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Sample records for catalytic asymmetric conjugate

  1. Exploring the Catalytic Promiscuity of Phenolic Acid Decarboxylases: Asymmetric, 1,6-Conjugate Addition of Nucleophiles Across 4-Hydroxystyrene.

    Science.gov (United States)

    Payer, Stefan E; Sheng, Xiang; Pollak, Hannah; Wuensch, Christiane; Steinkellner, Georg; Himo, Fahmi; Glueck, Silvia M; Faber, Kurt

    2017-06-19

    The catalytic promiscuity of a ferulic acid decarboxylase from Enterobacter sp. (FDC_ E s) and phenolic acid decarboxylases (PADs) for the asymmetric conjugate addition of water across the C=C bond of hydroxystyrenes was extended to the N-, C- and S-nucleophiles methoxyamine, cyanide and propanethiol to furnish the corresponding addition products in up to 91% ee . The products obtained from the biotransformation employing the most suitable enzyme/nucleophile pairs were isolated and characterized after optimizing the reaction conditions. Finally, a mechanistic rationale supported by quantum mechanical calculations for the highly ( S )-selective addition of cyanide is proposed.

  2. Catalytic enantioselective conjugate addition with Grignard reagents

    NARCIS (Netherlands)

    Lopez, Fernando; Minnaard, Adriaan J.; Feringa, Ben L.

    In this Account, recent advances in catalytic asymmetric conjugate addition of Grignard reagents are discussed. Synthetic methodology to perform highly enantioselective Cu-catalyzed conjugate addition of Grignard reagents to cyclic enones with ee's up to 96% was reported in 2004 from our

  3. Catalytic asymmetric addition of Grignard reagents to alkenyl-substituted aromatic N-heterocycles

    NARCIS (Netherlands)

    Jumde, Ravindra P; Lanza, Francesco; Veenstra, Marieke J; Harutyunyan, Syuzanna R

    2016-01-01

    Catalytic asymmetric conjugate addition reactions represent a powerful strategy to access chiral molecules in contemporary organic synthesis. However, their applicability to conjugated alkenyl-N-heteroaromatic compounds, of particular interest in medicinal chemistry, has lagged behind applications

  4. Asymmetric Conjugate Addition of Grignard Reagents to Pyranones

    NARCIS (Netherlands)

    Mao, Bin; Fananas Mastral, Martin; Feringa, Ben L.

    2013-01-01

    An efficient enantioselective synthesis of lactones was developed based on the catalytic asymmetric conjugate addition (ACA) of alkyl Grignard reagents to pyranones. The use of 2H-pyran-2-one for the first time in the ACA with Grignard reagents allows for a variety of further transformations to

  5. Asymmetric conjugate addition of alkylzirconium reagents to α,β-unsaturated lactones.

    Science.gov (United States)

    Maciver, Eleanor E; Maksymowicz, Rebecca M; Wilkinson, Nancy; Roth, Philippe M C; Fletcher, Stephen P

    2014-06-20

    The asymmetric synthesis of β-substituted lactones by catalytic asymmetric conjugate addition of alkyl groups to α,β-unsaturated lactones is reported. The method uses alkylzirconium nucleophiles prepared in situ from alkenes and the Schwartz reagent. Enantioselective additions to 6- and 7-membered lactones proceed at rt, tolerate a wide variety of functional groups, and are readily scalable. The method was used in a formal asymmetric synthesis of mitsugashiwalactone.

  6. Microscale Synthesis of Chiral Alcohols via Asymmetric Catalytic Transfer Hydrogenation

    Science.gov (United States)

    Peeters, Christine M.; Deliever, Rik; De Vos, Dirk

    2009-01-01

    Synthesis of pure enantiomers is a key issue in industry, especially in areas connected to life sciences. Catalytic asymmetric synthesis has emerged as a powerful and practical tool. Here we describe an experiment on racemic reduction and asymmetric reduction via a catalytic hydrogen transfer process. Acetophenone and substituted acetophenones are…

  7. Catalytic asymmetric alkylation of ketones using organometallic reagents

    NARCIS (Netherlands)

    Madduri, Ashoka V.R.; Harutyunyan, Syuzanna R.; Minnaard, Adriaan J.

    2013-01-01

    The catalytic asymmetric synthesis of tertiary alcohols by the addition of organometallic reagents to ketones is of central importance in organic chemistry. The resulting quaternary stereocentres are difficult to prepare selectively by other means despite their widespread occurrence in natural

  8. Asymmetric Conjugate Addition of α-Cyanoketones to Enones Using Diaminomethylenemalononitrile Organocatalyst.

    Science.gov (United States)

    Nakashima, Kosuke; Noda, Yuta; Hirashima, Shin-Ichi; Koseki, Yuji; Miura, Tsuyoshi

    2018-02-16

    A diaminomethylenemalononitrile organocatalyst efficiently catalyzed the asymmetric conjugate addition of α-cyanoketones to vinyl ketones to give the corresponding 1,5-dicarbonyl compounds, which bear an all-carbon quaternary stereogenic center with high enantioselectivities. This report is the first example of the asymmetric conjugate addition of α-cyanoketones to vinyl ketones using an organocatalyst.

  9. Copper-catalyzed asymmetric conjugate addition of Grignard reagents to cyclic enones

    NARCIS (Netherlands)

    Feringa, Bernard; Badorrey, R; Pena, D; Harutyunyan, [No Value; Minnaard, AJ; Harutyunyan, Syuzanna R.

    2004-01-01

    It is no longer necessary to use dialkylzinc reagents to obtain enantioselectivities >95% in the copper-catalyzed asymmetric conjugate addition of organometallic compounds to cyclic enones. We now report how this can be accomplished by using inexpensive and readily available Grignard reagents.

  10. Catalytic Asymmetric Nitro-Mannich Reactions with a Yb/K Heterobimetallic Catalyst

    Directory of Open Access Journals (Sweden)

    Tatsuya Nitabaru

    2010-03-01

    Full Text Available A catalytic asymmetric nitro-Mannich (aza-Henry reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically active 1,2-diamines.

  11. Catalytic Asymmetric Synthesis of Dihydrofurans and Cyclopentenols with Tertiary Stereocenters

    NARCIS (Netherlands)

    Wu, Zhongtao; Madduri, Ashoka V.R.; Harutyunyan, Syuzanna R.; Minnaard, Adriaan J.

    A new asymmetric synthesis of dihydrofurans and cyclopentenols has been developed and is based on the copper-catalyzed 1,2-addition of Grignard reagents to enones in combination with Sonogashira coupling/cyclization or ring-closing metathesis. By this approach, dihydrofurans with an

  12. Catalytic asymmetric synthesis of acyclic arrays by tandem 1,4-addition-aldol reactions

    NARCIS (Netherlands)

    Howell, Gareth P.; Fletcher, Stephen P.; Geurts, Koen; ter Horst, Bjorn; Feringa, Ben L.

    2006-01-01

    Herein, we report efficient acyclic stereocontrol in tandem 1,4-addition-aldol reactions triggered by catalytic asymmetric organometallic addition. Grignard reagents add to alpha,beta-unsaturated thioesters in a 1,4-fashion and the resulting magnesium enolatesare trapped with aromatic or aliphatic

  13. Recent advances in the catalytic asymmetric synthesis of β-amino acids

    NARCIS (Netherlands)

    Weiner, Barbara; Szymanski, Wiktor; Janssen, Dick B.; Minnaard, Adriaan J.; Feringa, Ben L.

    2010-01-01

    In this critical review, the progress in catalytic asymmetric synthesis of β-amino acids is discussed, covering the literature since 2002. The review treats transition metal catalysis, organocatalysis and biocatalysis and covers the most important synthetic methods, such as hydrogenation, the

  14. A Catalytic, Asymmetric Formal Synthesis of (+)-Hamigeran B

    KAUST Repository

    Mukherjee, Herschel

    2011-03-04

    A concise asymmetric, formal synthesis of (+)-hamigeran B is reported. A Pd-catalyzed, decarboxylative allylic alkylation, employing a trifluoromethylated derivative of t-BuPHOX, is utilized as the enantioselective step to form the critical quaternary carbon center in excellent yield and enantioselectivity. The product is converted in three steps to a late-stage intermediate previously used in the synthesis of hamigeran B.

  15. Direct Catalytic Asymmetric Mannich-Type Reaction of Alkylamides.

    Science.gov (United States)

    Arteaga, Fernando Arteaga; Liu, Zijian; Brewitz, Lennart; Chen, Jianyang; Sun, Bo; Kumagai, Naoya; Shibasaki, Masakatsu

    2016-05-20

    Direct enolate formation coupled with subsequent enantioselective C-C bond formation remains a topic of intense interest in asymmetric catalysis. This methodology is achieved even with low acidic amides without an electron-withdrawing group at the α-position in the context of a Mannich-type reaction. Acetate-, propionate-, and butyrate-type 7-azaindoline amides served as enolate precursors to afford the desired Mannich adducts with high stereoselectivity, and ligand-enabled diastereo-divergency provided access to both anti/syn diastereomers. The facile transformation of the amide moiety ensures the synthetic utility of the Mannich adducts.

  16. Green Synthesis of (R)-Terbutaline for Recyclable Catalytic Asymmetric Transfer Hydrogenation in Ionic Liquids.

    Science.gov (United States)

    Uchimoto, Hitomi; Ikeda, Miki; Tanida, Saori; Ohhashi, Kayo; Chihara, Yoshiko; Shigeta, Takashi; Arimitsu, Kenji; Yamashita, Masayuki; Nishide, Kiyoharu; Kawasaki, Ikuo

    2017-01-01

    We synthesize optically active (R)-terbutaline 2, which is an anti-asthmatic drug, through recyclable catalytic asymmetric transfer hydrogenation (RCATH). Various chloroketones 4 were prepared and RCATH was performed on them. The products exhibit moderate to high enantioselectivity. In particular, the hydrogenation of acyl substituted substrates 4c yields chiral secondary alcohols 5c in good yield and enantioselectivity. Furthermore, (R)-terbutaline 2 can be synthesized in one step from the resulting secondary alcohol 5 without racemization.

  17. Asymmetric rifting, breakup and magmatism across conjugate margin pairs: insights from Newfoundland to Ireland

    Science.gov (United States)

    Peace, Alexander L.; Welford, J. Kim; Foulger, Gillian R.; McCaffrey, Ken J. W.

    2017-04-01

    Continental extension, subsequent rifting and eventual breakup result in the development of passive margins with transitional crust between extended continental crust and newly created oceanic crust. Globally, passive margins are typically classified as either magma-rich or magma-poor. Despite this simple classification, magma-poor margins like the West Orphan Basin, offshore Newfoundland, do exhibit some evidence of localized magmatism, as magmatism to some extent invariably accompanies all continental breakup. For example, on the Newfoundland margin, a small volcanic province has been interpreted near the termination of the Charlie Gibbs Fracture Zone, whereas on the conjugate Irish margin within the Rockall Basin, magmatism appears to be more widespread and has been documented both in the north and in the south. The broader region over which volcanism has been identified on the Irish margin is suggestive of magmatic asymmetry across this conjugate margin pair and this may have direct implications for the mechanisms governing the nature of rifting and breakup. Possible causes of the magmatic asymmetry include asymmetric rifting (simple shear), post-breakup thermal anomalies in the mantle, or pre-existing compositional zones in the crust that predispose one of the margins to more melting than its conjugate. A greater understanding of the mechanisms leading to conjugate margin asymmetry will enhance our fundamental understanding of rifting processes and will also reduce hydrocarbon exploration risk by better characterizing the structural and thermal evolution of hydrocarbon bearing basins on magma-poor margins where evidence of localized magmatism exists. Here, the latest results of a conjugate margin study of the Newfoundland-Ireland pair utilizing seismic interpretation integrated with other geological and geophysical datasets are presented. Our analysis has begun to reveal the nature and timing of rift-related magmatism and the degree to which magmatic asymmetry

  18. Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors

    Directory of Open Access Journals (Sweden)

    Thibault E. Schmid

    2015-12-01

    Full Text Available The copper-catalyzed asymmetric conjugate addition (ACA of nucleophiles onto polyenic Michael acceptors represents an attractive and powerful methodology for the synthesis of relevant chiral molecules, as it enables in a straightforward manner the sequential generation of two or more stereogenic centers. In the last decade, various chiral copper-based catalysts were evaluated in combination with different nucleophiles and Michael acceptors, and have unambiguously demonstrated their usefulness in the control of the regio- and enantioselectivity of the addition. The aim of this review is to report recent breakthroughs achieved in this challenging field.

  19. Nucleoside Phosphate-Conjugates Come of Age: Catalytic Transformation, Polymerase Recognition and Antiviral Properties.

    Science.gov (United States)

    Groaz, Elisabetta; Herdewijn, Piet

    2015-01-01

    Over the past few decades, different types of nucleoside phosphate-conjugates have been under extensive investigation due to their favorable molecular lability with interesting catalytic hydrolysis mechanisms, recognition as polymerase substrates, and especially for their development as antiviral/ anticancer protide therapeutics. The antiviral conjugates such as nucleoside phosphoesters and phosphoramidates that were discovered and developed in the initial years have been well reviewed by the pioneers in the field. In the present review, we will discuss the basic chemical and biological principles behind consideration of some representative structural classes. We will also summarize the chemical and biological properties of some of the more recent analogues that were synthesized and evaluated in our laboratory and by others. This includes new principles for their application as direct substrates of polymerases, nucleobasedependent catalytic and antiviral activity, and a plausible 'prodrug of a prodrug' strategy for tissue/organ-specific targeted drug delivery.

  20. Catalytic Asymmetric Roskamp Reaction of Silyl Diazoalkane: Synthesis of Enantioenriched α-Silyl Ketone.

    Science.gov (United States)

    Kim, Jae Yeon; Kang, Byung Chul; Ryu, Do Hyun

    2017-11-03

    A catalytic enantioselective Roskamp reaction of silyl diazoalkane to synthesize a highly optically active α-silyl ketone from aldehydes is described. In the presence of a chiral oxazaborolidinium ion catalyst, the reaction provides α-chiral silyl ketones with good yields (up to 97%) and high enantioselectivities (up to >99% ee). In addition, a one-pot procedure using an asymmetric Roskamp/reduction strategy gives highly optically active syn-β-hydroxysilane in good yields (up to 94%) with high enantioselectivities (up to 99% ee) and syn stereoselectivities (>20:1).

  1. α-Halo Amides as Competent Latent Enolates: Direct Catalytic Asymmetric Mannich-Type Reaction.

    Science.gov (United States)

    Sun, Bo; Balaji, Pandur Venkatesan; Kumagai, Naoya; Shibasaki, Masakatsu

    2017-06-21

    α-Halogenated carbonyl compounds are susceptible to dehalogenation and thus largely neglected as enolate precursors in catalytic enantioselective C-C bond-forming reactions. By merging the increased stability of the α-C-halogen bond of amides and the direct enolization methodology of the designed amide, we explored a direct catalytic asymmetric Mannich-type reaction of α-halo 7-azaindoline amides with N-carbamoyl imines. All α-halo substituents, α-F, -Cl, -Br, -I amides, were tolerated to provide the Mannich-adducts in a highly stereoselective manner without undesirable dehalogenation. The diastereoselectivity switched intriguingly depending on the substitution pattern of the aromatic imines, which is ascribed to stereochemical differentiation based on the open transition-state model. Functional group interconversion of the 7-azaindoline amide moiety of the Mannich-adducts and further elaboration into a diamide without dehalogenation highlight the synthetic utility of the present protocol for accessing enantioenriched halogenated chemical entities.

  2. Asymmetric synthesis of cyclo-archaeol and beta-glucosyl cyclo-archaeol

    NARCIS (Netherlands)

    Ferrer, Catalina; Fodran, Peter; Barroso, Santiago; Gibson, Robert; Hopmans, Ellen C.; Damste, Jaap Sinninghe; Schouten, Stefan; Minnaard, Adriaan J.

    2013-01-01

    An efficient asymmetric synthesis of cyclo-archaeol and beta-glucosyl cyclo-archaeol is presented employing catalytic asymmetric conjugate addition and catalytic epoxide ring opening as the key steps. Their occurrence in deep sea hydrothermal vents has been confirmed by chromatographic comparison

  3. Conjugate-base-stabilized Brønsted acids: catalytic enantioselective Pictet-Spengler reactions with unmodified tryptamine.

    Science.gov (United States)

    Mittal, Nisha; Sun, Diana X; Seidel, Daniel

    2014-02-07

    A conjugate-base-stabilized Brønsted acid facilitates catalytic enantioselective Pictet-Spengler reactions with unmodified tryptamine. The chiral carboxylic acid catalyst is readily assembled in just two steps and enables the formation of β-carbolines with up to 92% ee. Achiral acid additives or in situ Boc-protection facilitate catalyst turnover.

  4. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.

    2011-02-24

    Contraction action! A simple protocol for the catalytic asymmetric synthesis of highly functionalized γ-quaternary acylcyclopentenes (see schematic) in up to 91 % overall yield and 92 % ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions.

  5. Synthesis of New Chiral Ligands Based on Thiophene Derivatives for Use in Catalytic Asymmetric Oxidation of Sulfides

    International Nuclear Information System (INIS)

    Jeong, Yong Chul; Ahn, Dae Jun; Lee, Woo Sun; Lee, Seung Han; Ahn, Kwang Hyun

    2011-01-01

    We discovered that the vanadium complexes of new Schiff base ligands and prepared from thiophene derivatives efficiently catalyze the asymmetric oxidation of sulfides by hydrogen peroxide to provide sulfoxides with enantioselectivities up to 79% ee and in yields up to 89%. Notably, Schiff base showed better or similar enantioselectivity than the well-studied Schiff base. These results suggest possible applications of Schiff bases derived from and in other catalytic asymmetric reactions. Chiral sulfoxides are important functional groups for various applications. For example, the biological activities of sulfoxide containing drugs such as omeprazole are strongly related to the chirality of the sulfoxide group; for this reason, esomeprazole, the enantiomerically pure form of omeprazole, was later developed. There are several chiral sulfoxide based drugs that have been introduced by the pharmaceutical industry including armodafinil, aprikalim, oxisurane, and ustiloxin. Chiral sulfoxides have also been utilized as chiral auxiliaries in asymmetric syntheses of chiral intermediates

  6. Iterative Cr-mediated catalytic asymmetric allylation to synthesize syn/syn- and anti/anti-1,3,5-triols.

    Science.gov (United States)

    Zhang, Zhiyu; Aubry, Sylvain; Kishi, Yoshito

    2008-07-17

    Iterative use of Cr-mediated catalytic asymmetric allylation could give a simple access to 1,3-polyols. Using syn/syn- and anti/anti-1,3,5-triols as representative examples, the feasibility of this approach is studied, thereby demonstrating that (1) the pre-existing TMS-protected alcohol at the beta-position does not give a significant effect on the Cr-mediated catalytic asymmetric allylation and (2) this synthetic route furnishes the expected syn/syn- and anti/anti-1,3,5-triols at the useful level of asymmetric induction and yield.

  7. NHC-Cu(I) catalysed asymmetric conjugate silyl transfer to unsaturated lactones: application in kinetic resolution.

    Science.gov (United States)

    Pace, Vittorio; Rae, James P; Harb, Hassan Y; Procter, David J

    2013-06-07

    The scope of the asymmetric silyl transfer to unsaturated lactones utilising a C2-symmetric NHC-Cu(I) catalyst has been established and kinetic resolutions mediated by silyl transfer have been used to prepare enantiomerically enriched anti-4,5-disubstituted 5-membered lactones. The method has been exploited in an expedient synthesis of (+)-blastmycinone.

  8. Catalytic Asymmetric Mannich Reaction with N-Carbamoyl Imine Surrogates of Formaldehyde and Glyoxylate.

    Science.gov (United States)

    You, Yang'en; Zhang, Long; Cui, Linfeng; Mi, Xueling; Luo, Sanzhong

    2017-10-23

    N,O-acetals (NOAcs) were developed as bench stable surrogates for N-carbamoyl, (Boc, Cbz and Fmoc) formaldehyde and glyoxylate imines in asymmetric Mannich reactions. The NOAcs can be directly utilized in the chiral primary amine catalyzed Mannich reactions of both acyclic and cyclic β-ketocarbonyls with high yields and excellent stereoselectivity. The current reaction offers a straightforward approach in the asymmetric synthesis of α- or β-amino carbonyls bearing chiral quaternary centers in a practical and highly stereocontrolled manner. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Continuous-flow catalytic asymmetric hydrogenations: Reaction optimization using FTIR inline analysis

    Directory of Open Access Journals (Sweden)

    Magnus Rueping

    2012-02-01

    Full Text Available The asymmetric organocatalytic hydrogenation of benzoxazines, quinolines, quinoxalines and 3H-indoles in continuous-flow microreactors has been developed. Reaction monitoring was achieved by using an inline ReactIR flow cell, which allows fast and convenient optimization of reaction parameters. The reductions proceeded well, and the desired products were isolated in high yields and with excellent enantioselectivities.

