dichromate in media containing phosphoric acid of 3-12M concentration: the change in absorption of vanadium(IV) is followed in the region 660 mmicro using a red filter. It is more convenient to carry out the titration in 3M phosphoric acid because at higher concentrations chloride, nitrate, cerium(III) and manganese(II) may interfere. Photoelcetric titration is more convenient than potentiometric because the former can be made in a 3M phosphoric acid medium, whereas the latter is possible only in 12M phosphoric acid. The simultaneous differential photometric titration of iron(II) and vanadium(IV) is also possible. Conditions have been found for the photometric titration of cerium(III) and of cerium(III) plus iron(II). The titration is carried out (at 450 mmicro or with a blue filter) in about 10.5M phosphoric acid. Application of the method to a cerium mineral is considered.

  16. Loss of EEG Network Efficiency Is Related to Cognitive Impairment in Dementia With Lewy Bodies.

    Science.gov (United States)

    van Dellen, Edwin; de Waal, Hanneke; van der Flier, Wiesje M; Lemstra, Afina W; Slooter, Arjen J C; Smits, Lieke L; van Straaten, Elisabeth C W; Stam, Cornelis J; Scheltens, Philip

    2015-11-01

    The aim of this study was to test whether disturbed EEG resting-state functional connectivity and network organization are a potential neurophysiological substrate of cognitive impairment in dementia with Lewy bodies. EEG recordings were obtained in dementia with Lewy bodies patients, Alzheimer's disease patients and controls, matched for age and sex (N = 66 for each group; 14 [21%] female; mean age: 70 years). We analyzed functional connectivity of band-filtered EEG time series using the phase lag index. Functional brain network topology was analyzed with the minimum spanning tree. Mini-Mental State Examination, Trail Making Test A, and Visual Association Test were used as cognitive measures. Dementia with Lewy bodies patients showed lower connectivity strength in the alpha frequency band, compared to both controls and Alzheimer's disease patients (P dementia with Lewy bodies patients was less efficient and contained less hubs (P dementia with Lewy bodies patients, lower alpha band phase lag index correlated with Visual Association Test scores and Trail Making Test scores (ρ = 0.33 and ρ = 0.31, respectively), whereas leaf fraction (a measure of 'network efficiency') correlated with Visual Association Test scores (ρ = 0.29) and Mini-Mental State Examination scores (ρ = 0.27). Functional networks of dementia with Lewy bodies patients are characterized by decreased connectivity strength and a loss of network efficiency and hubs. Severity of these disturbances is related to cognitive impairment, suggesting that network disturbances mediate between neuropathology and the clinical syndrome in dementia with Lewy bodies. © 2015 International Parkinson and Movement Disorder Society.

  17. Characterization of the acid strength of SiO[sub 2]-ZrO[sub 2] mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bosman, H.J.M.; Kruissink, E.C.; Spoel, J. van der; Brink, F. van den (DSM Research B.V., Gelenee (Netherlands))

    1994-08-01

    The preparation of SiO[sub 2]-ZrO[sub 2] mixed oxides and the single oxides SiO[sub 2] and ZrO[sub 2] from H[sub 2]SiF[sub 6] and/or H[sub 2]ZrF[sub 6] is described. The catalysts are characterized using Hammett colour indicators, temperature programmed desorption of ammonia, XRD, XPS, and infrared spectroscopy. New IR bands and absence of XRD crystallinity show mixing of SiO[sub 2] and ZrO[sub 2] on an atomic scale in the amorphous coprecipitate. However, as could be concluded from the difference between surface concentrations of Zr and Si measured with XPS and the mean bulk concentrations, the ZrO[sub 2] precipitates somewhat more quickly than SiO[sub 2]. The acid strength of the SiO[sub 2]-ZrO[sub 2] mixed oxides corresponds to an H[sub 0] value between -11.4 and 13.8 (super-acidity). There is a fair correlation between the surface concentration of strong acid sites, determined from NH[sub 3] TPD, and the performance in the acid catalyzed dehydration of cyclohexanol to cyclohexene. In addition to the concentration of acid sites, their acid strength is an important factor determining the performance of the SiO[sub 2]-ZrO[sub 2] catalysts in the dehydration of cyclohexanol. The acid strength needed for the dehydration of cyclohexanol corresponds to H[sub 0] [<=] +2.8. Chemically mixed SiO[sub 2]-ZrO[sub 2] oxides contain strong acid sites as opposed to the single oxides SiO[sub 2] and ZrO[sub 2], which contain only weak acid sites. XPS shows an oxygen depletion on the surface of the mixed oxides, which indicates that the strong acid sites are of the Lewis type. 27 refs., 11 figs., 4 tabs.

  18. Historical perspectives: The role of the NASA Lewis Research Center in the national space nuclear power programs

    Science.gov (United States)

    Bloomfield, H. S.; Sovie, R. J.

    1991-01-01

    The history of the NASA Lewis Research Center's role in space nuclear power programs is reviewed. Lewis has provided leadership in research, development, and the advancement of space power and propulsion systems. Lewis' pioneering efforts in nuclear reactor technology, shielding, high temperature materials, fluid dynamics, heat transfer, mechanical and direct energy conversion, high-energy propellants, electric propulsion and high performance rocket fuels and nozzles have led to significant technical and management roles in many national space nuclear power and propulsion programs.

  19. Historical perspectives - The role of the NASA Lewis Research Center in the national space nuclear power programs

    Science.gov (United States)

    Bloomfield, H. S.; Sovie, R. J.

    1991-01-01

    The history of the NASA Lewis Research Center's role in space nuclear power programs is reviewed. Lewis has provided leadership in research, development, and the advancement of space power and propulsion systems. Lewis' pioneering efforts in nuclear reactor technology, shielding, high temperature materials, fluid dynamics, heat transfer, mechanical and direct energy conversion, high-energy propellants, electric propulsion and high performance rocket fuels and nozzles have led to significant technical and management roles in many natural space nuclear power and propulsion programs.

  20. John Strong (1941 - 2006)

    CERN Multimedia

    Wickens, F

    Our friend and colleague John Strong was cruelly taken from us by a brain tumour on Monday 31st July, a few days before his 65th birthday John started his career working with a group from Westfield College, under the leadership of Ted Bellamy. He obtained his PhD and spent the early part of his career on experiments at Rutherford Appleton Laboratory (RAL), but after the early 1970s his research was focussed on experiments in CERN. Over the years he made a number of notable contributions to experiments in CERN: The Omega spectrometer adopted a system John had originally developed for experiments at RAL using vidicon cameras to record the sparks in the spark chambers; He contributed to the success of NA1 and NA7, where he became heavily involved in the electronic trigger systems; He was responsible for the second level trigger system for the ALEPH detector and spent five years leading a team that designed and built the system, which ran for twelve years with only minor interventions. Following ALEPH he tur...