  10. Catalytic asymmetric allylation of aliphatic aldehydes by chiral bipyridine N,N'-dioxides

    Czech Academy of Sciences Publication Activity Database

    Hrdina, R.; Boyd, T.; Valterová, Irena; Hodačová, Jana; Kotora, Martin

    -, č. 20 (2008), s. 3141-3144 ISSN 0936-5214 Grant - others:GA MŠk(CZ) LC06070 Program:LC Institutional research plan: CEZ:AV0Z40550506 Keywords : allylations * aldehydes * Lewis base * asymmetric catalysis * solvent effect Subject RIV: CC - Organic Chemistry Impact factor: 2.659, year: 2008

  11. Direct Catalytic Asymmetric Mannich-Type Reaction of α-N3 Amide.

    Science.gov (United States)

    Sun, Zhongdong; Weidner, Karin; Kumagai, Naoya; Shibasaki, Masakatsu

    2015-12-01

    An α-N3 7-azaindoline amide serves as a latent enolate to directly engage in an asymmetric Mannich-type reaction with N-thiophosphinoyl imines by the action of a cooperative catalyst. The thus-obtained highly enantioenriched anti-adduct was transformed into β-amino-α-azido acid in high yield by simple acidic treatment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Catalytic enantioselective conjugate addition of diethylzinc using NiII-DAIB complexes

    NARCIS (Netherlands)

    Jansen, Johan F.G.A.; Feringa, Bernard

    The conjugate addition of diethylzinc to chalcone, catalyzed by a NiII complex of the chiral aminoalcohol (-)-DAIB, resulted in the formation of (R)-1,3-diphenyl-penta-1-one with enantiomeric excess up to 85%.

  13. Asymmetrically Substituted and π-Conjugated 2,2'-Bipyridine Derivatives: Synthesis, Spectroscopy, Computation, and Crystallography.

    Science.gov (United States)

    Bodapati, Ramakrishna; Sarma, Monima; Kanakati, Arunkumar; Das, Samar K

    2015-12-18

    A new series of monosubstituted styryl- and bistyryl-2,2'-bipyridine luminophores (compounds 16-23) have been synthesized via Horner-Wadsworth-Emmons reaction involving a monophosphonate and donor aromatic aldehydes. In the title chromophores, the amino donors are varied between acyclic and cyclic while the alkoxy donors are varied in terms of their number and position. The absorption maxima of these chromophores shift predominantly due to intramolecular charge transfer (ICT) between different donor and acceptor moieties. The title donor-acceptor molecules exhibit intense fluorescence in solution at room temperature, and their emissive behavior has been found to be highly sensitive to solvent polarity. The fluorescence spectra and quantum yields of all the chromophores were recorded in four different solvent media, and the chromophores 16, 17, 19, and 21 exhibit fluorescence in the solid state too. The influence of the nature and position of the donor functionalities in the conjugated backbone of the bipyridine moiety on the electronic absorption properties of the title chromophores (16-23) has been demonstrated, which has further been corroborated by DFT and TD-DFT computation both in gas phase and in solution phase. The crystal structure of compound 18 has been described as a representative member of the family (16-23).

  14. Embedding SAS approach into conjugate gradient algorithms for asymmetric 3D elasticity problems

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hsin-Chu; Warsi, N.A. [Clark Atlanta Univ., GA (United States); Sameh, A. [Univ. of Minnesota, Minneapolis, MN (United States)

    1996-12-31

    In this paper, we present two strategies to embed the SAS (symmetric-and-antisymmetric) scheme into conjugate gradient (CG) algorithms to make solving 3D elasticity problems, with or without global reflexive symmetry, more efficient. The SAS approach is physically a domain decomposition scheme that takes advantage of reflexive symmetry of discretized physical problems, and algebraically a matrix transformation method that exploits special reflexivity properties of the matrix resulting from discretization. In addition to offering large-grain parallelism, which is valuable in a multiprocessing environment, the SAS scheme also has the potential for reducing arithmetic operations in the numerical solution of a reasonably wide class of scientific and engineering problems. This approach can be applied directly to problems that have global reflexive symmetry, yielding smaller and independent subproblems to solve, or indirectly to problems with partial symmetry, resulting in loosely coupled subproblems. The decomposition is achieved by separating the reflexive subspace from the antireflexive one, possessed by a special class of matrices A, A {element_of} C{sup n x n} that satisfy the relation A = PAP where P is a reflection matrix (symmetric signed permutation matrix).

  15. Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

    KAUST Repository

    Pluta, Roman

    2018-02-09

    A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.

  16. CATALYTIC ENANTIOSELECTIVE CONJUGATE ADDITION OF DIETHYLZINC USING NI(II) DAIB COMPLEXES

    NARCIS (Netherlands)

    JANSEN, JFGA; FERINGA, BL

    The conjugate addition of diethylzinc to chalcone, catalyzed by a NiII complex of the chiral amino-alcohol (-)-DAIB, resulted in the formation of (R)-1,3-diphenyl-penta-1-one with enantiomeric excess up to 85%.

  17. Catalytic Asymmetric Synthesis of Fluoroalkyl-Containing Compounds by Three-Component Photoredox Chemistry.

    Science.gov (United States)

    Ma, Jiajia; Xie, Xiulan; Meggers, Eric

    2018-01-02

    Multicomponent reactions allow the construction of molecular complexity in an economical fashion, fluorinated compounds play an important role in pharmaceuticals and agrochemicals, whereas visible light is an abundant and sustainable source of energy for activating chemical transformations. Here we report a visible-light-induced asymmetric three-component fluoroalkylation reaction scheme catalyzed by a chiral-at-rhodium Lewis acid. The photoredox process is mediated by the inexpensive, commercially available organic photoredox mediator 4,4'-difluorobenzil, which upon activation by visible light induces the generation of perfluoroalkyl radicals from their sulfinates via single electron transfer oxidation. The fluorinated radicals are trapped by electron-rich C-C double bonds to deliver α-oxy carbon-centered radicals, followed by a subsequent stereocontrolled reaction with acceptor-substituted alkenes. This three-component fluoroalkylation scheme provides a range of complex fluoroalkyl-containing chiral compounds under dual C-C bond formation with high enantioselectivities (up to 98 % ee) and modest diastereoselectivities (up to 6:1 dr). Excellent diastereoselectivities (up to >38:1:1 dr) for natural chiral compound derivatives are observed. Broad substrate scope (25 examples), excellent functional group tolerance, scalability of the reaction, along with the option to recover the chiral catalyst and photoredox mediator reveal the practicability of this methodology in organic synthesis for the rapid synthesis of fluorinated chiral molecules. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Flavin-cyclodextrin conjugates: effect of the structure on the catalytic activity in enantioselective sulfoxidations

    Czech Academy of Sciences Publication Activity Database

    Hartman, T.; Herzig, Vladimír; Buděšínský, Miloš; Jindřich, J.; Cibulka, R.; Kraus, Tomáš

    2012-01-01

    Roč. 23, 22/23 (2012), s. 1571-1583 ISSN 0957-4166 R&D Projects: GA ČR GA203/09/1919 Grant - others:GA ČR(CZ) GAP207/12/0447 Institutional support: RVO:61388963 Keywords : enzyme mimics * aqueous hydrogen - peroxide * asymmetric sulfide oxidation * kinetic resolution * molecular-oxygen Subject RIV: CC - Organic Chemistry Impact factor: 2.115, year: 2012

  19. Direct Catalytic Asymmetric Mannich-Type Reaction of α- and β-Fluorinated Amides.

    Science.gov (United States)

    Brewitz, Lennart; Arteaga, Fernando Arteaga; Yin, Liang; Alagiri, Kaliyamoorthy; Kumagai, Naoya; Shibasaki, Masakatsu

    2015-12-23

    The last two decades have witnessed the emergence of direct enolization protocols providing atom-economical and operationally simple methods to use enolates for stereoselective C-C bond-forming reactions, eliminating the inherent drawback of the preformation of enolates using stoichiometric amounts of reagents. In its infancy, direct enolization relied heavily on the intrinsic acidity of the latent enolates, and the reaction scope was limited to readily enolizable ketones and aldehydes. Recent advances in this field enabled the exploitation of carboxylic acid derivatives for direct enolization, offering expeditious access to synthetically versatile chiral building blocks. Despite the growing demand for enantioenriched fluorine-containing small molecules, α- and β-fluorinated carbonyl compounds have been neglected in direct enolization chemistry because of the competing and dominating defluorination pathway. Herein we present a comprehensive study on direct and highly stereoselective Mannich-type reactions of α- and β-fluorine-functionalized 7-azaindoline amides that rely on a soft Lewis acid/hard Brønsted base cooperative catalytic system to guarantee an efficient enolization while suppressing undesired defluorination. This protocol contributes to provide a series of fluorinated analogs of enantioenriched β-amino acids for medicinal chemistry.

  20. Catalytic activity control of restriction endonuclease--triplex forming oligonucleotide conjugates.

    Science.gov (United States)

    Silanskas, Arunas; Zaremba, Mindaugas; Sasnauskas, Giedrius; Siksnys, Virginijus

    2012-02-15

    Targeting of individual genes in complex genomes requires endonucleases of extremely high specificity. To direct cleavage at the unique site(s) in the genome, both naturally occurring and artificial enzymes have been developed. These include homing endonucleases, zinc-finger nucleases, transcription activator-like effector nucleases, and restriction or chemical nucleases coupled to a triple-helix forming oligonucleotide (TFO). The desired cleavage has been demonstrated both in vivo and in vitro for several model systems. However, to limit cleavage strictly to unique sites and avoid undesired reactions, endonucleases with controlled activity are highly desirable. In this study we present a proof-of-concept demonstration of two strategies to generate restriction endonuclease-TFO conjugates with controllable activity. First, we combined the restriction endonuclease caging and TFO coupling procedures to produce a caged MunI-TFO conjugate, which can be activated by UV-light upon formation of a triple helix. Second, we coupled TFO to a subunit interface mutant of restriction endonuclease Bse634I which shows no activity due to impaired dimerization but is assembled into an active dimer when two Bse634I monomers are brought into close proximity by triple helix formation at the targeted site. Our results push the restriction endonuclease-TFO conjugate technology one step closer to potential in vivo applications.

  1. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei

    2016-10-13

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

  2. Catalytic asymmetric access to alpha,beta unsaturated delta-lactones through a vinylogous aldol reaction: application to the total synthesis of the Prelog-Djerassi lactone.

    Science.gov (United States)

    Bluet, G; Bazán-Tejeda, B; Campagne, J M

    2001-11-15

    [reaction--see text] A one-step catalytic asymmetric access to alpha,beta unsaturated delta-lactones is described, using a vinylogous Mukaiyama-aldol reaction between a gamma-substituted dienolate and various aldehydes in the presence of Carreira catalyst CuF.(S)-tolBinap. This methodology has been further applied to a straightforward access to the Prelog-Djerassi lactone.

  3. Catalytic asymmetric formation of delta-lactones from unsaturated acyl halides.

    Science.gov (United States)

    Tiseni, Paolo S; Peters, René

    2010-02-22

    Previously unexplored enantiopure zwitterionic ammonium dienolates have been utilized in this work as reactive intermediates that act as diene components in hetero-Diels-Alder reactions (HDAs) with aldehydes to produce optically active delta-lactones, subunits of numerous bioactive products. The dienolates were generated in situ from E/Z mixtures of alpha,beta-unsaturated acid chlorides by use of a nucleophilic quinidine derivative and Sn(OTf)(2) as co-catalyst. The latter component was not directly involved in the cycloaddition step with aldehydes and simply facilitated the formation of the reactive dienolate species. The scope of the cycloaddition was considerably improved by use of a complex formed from Er(OTf)(3) and a simple commercially available norephedrine-derived ligand that tolerated a broad range of aromatic and heteroaromatic aldehydes for a cooperative bifunctional Lewis-acid-/Lewis-base-catalyzed reaction, providing alpha,beta-unsaturated delta-lactones with excellent enantioselectivities. Mechanistic studies confirmed the formation of the dienolate intermediates for both catalytic systems. The active Er(III) complex is most likely a monomeric species. Interestingly, all lanthanides can catalyze the title reaction, but the efficiency in terms of yield and enantioselectivity depends directly on the radius of the Ln(III) ion. Similarly, use of the pseudolanthanides Sc(III) and Y(III) also resulted in product formation, whereas the larger La(III) and other transition metal salts, as well as main group metal salts, proved to be inefficient. In addition, various synthetic transformations of 6-CCl(3)- or 4-silyl-substituted alpha,beta-unsaturated delta-lactones, giving access to a number of valuable delta-lactone building blocks, were investigated.

  4. Catalytic

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi

    2014-03-01

    Full Text Available A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt% were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.

  5. Asymmetric Synthesis of exo-Isobrevicomin and exo-Brevicomin via Conjugated Addition of Primary Alkyl Iodides to a,b-Unsaturated Ketones

    Directory of Open Access Journals (Sweden)

    Sousa Andréa L. de

    2002-01-01

    Full Text Available (--exo-Isobrevicomin (1 and (+-exo-brevicomin (2 are volatile substances produced by males of the beetles Dendroctonus ponderosae, which inhabit pine trees found in the northern hemisphere, frequently causing the death of their host. In order to obtain these aggregation pheromones, which present the 6,8-dioxabicyclo[3.2.1]octane structure, the synthetic strategies utilized in this work had as key steps the Sharpless asymmetric dihydroxylation and the conjugated addition, promoted by the Zn(Cu couple in aqueous medium and accelerated by ultrasound. The conjugated addition of acetonides 13 and 14 to the respective unsaturated ketones (methyl vinyl ketone and ethyl vinyl ketone furnished the adducts 15 and 16. The intramolecular catalyzed cyclization of compounds 15 and 16 with phosphotungstic acid (H3PW12O40 produced exo-isobrevicomin (1 and exo-brevicomin (2.

  6. Solvent dependent asymmetric hydrogenation with self-assembled catalysts: a combined catalytic, NMR- and IR-study.

    Science.gov (United States)

    Shuklov, Ivan A; Dubrovina, Natalia V; Barsch, Enrico; Ludwig, Ralf; Michalik, Dirk; Börner, Armin

    2009-03-28

    For the first time the hydrogen bond based structure of self-aggregated Rh-phosphine complexes in fluorinated alcohols was directly determined, which gives a rationale for the high enantioselectivity observed in the asymmetric hydrogenation.

  7. Catalytic diastereoselective tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts by C-C bond cleavage

    KAUST Repository

    Yang, Wenguo

    2012-02-08

    Through the cleavage of the C-C bond, the first catalytic tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts has been presented. Various S N2′-like C-, S-, and P-allylic compounds could be obtained with exclusive E configuration in good to excellent yields. The Michael product could also be easily prepared by tuning the β-C-substituent group of the α-methylene ester under the same reaction conditions. Calculated relative energies of various transition states by DFT methods strongly support the observed chemoselectivity and diastereoselectivity. © 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  8. Synthesis of (R)-BINOL-Derived (Cyclopentadienone)iron Complexes and Their Application in the Catalytic Asymmetric Hydrogenation of Ketones

    NARCIS (Netherlands)

    Gajewski, Piotr; Renom-Carrasco, Marc; Facchini, Sofia Vailati; Pignataro, Luca; Lefort, Laurent; de Vries, Johannes G.; Ferraccioli, Raffaella; Piarulli, Umberto; Gennari, Cesare

    A family of chiral (cyclopentadienone)iron complexes, featuring an (R)-BINOL-derived backbone, and their application in the asymmetric hydrogenation of ketones are described. The complexes differ from each other in the substituents at the 3,3-positions of the binaphthyl residue (H, OH, OR, OCOR,

  9. A Ligand Structure-Activity Study of DNA-Based Catalytic Asymmetric Hydration and Diels-Alder Reactions

    NARCIS (Netherlands)

    Rosati, F.; Roelfes, J.G.

    A structure-activity relationship study of the first generation ligands for the DNA-based asymmetric hydration of enones and Diels-Alder reaction in water is reported. The design of the ligand was optimized resulting in a maximum ee of 83% in the hydration reaction and 75% in the Diels-Alder

  10. Structure Investigation of Ti(IV)BODOLates Involved in the Catalytic Asymmetric Reduction of Ketones Using Catecholborane

    DEFF Research Database (Denmark)

    Sarvary, Ian; Norrby, Per-Ola; Frejd, Torbjörn

    2004-01-01

    The complexes formed on mixing Ti(OiPr)4 and bicyclo-octanediols (BODOLs) 1 and 2 (1:1) are useful as chiral catalysts in asymmetric reductions and were investigated by 1HNMR-spectroscopy and by computational methods. A consistent picture emerged of head-to-tail dimers being kept together via a T...

  11. Direct Catalytic Asymmetric Mannich-Type Reaction en Route to α-Hydroxy-β-amino Acid Derivatives.

    Science.gov (United States)

    Sun, Bo; Pluta, Roman; Kumagai, Naoya; Shibasaki, Masakatsu

    2018-02-02

    A direct catalytic Mannich-type reaction of α-oxygen-functionalized amides was achieved. The use of 7-azaindoline amide was crucial to facilitate direct enolization and subsequent stereoselective addition to imines in a cooperative catalytic system comprising a soft Lewis acid and Brønsted base. The operationally simple room-temperature protocol furnished a syn-Mannich adduct with high stereoselectivity. Divergent functional group transformation of the amide moiety of the product allowed for expeditious access to enantioenriched syn-configured α-hydroxy-β-amino carboxylic acid derivatives, highlighting the synthetic utility of the present catalysis.

  12. Calcium(ii)-catalyzed enantioselective conjugate additions of amines.

    Science.gov (United States)

    Uno, Brice E; Dicken, Rachel D; Redfern, Louis R; Stern, Charlotte M; Krzywicki, Greg G; Scheidt, Karl A

    2018-02-14

    The direct enantioselective chiral calcium(ii)·phosphate complex (Ca[CPA] 2 )-catalyzed conjugate addition of unprotected alkyl amines to maleimides was developed. This mild catalytic system represents a significant advance towards the general convergent asymmetric amination of α,β-unsaturated electrophiles, providing medicinally relevant chiral aminosuccinimide products in high yields and enantioselectivities. Furthermore, the catalyst can be reused directly from a previously chromatographed reaction and still maintain both high yield and selectivity.

  13. Dinuclear PhosphoiminoBINOL-Pd Container for Malononitrile: Catalytic Asymmetric Double Mannich Reaction for Chiral 1,3-Diamine Synthesis.

    Science.gov (United States)

    Arai, Takayoshi; Sato, Katsuya; Nakamura, Ayu; Makino, Hiroki; Masu, Hyuma

    2018-01-16

    A phosphoiminoBINOL ligand was designed to form a dinuclear metal complex that could hold a malononitrile molecule. The dinuclear bis(phosphoimino)binaphthoxy-Pd 2 (OAc) 2 complex catalyzed a double Mannich reaction of N-Boc-imines with malononitrile to give chiral 1,3-diamines with high enantioselectivity. The rational asymmetric catalyst, which smoothly introduces the first coupling product to the second coupling reaction while avoiding the reverse reaction, facilitates the over-reaction into a productive reaction process.

  14. Catalytic asymmetric aza-Morita-Baylis-Hillman reaction of methyl acrylate: role of a bifunctional La(O-iPr)3/linked-BINOL complex.

    Science.gov (United States)

    Yukawa, Takafumi; Seelig, Bianca; Xu, Yingjie; Morimoto, Hiroyuki; Matsunaga, Shigeki; Berkessel, Albrecht; Shibasaki, Masakatsu

    2010-09-01

    The catalytic asymmetric aza-Morita-Baylis-Hillman reaction using unactivated methyl acrylate is described. A simple Lewis acidic metal catalyst, such as La(OTf)(3), was not suitable for the reaction, but rare earth metal alkoxide/linked-BINOL complexes possessing bifunctional Lewis acid and Brønsted base properties efficiently promoted the reaction in combination with an achiral nucleophilic organocatalyst. The combined use of a La(O-iPr)(3)/(S,S)-TMS-linked-BINOL complex with a catalytic amount of DABCO promoted the aza-Morita-Baylis-Hillman reaction of a broad range of N-diphenylphosphinoyl imines. Products from aryl, heteroaryl, and alkenyl imines were obtained in 67-99% yield and 81-95% ee. It is noteworthy that isomerizable alkyl imines could be employed as well, giving products in 78-89% yield and 94-98% ee. Initial rate kinetic studies as well as kinetic isotope effect experiments using alpha-deuterio-methyl acrylate support the importance of both the nucleophilicity of La-enolate and the Brønsted basicity of a La-catalyst for promoting the reaction.

  15. Catalytic Asymmetric Mukaiyama-Mannich Reaction of Cyclic C-Acylimines with Difluoroenoxysilanes: Access to Difluoroalkylated Indolin-3-ones.

    Science.gov (United States)

    Li, Jin-Shan; Liu, Yong-Jie; Zhang, Guang-Wu; Ma, Jun-An

    2017-12-01

    A catalytic enantioselective Mukaiyama-Mannich reaction of cyclic C-acylimines with difluoroenoxysilanes is reported. (S)-TRIP enables the enantioselective synthesis of a series of novel difluoroalkylated indolin-3-ones bearing a quaternary stereocenter in up to 97% yield and 98% ee. The synthetic utility of this protocol is highlighted by efficient conversion of the products to the corresponding indolin-3-one derivatives without any erosion of the enantiopurity.

  16. Gene-silencing potency of symmetric and asymmetric lipid-conjugated siRNAs and its correlation with dicer recognition.

    Science.gov (United States)

    Kubo, Takanori; Yanagihara, Kazuyoshi; Sato, Yuichiro; Nishimura, Yoshio; Kondo, Shinichi; Seyama, Toshio

    2013-12-18

    Three types of siRNAs and three types of left-overhang siRNAs (LoRNAs) were synthesized along with their conjugations with palmitic acid (C16) to investigate the correlation between Dicer recognition and gene-silencing potency. The siRNA types were composed of 21-nucleotide (nt), 23-nt, and 25-nt lengths of sense and antisense strands with a 2-nt overhang at each 3'-end. The three LoRNA types were composed of a 21-nt, a 23-nt, and a 25-nt length of sense strand with a 2-nt DNA at the 3'-blunt-end and a 23-nt, a 25-nt, and a 27-nt length of antisense strand with a 2-nt overhang at the 3'-end. Additionally, each of these siRNAs and LoRNAs was modified with a C16 at the 5'- or 3'-end of the sense strand; these were named C16-siRNAs and C16-LoRNAs, respectively. The siRNAs and C16-siRNAs were barely cleaved by Dicer, and their gene-silencing efficacies were not excellent, contrary to our expectations. In contrast, most of the LoRNAs and C16-LoRNAs became substrates of Dicer, and they showed both strong gene-silencing efficacies and high nuclease resistance. Among the LoRNAs, the 25D-C16/27-nt LoRNA, which is composed of a 25-nt sense strand with a 2-nt DNA conjugated with C16 at the 3'-end and a 27-nt antisense strand with a 2-nt overhang at the 3'-end, showed an excellent gene-silencing effect with high cell membrane permeability and strong resistance against nuclease degradation. Additionally, the Lo25D-C16/27RNA excelled in all three aspects, nuclease resistance, cell membrane permeability, and RNAi efficacy, compared with the cholesterol conjugation. We are certain that Lo25D-C16/27RNA can be useful as a new generation of RNAi molecules with which to overcome some of the limitations of RNAi technology.

  17. Thermodynamically accurate modeling of the catalytic cycle of photosynthetic oxygen evolution: a mathematical solution to asymmetric Markov chains.

    Science.gov (United States)

    Vinyard, David J; Zachary, Chase E; Ananyev, Gennady; Dismukes, G Charles

    2013-07-01

    Forty-three years ago, Kok and coworkers introduced a phenomenological model describing period-four oscillations in O2 flash yields during photosynthetic water oxidation (WOC), which had been first reported by Joliot and coworkers. The original two-parameter Kok model was subsequently extended in its level of complexity to better simulate diverse data sets, including intact cells and isolated PSII-WOCs, but at the expense of introducing physically unrealistic assumptions necessary to enable numerical solutions. To date, analytical solutions have been found only for symmetric Kok models (inefficiencies are equally probable for all intermediates, called "S-states"). However, it is widely accepted that S-state reaction steps are not identical and some are not reversible (by thermodynamic restraints) thereby causing asymmetric cycles. We have developed a mathematically more rigorous foundation that eliminates unphysical assumptions known to be in conflict with experiments and adopts a new experimental constraint on solutions. This new algorithm termed STEAMM for S-state Transition Eigenvalues of Asymmetric Markov Models enables solutions to models having fewer adjustable parameters and uses automated fitting to experimental data sets, yielding higher accuracy and precision than the classic Kok or extended Kok models. This new tool provides a general mathematical framework for analyzing damped oscillations arising from any cycle period using any appropriate Markov model, regardless of symmetry. We illustrate applications of STEAMM that better describe the intrinsic inefficiencies for photon-to-charge conversion within PSII-WOCs that are responsible for damped period-four and period-two oscillations of flash O2 yields across diverse species, while using simpler Markov models free from unrealistic assumptions. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Enhanced activity of lysozyme-AgNP conjugate with synergic antibacterial effect without damaging the catalytic site of lysozyme.

    Science.gov (United States)

    Ernest, Vinita; Gajalakshmi, Sekar; Mukherjee, Amitava; Chandrasekaran, Natarajan

    2014-10-01

    The conjugation of silver nanoparticles (AgNPs) with biomolecules such as oligosaccharides, DNA, proteins has attracted great attention of scientists recently. In this study, lysozyme-AgNP conjugates were evaluated for its synergic antimicrobial effect. AgNPs were synthesized and characterized using UV-Visible, X-ray diffraction analysis (XRD) and atomic force microscopy (AFM). AgNP (0-1 mM) was interacted with lysozyme for multi-spectrophotometric studies. Lysozyme was immobilized on AgNP at different ratios and the resulting nano-bio-conjugate was tested against Escherichia coli for potent synergic antibacterial effects. A surface plasmon peak at 420 nm confirmed the presence of AgNPs and spherical to oval-shaped AgNPs were observed by AFM. The particle size was calculated to be 25 nm by XRD analysis. The maximum immobilization efficiency (98%) was achieved at 0.01:1 ratio of enzyme:AgNP. UV-Visible and fluorescence spectral studies revealed the binding of AgNPs to lysozyme by the formation of ground-state complex and the binding parameters were calculated. Circular dichroism studies confirmed decrease by 11% in the α-helical and 29.32% in β-sheets of lysozyme upon AgNP interaction. FTIR spectra revealed the binding of AgNP through thiol (-SH) linkages of lysozyme. Our results showed that the antimicrobial activity of lysozyme-AgNP conjugate was enhanced up to 86% decrease in the cell growth. In summary, the immobilization of lysozyme on AgNP has yielded a nano-bio-conjugate with synergistic antibacterial properties.

  19. Catalytic asymmetric alkylation of acylsilanes

    NARCIS (Netherlands)

    Rong, Jiawei; Oost, Rik; Desmarchelier, Alaric; Minnaard, Adriaan J; Harutyunyan, Syuzanna R

    2015-01-01

    The highly enantioselective addition of Grignard reagents to acylsilanes is catalyzed by copper diphosphine complexes. This transformation affords -silylated tertiary alcohols in up to 97% yield and 98:2 enantiomeric ratio. The competing Meerwein-Ponndorf-Verley reduction is suppressed by the use of

  20. Catalytic asymmetric Meerwein-Ponndorf-Verley reduction of glyoxylates induced by a chiral N,N'-dioxide/Y(OTf)3complex.

    Science.gov (United States)

    Wu, Wangbin; Zou, Sijia; Lin, Lili; Ji, Jie; Zhang, Yuheng; Ma, Baiwei; Liu, Xiaohua; Feng, Xiaoming

    2017-03-18

    An asymmetric Meerwein-Ponndorf-Verley (MPV) reduction of glyoxylates was for the first time accomplished via an N,N'-dioxide/Y(OTf) 3 complex with aluminium alkoxide and molecular sieves (MSs) as crucial additives. A variety of optically active α-hydroxyesters were obtained with excellent results. A possible reaction mechanism was proposed based on the experiments.

  1. Role of Nearby Charges on the Electronic Structure of π-Conjugated Molecules: Symmetric versus Asymmetric Charge Distributions in Oligo(p-phenyleneethynylene)

    DEFF Research Database (Denmark)

    Kirketerp, Maj-Britt Suhr; Ryhding, Torben; Støchkel, Kristian

    2011-01-01

    Oligo(p-phenyleneethynylene)s (OPEs) are conjugated oligomers of great interest within materials science and molecular electronics on account of their highly applicable electronic and optical properties. Here we use gas-phase action spectroscopy to elucidate how the intrinsic electronic properties......-pole ion trap, accelerated to 50-keV kinetic energies, mass-to-charge selected by a magnet, and photoexcited in a crossed-beam configuration. Fragment ions were finally mass-analyzed by an electrostatic analyzer. The setup enables photodissociation mass spectrometry and action spectroscopy...... in the gas phase. Simple electrostatic considerations lead to an energy difference like the one found from the experiment. The work presented here addresses how the electronic properties of a π-conjugated system are affected by nearby charges, a question of fundamental interest in, for example, molecular...

  2. Hydrodehalogenation of alkyl iodides with base-mediated hydrogenation and catalytic transfer hydrogenation: application to the asymmetric synthesis of N-protected α-methylamines.

    Science.gov (United States)

    Mandal, Pijus K; Birtwistle, J Sanderson; McMurray, John S

    2014-09-05

    We report a very mild synthesis of N-protected α-methylamines from the corresponding amino acids. Carboxyl groups of amino acids are reduced to iodomethyl groups via hydroxymethyl intermediates. Reductive deiodination to methyl groups is achieved by hydrogenation or catalytic transfer hydrogenation under alkaline conditions. Basic hydrodehalogenation is selective for the iodomethyl group over hydrogenolysis-labile protecting groups, such as benzyloxycarbonyl, benzyl ester, benzyl ether, and 9-fluorenyloxymethyl, thus allowing the conversion of virtually any protected amino acid into the corresponding N-protected α-methylamine.

  3. Asymmetric Ion-Pairing Catalysis

    Science.gov (United States)

    Brak, Katrien

    2014-01-01

    Charged intermediates and reagents are ubiquitous in organic transformations. The interaction of these ionic species with chiral neutral, anionic, or cationic small molecules has emerged as a powerful strategy for catalytic, enantioselective synthesis. This review describes developments in the burgeoning field of asymmetric ion-pairing catalysis with an emphasis on the insights that have been gleaned into the structural and mechanistic features that contribute to high asymmetric induction. PMID:23192886

  4. Multicatalyst system in asymmetric catalysis

    CERN Document Server

    Zhou, Jian

    2014-01-01

    This book introduces multi-catalyst systems by describing their mechanism and advantages in asymmetric catalysis.  Helps organic chemists perform more efficient catalysis with step-by-step methods  Overviews new concepts and progress for greener and economic catalytic reactions  Covers topics of interest in asymmetric catalysis including bifunctional catalysis, cooperative catalysis, multimetallic catalysis, and novel tandem reactions   Has applications for pharmaceuticals, agrochemicals, materials, and flavour and fragrance

  5. DNA-based asymmetric catalysis

    NARCIS (Netherlands)

    Boersma, Arnold J.; Megens, Rik P.; Feringa, Ben L.; Roelfes, Gerard

    2010-01-01

    The unique chiral structure of DNA has been a source of inspiration for the development of a new class of bio-inspired catalysts. The novel concept of DNA-based asymmetric catalysis, which was introduced only five years ago, has been applied successfully in a variety of catalytic enantioselective

  6. Asymmetric total synthesis of Apocynaceae hydrocarbazole alkaloids (+)-deethylibophyllidine and (+)-limaspermidine.

    Science.gov (United States)

    Du, Ji-Yuan; Zeng, Chao; Han, Xiao-Jie; Qu, Hu; Zhao, Xian-He; An, Xian-Tao; Fan, Chun-An

    2015-04-01

    An unprecedented asymmetric catalytic tandem aminolysis/aza-Michael addition reaction of spirocyclic para-dienoneimides has been designed and developed through organocatalytic enantioselective desymmetrization. A unified strategy based on this key tandem methodology has been divergently explored for the asymmetric total synthesis of two natural Apocynaceae alkaloids, (+)-deethylibophyllidine and (+)-limaspermidine. The present studies not only enrich the tandem reaction design concerning the asymmetric catalytic assembly of a chiral all-carbon quaternary stereocenter contained in the densely functionalized hydrocarbazole synthons but also manifest the potential for the application of the asymmetric catalysis based on the para-dienone chemistry in asymmetric synthesis of natural products.

  7. Toward a catalytic site in DNA

    DEFF Research Database (Denmark)

    Jakobsen, Ulla; Rohr, Katja; Vogel, Stefan

    2007-01-01

    A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented.......A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented....

  8. Catalytic Asymmetric Alkylation of Aryl Heteroaryl Ketones

    NARCIS (Netherlands)

    Ortiz, Pablo; Harutyunyan, Syuzanna; del Hoyo, Ana

    Tertiary diarylmethanols are highly bioactive structural motifs. A new strategy to access chiral tertiary diarylmethanols through copper-catalyzed direct alkylation of (di)(hetero)aryl ketones by using Grignard reagents was developed. The low reactivity and the similarity of the enantiotopic faces

  9. Palladium catalysed asymmetric alkylation of benzophenone Schiff ...

    Indian Academy of Sciences (India)

    Dongdaemun-Gu, Seoul 130-701, Republic of Korea. bDepartment of ..... Anionic effect of imidazolium based ionic liquids in catalytic asymmetric PT alkylationa promoted by palladium catalyst.b. Entry ... d: compared with the run involving catalyst only under similar PT conditions (entry 10, table 1) throw some light in this ...

  10. Magnetically Retrievable Catalysts for Asymmetric Synthesis

    Science.gov (United States)

    Surface modification of magnetic nanoparticles with chiral scaffolds for asymmetric catalytic applications is an elegant way of providing a special pseudo homogenous phase which could be separated using an external magnet. In this review, we summarize the use of magnetic nanopart...

  11. The catalystic asymmetric synthesis of optically active epoxy ketones

    NARCIS (Netherlands)

    Marsman, Bertha Gerda

    1981-01-01

    In this thesis the use of catalytic asymmetric synthesis to prepare optically active epoxy ketones is described. This means that the auxiliary chirality, necessary to obtain an optically active product, is added in a catalytic quantity . In principle this is a very efficient way to make opticlly

  12. Conjugal violence

    Directory of Open Access Journals (Sweden)

    Simona Mihaiu

    2015-10-01

    Full Text Available Scientific knowledge of different aspects related to conjugal violence is highly important for people directly involved, such as researchers, practitioners and the entire society. In this respect, globally, specialised studies continue to advance, offer correct definitions, clear descriptions, convincing assessments to certain issues, encouraging thus long-term research, since some specialists have managed to overcome restrictive or ideological methods and explanations. Moreover, in practice, debates reach almost all social, political and legal dimensions regarding appropriate and efficient forms of preventing conjugal violence. Unfortunately, in Romania there are fewer research and prevention approaches of this social problem. In general, attention is directed to domestic violence and conjugal violence is dealt with only implicitly. Considering the given context, the aim of the paper is to outline, by analysing specialised literature, a new research direction and implicitly, social intervention. I specify that this article represents a stage in the ongoing postdoctoral research project, entitled "Conjugal homicide. Aggressors and victims".

  13. Asymmetric Crater

    Science.gov (United States)

    2004-01-01

    [figure removed for brevity, see original site] Released 18 December 2003Asymmetric craters such as the one in the center of this image are fairly rare. The more typical symmetric craters are formed when meteors impact a surface over a wide range of angles. Only very low impact angles (within 15o of horizontal) result in asymmetric structures such as this one. The bilateral symmetry of the ejecta, like two wings on either side of the elliptical crater, is typical of oblique impacts. The small crater downrange from the main crater could have been caused by the impactor breaking apart before impact or possibly a 'decapitation' of the impactor as it hit with the 'head' traveling farther to form the smaller structure.Image information: VIS instrument. Latitude -8.5, Longitude 227.5 East (132.5 West). 19 meter/pixel resolution.Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  14. Asymmetric collider

    International Nuclear Information System (INIS)

    Bharadwaj, V.; Colestock, P.; Goderre, G.; Johnson, D.; Martin, P.; Holt, J.; Kaplan, D.

    1993-01-01

    The study of CP violation in beauty decay is one of the key challenges facing high energy physics. Much work has not yielded a definitive answer how this study might best be performed. However, one clear conclusion is that new accelerator facilities are needed. Proposals include experiments at asymmetric electron-positron colliders and in fixed-target and collider modes at LHC and SSC. Fixed-target and collider experiments at existing accelerators, while they might succeed in a first observation of the effect, will not be adequate to study it thoroughly. Giomataris has emphasized the potential of a new approach to the study of beauty CP violation: the asymmetric proton collider. Such a collider might be realized by the construction of a small storage ring intersecting an existing or soon-to-exist large synchrotron, or by arranging collisions between a large synchrotron and its injector. An experiment at such a collider can combine the advantages of fixed-target-like spectrometer geometry, facilitating triggering, particle identification and the instrumentation of a large acceptance, while the increased √s can provide a factor > 100 increase in beauty-production cross section compared to Tevatron or HERA fixed-target. Beams crossing at a non-zero angle can provide a small interaction region, permitting a first-level decay-vertex trigger to be implemented. To achieve large √s with a large Lorentz boost and high luminosity, the most favorable venue is the high-energy booster (HEB) at the SSC Laboratory, though the CERN SPS and Fermilab Tevatron are also worth considering

  15. Towards chiral diamines as chiral catalytic precursors for the borane ...

    Indian Academy of Sciences (India)

    2)-2-anilinomethylpiperidine (2) have been employed as chiral catalytic sources in the borane-mediated asymmetric reduction of prochiral ketones thus providing the resulting secondary alcohols in good enantiomeric purities (up to 81% ) ...

  16. Synthesis and Catalytic Activity of Two New Cyclic Tetraaza Ligands

    Directory of Open Access Journals (Sweden)

    Burkhard König

    2003-05-01

    Full Text Available Two new chiral cyclic tetraaza ligands were synthesized and characterized. Their catalytic activity was tested in the asymmetric addition of diethylzinc to benzaldehyde. The expected secondary alcohol was obtained in moderate yields, but with very low enantioselectivity.

  17. Asymmetric fluorocyclizations of alkenes.

    Science.gov (United States)

    Wolstenhulme, Jamie R; Gouverneur, Véronique

    2014-12-16

    .g., TRIP and derivatives) brings into solution the resulting chiral Selectfluor reagent, now capable of asymmetric fluorocyclization. This strategy is best applied to a subset of substrates bearing a nucleophilic pendent group (benzamide is best) capable of hydrogen bonding for association with the chiral phosphate catalyst. These contributions focused on fluoroheterocyclization involving either O- or N-nucleophiles. As for other halocyclizations, alkenes armed with π C-nucleophiles represent the most demanding class of substrates for asymmetric F(+)-induced electrophilic fluorination-cyclization. Successful implementation required the design of new chiral Selectfluor reagents featuring stereogenicity on the DABCO core. These reagents, accessible from chiral vicinal diamines, allowed the synthesis of unusual chiral fluorine-containing tetracyclic compounds, some composed of carbon, hydrogen, and fluorine exclusively. The challenges associated with F(+)-induced fluorocarbocyclizations prompted methodologists to consider chemistry where the Csp(3)-F bond formation event follows a catalyst-controlled cyclization. An exciting development built on in the area of transition metal π-cyclization of polyenes leading to cationic metal-alkyl intermediates. When intercepted by oxidative fluorodemetalation with a F(+) source, the resulting products are complex polycyclic structures emerging from an overall catalytic cascade fluorocarbocyclization. Complementing F(+)-based reactions, examples of fluorocyclizations with fluoride in the presence of an oxidant were reported. Despite some exciting developments, the field of asymmetric fluorocyclizations is in its infancy and undoubtedly requires new activation modes, catalysts, as well as F(+) and F(-) reagents to progress into general retrosynthetic approach toward enantioenriched fluorocycles. Numerous opportunities emerge, not least the use of a latent fluorine source as a means to minimize background fluorination.

  18. Biomimetic asymmetric hydrogenation: in situ regenerable Hantzsch esters for asymmetric hydrogenation of benzoxazinones.

    Science.gov (United States)

    Chen, Qing-An; Chen, Mu-Wang; Yu, Chang-Bin; Shi, Lei; Wang, Duo-Sheng; Yang, Yan; Zhou, Yong-Gui

    2011-10-19

    A catalytic amount of Hantzsch ester that could be regenerated in situ by Ru complexes under hydrogen gas has been employed in the biomimetic asymmetric hydrogenation of benzoxazinones with up to 99% ee in the presence of chiral phosphoric acid. The use of hydrogen gas as a reductant for the regeneration of Hantzsch esters makes this hydrogenation an ideal atom economic process.