  1. Stirring Strongly Coupled Plasma

    CERN Document Server

    Fadafan, Kazem Bitaghsir; Rajagopal, Krishna; Wiedemann, Urs Achim

    2009-01-01

    We determine the energy it takes to move a test quark along a circle of radius L with angular frequency w through the strongly coupled plasma of N=4 supersymmetric Yang-Mills (SYM) theory. We find that for most values of L and w the energy deposited by stirring the plasma in this way is governed either by the drag force acting on a test quark moving through the plasma in a straight line with speed v=Lw or by the energy radiated by a quark in circular motion in the absence of any plasma, whichever is larger. There is a continuous crossover from the drag-dominated regime to the radiation-dominated regime. In the crossover regime we find evidence for significant destructive interference between energy loss due to drag and that due to radiation as if in vacuum. The rotating quark thus serves as a model system in which the relative strength of, and interplay between, two different mechanisms of parton energy loss is accessible via a controlled classical gravity calculation. We close by speculating on the implicati...

  2. Strong-interaction nonuniversality

    International Nuclear Information System (INIS)

    Volkas, R.R.; Foot, R.; He, X.; Joshi, G.C.

    1989-01-01

    The universal QCD color theory is extended to an SU(3) 1 direct product SU(3) 2 direct product SU(3) 3 gauge theory, where quarks of the ith generation transform as triplets under SU(3)/sub i/ and singlets under the other two factors. The usual color group is then identified with the diagonal subgroup, which remains exact after symmetry breaking. The gauge bosons associated with the 16 broken generators then form two massive octets under ordinary color. The interactions between quarks and these heavy gluonlike particles are explicitly nonuniversal and thus an exploration of their physical implications allows us to shed light on the fundamental issue of strong-interaction universality. Nonuniversality and weak flavor mixing are shown to generate heavy-gluon-induced flavor-changing neutral currents. The phenomenology of these processes is studied, as they provide the major experimental constraint on the extended theory. Three symmetry-breaking scenarios are presented. The first has color breaking occurring at the weak scale, while the second and third divorce the two scales. The third model has the interesting feature of radiatively induced off-diagonal Kobayashi-Maskawa matrix elements

  3. Lewis Structures Are Models for Predicting Molecular Structure, Not Electronic Structure

    Science.gov (United States)

    Purser, Gordon H.

    1999-07-01

    This article argues against a close relationship between Lewis dot structures and electron structure obtained from quantum mechanical calculations. Lewis structures are a powerful tool for structure prediction, though they are classical models of bonding and do not predict electronic structure. The "best" Lewis structures are those that, when combined with the VSEPR model, allow the accurate prediction of molecular properties, such as polarity, bond length, bond angle, and bond strength. These structures are achieved by minimizing formal charges within the molecule, even if it requires an expanded octet on atoms beyond the second period. Lewis structures that show an expanded octet do not imply full d-orbital involvement in the bonding. They suggest that the presence of low-lying d-orbitals is important in producing observed molecular structures. Based on this work, the presence of electron density, not a large separation in charge, is responsible for the short bond lengths and large angles in species containing nonmetal atoms from beyond the second period. This result contradicts results obtained from natural population analysis, a method that attempts to derive Lewis structures from molecular orbital calculations.

  4. Stochastic Modeling of Rainfall in Peninsular Malaysia Using Bartlett Lewis Rectangular Pulses Models

    Directory of Open Access Journals (Sweden)

    Ibrahim Suliman Hanaish

    2011-01-01

    Full Text Available Three versions of Bartlett Lewis rectangular pulse rainfall models, namely, the Original Bartlett Lewis (OBL, Modified Bartlett Lewis (MBL, and 2N-cell-type Bartlett Lewis model (BL2n, are considered. These models are fitted to the hourly rainfall data from 1970 to 2008 obtained from Petaling Jaya rain gauge station, located in Peninsular Malaysia. The generalized method of moments is used to estimate the model parameters. Under this method, minimization of two different objective functions which involve different weight functions, one weight is inversely proportional to the variance and another one is inversely proportional to the mean squared, is carried out using Nelder-Mead optimization technique. For the purpose of comparison of the performance of the three different models, the results found for the months of July and November are used for illustration. This performance is assessed based on the goodness of fit of the models. In addition, the sensitivity of the parameter estimates to the choice of the objective function is also investigated. It is found that BL2n slightly outperforms OBL. However, the best model is the Modified Bartlett Lewis MBL, particularly when the objective function considered involves weight which is inversely proportional to the variance.

  5. Designation of highly efficient catalysts for one pot conversion of glycerol to lactic acid

    Science.gov (United States)

    Tao, Meilin; Dan Zhang; Guan, Hongyu; Huang, Guohui; Wang, Xiaohong

    2016-07-01

    Production of lactic acid from glycerol is a cascade catalytic procedure using multifunctional catalysts combined with oxidative and acidic catalytic sites. Therefore, a series of silver-exchanged phosphomolybdic acid catalysts (AgxH3-xPMo12O40, x = 1 ~ 3, abbreviated as AgxPMo) was designed and applied in glycerol oxidation with O2 as an oxidant to produce lactic acid (LA) without adding any base. Among all, total silver exchanged phosphomolybdic acid (Ag3PMo) was found to be the most active one with LA selectivity of 93% at 99% conversion under mild conditions of 5 h at 60 °C. The exceptionally high efficiency was contributed to the generation of strong Lewis acid sites, enhanced redox potentials and water-tolerance. More importantly, Ag3PMo was tolerant in crude glycerol from biodiesel production. And the reaction mechanism was also discussed. Meanwhile, Ag3PMo acted as a heterogeneous catalyst for 12 recycles without loss of activity.

  6. Strong expectations cancel locality effects: evidence from Hindi.

    Directory of Open Access Journals (Sweden)

    Samar Husain

    Full Text Available Expectation-driven facilitation (Hale, 2001; Levy, 2008 and locality-driven retrieval difficulty (Gibson, 1998, 2000; Lewis & Vasishth, 2005 are widely recognized to be two critical factors in incremental sentence processing; there is accumulating evidence that both can influence processing difficulty. However, it is unclear whether and how expectations and memory interact. We first confirm a key prediction of the expectation account: a Hindi self-paced reading study shows that when an expectation for an upcoming part of speech is dashed, building a rarer structure consumes more processing time than building a less rare structure. This is a strong validation of the expectation-based account. In a second study, we show that when expectation is strong, i.e., when a particular verb is predicted, strong facilitation effects are seen when the appearance of the verb is delayed; however, when expectation is weak, i.e., when only the part of speech "verb" is predicted but a particular verb is not predicted, the facilitation disappears and a tendency towards a locality effect is seen. The interaction seen between expectation strength and distance shows that strong expectations cancel locality effects, and that weak expectations allow locality effects to emerge.

  7. Some thiazine dyes as redox indicators in the estimations of U(VI), Mo(VI), V(V), Cr(VI) and Cu(II) with Fe(II) in strong phosphoric acid medium

    International Nuclear Information System (INIS)

    Krishna Murty, N.; Satyanarayana, V.

    1977-01-01

    U(VI) and Mo(VI) in 11.5-12.5M, Cr(VI) in 8.5 10.3M and V(V) and V(IV) in 10.5 12.0M phosphoric acid medium can be estimated with Fe(II) visually using azure A, azure B, azure C, toluidine blue and new methylene blue. (author)

  8. NASA Lewis Helps Develop Advanced Saw Blades for the Lumber Industry

    Science.gov (United States)

    1998-01-01

    NASA Lewis Research Center's Structures and Material Divisions are centers of excellence in high-temperature alloys for aerospace applications such as advanced aircraft and rocket engines. Lewis' expertise in these fields was enlisted in the development of a new generation of circular sawblades for the lumber industry to use in cutting logs into boards. The U.S. Department of Agriculture's (USDA) Forest Products Laboratory and their supplier had succeeded in developing a thinner sawblade by using a nickel-based alloy, but they needed to reduce excessive warping due to residual stresses. They requested assistance from Lewis' experts, who successfully eliminated the residual stress problem and increased blade strength by over 12 percent. They achieved this by developing an innovative heat treatment based on their knowledge of nickel-based superalloys used in aeropropulsion applications.

  9. Robot-assisted Ivor-Lewis esophagectomy with intrathoracic robot-sewn anastomosis.

    Science.gov (United States)

    Jin, Runsen; Xiang, Jie; Han, Dingpei; Zhang, Yajie; Li, Hecheng

    2017-11-01

    This video clip demonstrated a performance of robot-assisted Ivor-Lewis esophagectomy with intrathoracic robot-sewn anastomosis. The patient had an esophageal mass located approximately 33 cm away from incisor, and robot-assisted Ivor-Lewis esophagectomy was applied for him. Importantly, a double-layer esophago-gastric anastomosis was made by robotic hand-sewn suture. Our early experience demonstrated that the robot-sewn intrathoracic anastomosis is feasible and safe with a lower complication rate and the absence of anastomotic leakage.

  10. Anatomy of an organizational change effort at the Lewis Research Center

    Science.gov (United States)

    Hawker, James R.; Dali, Richard S.

    1988-01-01

    By 1979, after a long decline following the end of the Apollo program, the Lewis Research Center found its very existence endangered because it was not doing the kind of research that could attract funding at the time. New management under Andrew J. Stofan applied a program of strategic planning, participative management, and consensus decision making. A corporate-cultural change was effected which enabled Lewis to commit itself to four fundable research and development projects. Morale-building and training programs which were essential to this change are described.

  11. Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination.

    Science.gov (United States)

    Dakarapu, Udaya Sree; Bokka, Apparao; Asgari, Parham; Trog, Gabriela; Hua, Yuanda; Nguyen, Hiep H; Rahman, Nawal; Jeon, Junha

    2015-12-04

    A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel.

  12. The Birkhoff-Lewis Fixed Point Theorem and a Conjecture of V. I. Arnold.

    Science.gov (United States)

    1983-09-01

    DAAG29 N8 C004 G1/ I 11111. L 28 12.5= 332 1111 L 1. 11.25 1.4 jf1. MiCRCOPY RLSL)LU11N lILr’l CHIARi N-M NAL 1 AN AL AA MRC Technical Summary Report...2569 THE BIRKHOFF-LEWIS FIXED POINT THEOREM AND A CONJECTURE OF V. I. ARNOLD Charles C. Conley and Eduard Zehnder ’Z Mathematics Research Center...UNIVERSITY OF WISCONSIN - MADISON MATHEMATICS RESEARCH CENTER THE BIRKHOFF-LEWIS FIXED POINT THEOREM AND A CONJECTURE OF V. I. ARNOLD Charles C. Conley and

  13. NASA Lewis Launch Collision Probability Model Developed and Analyzed

    Science.gov (United States)

    Bollenbacher, Gary; Guptill, James D

    1999-01-01

    There are nearly 10,000 tracked objects orbiting the earth. These objects encompass manned objects, active and decommissioned satellites, spent rocket bodies, and debris. They range from a few centimeters across to the size of the MIR space station. Anytime a new satellite is launched, the launch vehicle with its payload attached passes through an area of space in which these objects orbit. Although the population density of these objects is low, there always is a small but finite probability of collision between the launch vehicle and one or more of these space objects. Even though the probability of collision is very low, for some payloads even this small risk is unacceptable. To mitigate the small risk of collision associated with launching at an arbitrary time within the daily launch window, NASA performs a prelaunch mission assurance Collision Avoidance Analysis (or COLA). For the COLA of the Cassini spacecraft, the NASA Lewis Research Center conducted an in-house development and analysis of a model for launch collision probability. The model allows a minimum clearance criteria to be used with the COLA analysis to ensure an acceptably low probability of collision. If, for any given liftoff time, the nominal launch vehicle trajectory would pass a space object with less than the minimum required clearance, launch would not be attempted at that time. The model assumes that the nominal positions of the orbiting objects and of the launch vehicle can be predicted as a function of time, and therefore, that any tracked object that comes within close proximity of the launch vehicle can be identified. For any such pair, these nominal positions can be used to calculate a nominal miss distance. The actual miss distances may differ substantially from the nominal miss distance, due, in part, to the statistical uncertainty of the knowledge of the objects positions. The model further assumes that these position uncertainties can be described with position covariance matrices

  14. Unraveling the Complexities: An Investigation of the Factors That Induce Load in Chemistry Students Constructing Lewis Structures

    Science.gov (United States)

    Tiettmeyer, Jessica M.; Coleman, Amelia F.; Balok, Ryan S.; Gampp, Tyler W.; Duffy, Patrick L.; Mazzarone, Kristina M.; Grove, Nathaniel P.

    2017-01-01

    Mastering the ability to construct and manipulate Lewis structures is an important first step along the journey to reaching representational competence. Lewis structures serve as a convenient organizational scheme that can help students to scaffold their chemical knowledge and help them to apply it to predict a variety of physical and chemical…

  15. Lewis acidic (choline chloride. 3ZnCl 2) ionic liquid: A green and ...

    Indian Academy of Sciences (India)

    Abstract. A green and convenient procedure for the one-pot multicomponent synthesis of 4-((3-indolyl)(aryl)methyl)-N,N-dimethylanilines using (choline chloride.3ZnCl2) ionic liquid as catalyst, at 100°C and under solvent-free condition is described. Utilizing environmentally benign reagents, elimination of organic solvents, ...

  16. Chemistry of N-F Containing HEDM Materials and on Lewis Acidity of LiF

    National Research Council Canada - National Science Library

    Vij, Vandana

    2000-01-01

    .... In order to prepare other more stable N5(+) salts for application as high energy density material, it was necessary to prepare the corresponding precursors in an efficient manner and in large quantities...

  17. Lewis Acid-Base Properties of a Low Carbon Aluminium Killed Steel ...

    African Journals Online (AJOL)

    NJD

    a particular use.7–9 Low carbon aluminium killed (LCAK) steel. (steel deoxidized with aluminium in order to reduce the oxygen content to a minimum so that no reaction occurs between carbon and oxygen during solidification) was considered. This type of steel is used mostly by the packaging industry. Organic coatings.

  18. History of the application of the generalized Lewis acid-base theory to metals

    International Nuclear Information System (INIS)

    Brewer, L.