  19. Photophysicochemical behaviour and antimicrobial properties of monocarboxy Mg (II) and Al (III) phthalocyanine-magnetite conjugates

    Science.gov (United States)

    Idowu, Mopelola Abidemi; Xego, Solami; Arslanoglu, Yasin; Mark, John; Antunes, Edith; Nyokong, Tebello

    2018-03-01

    Asymmetric Mg (II) or Al (III) phthalocyanine (containing a COOH group and 3-pyridylsulfanyl units) was conjugated via an amide bond to amino functionalized magnetic nanoparticle (AIMN) to form MgPc-AIMN or AlPc-AIMN conjugate, and characterized. The photophysicochemical behaviour of the phthalocyanine-AIMN conjugates was investigated and compared to the asymmetric Pcs and to the simple mixture of Pc with AIMNs without a chemical bond, (MPc-AIMN (mixed)). The directed covalent linkage of AIMNs to the asymmetrical metallopthalocyanines afforded improvements in the singlet oxygen (VΔ) and triplet state quantum yield (VT) as well as singlet oxygen lifetimes for the MPcs-AIMN-linked conjugates compared to MPc-AIMN (mixed) and MPcs alone. The asymmetric phthalocyanines and their conjugates showed effective antimicrobial activity against Escherichia coli bacteria under illumination.

  20. Cu2+ or Fe3+ Terpyridine/Aptamer Conjugates

    NARCIS (Netherlands)

    Biniuri, Yonatan; Albada, Bauke; Wolff, Mariusz; Golub, Eyal; Gelman, Dmitri; Willner, Itamar

    2018-01-01

    A concept to tailor catalytic nucleic acid structures is introduced. The method involves the covalent conjugation of catalytically active metal ion complexes to sequence-specific ligand-binding nucleic acids (aptamers) yielding hybrids termed "nucleoapzymes" that act as enzyme-mimicking nucleic acid

  1. Glutathione Conjugation

    Science.gov (United States)

    Shimabukuro, R. H.; Frear, D. S.; Swanson, H. R.; Walsh, W. C.

    1971-01-01

    The primary factor for atrazine selectivity in corn (Zea mays) is the activity of a soluble enzyme, glutathione S-transferase, which detoxifies atrazine by catalyzing the formation of an atrazine-glutathione conjugate (GS-atrazine). The nonenzymatic, benzoxazinone-catalyzed hydrolysis of atrazine to hydroxyatrazine contributed to the total resistance of corn to atrazine, but the nonenzymatic detoxication pathway does not seem to be essential for resistance. All corn lines investigated, except for susceptible GT112, rapidly detoxified atrazine by glutathione conjugation. Only GT112 had low glutathione S-transferase activity. Hydroxyatrazine was found in significant quantities only when atrazine was introduced initially into the roots. The amount of hydroxyatrazine formed was nearly equal for susceptible GT112 and most of the resistant corn lines investigated. This investigation indicates that some plants protect themselves against toxic organic halide compounds with a mechanism similar to that known to exist in animals. PMID:5543779

  2. Asymmetric Ashes

    Science.gov (United States)

    2006-11-01

    that oscillate in certain directions. Reflection or scattering of light favours certain orientations of the electric and magnetic fields over others. This is why polarising sunglasses can filter out the glint of sunlight reflected off a pond. When light scatters through the expanding debris of a supernova, it retains information about the orientation of the scattering layers. If the supernova is spherically symmetric, all orientations will be present equally and will average out, so there will be no net polarisation. If, however, the gas shell is not round, a slight net polarisation will be imprinted on the light. This is what broad-band polarimetry can accomplish. If additional spectral information is available ('spectro-polarimetry'), one can determine whether the asymmetry is in the continuum light or in some spectral lines. In the case of the Type Ia supernovae, the astronomers found that the continuum polarisation is very small so that the overall shape of the explosion is crudely spherical. But the much larger polarization in strongly blue-shifted spectral lines evidences the presence, in the outer regions, of fast moving clumps with peculiar chemical composition. "Our study reveals that explosions of Type Ia supernovae are really three-dimensional phenomena," says Dietrich Baade. "The outer regions of the blast cloud is asymmetric, with different materials found in 'clumps', while the inner regions are smooth." "This study was possible because polarimetry could unfold its full strength thanks to the light-collecting power of the Very Large Telescope and the very precise calibration of the FORS instrument," he adds. The research team first spotted this asymmetry in 2003, as part of the same observational campaign (ESO PR 23/03 and ESO PR Photo 26/05). The new, more extensive results show that the degree of polarisation and, hence, the asphericity, correlates with the intrinsic brightness of the explosion. The brighter the supernova, the smoother, or less clumpy

  3. Protease-catalysed Direct Asymmetric Mannich Reaction in Organic Solvent

    Science.gov (United States)

    Xue, Yang; Li, Ling-Po; He, Yan-Hong; Guan, Zhi

    2012-10-01

    We reported the first enzyme-catalysed, direct, three-component asymmetric Mannich reaction using protease type XIV from Streptomyces griseus (SGP) in acetonitrile. Yields of up to 92% with enantioselectivities of up to 88% e.e. and diastereoselectivities of up to 92:8 (syn:anti) were achieved under the optimised conditions. This enzyme's catalytic promiscuity expands the application of this biocatalyst and provides a potential alternative method for asymmetric Mannich reactions.

  4. Metal-Catalyzed Asymmetric Michael Addition in Natural Product Synthesis.

    Science.gov (United States)

    Hui, Chunngai; Pu, Fan; Xu, Jing

    2017-03-23

    Asymmetric catalysis for chiral compound synthesis is a rapidly growing field in modern organic chemistry. Asymmetric catalytic processes have been indispensable for the synthesis of enantioselective materials to meet demands from various fields. Michael addition has been used extensively for the construction of C-C bonds under mild conditions. With the discovery and development of organo- and metal-catalyzed asymmetric Michael additions, the synthesis of enantioselective and/or diastereoselective Michael adducts has become possible and increasingly prevalent in the literature. In particular, metal-catalyzed asymmetric Michael addition has been employed as a key reaction in natural product synthesis for the construction of contiguous quaternary stereogenic center(s), which is still a difficult task in organic synthesis. Previously reported applications of metal-catalyzed asymmetric Michael additions in natural product synthesis are presented here and discussed in depth. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Catalytic devices

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ming; Zhang, Xiang

    2018-01-23

    This disclosure provides systems, methods, and apparatus related to catalytic devices. In one aspect, a device includes a substrate, an electrically insulating layer disposed on the substrate, a layer of material disposed on the electrically insulating layer, and a catalyst disposed on the layer of material. The substrate comprises an electrically conductive material. The substrate and the layer of material are electrically coupled to one another and configured to have a voltage applied across them.

  6. Asymmetric photoredox transition-metal catalysis activated by visible light

    Science.gov (United States)

    Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

    2014-11-01

    Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the `green' synthesis of non-racemic chiral molecules.

  7. Metal-catalyzed Asymmetric Hetero-Diels-Alder Reactions of Unactivated Dienes with Glyoxylates

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Yao, Sulan; Graven, Anette

    1998-01-01

    The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo- and enantiose...

  8. Asymmetric bipolar membrane: A tool to improve product purity

    NARCIS (Netherlands)

    Balster, J.H.; Sumbharaju, R.; Srikantharajah, S.; Punt, Ineke G.M.; Stamatialis, Dimitrios; Jordan, V.; Wessling, Matthias

    2007-01-01

    Bipolar membranes (BPMs) are catalytic membranes for electro-membrane processes splitting water into protons and hydroxyl ions. To improve selectivity and current efficiency of BPMs, we prepare new asymmetric BPMs with reduced salt leakages. The flux of salt ions across a BPM is determined by the

  9. Organocatalyzed Asymmetric Synthesis of Axially, Planar, and Helical Chiral Compounds.

    Science.gov (United States)

    Shirakawa, Seiji; Liu, Shiyao; Kaneko, Shiho

    2016-02-04

    Axially, planar, and helical chiral compounds are indispensable building blocks in modern organic synthesis. A wide variety of chiral ligands and catalysts were designed based on these chiral scaffolds, and these chiral ligands and catalysts were used for various catalytic asymmetric transformations to produce important chiral compounds in an optically enriched form. Furthermore, these chiral skeletons are found in the structure of biologically active natural products. Thus, the development of efficient enantioselective methods for the synthesis of these chiral compounds is an important task in the field of organic chemistry. In the last few years, organocatalyzed approaches, which are one of the most reliable catalytic asymmetric methods, became a hot topic. This Focus Review summarizes asymmetric organocatalytic methods for the synthesis of axially, planar, and helical chiral compounds as useful chiral building blocks. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Chiral Brønsted Acids for Asymmetric Organocatalysis

    Science.gov (United States)

    Kampen, Daniela; Reisinger, Corinna M.; List, Benjamin

    Chiral Brønsted acid catalysis is an emerging area of organocatalysis. Since the pioneering studies of the groups of Akiyama and Terada in 2004 on the use of chiral BINOL phosphates as powerful Brønsted acid catalysts in asymmetric Mannich-type reactions, numerous catalytic asymmetric transformations involving imine activation have been realized by means of this catalyst class, including among others Friedel-Crafts, Pictet-Spengler, Strecker, cycloaddition reactions, transfer hydrogenations, and reductive aminations. More recently, chiral BINOL phosphates found application in multicomponent and cascade reactions as for example in an asymmetric version of the Biginelli reaction. With the introduction of chiral BINOL-derived N-triflyl phosphoramides in 2006, asymmetric Brønsted acid catalysis is no longer restricted to reactive substrates. Also certain carbonyl compounds can be activated through these stronger Brønsted acid catalysts. In dealing with sensitive substrate classes, chiral dicarboxylic acids proved of particular value.

  11. Catalytic Enantioselective Synthesis of Naturally Occurring Butenolides via Hetero-Allylic Alkylation and Ring Closing Metathesis

    NARCIS (Netherlands)

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; Zijl, Anthoni W. van; Fletcher, Stephen P.; Minnaard, Adriaan J.; Feringa, Bernard

    2011-01-01

    An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey

  12. Catalytic enantioselective synthesis of naturally occurring butenolides via hetero-allylic alkylation and ring closing metathesis.

    Science.gov (United States)

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; van Zijl, Anthoni W; Fletcher, Stephen P; Minnaard, Adriaan J; Feringa, Ben L

    2011-03-04

    An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey lactone, (-)-cognac lactone, (-)-nephrosteranic acid, and (-)-roccellaric acid.

  13. Segmented conjugated polymers

    Indian Academy of Sciences (India)

    Segmented conjugated polymers, wherein the conjugation is randomly truncated by varying lengths of non-conjugated segments, form an interesting class of polymers as they not only represent systems of varying stiffness, but also ones where the backbone can be construed as being made up of chromophores of varying ...

  14. Towards chiral diamines as chiral catalytic precursors for the borane ...

    Indian Academy of Sciences (India)

    Administrator

    anilinomethylpiperidine (2) have been employed as chiral catalytic sources in the borane-mediated asymmetric reduction of prochiral ketones ..... 7⋅86 min (S) and 8.53 min (R)]. 2.7c (S)-2-Bromo-1-(4-bromophenyl)ethanol [(S)– ... of (a) compound 8 and (b) compound 15-TFA salt (Hydrogen atoms were omitted for clarity).

  15. Asymmetrical field emitter

    Science.gov (United States)

    Fleming, J.G.; Smith, B.K.

    1995-10-10

    A method is disclosed for providing a field emitter with an asymmetrical emitter structure having a very sharp tip in close proximity to its gate. One preferred embodiment of the present invention includes an asymmetrical emitter and a gate. The emitter having a tip and a side is coupled to a substrate. The gate is connected to a step in the substrate. The step has a top surface and a side wall that is substantially parallel to the side of the emitter. The tip of the emitter is in close proximity to the gate. The emitter is at an emitter potential, and the gate is at a gate potential such that with the two potentials at appropriate values, electrons are emitted from the emitter. In one embodiment, the gate is separated from the emitter by an oxide layer, and the emitter is etched anisotropically to form its tip and its asymmetrical structure. 17 figs.

  16. Copper-catalyzed asymmetric allylic alkylation and asymmetric conjugate addition in natural product synthesis

    NARCIS (Netherlands)

    Huang, Yange

    2013-01-01

    In dit proefschrift wordt de koper-gekatalyseerde hetero AAA en ACA toegepast in de totaalsynthese van een aantal biologisch actieve moleculen. In het tweede deel van dit proefschrift ligt de focus op een nieuwe katalytische asymmetrische route naar 1,4-dieenen met een methyl gesubstitueerd chiraal

  17. Renaissance of pyridine-oxazolines as chiral ligands for asymmetric catalysis.

    Science.gov (United States)

    Yang, Guoqiang; Zhang, Wanbin

    2018-03-05

    Oxazoline-containing ligands have been widely employed in numerous asymmetric catalytic reactions. Pyridine-oxazoline-type ligands, a class of hybrid ligands, were designed earlier than bisoxazoline and phosphine-oxazoline ligands; however, their unique properties have only been discovered recently. Pyridine-oxazoline-type chiral ligands are rapidly becoming popular for use in asymmetric catalysis, especially for several new and efficient asymmetric methodologies. Several types of challenging asymmetric reactions have been discovered recently using pyridine-oxazoline-type ligands showing their special properties and potential for future application in a wide range of new catalytic methodologies. This review provides an overview of this field, with the aim of highlighting both ligand design and synthetic methodology development.

  18. Asymmetric reactions in continuous flow

    Directory of Open Access Journals (Sweden)

    Xiao Yin Mak

    2009-04-01

    Full Text Available An overview of asymmetric synthesis in continuous flow and microreactors is presented in this review. Applications of homogeneous and heterogeneous asymmetric catalysis as well as biocatalysis in flow are discussed.

  19. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

    Directory of Open Access Journals (Sweden)

    Erli Sugiono

    2013-11-01

    Full Text Available A continuous-flow asymmetric organocatalytic photocyclization–transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

  20. How Is Nature Asymmetric?

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 7; Issue 6. How Is Nature Asymmetric? - Discrete Symmetries in Particle Physics and their Violation ... Indian Institute of Technology, Chennai. Aligarh Muslim University. University of Rajasthan, Jaipur. Indian Institute of Science, Bangalore 560012, India.

  1. Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

    Directory of Open Access Journals (Sweden)

    Johannes Schörgenhumer

    2017-08-01

    Full Text Available Chiral phase-transfer catalysis is one of the major catalytic principles in asymmetric catalysis. A broad variety of different catalysts and their use for challenging applications have been reported over the last decades. Besides asymmetric C–C bond forming reactions the use of chiral phase-transfer catalysts for enantioselective α-heterofunctionalization reactions of prochiral nucleophiles became one of the most important field of application of this catalytic principle. Based on several highly spectacular recent reports, we thus wish to discuss some of the most important achievements in this field within the context of this review.

  2. The biochemistry of drug metabolism--an introduction: part 4. reactions of conjugation and their enzymes.

    Science.gov (United States)

    Testa, Bernard; Krämer, Stefanie D

    2008-11-01

    This review continues a general presentation of the metabolism of drugs and other xenobiotics begun in three recent issues of Chemistry & Biodiversity. The present Part is dedicated to reactions of conjugation, namely methylation, sulfonation, and phosphorylation, glucuronidation and other glycosidations, acetylation and other acylations, the formation and fate of coenzyme A conjugates, glutathione conjugation, and the reaction of amines with carbonyl compounds. It presents the many transferases involved, their nomenclature, relevant biochemical properties, catalytic mechanisms, and the reactions they catalyze. Nonenzymatic reactions, mainly of glutathione conjugation, also receive due attention. A number of medicinally, environmentally, and toxicologically relevant examples are presented and discussed.

  3. Pd(II-dissolved in ionic liquids: a recyclable catalytic system for the selective biphasic hydrogenation of dienes to monoenes

    Directory of Open Access Journals (Sweden)

    Dupont Jairton

    2000-01-01

    Full Text Available Palladium acetylacetonate dissolved in 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid catalyses the selective two-phase hydrogenation of conjugated and non-conjugated (functionalized and non-functionalized dienes into the respective monoenes. The system does not require the use of organic solvents, the products are removed by simple decantation or distillation and the recovered ionic catalytic solution can be reused several times without any significant changes in its catalytic activity and selectivity.

  4. Direct Asymmetric Vinylogous and Bisvinylogous Mannich-Type Reaction Catalyzed by a Copper(I) Complex.

    Science.gov (United States)

    Zhang, Hai-Jun; Shi, Chang-Yun; Zhong, Feng; Yin, Liang

    2017-02-15

    A direct catalytic asymmetric vinylogous Mannich-type reaction has been disclosed in good yield, excellent regio-, diastereo- and enantioselectivity. The key to control the regioselectivity is the combination of a bulky N-acylpyrazole and a bulky bisphosphine ligand. The catalytic system was extended to a bisvinylogous Mannich-type reaction by changing the ligand. The synthetic utility of the vinylogous products was demonstrated by several transformations.

  5. Multipartite asymmetric quantum cloning

    International Nuclear Information System (INIS)

    Iblisdir, S.; Gisin, N.; Acin, A.; Cerf, N.J.; Filip, R.; Fiurasek, J.

    2005-01-01

    We investigate the optimal distribution of quantum information over multipartite systems in asymmetric settings. We introduce cloning transformations that take N identical replicas of a pure state in any dimension as input and yield a collection of clones with nonidentical fidelities. As an example, if the clones are partitioned into a set of M A clones with fidelity F A and another set of M B clones with fidelity F B , the trade-off between these fidelities is analyzed, and particular cases of optimal N→M A +M B cloning machines are exhibited. We also present an optimal 1→1+1+1 cloning machine, which is an example of a tripartite fully asymmetric cloner. Finally, it is shown how these cloning machines can be optically realized

  6. Asymmetric Evolutionary Games.

    Science.gov (United States)

    McAvoy, Alex; Hauert, Christoph

    2015-08-01

    Evolutionary game theory is a powerful framework for studying evolution in populations of interacting individuals. A common assumption in evolutionary game theory is that interactions are symmetric, which means that the players are distinguished by only their strategies. In nature, however, the microscopic interactions between players are nearly always asymmetric due to environmental effects, differing baseline characteristics, and other possible sources of heterogeneity. To model these phenomena, we introduce into evolutionary game theory two broad classes of asymmetric interactions: ecological and genotypic. Ecological asymmetry results from variation in the environments of the players, while genotypic asymmetry is a consequence of the players having differing baseline genotypes. We develop a theory of these forms of asymmetry for games in structured populations and use the classical social dilemmas, the Prisoner's Dilemma and the Snowdrift Game, for illustrations. Interestingly, asymmetric games reveal essential differences between models of genetic evolution based on reproduction and models of cultural evolution based on imitation that are not apparent in symmetric games.

  7. Asymmetric Evolutionary Games.

    Directory of Open Access Journals (Sweden)

    Alex McAvoy

    2015-08-01

    Full Text Available Evolutionary game theory is a powerful framework for studying evolution in populations of interacting individuals. A common assumption in evolutionary game theory is that interactions are symmetric, which means that the players are distinguished by only their strategies. In nature, however, the microscopic interactions between players are nearly always asymmetric due to environmental effects, differing baseline characteristics, and other possible sources of heterogeneity. To model these phenomena, we introduce into evolutionary game theory two broad classes of asymmetric interactions: ecological and genotypic. Ecological asymmetry results from variation in the environments of the players, while genotypic asymmetry is a consequence of the players having differing baseline genotypes. We develop a theory of these forms of asymmetry for games in structured populations and use the classical social dilemmas, the Prisoner's Dilemma and the Snowdrift Game, for illustrations. Interestingly, asymmetric games reveal essential differences between models of genetic evolution based on reproduction and models of cultural evolution based on imitation that are not apparent in symmetric games.

  8. Asymmetric synthesis of syn-propargylamines and unsaturated β-amino acids under Brønsted base catalysis

    Science.gov (United States)

    Wang, Yingcheng; Mo, Mingjie; Zhu, Kongxi; Zheng, Chao; Zhang, Hongbin; Wang, Wei; Shao, Zhihui

    2015-01-01

    Propargylamines are important intermediates for the synthesis of polyfunctional amino derivatives and natural products and biologically active compounds. The classic method of synthesizing chiral propargylamines involves the asymmetric alkynylation of imines. Here, we report a significant advance in the catalytic asymmetric Mannich-type synthesis of propargylamines through catalytic asymmetric addition of carbon nucleophiles to C-alkynyl imines, culminating in a highly syn-selective catalytic asymmetric Mannich reaction of C-alkynyl imines that provide syn-configured propargylamines with two adjacent stereogenic centres and a transition metal-free organocatalytic asymmetric approach to β-alkynyl-β-amino acids with high efficiency and practicality, via a chiral Brønsted base-catalysed asymmetric Mannich-type reaction of in situ generated challenging N-Boc C-alkynyl imines from previously unreported C-alkynyl N-Boc-N,O-acetals, with α-substituted β-keto esters and less-acidic malonate (thio)esters as nucleophiles, respectively. A catalytic activation strategy is also disclosed, which may have broad implications for use in catalysis and synthesis. PMID:26423837

  9. Catalytic Oligopeptide Synthesis.

    Science.gov (United States)

    Liu, Zijian; Noda, Hidetoshi; Shibasaki, Masakatsu; Kumagai, Naoya

    2018-02-02

    Waste-free catalytic assembly of α-amino acids is fueled by a multiboron catalyst that features a characteristic B 3 NO 2 heterocycle, providing a versatile catalytic protocol wherein functionalized natural α-amino acid units are accommodated and commonly used protecting groups are tolerated. The facile dehydrative conditions eliminate the use of engineered peptide coupling reagents, exemplifying a greener catalytic alternative for peptide coupling. The catalysis is sufficiently robust to enable pentapeptide synthesis, constructing all four amide bond linkages in a catalytic fashion.

  10. Qualidade conjugal: mapeando conceitos

    Directory of Open Access Journals (Sweden)

    Clarisse Mosmann

    2006-12-01

    Full Text Available Apesar da ampla utilização do conceito de qualidade conjugal, identifica-se falta de clareza conceitual acerca das variáveis que o compõem. Esse artigo apresenta revisão da literatura na área com o objetivo de mapear o conceito de qualidade conjugal. Foram analisadas sete principais teorias sobre o tema: Troca Social, Comportamental, Apego, Teoria da Crise, Interacionismo Simbólico. Pelos postulados propostos nas diferentes teorias, podem-se identificar três grupos de variáveis fundamentais na definição da qualidade conjugal: recursos pessoais dos cônjuges, contexto de inserção do casal e processos adaptativos. Neste sentido, a qualidade conjugal é resultado do processo dinâmico e interativo do casal, razão deste caráter multidimensional.

  11. Conjugated Polymer Solar Cells

    National Research Council Canada - National Science Library

    Paraschuk, Dmitry Y

    2006-01-01

    This report results from a contract tasking Moscow State University as follows: Conjugated polymers are promising materials for many photonics applications, in particular, for photovoltaic and solar cell devices...

  12. Polymers for Protein Conjugation

    Directory of Open Access Journals (Sweden)

    Gianfranco Pasut

    2014-01-01

    Full Text Available Polyethylene glycol (PEG at the moment is considered the leading polymer for protein conjugation in view of its unique properties, as well as to its low toxicity in humans, qualities which have been confirmed by its extensive use in clinical practice. Other polymers that are safe, biodegradable and custom-designed have, nevertheless, also been investigated as potential candidates for protein conjugation. This review will focus on natural polymers and synthetic linear polymers that have been used for protein delivery and the results associated with their use. Genetic fusion approaches for the preparation of protein-polypeptide conjugates will be also reviewed and compared with the best known chemical conjugation ones.

  13. Asymmetric Organocatalysis and Photoredox Catalysis for the α-Functionalization of Tetrahydroisoquinolines

    KAUST Repository

    Hou, Hong

    2018-03-14

    The asymmetric α‐alkylation of tetrahydroisoquinolines with cyclic ketones has been accomplished in the presence of a combined catalytic system consisting of a visible‐light photoredox catalyst and a chiral primary amine organocatalyst. The desired products were obtained in good yields, high enantioselectivity, and good to excellent diastereoselectivity. (PC: photoredox cycle, EN: enamine cycle).

  14. Chiral bicycle imidazole nucleophilic catalysts: rational design, facile synthesis, and successful application in asymmetric Steglich rearrangement.

    Science.gov (United States)

    Zhang, Zhenfeng; Xie, Fang; Jia, Jia; Zhang, Wanbin

    2010-11-17

    A new type of chiral bicycle imidazole nucleophilic catalyst was rationally designed, facilely synthesized, and successfully applied in an asymmetric Steglich rearrangement with good to excellent yield and enantioselectivity at ambient temperature. Moreover, it can be easily recycled with almost no reduction of catalytic efficiency. This is the first example for the successful chiral imidazole nucleophilic catalyst without H-bonding assistance.

  15. Organizing for Asymmetric Collaboration

    DEFF Research Database (Denmark)

    Nielsen, Jørn Flohr; Sørensen, Henrik B.

    they meet each other. On the contrary, we assume that asymmetry is both important and normal; moreover, asymmetry should be considered to be more complex than economists indicate with their concept of asymmetric information. Thus, the aim of the paper is to explore how asymmetries related to partners...... to support better diagnosis and as a starting point for more detailed analysis, including interpersonal and processual perspectives, Furthermore, we propose how different situations need different kinds of change interventions. Although including asymmetries in interorganizational analysis does add more...

  16. Asymmetric synthesis v.4

    CERN Document Server

    Morrison, James

    1984-01-01

    Asymmetric Synthesis, Volume 4: The Chiral Carbon Pool and Chiral Sulfur, Nitrogen, Phosphorus, and Silicon Centers describes the practical methods of obtaining chiral fragments. Divided into five chapters, this book specifically examines initial chiral transmission and extension. The opening chapter describes the so-called chiral carbon pool, the readily available chiral carbon fragments used as building blocks in synthesis. This chapter also provides a list of 375 chiral building blocks, along with their commercial sources, approximate prices, and methods of synthesis. Schemes involving

  17. Colon Cryptogenesis: Asymmetric Budding

    Science.gov (United States)

    Tan, Chin Wee; Hirokawa, Yumiko; Gardiner, Bruce S.; Smith, David W.; Burgess, Antony W.

    2013-01-01

    The process of crypt formation and the roles of Wnt and cell-cell adhesion signaling in cryptogenesis are not well described; but are important to the understanding of both normal and cancer colon crypt biology. A quantitative 3D-microscopy and image analysis technique is used to study the frequency, morphology and molecular topography associated with crypt formation. Measurements along the colon reveal the details of crypt formation and some key underlying biochemical signals regulating normal colon biology. Our measurements revealed an asymmetrical crypt budding process, contrary to the previously reported symmetrical fission of crypts. 3D immunofluorescence analyses reveals heterogeneity in the subcellular distribution of E-cadherin and β-catenin in distinct crypt populations. This heterogeneity was also found in asymmetrical budding crypts. Singular crypt formation (i.e. no multiple new crypts forming from one parent crypt) were observed in crypts isolated from the normal colon mucosa, suggestive of a singular constraint mechanism to prevent aberrant crypt production. The technique presented improves our understanding of cryptogenesis and suggests that excess colon crypt formation occurs when Wnt signaling is perturbed (e.g. by truncation of adenomatous polyposis coli, APC protein) in most colon cancers. PMID:24205248

  18. Colon cryptogenesis: asymmetric budding.

    Directory of Open Access Journals (Sweden)

    Chin Wee Tan

    Full Text Available The process of crypt formation and the roles of Wnt and cell-cell adhesion signaling in cryptogenesis are not well described; but are important to the understanding of both normal and cancer colon crypt biology. A quantitative 3D-microscopy and image analysis technique is used to study the frequency, morphology and molecular topography associated with crypt formation. Measurements along the colon reveal the details of crypt formation and some key underlying biochemical signals regulating normal colon biology. Our measurements revealed an asymmetrical crypt budding process, contrary to the previously reported symmetrical fission of crypts. 3D immunofluorescence analyses reveals heterogeneity in the subcellular distribution of E-cadherin and β-catenin in distinct crypt populations. This heterogeneity was also found in asymmetrical budding crypts. Singular crypt formation (i.e. no multiple new crypts forming from one parent crypt were observed in crypts isolated from the normal colon mucosa, suggestive of a singular constraint mechanism to prevent aberrant crypt production. The technique presented improves our understanding of cryptogenesis and suggests that excess colon crypt formation occurs when Wnt signaling is perturbed (e.g. by truncation of adenomatous polyposis coli, APC protein in most colon cancers.

  19. Asymmetric quantum cloning machines

    International Nuclear Information System (INIS)

    Cerf, N.J.

    1998-01-01

    A family of asymmetric cloning machines for quantum bits and N-dimensional quantum states is introduced. These machines produce two approximate copies of a single quantum state that emerge from two distinct channels. In particular, an asymmetric Pauli cloning machine is defined that makes two imperfect copies of a quantum bit, while the overall input-to-output operation for each copy is a Pauli channel. A no-cloning inequality is derived, characterizing the impossibility of copying imposed by quantum mechanics. If p and p ' are the probabilities of the depolarizing channels associated with the two outputs, the domain in (√p,√p ' )-space located inside a particular ellipse representing close-to-perfect cloning is forbidden. This ellipse tends to a circle when copying an N-dimensional state with N→∞, which has a simple semi-classical interpretation. The symmetric Pauli cloning machines are then used to provide an upper bound on the quantum capacity of the Pauli channel of probabilities p x , p y and p z . The capacity is proven to be vanishing if (√p x , √p y , √p z ) lies outside an ellipsoid whose pole coincides with the depolarizing channel that underlies the universal cloning machine. Finally, the tradeoff between the quality of the two copies is shown to result from a complementarity akin to Heisenberg uncertainty principle. (author)

  20. Symmetric Decomposition of Asymmetric Games.

    Science.gov (United States)

    Tuyls, Karl; Pérolat, Julien; Lanctot, Marc; Ostrovski, Georg; Savani, Rahul; Leibo, Joel Z; Ord, Toby; Graepel, Thore; Legg, Shane

    2018-01-17

    We introduce new theoretical insights into two-population asymmetric games allowing for an elegant symmetric decomposition into two single population symmetric games. Specifically, we show how an asymmetric bimatrix game (A,B) can be decomposed into its symmetric counterparts by envisioning and investigating the payoff tables (A and B) that constitute the asymmetric game, as two independent, single population, symmetric games. We reveal several surprising formal relationships between an asymmetric two-population game and its symmetric single population counterparts, which facilitate a convenient analysis of the original asymmetric game due to the dimensionality reduction of the decomposition. The main finding reveals that if (x,y) is a Nash equilibrium of an asymmetric game (A,B), this implies that y is a Nash equilibrium of the symmetric counterpart game determined by payoff table A, and x is a Nash equilibrium of the symmetric counterpart game determined by payoff table B. Also the reverse holds and combinations of Nash equilibria of the counterpart games form Nash equilibria of the asymmetric game. We illustrate how these formal relationships aid in identifying and analysing the Nash structure of asymmetric games, by examining the evolutionary dynamics of the simpler counterpart games in several canonical examples.

  1. Preparation of asymmetric porous materials

    Science.gov (United States)

    Coker, Eric N [Albuquerque, NM

    2012-08-07

    A method for preparing an asymmetric porous material by depositing a porous material film on a flexible substrate, and applying an anisotropic stress to the porous media on the flexible substrate, where the anisotropic stress results from a stress such as an applied mechanical force, a thermal gradient, and an applied voltage, to form an asymmetric porous material.

  2. Metal-conjugated affinity labels: A new concept to create enantioselective artificial metalloenzymes

    KAUST Repository

    Reiner, Thomas

    2013-02-20

    How to train a protein: Metal-conjugated affinity labels were used to selectively position catalytically active metal centers in the binding pocket of proteases. The resulting artificial metalloenzymes achieve up to 82% e.r. in the hydrogenation of ketones. The modular setup enables a rapid generation of artificial metalloenzyme libraries, which can be adapted to a broad range of catalytic conditions. 2013 The Authors.

  3. Engineering of Syndiotactic and Isotactic Polystyrene-Based Copolymers via Stereoselective Catalytic Polymerization

    Directory of Open Access Journals (Sweden)

    Eva Laur

    2017-04-01

    Full Text Available This contribution presents an updated overview of the different copolymers containing stereoregular polystyrene blocks. Special emphasis is placed on syndiospecific and isospecific copolymerization of styrene with co-monomers (ethylene and α-olefins, conjugated and non-conjugated dienes, styrene derivatives, etc.. The catalytic systems involved are described and the polymerization mechanisms are discussed. Alternative approaches (simultaneous, living, chain-transfer and graft copolymerization and the resulting detailed structures and characteristics of the copolymers are also reported.

  4. Non-Classical C–H···X Hydrogen Bonding and Its Role in Asymmetric Organocatalysis

    KAUST Repository

    Ajitha, Manjaly John

    2016-08-17

    Non-classical hydrogen bonds (NCHBs) have attracted significant interest in the past decade particularly because of their important role in asymmetric catalytic systems. These weak interactions (< 4 kcal/mol) offer much flexibility in the preorganization of molecular entities required to achieve high enantioselectivity. Herein, we review some recent important organocatalytic asymmetric reactions where a NCHB serves as a critical factor in determining the stereoselectivity.

  5. Asymmetric Higgsino dark matter.

    Science.gov (United States)

    Blum, Kfir; Efrati, Aielet; Grossman, Yuval; Nir, Yosef; Riotto, Antonio

    2012-08-03

    In the supersymmetric framework, prior to the electroweak phase transition, the existence of a baryon asymmetry implies the existence of a Higgsino asymmetry. We investigate whether the Higgsino could be a viable asymmetric dark matter candidate. We find that this is indeed possible. Thus, supersymmetry can provide the observed dark matter abundance and, furthermore, relate it with the baryon asymmetry, in which case the puzzle of why the baryonic and dark matter mass densities are similar would be explained. To accomplish this task, two conditions are required. First, the gauginos, squarks, and sleptons must all be very heavy, such that the only electroweak-scale superpartners are the Higgsinos. With this spectrum, supersymmetry does not solve the fine-tuning problem. Second, the temperature of the electroweak phase transition must be low, in the (1-10) GeV range. This condition requires an extension of the minimal supersymmetric standard model.

  6. Asymmetric black dyonic holes

    Directory of Open Access Journals (Sweden)

    I. Cabrera-Munguia

    2015-04-01

    Full Text Available A 6-parametric asymptotically flat exact solution, describing a two-body system of asymmetric black dyons, is studied. The system consists of two unequal counterrotating Kerr–Newman black holes, endowed with electric and magnetic charges which are equal but opposite in sign, separated by a massless strut. The Smarr formula is generalized in order to take into account their contribution to the mass. The expressions for the horizon half-length parameters σ1 and σ2, as functions of the Komar parameters and of the coordinate distance, are displayed, and the thermodynamic properties of the two-body system are studied. Furthermore, the seven physical parameters satisfy a simple algebraic relation which can be understood as a dynamical scenario, in which the physical properties of one body are affected by the ones of the other body.

  7. Antibody proteases: induction of catalytic response.

    Science.gov (United States)

    Gabibov, A G; Friboulet, A; Thomas, D; Demin, A V; Ponomarenko, N A; Vorobiev, I I; Pillet, D; Paon, M; Alexandrova, E S; Telegin, G B; Reshetnyak, A V; Grigorieva, O V; Gnuchev, N V; Malishkin, K A; Genkin, D D

    2002-10-01

    Most of the data accumulated throughout the years on investigation of catalytic antibodies indicate that their production increases on the background of autoimmune abnormalities. The different approaches to induction of catalytic response toward recombinant gp120 HIV-1 surface protein in mice with various autoimmune pathologies are described. The peptidylphosphonate conjugate containing structural part of gp120 molecule is used for reactive immunization of NZB/NZW F1, MRL, and SJL mice. The specific modification of heavy and light chains of mouse autoantibodies with Val-Ala-Glu-Glu-Glu-Val-PO(OPh)2 reactive peptide was demonstrated. Increased proteolytic activity of polyclonal antibodies in SJL mice encouraged us to investigate the production of antigen-specific catalytic antibodies on the background of induced experimental autoimmune encephalomyelitis (EAE). The immunization of autoimmune-prone mice with the engineered fusions containing the fragments of gp120 and encephalitogenic epitope of myelin basic protein (MBP(89-104)) was made. The proteolytic activity of polyclonal antibodies isolated from the sera of autoimmune mice immunized by the described antigen was shown. Specific immune response of SJL mice to these antigens was characterized. Polyclonal antibodies purified from sera of the immunized animals revealed proteolytic activity. The antiidiotypic approach to raise the specific proteolytic antibody as an "internal image" of protease is described. The "second order" monoclonal antibodies toward subtilisin Carlsberg revealed pronounced proteolytic activity.

  8. Catalytic distillation process

    Science.gov (United States)

    Smith, L.A. Jr.

    1982-06-22

    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  9. Catalytic Functions of Standards

    NARCIS (Netherlands)

    K. Blind (Knut)

    2009-01-01

    textabstractThe three different areas and the examples have illustrated several catalytic functions of standards for innovation. First, the standardisation process reduces the time to market of inventions, research results and innovative technologies. Second, standards themselves promote the

  10. Catalytic distillation structure

    Science.gov (United States)

    Smith, L.A. Jr.

    1984-04-17

    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  11. DNA-cell conjugates

    Science.gov (United States)

    Hsiao, Shih-Chia; Francis, Matthew B.; Bertozzi, Carolyn; Mathies, Richard; Chandra, Ravi; Douglas, Erik; Twite, Amy; Toriello, Nicholas; Onoe, Hiroaki

    2016-05-03

    The present invention provides conjugates of DNA and cells by linking the DNA to a native functional group on the cell surface. The cells can be without cell walls or can have cell walls. The modified cells can be linked to a substrate surface and used in assay or bioreactors.

  12. Photoluminescence in conjugated polymers

    International Nuclear Information System (INIS)

    Furst, J.E.; Laugesen, R.; Dastoor, P.; McNeill, C.

    2002-01-01

    Full text: Conjugated polymers combine the electronic and optical properties of semiconductors with the processability of polymers. They contain a sequence of alternate single and double carbon bonds so that the overlap of unhybridised p z orbitals creates a delocalised ρ system which gives semiconducting properties with p-bonding (valence) and p* -antibonding (conduction) bands. Photoluminesence (PL) in conjugated polymers results from the radiative decay of singlet excitons confined to a single chain. The present work is the first in a series of studies in our laboratory that will characterize the optical properties of conjugated polymers. The experiment involves the illumination of thin films of conjugated polymer with UV light (I=360 nm) and observing the subsequent fluorescence using a custom-built, fluorescence spectrometer. Photoluminesence spectra provide basic information about the structure of the polymer film. A typical spectrum is shown in the accompanying figure. The position of the first peak is related to the polymer chain length and resolved multiple vibronic peaks are an indication of film structure and morphology. We will also present results related to the optical degradation of these materials when exposed to air and UV light

  13. Ultraviolet phase conjugation

    International Nuclear Information System (INIS)

    Slatkine, M.; Bigio, I.J.; Fisher, R.A.; Maloney, M.L.; Busse, J.R.; Tercovich, R.G.; Feldman, B.J.

    1981-01-01

    Diffraction-limited phase conjugate reflection of an injection-locked high-power (approx. 1 MW) ultraviolet excimer laser beam has been demonstrated via stimulated Brillouin scattering. Reflectivities higher than 70% were attained. Limitations as well as coherence and power requirements for image retention are discussed

  14. Crisis and Conjugal Power

    Science.gov (United States)

    Bahr, Stephen L.; Rollins, Boyd C.

    1971-01-01

    It was hypothesized that the more equalitarian the conjugal power structure in a noncrisis situation, the more likely the relative marital power will change during a crisis. This was tested using an observational experimental method, and the hypothesis was supported. (Author/CG)

  15. Peptide-Carrier Conjugation

    DEFF Research Database (Denmark)

    Hansen, Paul Robert

    2015-01-01

    To produce antibodies against synthetic peptides it is necessary to couple them to a protein carrier. This chapter provides a nonspecialist overview of peptide-carrier conjugation. Furthermore, a protocol for coupling cysteine-containing peptides to bovine serum albumin is outlined....

  16. [Biomechanic of the asymmetrical headgear].

    Science.gov (United States)

    Sander, F G

    1990-11-01

    The asymmetrical headgear is a very useful treatment device for the unilateral distalisation of molars or for the correction of an unilateral anchorage loss. 1. The dimension of the asymmetrical effect depends on the configuration of the outer bows. 2. The function of an asymmetrical face-bow can be increased or decreased by eccentric bendings. 3. According to the geometry at the outer-bows the force at the outer-bow is divided at a different percentage onto the molars. 4. While the forces increase the asymmetrical effect will decrease when the outer-bow is too flexible. 5. Attention has to be payed at each control-appointment to the distance of the longer outer-bow to the cheek. 6. The asymmetrical swivel face-bow did not produce a greater asymmetrical function than other asymmetrical headgears. The reason of this fact is, that only the geometry of the outer-bows is responsible for the unilateral distalisation. 7. The asymmetrical swivel face-bow as described above is advisable to use because eccentric bendings and less forces at the outer-bows will decrease, stop or even reverse the asymmetrical effect. 8. The side-effect of any asymmetrical face-bow is a lateral force-component. This force-component can cause a cross-bite at the molar which has to be more distalized. The molar which is not be moved by the asymmetrical face-bow will be moved buccally by this force-component. 9. The swivel face-bow according to Sander prevents the buccal movement of the molar which should not be moved. But the tendency to create a cross-bite for the molar which should be more distalized, increases. 10. The swivel face-bow according to Sander can be combined with all well-known extraoral tractions. 11. Equal forces at the outer-bows can be reached while using a cervical-pull neckstrap according to Sander. 12. The asymmetrical face-bow and the bite-jumping-appliance can be used simultaneously if the face-bow inserts directly into the attachments of the molar bands.