    1988-11-01

    The history of my experiences with intermetallics has been found useful by students seeking my advice on which directions in science they should be emphasizing. In response to their question, I point to a mobile in my office consisting of seven hands pointing in different directions. Science comes up with so many unexpected developments that one's education should have a broad enough base to allow one to branch out in any direction to take advantage of unexpected opportunities. My historical presentation will be a personal account that I hope will serve as a guide to students. There have been many unexpected abrupt changes in my research

  19. Lewis acidic (choline chloride.3ZnCl2) ionic liquid: A green and ...

    Indian Academy of Sciences (India)

    agents17,18 and are an integral part of many bioactive compounds, prodrugs and pharmaceuticals.19–21 Tri- arylmethanes containing indole nucleus are of much importance as they are widely distributed in nature and used in drug design.22–24 The principle synthetic avenue to triarylmethanes comprises a double ...

  20. Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis.

    Science.gov (United States)

    McKinty, Adam M; Stephan, Douglas W

    2016-03-07

    The series of tridentate complexes of Ru-alkylidenes (L)Ru(CHPh)(SCH2CH2)2E (E = O, L = SIMes 1, PCy3 2, E = S, L = SIMes 3, PCy3 4; E = PPh 7, L = PCy3), (L)Ru(CHPh)(SC6H4)2S (L = SIMes 5, PCy3 6), (L)Ru(CHPh) (OCH2CH2)2O (L = SIMes 8, PCy3 9) were prepared and shown to react with one equivalent of BCl3 to give the complexes (L)Ru(CHPh)Cl[E(CH2CH2S)2BCl2] (E = O, L = SIMes 10, PCy3 11, E = S, L = SIMes 12a/b, PCy3 13, E = PPh, L = PCy3 16) and (L)Ru(CHPh)(SC6H4)2O (L = SIMes 14, PCy3 15). In the case of 1 and 2 reaction with two equivalents of BCl3 affording the corresponding cation via chloride abstraction. These cations coordinate MeCN to give the six coordinate Ru cation salts [(L)Ru(CHPh)- (NCMe)(O(CH2CH2S)2BCl2)][BCl4] L = SIMes 17, PCy3 18). The generated five coordinate cations derived from 2-9 via addition of two equivalents of BCl3 were evaluated in standard preliminary tests for olefin metathesis catalysis.

  1. Lewis acidic (choline chloride.3ZnCl2) ionic liquid: A green and ...

    Indian Academy of Sciences (India)

    In the present era of chemical synthesis, avoidance of toxic solvents and reagents, reduction of waste and cre- ating reusable reaction media are the key interests of synthetic organic chemists world over.1,2 In this con- text, ionic liquids are the versatile alternative, as a result of their green credentials such as undetectable ...

  2. An N-heterocyclic carbene/Lewis acid strategy for the stereoselective synthesis of spirooxindole lactones.

    Science.gov (United States)

    Dugal-Tessier, Julien; O'Bryan, Elizabeth A; Schroeder, Thomas B H; Cohen, Daniel T; Scheidt, Karl A

    2012-05-14

    A cooperative catalysis approach for the enantioselective formal [3+2] addition of α,β-unsaturated aldehydes to isatins has been developed. Homoenolate annulations of β-aryl enals catalyzed by an N-heterocyclic carbene (NHC) require the addition of lithium chloride for high levels of enantioselectivity. This NHC-catalyzed annulation has been used for the total synthesis of maremycin B. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Homogeneous and Supported Niobium Catalysts as Lewis Acid and Radical Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wayne Tikkanen

    2006-12-31

    The synthesis of tetrachlorotetraphenylcyclopentadienyl group 5 metal complexes has been accomplished through two routes, one a salt metathesis with lithiumtetraphenylcyclopentadiende and the other, reaction with trimethyltintetraphenylcyclopentadiene. The reactants and products have been characterized by {sup 1}H and {sup 13}C({sup 1}H) NMR spectroscopy. The niobium complex promotes the silylcyanation of butyraldehyde. The grafting of metal complexes to silica gel surfaces has been accomplished using tetrakisdimethylamidozirconium as the metal precursor. The most homogeneous binding as determined by CP-MAS {sup 13}C NMR and infrared spectroscopy was obtained with drying at 500 C at 3 mtorr vacuum. The remaining amido groups can be replaced by reaction with alcohols to generate surface bound metal alkoxides. These bound catalysts promote silylcyanation of aryl aldehydes and can be reused three times with no loss of activity.

  4. Methanofullerene-Based Palladium Bis(amino)aryl Complexes and Applications in Lewis Acid Catalysis

    NARCIS (Netherlands)

    Koten, G. van; Meijer, M.D.; Ronde, N.; Vogt, D.; Klink, G.P.M. van

    2001-01-01

    Synthetic routes have been developed for the attachment of palladium(II) bis(amino)aryl (NCN or C6H2{CH2NMe2}2-2,6)- complexes to C60. Using diazo and Bingel addition reactions, various methanofullerene NCN-SiMe3 compounds (C60-L-NCN-SiMe3, L = C(Me), C(CO2Et)CO2CH2, and C(Me)C6H4CC) have been

  5. Design and Performance of Rigid Nanosize Multimetallic Cartwheel Pincer Compounds as Lewis-Acid Catalysts

    NARCIS (Netherlands)

    Koten, G. van; Dijkstra, H.P.; Meijer, M.D.; Patel, J.; Kreiter, R.; Klink, G.P.M. van; Lutz, M.H.; Spek, A.L.; Canty, A.J.

    2001-01-01

    Novel strategies for the preparation of rigid cartwheel pincer metal complexes have been developed. The aromatic backbone of these materials ensures a high rigidity, which is expected to be important for a high retention when these multimetallic nanosize complexes are applied as homogeneous

  6. Method for separating constituents from solution employing a recyclable Lewis acid metal-hydroxy gel

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, D.H.

    1995-12-31

    This invention permits radionuclides, heavy metals, and organics to be extracted from solution by scavenging them with an amorphous gel. In the preferred embodiment, a contaminated solution (e.g. from soil washing, decontamination, or groundwater pumping) is transferred to a reaction vessel. The contaminated solution is contacted by the sequestering reagent which might contain for example, aluminate and EDTA anions in a 2.5 M NaOH solution. The pH of the reagent bearing solution is lowered on contact with the contaminated solution, or for example by bubbling carbon dioxide through it, causing an aluminum hydroxide gel to precipitate as the solution drops below the range of 1.8 to 2.5 molar NaOH (less than pH 14). This precipitating gel scavenges waste contaminants as it settles through solution leaving a clean supernatant which is then separated from the gel residue by physical means such as centrifugation, or simple settling. The gel residue containing concentrated contaminants is then redissolved releasing contaminants for separations and processing. This is a critical point: the stabilized gel used in this invention is readily re-dissolved by merely increasing the pH above the gels phase transition to aqueous anions. Thus, concentrated contaminants trapped in the gel can be released for convenient separation from the sequestering reagent, and said reagent can then be recycled.

  7. Reduction of RPT6/S8 (a Proteasome Component) and Proteasome Activity in the Cortex is Associated with Cognitive Impairment in Lewy Body Dementia.