  17. Defeating the Modern Asymmetric Threat

    National Research Council Canada - National Science Library

    Connor, Robert

    2002-01-01

    ...) ending a horrific 19 year-old low-intensity conflict, Over the course of nearly two decades, the LTTE came to exemplify the modern asymmetric threat as they battled the Sri Lankan Armed Forces (SLAF...

  18. Combining silver- and organocatalysis: an enantioselective sequential catalytic approach towards pyrano-annulated pyrazoles.

    Science.gov (United States)

    Hack, Daniel; Chauhan, Pankaj; Deckers, Kristina; Mizutani, Yusuke; Raabe, Gerhard; Enders, Dieter

    2015-02-11

    A one-pot asymmetric Michael addition/hydroalkoxylation sequence, catalyzed by a sequential catalytic system consisting of a squaramide and a silver salt, provides a new series of chiral pyrano-annulated pyrazole derivatives in excellent yields (up to 95%) and high enantioselectivities (up to 97% ee).

  19. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...

  20. 76 FR 53480 - Prospective Grant of Exclusive License: Conjugate Vaccines Against B. anthracis

    Science.gov (United States)

    2011-08-26

    ... toxin, which has 3 components: a receptor-binding protein known as ``protective antigen'' (PA) and 2 catalytic proteins known as ``lethal factor'' (LF) and ``edema factor'' (EF). Although production of an.../0, Schneerson et al., ``Methods for Preparing Immunogenic Conjugates'', U.S. Patent Application...

  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. Catalytic Conia-ene and related reactions.

    Science.gov (United States)

    Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter

    2015-10-07

    Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years.

  3. Alkaline earth metal catalysts for asymmetric reactions.

    Science.gov (United States)

    Kobayashi, Shū; Yamashita, Yasuhiro

    2011-01-18

    The group 2 alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) are among the most common elements on Earth, abundant in both the sea and the Earth's crust. Although they are familiar in our daily lives, their application to organic synthesis has, so far, been limited. Some particularly useful properties of these elements include (i) low electronegativity, (ii) a stable oxidation state of +2, meaning that they can potentially form two covalent bonds with anions, and (iii) the ability to occupy a variety of coordination sites due to their large ionic radius. Furthermore, the alkaline earth metals, found between the group 1 and group 3 elements, show mild but significant Lewis acidity, which can be harnessed to control coordinative molecules via a Lewis acid-base interaction. Taken together, these characteristics make the metals Ca, Sr, and Ba very promising components of highly functionalized acid-base catalysts. In this Account, we describe the development of chiral alkaline earth metal catalysts for asymmetric carbon-carbon bond-forming reactions. Recently prepared chiral alkaline earth metal complexes have shown high diastereo- and enantioselectivities in fundamental and important chemical transformations. We chose chiral bisoxazoline (Box) derivatives bearing a methylene tether as a ligand for chiral modification. These molecules are very useful because they can covalently coordinate to alkaline earth metals in a bidentate fashion through deprotonation of the tether portion. It was found that chiral calcium-Box complexes could successfully promote catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions with high diastereo- and enantioselectivities. Both the calcium-Box complexes and chiral strontium-bis-sulfonamide and chiral barium-BINOLate complexes could catalyze asymmetric 1,4-addition reactions with high enantioselectivities. Furthermore, we designed a calcium-neutral coordinative ligand complex as a new type of chiral alkaline

  4. Asymmetric Flexible Supercapacitor Stack

    Directory of Open Access Journals (Sweden)

    Leela Mohana Reddy A

    2008-01-01

    Full Text Available AbstractElectrical double layer supercapacitor is very significant in the field of electrical energy storage which can be the solution for the current revolution in the electronic devices like mobile phones, camera flashes which needs flexible and miniaturized energy storage device with all non-aqueous components. The multiwalled carbon nanotubes (MWNTs have been synthesized by catalytic chemical vapor deposition technique over hydrogen decrepitated Mischmetal (Mm based AB3alloy hydride. The polymer dispersed MWNTs have been obtained by insitu polymerization and the metal oxide/MWNTs were synthesized by sol-gel method. Morphological characterizations of polymer dispersed MWNTs have been carried out using scanning electron microscopy (SEM, transmission electron microscopy (TEM and HRTEM. An assymetric double supercapacitor stack has been fabricated using polymer/MWNTs and metal oxide/MWNTs coated over flexible carbon fabric as electrodes and nafion®membrane as a solid electrolyte. Electrochemical performance of the supercapacitor stack has been investigated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy.

  5. Asymmetric Gepner models (revisited)

    Energy Technology Data Exchange (ETDEWEB)

    Gato-Rivera, B. [NIKHEF Theory Group, Kruislaan 409, 1098 SJ Amsterdam (Netherlands)] [Instituto de Fisica Fundamental, CSIC, Serrano 123, Madrid 28006 (Spain); Schellekens, A.N., E-mail: t58@nikhef.n [NIKHEF Theory Group, Kruislaan 409, 1098 SJ Amsterdam (Netherlands)] [Instituto de Fisica Fundamental, CSIC, Serrano 123, Madrid 28006 (Spain)] [IMAPP, Radboud Universiteit, Nijmegen (Netherlands)

    2010-12-11

    We reconsider a class of heterotic string theories studied in 1989, based on tensor products of N=2 minimal models with asymmetric simple current invariants. We extend this analysis from (2,2) and (1,2) spectra to (0,2) spectra with SO(10) broken to the Standard Model. In the latter case the spectrum must contain fractionally charged particles. We find that in nearly all cases at least some of them are massless. However, we identify a large subclass where the fractional charges are at worst half-integer, and often vector-like. The number of families is very often reduced in comparison to the 1989 results, but there are no new tensor combinations yielding three families. All tensor combinations turn out to fall into two classes: those where the number of families is always divisible by three, and those where it is never divisible by three. We find an empirical rule to determine the class, which appears to extend beyond minimal N=2 tensor products. We observe that distributions of physical quantities such as the number of families, singlets and mirrors have an interesting tendency towards smaller values as the gauge groups approaches the Standard Model. We compare our results with an analogous class of free fermionic models. This displays similar features, but with less resolution. Finally we present a complete scan of the three family models based on the triply-exceptional combination (1,16{sup *},16{sup *},16{sup *}) identified originally by Gepner. We find 1220 distinct three family spectra in this case, forming 610 mirror pairs. About half of them have the gauge group SU(3)xSU(2){sub L}xSU(2){sub R}xU(1){sup 5}, the theoretical minimum, and many others are trinification models.

  6. High Mobility Conjugated Polymers

    Science.gov (United States)

    2007-10-20

    blends with poly(3- hexylthiophene) (PHT) could be readily fabricated as uniform nanofibers by co- electrospinning their solutions with another solution...We have demonstrated that nanofibers of conjugated 10 - polymers and their blends could be conveniently fabricated by electrospinning . Furthermore, we...luminance o - - characteristics of an ITO/ PEDOT /TAPC k D r a Vol gt, V, (V) /BPQ-PPO/LiF/A! device are shown in Fig. 30. (A) Current density-voltage

  7. Steam reformer with catalytic combustor

    Science.gov (United States)

    Voecks, Gerald E. (Inventor)

    1990-01-01

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  8. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Preferred Customer

    acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...

  9. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Based on the property that in 0.12 M sulfuric acid medium titanium(IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of titanium is

  10. Catalytic Three-Component Machinery: Control of Catalytic Activity by Machine Speed.

    Science.gov (United States)

    Paul, Indrajit; Goswami, Abir; Mittal, Nikita; Schmittel, Michael

    2018-01-02

    Three supramolecular slider-on-deck systems DS1-DS3 were obtained as two-component aggregates from the sliders S1-S3 and deck D with its three zinc porphyrin (ZnPor) binding sites. The binding of the two-footed slider to the deck varies with the donor qualities of and the steric hindrance at the pyridine/pyrimidine (pyr) feet, and was effected by two N pyr →ZnPor interactions. Accordingly, the sliders move over the three zinc porphyrins in the deck at different speeds, namely with 32.2, 220, and 440 kHz at room temperature. The addition of N-methylpyrrolidine as an organocatalyst to DS1-DS3 generates catalytic three-component machineries. By using a conjugate addition as a probe reaction, we observed a correlation between the operating speed of the slider-on-deck systems and the yields of the catalytic reaction. As the thermodynamic binding of the slider decreases, both the frequency of the sliding motion and the yield of the catalytic reaction increase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Enantioselective conjugate addition nitro-Mannich reactions: solvent controlled synthesis of acyclic anti- and syn-β-nitroamines with three contiguous stereocenters.

    Science.gov (United States)

    Anderson, James C; Stepney, Gregory J; Mills, Matthew R; Horsfall, Lisa R; Blake, Alexander J; Lewis, William

    2011-04-01

    We report an enantioselective conjugate addition nitro-Mannich reaction protocol which combines dialkylzinc, aromatic nitro alkene and imine to form two C-C bonds and three contiguous stereocenters in one reaction vessel. Absolute stereochemistry was controlled from the initial 1,4-addition of dialkylzinc to aromatic nitroalkenes by known copper-chiral ligand catalysts. The choice of solvent dictated the formation of either the syn,anti or syn,syn diastereoisomers, two of the four possible diastereoisomers. The syn,syn isomer is a rare example of a syn-selective nitro-Mannich reaction. The diastereoselectivity is dependent upon the presence or not of Zn(O(2)CCF(3))(2) in the reaction mixture and empirical transition state models are proposed to account for the observed stereochemical course of the two reaction conditions. The extent of enantioselectivity and structural diversity of the process is limited by current methodology for the catalytic asymmetric addition of dialkylzincs to nitrostyrenes. The synthetically versatile products are the most complex β-nitro amines prepared using the nitro-Mannich reaction and are formed in high yield and enantioselectivity.

  12. Extremal asymmetric universal cloning machines

    Science.gov (United States)

    Jiang, Mingming; Yu, Sixia

    2010-05-01

    The trade-offs among various output fidelities of asymmetric universal cloning machines are investigated. First we find out all the attainable optimal output fidelities for the 1 to 3 asymmetric universal cloning machine and it turns out that there are two kinds of extremal machines which have to cooperate in order to achieve some of the optimal output fidelities. Second we construct a family of extremal cloning machines that includes the universal symmetric cloning machine as well as an asymmetric 1 to 1+N cloning machine for qudits with two different output fidelities such that the optimal trade-off between the measurement disturbance and state estimation is attained in the limit of infinite N.

  13. Does asymmetric correlation affect portfolio optimization?

    Science.gov (United States)

    Fryd, Lukas

    2017-07-01

    The classical portfolio optimization problem does not assume asymmetric behavior of relationship among asset returns. The existence of asymmetric response in correlation on the bad news could be important information in portfolio optimization. The paper applies Dynamic conditional correlation model (DCC) and his asymmetric version (ADCC) to propose asymmetric behavior of conditional correlation. We analyse asymmetric correlation among S&P index, bonds index and spot gold price before mortgage crisis in 2008. We evaluate forecast ability of the models during and after mortgage crisis and demonstrate the impact of asymmetric correlation on the reduction of portfolio variance.

  14. A carbon nanotube confinement strategy to implement homogeneous asymmetric catalysis in the solid phase.

    Science.gov (United States)

    Hashimoto, Kazuki; Kumagai, Naoya; Shibasaki, Masakatsu

    2015-03-09

    A readily recyclable asymmetric catalyst has been developed based on the self-assembly of a homogeneous catalyst in a fibrous network of multiwalled carbon nanotubes (MWNTs). Dimerization of an amide-based chiral ligand with a suitable spacer allows for the efficient formation of a heterogeneous catalyst by self-assembly on addition of Er(OiPr)3. The self-assembly proceeds in the MWNT fibrous network and small clusters of assembled catalyst are confined in the MWNTs, producing an easily handled solid-phase catalyst. The resulting MWNT-confined catalyst exhibits a good catalytic performance in a catalytic asymmetric Mannich-type reaction, which can be conducted in a repeated batch system and in a continuous-flow platform. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ideal 3D asymmetric concentrator

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Botella, Angel [Departamento Fisica Aplicada a los Recursos Naturales, Universidad Politecnica de Madrid, E.T.S.I. de Montes, Ciudad Universitaria s/n, 28040 Madrid (Spain); Fernandez-Balbuena, Antonio Alvarez; Vazquez, Daniel; Bernabeu, Eusebio [Departamento de Optica, Universidad Complutense de Madrid, Fac. CC. Fisicas, Ciudad Universitaria s/n, 28040 Madrid (Spain)

    2009-01-15

    Nonimaging optics is a field devoted to the design of optical components for applications such as solar concentration or illumination. In this field, many different techniques have been used for producing reflective and refractive optical devices, including reverse engineering techniques. In this paper we apply photometric field theory and elliptic ray bundles method to study 3D asymmetric - without rotational or translational symmetry - concentrators, which can be useful components for nontracking solar applications. We study the one-sheet hyperbolic concentrator and we demonstrate its behaviour as ideal 3D asymmetric concentrator. (author)

  16. Baker's yeast catalyzed asymmetric reduction of methyl acetoacetate in glycerol containing systems

    Directory of Open Access Journals (Sweden)

    Adi Wolfson

    2008-09-01

    Full Text Available The asymmetric hydrogenation of methyl acetoacetate was successfully performed with baker's yeast in pure glycerol and mixtures of glycerol and water. Though yeast viability was very low after exposure to glycerol, the enzymatic activity in pure glycerol was preserved for some days. In addition, a mixture of glycerol and water combined the advantageous of each individual solvent and resulted in high catalytic performance and efficient product extraction yield

  17. Mo-catalyzed asymmetric olefin metathesis in target-oriented synthesis: Enantioselective synthesis of (+)-africanol

    Science.gov (United States)

    Weatherhead, Gabriel S.; Cortez, G. A.; Schrock, Richard R.; Hoveyda, Amir H.

    2004-01-01

    Catalytic asymmetric ring-opening metathesis (AROM) provides an efficient method for the synthesis of a variety of optically enriched small organic molecules that cannot be easily prepared by alternative methods. The development of Mo-catalyzed AROM transformations that occur in tandem with ring-closing metathesis are described. The utility of the Mo-catalyzed AROM/ring-closing metathesis is demonstrated through an enantioselective approach to the synthesis of (+)-africanol. PMID:15056762

  18. Rhodium-catalyzed asymmetric hydrogenation of unprotected NH imines assisted by a thiourea.

    Science.gov (United States)

    Zhao, Qingyang; Wen, Jialin; Tan, Renchang; Huang, Kexuan; Metola, Pedro; Wang, Rui; Anslyn, Eric V; Zhang, Xumu

    2014-08-04

    Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. C2-Symmetric diamines and their derivatives as promising organocatalysts for asymmetric synthesis

    Science.gov (United States)

    Zlotin, S. G.; Kochetkov, S. V.

    2015-11-01

    The review is devoted to the application of C2-symmetric diamines and their derivatives as organocatalysts for asymmetric reactions (aldol, Michael, Mannich, Diels-Alder reactions, desymmetrization, allylation, etc.). Amino acid derivatives, di- and polyamides (sulfamides), bisureas, bisthioureas, bisamidines and bisguanidines are considered. Significant attention is given to the effect of the catalyst structure on the mechanism of catalytic action. Successful applications of such catalysts in enantioselective synthesis of chiral biologically active compounds are summarized. The bibliography includes 181 references.

  20. Catalytic thermal barrier coatings

    Science.gov (United States)

    Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh

    2009-06-02

    A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

  1. Carboxy-directed asymmetric hydrogenation of α-alkyl-α-aryl terminal olefins: highly enantioselective and chemoselective access to a chiral benzylmethyl center.

    Science.gov (United States)

    Yang, Shuang; Zhu, Shou-Fei; Guo, Na; Song, Song; Zhou, Qi-Lin

    2014-04-07

    A carboxy-directed asymmetric hydrogenation of α-alkyl-α-aryl terminal olefins was developed by using a chiral spiro iridium catalyst, providing a highly efficient approach to the compounds with a chiral benzylmethyl center. The carboxy-directed hydrogenation prohibited the isomerization of the terminal olefins, and realized the chemoselective hydrogenation of various dienes. The concise enantioselective syntheses of (S)-curcudiol and (S)-curcumene were achieved by using this catalytic asymmetric hydrogenation as a key step.

  2. JET and COMPASS asymmetrical disruptions

    Czech Academy of Sciences Publication Activity Database

    Gerasimov, S.N.; Abreu, P.; Baruzzo, M.; Drozdov, V.; Dvornova, A.; Havlíček, Josef; Hender, T.C.; Hronová-Bilyková, Olena; Kruezi, U.; Li, X.; Markovič, Tomáš; Pánek, Radomír; Rubinacci, G.; Tsalas, M.; Ventre, S.; Villone, F.; Zakharov, L.E.

    2015-01-01

    Roč. 55, č. 11 (2015), s. 113006-113006 ISSN 0029-5515 R&D Projects: GA MŠk(CZ) LM2011021 Institutional support: RVO:61389021 Keywords : tokamak * asymmetrical disruption * JET * COMPASS Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 4.040, year: 2015

  3. Catalytic Membranes Embedding Selective Catalysts: Preparation and Applications

    Science.gov (United States)

    Drioli, Enrico; Fontananova, Enrica

    The embedding of a catalyst in membranes is today recognized as a promising strategy to develop highly efficient and eco-friendly heterogeneous catalytic chemical processes. When a catalyst is heterogenized within or on the surface of a membrane, the membrane composition (characteristics of the membrane material: hydrophobic or hydrophilic, presence of chemical groups with specific functionality, etc.) and the membrane structure (dense or porous, symmetric or asymmetric), can positively influence the catalyst performance, not only by the selective sorption and diffusion of reagents and/or products, but also influencing the catalyst activity by electronic and conformational effect. These effects are similar to those occurring in biological membranes. In this chapter, after a preliminary presentation of the basic principles of membrane reactors and polymer membranes, the preparation, characterization and applications of polymeric catalytic membranes, will be discussed.

  4. Polymer and Membrane Design for Low Temperature Catalytic Reactions

    KAUST Repository

    Villalobos, Luis Francisco

    2016-02-29

    Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane\\'s ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gavrilov, Konstantin N [Department of Chemistry, S.A. Esenin Ryazan State Pedagogical University, Ryazan (Russian Federation); Bondarev, Oleg G; Polosukhin, Aleksei I [A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow (Russian Federation)

    2004-07-31

    The data published during the last five years on the application of chiral derivatives of phosphorous acid in coordination chemistry and enantioselective catalysis are summarised and discussed. The effect of the nature of these ligands on the structure of metal complexes and on the efficiency of catalytic organic syntheses is shown. Hydroformylation, hydrogenation, allylic substitution and conjugate addition catalysed by transition metal complexes with optically active phosphites and hydrophosphoranes are considered. The prospects for the development of this field of research are demonstrated.

  6. Heterogeneous versus homogeneous copper(II) catalysis in enantioselective conjugate-addition reactions of boron in water.

    Science.gov (United States)

    Kitanosono, Taku; Xu, Pengyu; Kobayashi, Shū

    2014-01-01

    We have developed Cu(II)-catalyzed enantioselective conjugate-addition reactions of boron to α,β-unsaturated carbonyl compounds and α,β,γ,δ-unsaturated carbonyl compounds in water. In contrast to the previously reported Cu(I) catalysis that required organic solvents, chiral Cu(II) catalysis was found to proceed efficiently in water. Three catalyst systems have been exploited: cat. 1: Cu(OH)2 with chiral ligand L1; cat. 2: Cu(OH)2 and acetic acid with ligand L1; and cat. 3: Cu(OAc)2 with ligand L1. Whereas cat. 1 is a heterogeneous system, cat. 2 and cat. 3 are homogeneous systems. We tested 27 α,β-unsaturated carbonyl compounds and an α,β-unsaturated nitrile compound, including acyclic and cyclic α,β-unsaturated ketones, acyclic and cyclic β,β-disubstituted enones, acyclic and cyclic α,β-unsaturated esters (including their β,β-disubstituted forms), and acyclic α,β-unsaturated amides (including their β,β-disubstituted forms). We found that cat. 2 and cat. 3 showed high yields and enantioselectivities for almost all substrates. Notably, no catalysts that can tolerate all of these substrates with high yields and high enantioselectivities have been reported for the conjugate addition of boron. Heterogeneous cat. 1 also gave high yields and enantioselectivities with some substrates and also gave the highest TOF (43,200 h(-1) ) for an asymmetric conjugate-addition reaction of boron. In addition, the catalyst systems were also applicable to the conjugate addition of boron to α,β,γ,δ-unsaturated carbonyl compounds, although such reactions have previously been very limited in the literature, even in organic solvents. 1,4-Addition products were obtained in high yields and enantioselectivities in the reactions of acyclic α,β,γ,δ-unsaturated carbonyl compounds with diboron 2 by using cat. 1, cat. 2, or cat. 3. On the other hand, in the reactions of cyclic α,β,γ,δ-unsaturated carbonyl compounds with compound 2, whereas 1,4-addition products

  7. Highly enantio- and diastereoselective reactions of γ-substituted butenolides through direct vinylogous conjugate additions

    KAUST Repository

    Zhang, Wen

    2012-09-05

    The strength of the weak: An L-tert-leucine-derived amine-thiourea catalyst (see scheme, green box) promotes the asymmetric vinylogous conjugate addition reaction between γ-aryl- and alkyl-substituted butenolides with the butenamides and enoates shown. Computational studies show the preference for the observed stereochemistry is a result of favourable weak non-bonding interactions, which stabilize the transition state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Electrochromic in conjugated polymers

    International Nuclear Information System (INIS)

    Picado Valenzuela, Alfredo

    2007-01-01

    This revision considered object the description of one of the materials with the greatest potential in the field of electrochromic (mainly in the visible region): the conjugated polymers (CP), area of enormous potential both now and in a short time ahead. The CP are insulating materials and organic semiconductors in a state not doped. They can be doped positively or negatively being observed a significant increase in the conductivity and being generated a color change in these materials. The understanding of how optical properties vary based on the chemical structure of the polymer or its mixtures and more precisely of the alternatives that can be entered into the conjugated system or π system to obtain a material that besides to be flexible, environmentally stable, presents the colored states. The revision was centred chiefly in the polypyrrole (Ppy), the polythiophene (PTh) and their derivatives such as poly (3.4-ethylenedioxythiophene) (PEDOT). The advantage of using monomers with variable structure, to adjust the composition of the copolymer, or to blend with the PC, allows to obtain a variety of colored states that can be modulated through the visible spectrum and even with applications to wavelengths outside of this region. Because the PC presented at least two different colored states can be varied continuously as a function of the voltage applied. In some cases, they may submit multicoloured statements, which offers a range of possibilities for their application in flexible electronic devices type screens and windows. Applications include smart windows, camouflage clothing and data screens. This type of material is emerging as one of the substitutes of the traditional inorganic semiconductor, with the advantage of its low cost, high flexibility and the possibility to generate multiple colors through the handling of the monomers in the structure and control of energy of his band gap. (author) [es

  9. Generalized conjugate gradient squared

    Energy Technology Data Exchange (ETDEWEB)

    Fokkema, D.R.; Sleijpen, G.L.G. [Utrecht Univ. (Netherlands)

    1994-12-31

    In order to solve non-symmetric linear systems of equations, the Conjugate Gradient Squared (CGS) is a well-known and widely used iterative method. In practice the method converges fast, often twice as fast as the Bi-Conjugate Gradient method. This is what you may expect, since CGS uses the square of the BiCG polynomial. However, CGS may suffer from its erratic convergence behavior. The method may diverge or the approximate solution may be inaccurate. BiCGSTAB uses the BiCG polynomial and a product of linear factors in an attempt to smoothen the convergence. In many cases, this has proven to be very effective. Unfortunately, the convergence of BiCGSTAB may stall when a linear factor (nearly) degenerates. BiCGstab({ell}) is designed to overcome this degeneration of linear factors. It generalizes BiCGSTAB and uses both the BiCG polynomial and a product of higher order factors. Still, CGS may converge faster than BiCGSTAB or BiCGstab({ell}). So instead of using a product of linear or higher order factors, it may be worthwhile to look for other polynomials. Since the BiCG polynomial is based on a three term recursion, a natural choice would be a polynomial based on another three term recursion. Possibly, a suitable choice of recursion coefficients would result in method that converges faster or as fast as CGS, but less erratic. It turns out that an algorithm for such a method can easily be formulated. One particular choice for the recursion coefficients leads to CGS. Therefore one could call this algorithm generalized CGS. Another choice for the recursion coefficients leads to BiCGSTAB. It is therefore possible to mix linear factors and some polynomial based on a three term recursion. This way one may get the best of both worlds. The authors will report on their findings.

  10. Asymmetrically doped one-dimensional trans-polymers

    International Nuclear Information System (INIS)

    Caldas, Heron

    2009-01-01

    More than 30 years ago [H. Shirakawa, E.J. Louis, A.G. MacDiarmid, C.K. Chiang, A.J. Heeger, J. Chem. Soc. Chem. Comm. 578 (1977); S. Etemad, A.J. Heeger, Ann. Rev. Phys. Chem. 33 (1982) 443] it was discovered that doped trans-polyacetylene (CH) x , a one-dimensional (1D) conjugated polymer, exhibits electrical conductivity. In this work we show that an asymmetrically doped 1D trans-polymer has non-conventional properties, as compared to symmetrically doped systems. Depending on the level of asymmetry between the chemical potentials of the two involved fermionic species, the polymer can be in a partially or fully spin polarized state. Some possible experimental consequences of doped 1D trans-polymers used as 1D organic polarized conductors are discussed.

  11. Cyclodextrins in Asymmetric and Stereospecific Synthesis

    Directory of Open Access Journals (Sweden)

    Fliur Macaev

    2015-09-01

    Full Text Available Since their discovery, cyclodextrins have widely been used as green and easily available alternatives to promoters or catalysts of different chemical reactions in water. This review covers the research and application of cyclodextrins and their derivatives in asymmetric and stereospecific syntheses, with their division into three main groups: (1 cyclodextrins promoting asymmetric and stereospecific catalysis in water; (2 cyclodextrins’ complexes with transition metals as asymmetric and stereospecific catalysts; and (3 cyclodextrins’ non-metallic derivatives as asymmetric and stereospecific catalysts. The scope of this review is to systematize existing information on the contribution of cyclodextrins to asymmetric and stereospecific synthesis and, thus, to facilitate further development in this direction.

  12. Catalytic reforming methods

    Science.gov (United States)

    Tadd, Andrew R; Schwank, Johannes

    2013-05-14

    A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

  13. The central chirality of the metal atom and configurational relations in asymmetric reactions catalysed by metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Pavlov, Valerii A [N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)

    2004-12-31

    The recently published data on the dependence of the configuration of the reaction product on the structure of a catalytic metal complex (or an intermediate determining the asymmetric induction) in asymmetric catalytic reactions of hydrogen-transfer hydrogenation of acetophenone, hydroformylation of styrene, allylic alkylation of 1,3-diphenylprop-2-enyl acetate and alkylation of benzaldehyde with dialkylzinc are systematised. The applicabilities of octant and quadrant projections of the complexes are compared in order to establish the relationships between their structures and the enantioselectivities of the reactions. The known mechanisms of asymmetric induction in these reactions are discussed with regard to the C{sub 1} or C{sub 2} symmetry of the catalytic complex. The reasons for a decrease in the enantioselectivities of hydrogen-transfer hydrogenation, hydroformylation and alkylation by dialkylzinc [in the absence of Ti(OPr{sup i}){sub 4}] when performed with complexes with chiral C{sub 2}-symmetric ligands (as compared with complexes with asymmetric ligands) are considered.

  14. Reciprocity and conjugation fidelity in double phase conjugate mirrors

    Science.gov (United States)

    Delaye, Philippe; Fotiadi, Andrei A.; Roosen, Gerald

    1999-09-01

    It is well known that the conservation of energy in an optical system can be described by an invariant (intensity of the optical wave) during propagation. We identically show that reciprocity can be described by an invariant. This invariant is the overlap integral of two counterpropagating waves, that stays constant in every place of a reciprocal optical system. Applied to the double phase conjugate mirror (DPCM) this invariant can be rewritten as an equality between the ratio of the conjugation fidelity of the two ports of the DPCM and the ratio of the transmission in intensity of the two beams. If restricted to a plane wave case this relation becomes the well known equality of the diffraction efficiencies in both directions. We have implemented an experimental set-up that allows to show that the double phase conjugate mirror is reciprocal what confirms all the above discussion. We use the same set-up to measure the conjugation fidelity of the DPCM.

  15. Stable walking with asymmetric legs

    International Nuclear Information System (INIS)

    Merker, Andreas; Rummel, Juergen; Seyfarth, Andre

    2011-01-01

    Asymmetric leg function is often an undesired side-effect in artificial legged systems and may reflect functional deficits or variations in the mechanical construction. It can also be found in legged locomotion in humans and animals such as after an accident or in specific gait patterns. So far, it is not clear to what extent differences in the leg function of contralateral limbs can be tolerated during walking or running. Here, we address this issue using a bipedal spring-mass model for simulating walking with compliant legs. With the help of the model, we show that considerable differences between contralateral legs can be tolerated and may even provide advantages to the robustness of the system dynamics. A better understanding of the mechanisms and potential benefits of asymmetric leg operation may help to guide the development of artificial limbs or the design novel therapeutic concepts and rehabilitation strategies.

  16. Asymmetric information and macroeconomic dynamics

    Science.gov (United States)

    Hawkins, Raymond J.; Aoki, Masanao; Roy Frieden, B.

    2010-09-01

    We show how macroeconomic dynamics can be derived from asymmetric information. As an illustration of the utility of this approach we derive the equilibrium density, non-equilibrium densities and the equation of motion for the response to a demand shock for productivity in a simple economy. Novel consequences of this approach include a natural incorporation of time dependence into macroeconomics and a common information-theoretic basis for economics and other fields seeking to link micro-dynamics and macro-observables.

  17. Asymmetric Synthesis of Apratoxin E.

    Science.gov (United States)

    Mao, Zhuo-Ya; Si, Chang-Mei; Liu, Yi-Wen; Dong, Han-Qing; Wei, Bang-Guo; Lin, Guo-Qiang

    2016-10-21

    An efficient method for asymmetric synthesis of apratoxin E 2 is described in this report. The chiral lactone 8, recycled from the degradation of saponin glycosides, was utilized to prepare the non-peptide fragment 6. In addition to this "from nature to nature" strategy, olefin cross-metathesis (CM) was applied as an alternative approach for the formation of the double bond. Moreover, pentafluorophenyl diphenylphosphinate was found to be an efficient condensation reagent for the macrocyclization.

  18. DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

    NARCIS (Netherlands)

    García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard

    2016-01-01

    DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a

  19. Study of the nature and of the properties of paramagnetic centers observed by electron spin resonance in conjugated polymers

    International Nuclear Information System (INIS)

    Nechtschein, M.

    1967-06-01

    Conjugated polymers contain paramagnetic centers. It is established that these centers are free radicals and a model which defines their electronic structure is proposed. The interactions between these centers are studied, notably by dynamic polarisation experiments. Finally it is shown that the centers have catalytic properties. (author) [fr

  20. Asymmetric Wettability Directs Leidenfrost Droplets

    Energy Technology Data Exchange (ETDEWEB)

    Agapov, Rebecca L [ORNL; Boreyko, Jonathan B [ORNL; Briggs, Dayrl P [ORNL; Srijanto, Bernadeta R [ORNL; Retterer, Scott T [ORNL; Collier, Pat [ORNL; Lavrik, Nickolay V [ORNL

    2014-01-01

    Leidenfrost phenomena on nano- and microstructured surfaces are of great importance for increasing control over heat transfer in high power density systems utilizing boiling phenomena. They also provide an elegant means to direct droplet motion in a variety of recently emerging fluidic systems. Here, we report the fabrication and characterization of tilted nanopillar arrays (TNPAs) that exhibit directional Leidenfrost water droplets under dynamic conditions, namely on impact with Weber numbers 40 at T 325 C. The batch fabrication of the TNPAs was achieved by glancing-angle anisotropic reactive ion etching of a thermally dewet platinum mask, with mean pillar diameters of 100 nm and heights of 200-500 nm. In contrast to previously implemented macro- and microscopic Leidenfrost ratchets, our TNPAs induce no preferential directional movement of Leidenfrost droplets under conditions approaching steady-state film boiling, suggesting that the observed droplet directionality is not a result of asymmetric vapor flow. Using high-speed imaging, phase diagrams were constructed for the boiling behavior upon impact for droplets falling onto TNPAs, straight nanopillar arrays, and smooth silicon surfaces. The asymmetric impact and directional trajectory of droplets was exclusive to the TNPAs for impacts corresponding to the transition boiling regime, revealing that asymmetric wettability upon impact is the mechanism for the droplet directionality.

  1. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD

    2010-10-01

    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  2. Hydrazides and hydrazones as versatile Michael-Donors for iminium-catalyzed conjugate addition reactions

    OpenAIRE

    Fernández Chento, Maitane

    2014-01-01

    396 : il., graf. In the work compiled in this thesis is presented a series of strategies that have been studied and have lead to the asymmetric synthesis of useful building blocks in high yields and stereochemical control. These are reliant on the use of chiral secondary amines as the element that induces stereocontrol, where the activation of the substrate is based on the formation of an iminium ion intermediate within the catalytic cycle. In this sense, it has been demonstrated that, und...

  3. Sequential measurements of conjugate observables

    Energy Technology Data Exchange (ETDEWEB)

    Carmeli, Claudio [Dipartimento di Fisica, Universita di Genova, Via Dodecaneso 33, 16146 Genova (Italy); Heinosaari, Teiko [Department of Physics and Astronomy, Turku Centre for Quantum Physics, University of Turku, 20014 Turku (Finland); Toigo, Alessandro, E-mail: claudio.carmeli@gmail.com, E-mail: teiko.heinosaari@utu.fi, E-mail: alessandro.toigo@polimi.it [Dipartimento di Matematica ' Francesco Brioschi' , Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy)

    2011-07-15

    We present a unified treatment of sequential measurements of two conjugate observables. Our approach is to derive a mathematical structure theorem for all the relevant covariant instruments. As a consequence of this result, we show that every Weyl-Heisenberg covariant observable can be implemented as a sequential measurement of two conjugate observables. This method is applicable both in finite- and infinite-dimensional Hilbert spaces, therefore covering sequential spin component measurements as well as position-momentum sequential measurements.

  4. Protein carriers of conjugate vaccines

    Science.gov (United States)

    Pichichero, Michael E

    2013-01-01

    The immunogenicity of polysaccharides as human vaccines was enhanced by coupling to protein carriers. Conjugation transformed the T cell-independent polysaccharide vaccines of the past to T cell-dependent antigenic vaccines that were much more immunogenic and launched a renaissance in vaccinology. This review discusses the conjugate vaccines for prevention of infections caused by Hemophilus influenzae type b, Streptococcus pneumoniae, and Neisseria meningitidis. Specifically, the characteristics of the proteins used in the construction of the vaccines including CRM, tetanus toxoid, diphtheria toxoid, Neisseria meningitidis outer membrane complex, and Hemophilus influenzae protein D are discussed. The studies that established differences among and key features of conjugate vaccines including immunologic memory induction, reduction of nasopharyngeal colonization and herd immunity, and antibody avidity and avidity maturation are presented. Studies of dose, schedule, response to boosters, of single protein carriers with single and multiple polysaccharides, of multiple protein carriers with multiple polysaccharides and conjugate vaccines administered concurrently with other vaccines are discussed along with undesirable consequences of conjugate vaccines. The clear benefits of conjugate vaccines in improving the protective responses of the immature immune systems of young infants and the senescent immune systems of the elderly have been made clear and opened the way to development of additional vaccines using this technology for future vaccine products. PMID:23955057

  5. Four-Component Catalytic Machinery: Reversible Three-State Control of Organocatalysis by Walking Back and Forth on a Track.

    Science.gov (United States)

    Mittal, Nikita; Özer, Merve S; Schmittel, Michael

    2018-04-02

    A three-component supramolecular walker system is presented where a two-footed ligand (biped) walks back and forth on a tetrahedral 3D track upon the addition and removal of copper(I) ions, respectively. The addition of N-methylpyrrolidine as a catalyst to the walker system generates a four-component catalytic machinery, which acts as a three-state switchable catalytic ensemble in the presence of substrates for a conjugate addition. The copper(I)-ion-initiated walking process of the biped ligand on the track regulates the catalytic activity in three steps: ON versus int ON (intermediate ON) versus OFF. To establish the operation of the four-component catalytic machinery in a mixture of all constituents, forward and backward cycles were performed in situ illustrating that both the walking process and catalytic action are fully reversible and reproducible.

  6. Catalytic Antibodies: Concept and Promise

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 12; Issue 11. Catalytic Antibodies: Concept and Promise. Desirazu N Rao Bharath Wootla. General Article Volume 12 Issue ... Keywords. Catalytic antibodies; abzymes; hybridome technology; Diels– Alder reaction; Michaelis– Menten kinetics; Factor VIII.

  7. Catalytic interface erosion

    International Nuclear Information System (INIS)

    Meng, H.; Cohen, E.G.D.

    1995-01-01

    We study interface erosion processes: catalytic erosions. We present two cases. (1) The erosion of a completely occupied lattice by one single moving particle starting from somewhere inside the lattice, considering deterministic as well as probabilistic erosion rules. In the latter case, the eroded regions appear to have interfaces with continuously tunable fractal dimensions. (2) The kinetic roughening of an initially flat surface, where ballistic or diffusion-limited particles, which remain intact themselves, erode the surface coming from the outside, using the same erosion rules as in (1). Many features resembling realistic interfaces, for example, islands and inlets, are generated. The dependence of the surface width on the system size is due to both the erosion mechanism and the way particles move before reaching the surface

  8. Catalytic detritiation of water

    International Nuclear Information System (INIS)

    Rogers, M.L.; Lamberger, P.H.; Ellis, R.E.; Mills, T.K.

    1977-01-01

    A pilot-scale system has been used at Mound Laboratory to investigate the catalytic detritiation of water. A hydrophobic, precious metal catalyst is used to promote the exchange of tritium between liquid water and gaseous hydrogen at 60 0 C. Two columns are used, each 7.5 m long by 2.5 cm ID and packed with catalyst. Water flow is 5-10 cm 3 /min and countercurrent hydrogen flow is 9,000-12,000 cm 3 /min. The equipment, except for the columns, is housed in an inert atmosphere glovebox and is computer controlled. The hydrogen is obtained by electrolysis of a portion of the water stream. Enriched gaseous tritium is withdrawn for further enrichment. A description of the system is included along with an outline of its operation. Recent experimental data are discussed

  9. [Optimizing synthesis of conjugates of superoxide dismutase and catalase with aldehyde dextrans in surfactant microemulsions in heptane].

    Science.gov (United States)

    Eremin, A N; Metelitsa, D I

    1997-01-01

    Stable microemulsions in heptane retaining considerable amounts of the polar phase were obtained by using Aerosol OT (AOT), Triton X-45, and catalase. Conjugates of superoxide dismutase (SOD) and catalase with aldehyde dextrans (AD) were synthesized in surfactant microemulsions in heptane. Effects of the reaction duration, the microemulsion polar phase volume, and concentrations of enzymes and modifiers on the properties of these conjugates were studied. The catalytic properties of conjugates depended on the nature of the surfactants used to stabilize the microemulsions, the initial concentration of protein in the reaction mixture, and the enzyme: modifier ratio. The degree of modification of the enzymes and the stabilities of their conjugates during isolation from microemulsions by a water-acetone solution depended on the concentration of the AD used. The catalytic properties of the conjugates synthesized were compared, and their stabilities in the presence of H2O2 were described. We suggested a simple method of transformation of whole kinetic curves of H2O2 conversion in coordinates 1/ln([H2O2]0/[H2O2]t - 1/t for simultaneous measurement of the constant of the catalase inactivation rate by H2O2 (Cin, S-1) and the rate constant of the catalase complex 1 interaction with the second H2O2 molecule (C2, M-1 S-1). This method was tested experimentally. Values C2 and Cin for catalase and its conjugates with ADs were compared, and these results were discussed.

  10. Catalytic enantioselective N-nitroso aldol reaction of γ,δ-unsaturated δ-lactones.

    Science.gov (United States)

    Yanagisawa, Akira; Fujinami, Takeo; Oyokawa, Yu; Sugita, Takuya; Yoshida, Kazuhiro

    2012-05-18

    A catalytic asymmetric N-nitroso aldol reaction of γ,δ-didehydro-δ-lactones with nitrosoarenes was achieved using chiral tin dibromide as the chiral precatalyst and sodium ethoxide as the base precatalyst in the presence of ethanol. Optically active α-hydroxyamino ketones with up to 99% ee were regioselectively obtained in moderate to high yields from various δ-aryl-substituted γ,δ-didehydro-δ-valerolactones and o-substituted nitrosoarenes.