    Science.gov (United States)

    Alghamdi, Amani; Vallortigara, Julie; Howlett, David R; Broadstock, Martin; Hortobágyi, Tibor; Ballard, Clive; Thomas, Alan J; O'Brien, John T; Aarsland, Dag; Attems, Johannes; Francis, Paul T; Whitfield, David R

    2017-01-01

    Lewy body dementia is the second most common neurodegenerative dementia and is pathologically characterized by α-synuclein positive cytoplasmic inclusions, with varying amounts of amyloid-β (Aβ) and hyperphosphorylated tau (tau) aggregates in addition to synaptic loss. A dysfunctional ubiquitin proteasome system (UPS), the major proteolytic pathway responsible for the clearance of short lived proteins, may be a mediating factor of disease progression and of the development of α-synuclein aggregates. In the present study, protein expression of a key component of the UPS, the RPT6 subunit of the 19S regulatory complex was determined. Furthermore, the main proteolytic-like (chymotrypsin- and PGPH-) activities have also been analyzed. The middle frontal (Brodmann, BA9), inferior parietal (BA40), and anterior cingulate (BA24) gyrus' cortex were selected as regions of interest from Parkinson's disease dementia (PDD, n = 31), dementia with Lewy bodies (DLB, n = 44), Alzheimer's disease (AD, n = 16), and control (n = 24) brains. Clinical and pathological data available included the MMSE score. DLB, PDD, and AD were characterized by significant reductions of RPT6 (one-way ANOVA, p < 0.001; Bonferroni post hoc test) in prefrontal cortex and parietal cortex compared with controls. Strong associations were observed between RPT6 levels in prefrontal, parietal cortex, and anterior cingulate gyrus and cognitive impairment (p = 0.001, p = 0.001, and p = 0.008, respectively). These findings highlight the involvement of the UPS in Lewy body dementia and indicate that targeting the UPS may have the potential to slow down or reduce the progression of cognitive impairment in DLB and PDD.

  8. A systematic revision of Baconia Lewis (Coleoptera, Histeridae, Exosternini

    Directory of Open Access Journals (Sweden)

    Michael Caterino

    2013-10-01

    Full Text Available Here we present a complete revision of the species of Baconia. Up until now there have been 27 species assigned to the genus (Mazur, 2011, in two subgenera (Binhister Cooman and Baconia s. str., with species in the Neotropical, Nearctic, Palaearctic, and Oriental regions. We recognize all these species as valid and correctly assigned to the genus, and redescribe all of them. We synonymize Binhister, previously used for a polyphyletic assemblage of species with varied relationships in the genus. We move four species into Baconia from other genera, and describe 85 species as new, bringing the total for the genus to 116 species. We divide these into 12 informal species groups, leaving 13 species unplaced to group. We present keys and diagnoses for all species, as well as habitus photos and illustrations of male genitalia for nearly all. The genus now contains the following species and species groups: Baconia loricata group [B. loricata Lewis, 1885, B. patula Lewis, 1885, B. gounellei (Marseul, 1887a, B. jubaris (Lewis, 1901, B. festiva (Lewis, 1891, B. foliosoma sp. n., B. sapphirina sp. n., B. furtiva sp. n., B. pernix sp. n., B. applanatis sp. n., B. disciformis sp. n., B. nebulosa sp. n., B. brunnea sp. n.], B. godmani group [B. godmani (Lewis, 1888, B. venusta (J. E. LeConte, 1845, B. riehli (Marseul, 1862, comb. n., B. scintillans sp. n., B. isthmia sp. n., B. rossi sp. n., B. navarretei sp. n., B. maculata sp. n., B. deliberata sp. n., B. excelsa sp. n., B. violacea (Marseul, 1853, B. varicolor (Marseul, 1887b, B. dives (Marseul, 1862, B. eximia (Lewis, 1888, B. splendida sp. n., B. jacinta sp. n., B. prasina sp. n., B. opulenta sp. n., B. illustris (Lewis, 1900, B. choaspites (Lewis, 1901, B. lewisi Mazur, 1984], B. salobrus group [B. salobrus (Marseul, 1887b, B. turgifrons sp. n., B. crassa sp. n., B. anthracina sp. n., B. emarginata sp. n., B. obsoleta sp. n.], B. ruficauda group [B. ruficauda sp. n., B. repens sp. n.], B. angusta group [B

  9. Sialyl Lewis x expression in cervical scrapes of premalignant lesions

    Indian Academy of Sciences (India)

    Sialylated oligosaccharides of glycoproteins and glycolipids have been implicated in tumour progression and metastases. Altered expression of glycosidic antigens has been reported in cervical cancer. In cervix premalignant lesions, an increased expression of sialic acid has been reported. In the present study we ...

  10. Stress and Burden among Caregivers of Patients with Lewy Body Dementia

    Science.gov (United States)

    Leggett, Amanda N.; Zarit, Steven; Taylor, Angela; Galvin, James E.

    2011-01-01

    Purpose: Patients with Lewy body dementia (LBD) may present a unique set of symptoms and challenges to family caregivers compared with other types of dementia. Prominent difficulties include motor impairment, activities of daily living (ADLs) disability, recurrent behavioral and emotional problems (BEPs), and diagnostic difficulties. These…

  11. 76 FR 62835 - Notice of Inventory Completion: Fort Lewis College, Durango, CO

    Science.gov (United States)

    2011-10-11

    ... found along Rim Drive (County Road 239), near the Fort Lewis College Campus on City of Durango land... context is a Basketmaker III (7th century A.D.) pithouse, based on architecture, artifacts, and non... present. The temporal context of the site is the Pueblo I period (A.D. 700- 840) based on other artifacts...

  12. Daniel Day-Lewis lihvis Oscari-rolli neli aastat / Triin Tael

    Index Scriptorium Estoniae

    Tael, Triin

    2008-01-01

    Paul Thomas Andersoni Upton Sinclairi "Õli" järgi lavastatud "Veri hakkab voolama" ("There Will Be Blood"), peaosas Daniel Day-Lewis : Ameerika Ühendriigid 2007. Näitleja võitis oma rolliga parima meespeaosatäitja Oscari. Tema tööst rolli(de)ga

  13. Highlighting High Performance: Adam Joseph Lewis Center for Environmental Studies, Oberlin College, Oberlin, Ohio

    Energy Technology Data Exchange (ETDEWEB)

    2002-11-01

    Oberlin Colleges Adam Joseph Lewis Center for Environmental Studies is a high-performance building featuring an expansive photovoltaic system and a closed-loop groundwater heat pump system. Designers incorporated energy-efficient components and materials that are local, non-toxic, and durable.

  14. Highlighting High Performance Buildings: Adam Joseph Lewis Center for Environmental Studies

    Energy Technology Data Exchange (ETDEWEB)

    None

    2002-11-01

    Oberlin College's Adam Joseph Lewis Center for Environmental Studies is a high-performance building featuring an expansive photovoltaic system and a closed-loop groundwater heat pump system. Designers incorporated energy-efficient components and materials that are local, non-toxic, and durable.

  15. Curcumin reduces trabecular and cortical bone in naive and Lewis lung carcinoma-bearing mice

    Science.gov (United States)

    The present study investigated the effects of dietary supplementation with curcumin on bone microstructural changes in female C57BL/6 mice in the presence or absence of Lewis lung carcinoma. Morphometric analysis showed that in tumor-bearing mice curcumin at 2% and 4% dietary levels (w/w) significa...

  16. Macrophages in the retina of normal Lewis rats and their dynamics after injection of lipopolysaccharide

    NARCIS (Netherlands)

    Yang, P.; de Vos, A. F.; Kijlstra, A.

    1996-01-01

    To investigate the density, distribution, and morphology of macrophages (bone marrow-derived microglia) and major histocompatibility complex (MHC) class II-positive cells in the retina of Lewis rats and the dynamics of these cells after systemic lipopolysaccharide (LPS) injection.

  17. Tolerance controls encephalitogenicity of αB-crystallin in the Lewis rat

    NARCIS (Netherlands)

    Stipdonk, M.J.B. van; Willems, A.A.; Plomp, A.C.; Noort, J.M. van; Boog, C.J.P.

    2000-01-01

    The myelin-associated protein, αB-crystallin, is considered a candidate autoantigen in multiple sclerosis (MS). In the present study, we examined the potential of αB-crystallin to induce experimental autoimmune encephalomyelitis (EAE) in Lewis rats. Attempts to induce EAE with either bovine, rat or

  18. Elvin-Lewis Afr J Tradit Complement Altern Med. (2011) 8(S):13-26 13

    African Journals Online (AJOL)

    AJTCAM

    DEREPLICATIONS CAN AMPLIFY THE EXTENT AND WORTH OF TRADITIONAL. PHARMACOPEIAS. Memory Elvin-Lewis. Washington University, Box 1137 ... more likely to be viral in origin and the color and consistency of fecal excrement is often indicative of the cause of the problem .... would impact on such endeavors.

  19. Life on the Fringe: The Early Writings of Lewis Nkosi and Nat Nakasa1

    African Journals Online (AJOL)

    One evening in the late 1950s, Lewis Nkosi and his friend Nat Nakasa were walking through downtown Johannesburg when, as both later recalled, they decided to stop into a whites-only restaurant called The Texan. They ordered their coffees at the bar, knowing that the American man behind the counter expected them to ...

  20. Lewis Nkosi: A Fragile Soul's Quest for Home | Gall | English in Africa

    African Journals Online (AJOL)

    Lewis Nkosi left South Africa in 1961 on a permanent exit visa on his way to study at Harvard as a Nieman Fellow. During his seventy-three years, he lived in England, America, Zambia, Poland, and Switzerland, and he transitioned from denying homesickness (because he had no home) to feeling it acutely (because he had ...

  1. Sodium fusidate (fusidin) ameliorates the course of monophasic experimental allergic encephalomyelitis in the Lewis rat

    DEFF Research Database (Denmark)

    Di Marco, R; Puglisi, G; Papaccio, G

    2001-01-01

    We have evaluated the effect of the immunosuppressant sodium fusidate (fusidin) on the course of acute monophasic experimental encephalomyelitis (EAE) in male Lewis rats. Prophylactic treatment with fusidin, 80 or 120 mg/kg bd wt., markedly ameliorated the course of the disease in rats immunized...

  2. TREATMENT OF ACUTE EXPERIMENTAL ALLERGIC ENCEPHALOMYELITIS IN THE LEWIS RAT WITH THE SEX-HORMONE PROGESTERONE

    NARCIS (Netherlands)

    TROOSTER, WJ; TEELKEN, AW; LIJNEMA, TH; MEYER, E; MINDERHOUD, JM; NIEUWENHUIS, P

    1994-01-01

    In the present study we examined the effect of treatment with progesterone on experimental allergic encephalomyelitis (EAE), an animal model for the human neurological disease multiple sclerosis (MS). Acute EAE was induced in female Lewis rats by immunization with guinea pig spinal cord. From 4 days

  3. Dorothy L. Sayers and C. S. Lewis: Christian Postmodernism beyond Boundaries

    Science.gov (United States)

    Yuasa, Kyoko

    2012-01-01

    Modern critics do not consider science fiction and mystery novels to be "serious reading", but Dorothy L. Sayers and C. S. Lewis questioned the boundaries between "popular" and "serious" literature. Both Christian writers critically discuss the spiritual crisis of the modern world in each fiction genre. This paper…

  4. Random forest to differentiate dementia with Lewy bodies from Alzheimer's disease

    NARCIS (Netherlands)

    Dauwan, Meenakshi; van der Zande, Jessica J.; van Dellen, Edwin; Sommer, Iris E C; Scheltens, Philip; Lemstra, Afina W.; Stam, Cornelis J.

    2016-01-01

    Introduction The aim of this study was to build a random forest classifier to improve the diagnostic accuracy in differentiating dementia with Lewy bodies (DLB) from Alzheimer's disease (AD) and to quantify the relevance of multimodal diagnostic measures, with a focus on electroencephalography

  5. The Brainstem Pathologies of Parkinson's Disease and Dementia with Lewy Bodies

    NARCIS (Netherlands)

    Seidel, Kay; Mahlke, Josefine; Siswanto, Sonny; Krueger, Reijko; Heinsen, Helmut; Auburger, Georg; Bouzrou, Mohamed; Grinberg, Lea T.; Wicht, Helmut; Korf, Horst-Werner; den Dunnen, Wilfred; Rueb, Udo

    Parkinson's disease (PD) and dementia with Lewy bodies (DLB) are among the human synucleinopathies, which show alpha-synuclein immunoreactive neuronal and/or glial aggregations and progressive neuronal loss in selected brain regions (eg, substantia nigra, ventral tegmental area, pedunculopontine

  6. Distribution and habitat of the western gray squirrel (Sciurus griseus) on Fort Lewis, Washington.

    Science.gov (United States)

    L.A. Ryan; A.B. Carey

    1995-01-01

    Sciurus griseus has been accorded a "threatened" status by the Washington Department of Wildlife. Our objectives were to determine the distribution, abundance, and factors limiting the abundance of Sciurus griseus on Fort Lewis. Between June 1992 and August 1993 we conducted walking surveys for squirrels in 169 oak-...

  7. Sodium fusidate (fusidin) ameliorates the course of monophasic experimental allergic encephalomyelitis in the Lewis rat

    DEFF Research Database (Denmark)

    Di Marco, R; Puglisi, G; Papaccio, G

    2001-01-01

    We have evaluated the effect of the immunosuppressant sodium fusidate (fusidin) on the course of acute monophasic experimental encephalomyelitis (EAE) in male Lewis rats. Prophylactic treatment with fusidin, 80 or 120 mg/kg bd wt., markedly ameliorated the course of the disease in rats immunized ...

  8. ABO, Secretor and Lewis histo-blood group systems influence the digestive form of Chagas disease.

    Science.gov (United States)

    Bernardo, Cássia Rubia; Camargo, Ana Vitória Silveira; Ronchi, Luís Sérgio; de Oliveira, Amanda Priscila; de Campos Júnior, Eumildo; Borim, Aldenis Albaneze; Brandão de Mattos, Cinara Cássia; Bestetti, Reinaldo Bulgarelli; de Mattos, Luiz Carlos

    2016-11-01

    Chagas disease, caused by Trypanosoma cruzi, can affect the heart, esophagus and colon. The reasons that some patients develop different clinical forms or remain asymptomatic are unclear. It is believed that tissue immunogenetic markers influence the tropism of T. cruzi for different organs. ABO, Secretor and Lewis histo-blood group systems express a variety of tissue carbohydrate antigens that influence the susceptibility or resistance to diseases. This study aimed to examine the association of ABO, secretor and Lewis histo-blood systems with the clinical forms of Chagas disease. We enrolled 339 consecutive adult patients with chronic Chagas disease regardless of gender (cardiomyopathy: n=154; megaesophagus: n=119; megacolon: n=66). The control group was composed by 488 healthy blood donors. IgG anti-T. cruzi antibodies were detected by ELISA. ABO and Lewis phenotypes were defined by standard hemagglutination tests. Secretor (FUT2) and Lewis (FUT3) genotypes, determined by Polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP), were used to infer the correct histo-blood group antigens expressed in the gastrointestinal tract. The proportions between groups were compared using the χ2 test with Yates correction and Fisher's exact test and the Odds Ratio (OR) and 95% Confidence Interval (95% CI) were calculated. An alpha error of 5% was considered significant with p-values Chagas disease. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. From fruit flies to fallout: Ed Lewis and his science1

    Indian Academy of Sciences (India)

    Administrator

    a major impact on his life. The journal was. Science and the first book was Bertrand ...... ing research into the somatic effects of radiation was not to stop nuclear weapons tests; it was to provide policy makers .... environmental contamination with fission products whether from weapons tests or other sources” (Lewis 1959).

  10. Production of alpha-hydroxy carboxylic acids and esters from higher sugars using tandem catalyst systems

    Energy Technology Data Exchange (ETDEWEB)

    Orazov, Marat; Davis, Mark E.

    2017-11-07

    The present disclosure is directed to methods and composition used in the preparation of alpha-hydroxy carboxylic acids and esters from higher sugars using a tandem catalyst system comprising retro-aldol catalysts and Lewis acid catalysts. In some embodiments, these alpha-hydroxy carboxylic acids may be prepared from pentoses and hexoses. The retro-aldol and Lewis catalysts may be characterized by their respective ability to catalyze a 1,2-carbon shift reaction and a 1,2-hydride shift reaction on an aldose or ketose substrate.

  11. Sodium iron EDTA and ascorbic acid, but not polyphenol oxidase treatment, counteract the strong inhibitory effect of polyphenols from brown sorghum on the absorption of fortification iron in young women.

    Science.gov (United States)

    Cercamondi, Colin I; Egli, Ines M; Zeder, Christophe; Hurrell, Richard F

    2014-02-01

    In addition to phytate, polyphenols (PP) might contribute to low Fe bioavailability from sorghum-based foods. To investigate the inhibitory effects of sorghum PP on Fe absorption and the potential enhancing effects of ascorbic acid (AA), NaFeEDTA and the PP oxidase enzyme laccase, we carried out three Fe absorption studies in fifty young women consuming dephytinised Fe-fortified test meals based on white and brown sorghum varieties with different PP concentrations. Fe absorption was measured as the incorporation of stable Fe isotopes into erythrocytes. In study 1, Fe absorption from meals with 17 mg PP (8·5%) was higher than that from meals with 73 mg PP (3·2%) and 167 mg PP (2·7%; P< 0·001). Fe absorption from meals containing 73 and 167 mg PP did not differ (P= 0·9). In study 2, Fe absorption from NaFeEDTA-fortified meals (167 mg PP) was higher than that from the same meals fortified with FeSO₄ (4·6 v. 2·7%; P< 0·001), but still it was lower than that from FeSO₄-fortified meals with 17 mg PP (10·7%; P< 0·001). In study 3, laccase treatment decreased the levels of PP from 167 to 42 mg, but it did not improve absorption compared with that from meals with 167 mg PP (4·8 v. 4·6%; P= 0·4), whereas adding AA increased absorption to 13·6% (P< 0·001). These findings suggest that PP from brown sorghum contribute to low Fe bioavailability from sorghum foods and that AA and, to a lesser extent, NaFeEDTA, but not laccase, have the potential to overcome the inhibitory effect of PP and improve Fe absorption from sorghum foods.

  12. Strain dependence of adolescent Cannabis influence on heroin reward and mesolimbic dopamine transmission in adult Lewis and Fischer 344 rats.

    Science.gov (United States)

    Cadoni, Cristina; Simola, Nicola; Espa, Elena; Fenu, Sandro; Di Chiara, Gaetano

    2015-01-01

    Adolescent Cannabis exposure has been hypothesized to act as a gateway to opiate abuse. In order to investigate the role of genetic background in cannabinoid-opiate interactions, we studied the effect of Δ(9) -tetrahydrocannabinol (THC) exposure of adolescent Lewis and Fischer 344 rats on the responsiveness of accumbens shell and core dopamine (DA), as monitored by microdialysis, to THC and heroin at adulthood. Heroin reward and reinstatement by heroin priming were studied by conditioned place preference (CPP) and cognitive and emotional functions by object recognition, Y maze and elevated plus maze paradigms. THC stimulated shell DA in Lewis but not in Fischer 344 rats. Adolescent THC exposure potentiated DA stimulant effects of heroin in the shell and core of Lewis and only in the core of Fischer 344 rats. Control Lewis rats developed stronger CPP to heroin and resistance to extinction compared with Fischer 344 strain. In Lewis rats, THC exposure did not affect heroin CPP but potentiated the effect of heroin priming. In Fischer 344 rats, THC exposure increased heroin CPP and made it resistant to extinction. Lewis rats showed seeking reactions during extinction and hedonic reactions in response to heroin priming. Moreover, adolescent THC exposure affected emotional function only in Lewis rats. These observations suggest that long-term effects of Cannabis exposure on heroin addictive liability and emotionality are dependent on individual genetic background. © 2013 Society for the Study of Addiction.

  13. Students' Understanding of Acids/Bases in Organic Chemistry Contexts

    Science.gov (United States)

    Cartrette, David P.; Mayo, Provi M.

    2011-01-01

    Understanding key foundational principles is vital to learning chemistry across different contexts. One such foundational principle is the acid/base behavior of molecules. In the general chemistry sequence, the Bronsted-Lowry theory is stressed, because it lends itself well to studying equilibrium and kinetics. However, the Lewis theory of…

  14. Quantum electrodynamics of strong fields

    International Nuclear Information System (INIS)

    Greiner, W.

    1983-01-01

    Quantum Electrodynamics of Strong Fields provides a broad survey of the theoretical and experimental work accomplished, presenting papers by a group of international researchers who have made significant contributions to this developing area. Exploring the quantum theory of strong fields, the volume focuses on the phase transition to a charged vacuum in strong electric fields. The contributors also discuss such related topics as QED at short distances, precision tests of QED, nonperturbative QCD and confinement, pion condensation, and strong gravitational fields In addition, the volume features a historical paper on the roots of quantum field theory in the history of quantum physics by noted researcher Friedrich Hund

  15. Five novel missense mutations of the Lewis gene (FUT3) in African (Xhosa) and Caucasian populations in South Africa.

    Science.gov (United States)

    Pang, H; Liu, Y; Koda, Y; Soejima, M; Jia, J; Schlaphoff, T; Du Toit, E D; Kimura, H

    1998-06-01

    Five novel missense mutations, viz., C304 A, T370 G, G484 A, G667 A, and G808 A, in the Lewis gene (FUT3) were detected in African (Xhosa) and Caucasian individuals in South Africa. These single base substitutions may result in changes in amino acid residues from Gln102 to Lys in the 304 mutation, Ser124 to Ala in the 370 mutation, Asp162 to Asn in the 484 mutation, Gly223 to Arg in the 667 mutation, and Val270 to Met in the 808 mutation. Out of the five novel mutations identified in this investigation, four new alleles (le484,667, le484,667,808, Le304, and Le370) were determined in the Xhosa population and two new alleles (le202,314,484 and Le304) in the Caucasian population. The determination of alpha(1,3/1,4)fucosyltransferase activity, after transfection of plasmids containing the new alleles into COS7 cells, suggested that alleles le484,667 and le484,667,808 encoded an inactive enzyme, and that alleles Le304 and Le370 encoded a functional enzyme. In addition, we also examined the incidence of five common alleles, Le59, le59,508 le59,1067, le202,314, and le1067 in two populations by the polymerase chain reaction/restriction fragment length polymorphism method and compared differences in the allele frequencies of FUT3 among three ethnic groups (Orientals, Africans, and Caucasians).

  16. Process for the preparation of lactic acid and glyceric acid

    Science.gov (United States)

    Jackson, James E [Haslett, MI; Miller, Dennis J [Okemos, MI; Marincean, Simona [Dewitt, MI

    2008-12-02

    Hexose and pentose monosaccharides are degraded to lactic acid and glyceric acid in an aqueous solution in the presence of an excess of a strongly anionic exchange resin, such as AMBERLITE IRN78 and AMBERLITE IRA400. The glyceric acid and lactic acid can be separated from the aqueous solution. Lactic acid and glyceric acid are staple articles of commerce.

  17. Amyloid-β deposition and regional grey matter atrophy rates in dementia with Lewy bodies.

    Science.gov (United States)

    Sarro, Lidia; Senjem, Matthew L; Lundt, Emily S; Przybelski, Scott A; Lesnick, Timothy G; Graff-Radford, Jonathan; Boeve, Bradley F; Lowe, Val J; Ferman, Tanis J; Knopman, David S; Comi, Giancarlo; Filippi, Massimo; Petersen, Ronald C; Jack, Clifford R; Kantarci, Kejal

    2016-10-01

    Alzheimer's disease pathology frequently coexists with Lewy body disease at autopsy in patients with probable dementia with Lewy bodies. More than half of patients with probable dementia with Lewy bodies have high amyloid-β deposition as measured with 11 C-Pittsburgh compound B binding on positron emission tomography. Biomarkers of amyloid-β deposition precede neurodegeneration on magnetic resonance imaging during the progression of Alzheimer's disease, but little is known about how amyloid-β deposition relates to longitudinal progression of atrophy in patients with probable dementia with Lewy bodies. We investigated the associations between baseline 11 C-Pittsburgh compound B binding on positron emission tomography and the longitudinal rates of grey matter atrophy in a cohort of clinically diagnosed patients with dementia with Lewy bodies (n = 20), who were consecutively recruited to the Mayo Clinic Alzheimer's Disease Research Centre. All patients underwent 11 C-Pittsburgh compound B positron emission tomography and magnetic resonance imaging examinations at baseline. Follow-up magnetic resonance imaging was performed after a mean (standard deviation) interval of 2.5 (1.1) years. Regional grey matter loss was determined on three-dimensional T 1 -weighted magnetic resonance imaging with the tensor-based morphometry-symmetric normalization technique. Linear regression was performed between baseline 11 C-Pittsburgh compound B standard unit value ratio and longitudinal change in regional grey matter volumes from an in-house modified atlas. We identified significant associations between greater baseline 11 C-Pittsburgh compound B standard unit value ratio and greater grey matter loss over time in the posterior cingulate gyrus, lateral and medial temporal lobe, and occipital lobe as well as caudate and putamen nuclei, after adjusting for age (P bodies, higher amyloid-β deposition at baseline is predictive of faster neurodegeneration in the cortex and also in the

  18. Glucagon-like peptide-1 analogue, liraglutide, delays onset and reduces severity of experimental autoimmune encephalitis in Lewis rats

    Directory of Open Access Journals (Sweden)

    Brian DellaValle

    2016-11-01

    Full Text Available AbstractIntroduction: Recent findings indicate that metabolic disturbances are involved in multiple sclerosis (MS pathology and influence the susceptibility to treatment, directing attention towards anti-diabetic drugs such as metformin and pioglitazone. Liraglutide, a drug of the glucagon-like peptide-1 (GLP-1 family, is also anti-diabetic and weight-reducing and is moreover, directly neuroprotective and anti-inflammatory in a broad spectrum of experimental models of brain disease. In this study we investigate the potential for this FDA-approved drug, liraglutide, as a treatment for MS by utilizing the experimental model, experimental autoimmune encephalitis (EAE.Methods: EAE was induced in 30 female Lewis rats that subsequently received twice-daily liraglutide (200 µg/kg s.c. or saline. Healthy controls were included (saline, n=6, liraglutide, n=7. Clinical score and weight were assessed daily by blinded observers. Animals were killed at peak disease severity (day 11 or if exceeding humane endpoint (clinical score ≥4. Protein levels of manganese superoxide dismutase (MnSOD, amyloid precursor protein (APP, and glial fibrillary acidic protein (GFAP were determined.Results: Liraglutide treatment delayed disease onset (group clinical score significantly >0 by two days and markedly reduced disease severity (median clinical score 2 vs. 5; p=0.0003. Fourteen of 15 (93% of vehicle-treated rats reached the humane endpoint (clinical score ≥4 by day 11 compared to 5 of 15 (33% of liraglutide-treated rats (p=0.0004. Liraglutide substantially increased the mitochondrial antioxidant MnSOD (p<0.01 and reduced the neurodegenerative marker APP (p=0.036 in the brain. GFAP levels were not significantly changed with drug treatment (p=0.09Conclusion: We demonstrate, for the first time, that liraglutide treatment delays onset of EAE in Lewis rats and is associated with improved protective capacity against oxidative stress. These data suggest GLP-1 receptor

  19. Strong WW Interaction at LHC

    Energy Technology Data Exchange (ETDEWEB)

    Pelaez, Jose R

    1998-12-14

    We present a brief pedagogical introduction to the Effective Electroweak Chiral Lagrangians, which provide a model independent description of the WW interactions in the strong regime. When it is complemented with some unitarization or a dispersive approach, this formalism allows the study of the general strong scenario expected at the LHC, including resonances.

  20. Strong-back safety latch

    International Nuclear Information System (INIS)

    DeSantis, G.N.

    1995-01-01

    The calculation decides the integrity of the safety latch that will hold the strong-back to the pump during lifting. The safety latch will be welded to the strong-back and will latch to a 1.5-in. dia cantilever rod welded to the pump baseplate. The static and dynamic analysis shows that the safety latch will hold the strong-back to the pump if the friction clamps fail and the pump become free from the strong-back. Thus, the safety latch will meet the requirements of the Lifting and Rigging Manual for under the hook lifting for static loading; it can withstand shock loads from the strong-back falling 0.25 inch