  11. Synthesis method of asymmetric gold particles.

    Science.gov (United States)

    Jun, Bong-Hyun; Murata, Michael; Hahm, Eunil; Lee, Luke P

    2017-06-07

    Asymmetric particles can exhibit unique properties. However, reported synthesis methods for asymmetric particles hinder their application because these methods have a limited scale and lack the ability to afford particles of varied shapes. Herein, we report a novel synthetic method which has the potential to produce large quantities of asymmetric particles. Asymmetric rose-shaped gold particles were fabricated as a proof of concept experiment. First, silica nanoparticles (NPs) were bound to a hydrophobic micro-sized polymer containing 2-chlorotritylchloride linkers (2-CTC resin). Then, half-planar gold particles with rose-shaped and polyhedral structures were prepared on the silica particles on the 2-CTC resin. Particle size was controlled by the concentration of the gold source. The asymmetric particles were easily cleaved from the resin without aggregation. We confirmed that gold was grown on the silica NPs. This facile method for synthesizing asymmetric particles has great potential for materials science.

  12. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik

    2003-09-01

    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  13. Conjugated Fatty Acid Synthesis

    Science.gov (United States)

    Rawat, Richa; Yu, Xiao-Hong; Sweet, Marie; Shanklin, John

    2012-01-01

    Conjugated linolenic acids (CLNs), 18:3 Δ9,11,13, lack the methylene groups found between the double bonds of linolenic acid (18:3 Δ9,12,15). CLNs are produced by conjugase enzymes that are homologs of the oleate desaturases FAD2. The goal of this study was to map the domain(s) within the Momordica charantia conjugase (FADX) responsible for CLN formation. To achieve this, a series of Momordica FADX-Arabidopsis FAD2 chimeras were expressed in the Arabidopsis fad3fae1 mutant, and the transformed seeds were analyzed for the accumulation of CLN. These experiments identified helix 2 and the first histidine box as a determinant of conjugase product partitioning into punicic acid (18:3 Δ9cis,11trans,13cis) or α-eleostearic acid (18:3 Δ9cis,11trans,13trans). This was confirmed by analysis of a FADX mutant containing six substitutions in which the sequence of helix 2 and first histidine box was converted to that of FAD2. Each of the six FAD2 substitutions was individually converted back to the FADX equivalent identifying residues 111 and 115, adjacent to the first histidine box, as key determinants of conjugase product partitioning. Additionally, expression of FADX G111V and FADX G111V/D115E resulted in an approximate doubling of eleostearic acid accumulation to 20.4% and 21.2%, respectively, compared with 9.9% upon expression of the native Momordica FADX. Like the Momordica conjugase, FADX G111V and FADX D115E produced predominantly α-eleostearic acid and little punicic acid, but the FADX G111V/D115E double mutant produced approximately equal amounts of α-eleostearic acid and its isomer, punicic acid, implicating an interactive effect of residues 111 and 115 in punicic acid formation. PMID:22451660

  14. LG tools for asymmetric wargaming

    Science.gov (United States)

    Stilman, Boris; Yakhnis, Alex; Yakhnis, Vladimir

    2002-07-01

    Asymmetric operations represent conflict where one of the sides would apply military power to influence the political and civil environment, to facilitate diplomacy, and to interrupt specified illegal activities. This is a special type of conflict where the participants do not initiate full-scale war. Instead, the sides may be engaged in a limited open conflict or one or several sides may covertly engage another side using unconventional or less conventional methods of engagement. They may include peace operations, combating terrorism, counterdrug operations, arms control, support of insurgencies or counterinsurgencies, show of force. An asymmetric conflict can be represented as several concurrent interlinked games of various kinds: military, transportation, economic, political, etc. Thus, various actions of peace violators, terrorists, drug traffickers, etc., can be expressed via moves in different interlinked games. LG tools allow us to fully capture the specificity of asymmetric conflicts employing the major LG concept of hypergame. Hypergame allows modeling concurrent interlinked processes taking place in geographically remote locations at different levels of resolution and time scale. For example, it allows us to model an antiterrorist operation taking place simultaneously in a number of countries around the globe and involving wide range of entities from individuals to combat units to governments. Additionally, LG allows us to model all sides of the conflict at their level of sophistication. Intelligent stakeholders are represented by means of LG generated intelligent strategies. TO generate those strategies, in addition to its own mathematical intelligence, the LG algorithm may incorporate the intelligence of the top-level experts in the respective problem domains. LG models the individual differences between intelligent stakeholders. The LG tools make it possible to incorporate most of the known traits of a stakeholder, i.e., real personalities involved in

  15. Asymmetric effects in customer satisfaction

    DEFF Research Database (Denmark)

    Füller, Johann; Matzler, Kurt; Faullant, Rita

    2006-01-01

    The results of this study on customer satisfaction in snowboard areas show that the relationship between an attribute and overall satisfaction can indeed be asymmetric. A 30-item self-administered survey was completed by snowboarders (n=2526) in 51 areas in Austria, Germany, Switzerland and Italy....... Results show that waiting time is a dissatisfier; it has a significant impact on overall customer satisfaction in the low satisfaction condition and becomes insignificant in the high satisfaction situation. Restaurants and bars are hybrids, i.e. importance does not depend on performance. Slopes, fun...... and entertainment and employees have a slightly stronger impact when satisfaction is low....

  16. Research study of conjugate materials; Conjugate material no chosa kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-03-01

    The paper reported an introductory research on possibilities of new glass `conjugate materials.` The report took up the structure and synthetic process of conjugate materials to be researched/developed, classified them according to structural elements on molecular, nanometer and cluster levels, and introduced the structures and functions. Further, as glasses with new functions to be proposed, the paper introduced transparent and high-strength glass used for houses and vehicles, light modulation glass which realizes energy saving and optical data processing, and environmentally functional glass which realizes environmental cleaning or high performance biosensor. An initial survey was also conducted on rights of intellectual property to be taken notice of in Japan and abroad in the present situation. Reports were summed up and introduced of Osaka National Research Institute, Electrotechnical Laboratory, and National Industrial Research Institute of Nagoya which are all carrying out leading studies of conjugate materials. 235 refs., 135 figs., 6 tabs.

  17. Conjugated polymer nanoparticles, methods of using, and methods of making

    KAUST Repository

    Habuchi, Satoshi

    2017-03-16

    Embodiments of the present disclosure provide for conjugated polymer nanoparticle, method of making conjugated polymer nanoparticles, method of using conjugated polymer nanoparticle, polymers, and the like.

  18. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.

    2011-07-01

    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  19. Instability of asymmetric shaft system

    Science.gov (United States)

    Srinath, R.; Sarkar, Abhijit; Sekhar, A. S.

    2016-02-01

    In the present work, parametric instability of asymmetric shaft mounted on bearings is studied. Towards this end, four different models of increasing complexity are studied. The equations corresponding to these models are formulated in the inertial reference frame. These equations involve a periodically varying coefficient. This is similar to classical Mathieu equation but in a multi-degree of freedom context. As such, under suitable parameter combination these systems result in growing oscillation amplitudes or instability. For wider generalization, the equations and results are presented in a non-dimensional form. The unstable parameter regimes are found using the Floquet theory and perturbation methods. These results are also corroborated with existing results in the literature. The nature of the stability boundary and its dependence on various system parameters is discussed in elaborate detail. The stability boundary can be used to determine unstable operating speed ranges for different asymmetric shaft cross-sections. Further, material, geometry and bearing selection guidelines for ensuring stable operations can be inferred from these results.

  20. Field factors for asymmetric collimators

    International Nuclear Information System (INIS)

    Turner, J.R.; Butler, A.P.H.

    1996-01-01

    In recent years manufacturers have been supplying linear accelerators with either a single pair or a dual pair of collimators. The use of a model to relate off-axis field factors to on-axis field factors obviates the need for repeat measurements whenever the asymmetric collimators are employed. We have investigated the variation of collimator scatter Sc, with distance of the central ray x from the central axis for a variety of non square field sizes. Collimator scatter was measured by in-air measurements with a build-up cap. The Primaty-Off-Centre-Ratio (POCR) was measured in-air by scanning orthogonally across the beam with an ionization chamber. The result of the investigation is the useful prediction of off-axis field factors for a range of rectangular asymmetric fields using the simple product of the on-axis field factor and the POCR in air. The effect of asymmetry on the quality of the beam and hence the percent depth dose will be discussed. (author)

  1. Ruthenium-catalysed decomposition of formic acid: Fuel cell and catalytic applications

    KAUST Repository

    Piola, Lorenzo

    2017-08-08

    The decomposition of formic acid into H2 and CO2 was successfully performed using a ruthenium hydride catalyst, without any concomitant CO evolution. The reaction mechanism is investigated by means of density functional theory calculations (DFT). The generated H2 was further exploited in a fuel cell to produce electricity. The catalytic hydrogenation of conjugated olefins, using this dihydrogen generation procedure, is also reported.

  2. Catalytic cracking with deasphalted oil

    Energy Technology Data Exchange (ETDEWEB)

    Beaton, W.I.; Taylor, J.L.; Peck, L.B.; Mosby, J.F.

    1990-07-10

    This patent describes a catalytic cracking process. It comprises: hydrotreating resid; thereafter deasphalting the hydrotreated resid to produce substantially deasphalted oil; catalytically cracking the hydrotreated oil in a catalytic cracking unit in the presence of a cracking catalyst to produce upgraded oil leaving coked catalyst; and regenerating the coked catalyst in the presence of a combustion-supporting gas comprising excess molecular oxygen in an amount greater than the stoichiometric amount required for substantially completely combusting the coke on the catalyst to carbon dioxide.

  3. Antibody Drug Conjugates: Preclinical Considerations.

    Science.gov (United States)

    Bornstein, Gadi G

    2015-05-01

    The development path for antibody drug conjugates (ADCs) is more complex and challenging than for unmodified antibodies. While many of the preclinical considerations for both unmodified and antibody drug conjugates are shared, special considerations must be taken into account when developing an ADC. Unlike unmodified antibodies, an ADC must preferentially bind to tumor cells, internalize, and traffic to the appropriate intracellular compartment to release the payload. Parameters that can impact the pharmacological properties of this class of therapeutics include the selection of the payload, the type of linker, and the methodology for payload drug conjugation. Despite a plethora of in vitro assays and in vivo models to screen and evaluate ADCs, the challenge remains to develop improved preclinical tools that will be more predictive of clinical outcome. This review will focus on preclinical considerations for clinically validated small molecule ADCs. In addition, the lessons learned from Mylotarg®, the first in class FDA-approved ADC, are highlighted.

  4. Persistence Mechanisms of Conjugative Plasmids

    DEFF Research Database (Denmark)

    Bahl, Martin Iain; Hansen, Lars H.; Sørensen, Søren Johannes

    2009-01-01

    maintenance in the host cell. These importantly include the ability to self-mobilize in a process termed conjugative transfer, which may occur across species barriers. Other plasmid stabilizing mechanisms include the multimer resolution system, active partitioning, and post-segregational-killing of plasmid......Are plasmids selfish parasitic DNA molecules or an integrated part of the bacterial genome? This chapter reviews the current understanding of the persistence mechanisms of conjugative plasmids harbored by bacterial cells and populations. The diversity and intricacy of mechanisms affecting...... the successful propagation and long-term continued existence of these extra-chromosomal elements is extensive. Apart from the accessory genetic elements that may provide plasmid-harboring cells a selective advantage, special focus is placed on the mechanisms conjugative plasmids employ to ensure their stable...

  5. Catalytic Membrane Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Boyle, T.J.; Brinker, C.J.; Gardner, T.J.; Hughes, R.C.; Sault, A.G.

    1998-12-01

    The proposed "catalytic membrane sensor" (CMS) was developed to generate a device which would selectively identify a specific reagent in a complex mixture of gases. This was to be accomplished by modifying an existing Hz sensor with a series of thin films. Through selectively sieving the desired component from a complex mixture and identifying it by decomposing it into Hz (and other by-products), a Hz sensor could then be used to detect the presence of the select component. The proposed "sandwich-type" modifications involved the deposition of a catalyst layered between two size selective sol-gel layers on a Pd/Ni resistive Hz sensor. The role of the catalyst was to convert organic materials to Hz and organic by-products. The role of the membraneo was to impart both chemical specificity by molecukir sieving of the analyte and converted product streams, as well as controlling access to the underlying Pd/Ni sensor. Ultimately, an array of these CMS elements encompassing different catalysts and membranes were to be developed which would enable improved selectivity and specificity from a compiex mixture of organic gases via pattern recognition methodologies. We have successfully generated a CMS device by a series of spin-coat deposited methods; however, it was determined that the high temperature required to activate the catalyst, destroys the sensor.

  6. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)

    2013-11-01

    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  7. Phase conjugation of acoustic beams

    Science.gov (United States)

    Bunkin, F. V.; Vlasov, D. V.; Kravtsov, Iu. A.

    The paper presents a classification of methods for the phase conjugation (PC) of wave fields of various physical natures on the basis of such nonliner interactions as stimulated scattering, and three- and four-wave interactions. Among the latter, attention is given to holographic (volume and surface) and parametric PC schemes, permitting PC with amplification. The possibility of developing phase-conjugated devices using acoustic PC devices on the basis of various nonlinear effects is considered. Experimental results pertaining to the PC of sound fields are presented, and possible applications of acoustic PC devices are indicated.

  8. Worst Asymmetrical Short-Circuit Current

    DEFF Research Database (Denmark)

    Arana Aristi, Iván; Holmstrøm, O; Grastrup, L

    2010-01-01

    In a typical power plant, the production scenario and the short-circuit time were found for the worst asymmetrical short-circuit current. Then, a sensitivity analysis on the missing generator values was realized in order to minimize the uncertainty of the results. Afterward the worst asymmetrical...

  9. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    Directory of Open Access Journals (Sweden)

    Pankaj Chauhan

    2012-12-01

    Full Text Available Ball-milling and pestle and mortar grinding have emerged as powerful methods for the development of environmentally benign chemical transformations. Recently, the use of these mechanochemical techniques in asymmetric organocatalysis has increased. This review highlights the progress in asymmetric organocatalytic reactions assisted by mechanochemical techniques.

  10. Asymmetric Frontal Brain Activity and Parental Rejection

    NARCIS (Netherlands)

    Huffmeijer, R.; Alink, L.R.A.; Tops, M.; Bakermans-Kranenburg, M.J.; van IJzendoorn, M.H.

    2013-01-01

    Asymmetric frontal brain activity has been widely implicated in reactions to emotional stimuli and is thought to reflect individual differences in approach-withdrawal motivation. Here, we investigate whether asymmetric frontal activity, as a measure of approach-withdrawal motivation, also predicts

  11. Catalytic pyrolysis of lignocellulosic biomass

    NARCIS (Netherlands)

    Seshan, Kulathuiyer; Sa, Jacinto

    2014-01-01

    This chapter reports on the latest developments of biomass catalytic pyrolysis for the production of fuels. The primary focus is on the role of catalysts in the process, namely, their influence in the liquefaction of lignocellulosic biomass.

  12. Asymmetric synthesis of an axially chiral antimitotic biaryl via an atropo-enantioselective Suzuki cross-coupling.

    Science.gov (United States)

    Herrbach, Audrey; Marinetti, Angela; Baudoin, Olivier; Guénard, Daniel; Guéritte, Françoise

    2003-06-13

    A catalytic asymmetric synthesis of the axially chiral bridged biaryl (-)-2, a structural analogue of natural (-)-rhazinilam possessing original antimitotic properties, is described. The key step is an intermolecular asymmetric Suzuki coupling, furnishing the nonbridged biaryl (-)-6, precursor of (-)-2, with up to 40% ee using binaphthyl ligand 7a. Various known or new binaphthyl and ferrocenyl phosphines as well as phosphetanes were screened as ligands in this reaction, the conditions of which were optimized. The comparison with another Suzuki coupling system showed that 7a is the most versatile ligand described to date for this type of transformation. This work gives the first application of the asymmetric Suzuki coupling to a biologically relevant target.

  13. A case of asymmetrical arthrogryposis

    International Nuclear Information System (INIS)

    Hageman, G.; Vette, J.K.; Willemse, J.

    1983-01-01

    Following the introduction of the conception that arthrogryposis is a symptom and not a clinical entity, a case of the very rare asymmetric form of neurogenic arthrogryposis is presented. The asymmetry of congenital contractures and weakness is associated with hemihypotrophy. The value of muscular CT-scanning prior to muscle biopsy is demonstrated. Muscular CT-scanning shows the extension of adipose tissue, which has replaced damaged muscles and therby indicates the exact site for muscle biopsy. Since orthopaedic treatment in arthrogryposis can be unrewarding due to severe muscular degeneration, preoperative scanning may provide additional important information on muscular function and thus be of benefit for surgery. The advantage of muscular CT-scanning in other forms of arthrogryposis requires further determination. The differential diagnosis with Werdnig-Hoffmann disease is discussed. (author)

  14. Packing of soft asymmetric dumbbells.

    Science.gov (United States)

    Sarić, Anđela; Bozorgui, Behnaz; Cacciuto, Angelo

    2011-06-09

    We use numerical simulations to study the phase behavior of a system of purely repulsive soft dumbbells as a function of size ratio of the two components and their relative degree of deformability. We find a plethora of different phases, which includes most of the mesophases observed in self-assembly of block copolymers but also crystalline structures formed by asymmetric, hard binary mixtures. Our results detail the phenomenological behavior of these systems when softness is introduced in terms of two different classes of interparticle interactions: (a) the elastic Hertz potential, which has a finite energy cost for complete overlap of any two components, and (b) a generic power-law repulsion with tunable exponent. We discuss how simple geometric arguments can be used to account for the large structural variety observed in these systems and detail the similarities and differences in the phase behavior for the two classes of potentials under consideration.

  15. Asymmetric Digital Subscriber Line (ADSL

    Directory of Open Access Journals (Sweden)

    Slavko Šarić

    2012-10-01

    Full Text Available ADSL (Asymmetric Digital Subscriber Line is a technologythat allows transmission at 8.488 Mbps over the existingtelephone copper line (speed range depending on the distance.ADSL circuit connects the ADSL modems by twisted-pairtelephone lines creating three infonnation channels: high speedsimplex (maximum 9 Mbps, medium speed duplex channel(maximum 2 Mbps and plain old telephone service channel.ADSL technology supports up to seven synchronous channelsthat can be configured to meet the needs of the end user.One could simultaneously view four movies stored in MPEG 1fonnat on separate television sets (MPEG 1 transmitted at 1.5Mbps, hold a video-conference (transmitted at 348 kbps,download data files from a server at 128 kbps via ISDN andeven receive a telephone call.

  16. High pressure structural studies of conjugated molecules

    DEFF Research Database (Denmark)

    Knaapila, Matti; Torkkeli, Mika; Scherf, Ullrich

    2018-01-01

    This chapter highlights high pressure GPa level structural studies of conjugated polymers and their analogues: conjugated oligomers and molecules, and rigid rod polymers. Attention is placed on our recent studies of polyfluorenes.......This chapter highlights high pressure GPa level structural studies of conjugated polymers and their analogues: conjugated oligomers and molecules, and rigid rod polymers. Attention is placed on our recent studies of polyfluorenes....

  17. Enhanced photophysics of conjugated polymers

    Science.gov (United States)

    Chen, Liaohai [Darien, IL

    2007-06-12

    A particulate fluorescent conjugated polymer surfactant complex and method of making and using same. The particles are between about 15 and about 50 nm and when formed from a lipsome surfactant have a charge density similar to DNA and are strongly absorbed by cancer cells.

  18. Conjugal Pairing in Escherichia Coli

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 13; Issue 8. Conjugal Pairing in Escherichia Coli. Joshua Lederberg. Classics Volume 13 Issue 8 August 2008 pp 793-794. Fulltext. Click here to view fulltext PDF. Permanent link: https://www.ias.ac.in/article/fulltext/reso/013/08/0793-0794 ...

  19. Galois conjugates of topological phases

    Science.gov (United States)

    Freedman, M. H.; Gukelberger, J.; Hastings, M. B.; Trebst, S.; Troyer, M.; Wang, Z.

    2012-01-01

    Galois conjugation relates unitary conformal field theories and topological quantum field theories (TQFTs) to their nonunitary counterparts. Here we investigate Galois conjugates of quantum double models, such as the Levin-Wen model. While these Galois-conjugated Hamiltonians are typically non-Hermitian, we find that their ground-state wave functions still obey a generalized version of the usual code property (local operators do not act on the ground-state manifold) and hence enjoy a generalized topological protection. The key question addressed in this paper is whether such nonunitary topological phases can also appear as the ground states of Hermitian Hamiltonians. Specific attempts at constructing Hermitian Hamiltonians with these ground states lead to a loss of the code property and topological protection of the degenerate ground states. Beyond this, we rigorously prove that no local change of basis can transform the ground states of the Galois-conjugated doubled Fibonacci theory into the ground states of a topological model whose Hermitian Hamiltonian satisfies Lieb-Robinson bounds. These include all gapped local or quasilocal Hamiltonians. A similar statement holds for many other nonunitary TQFTs. One consequence is that these nonunitary TQFTs do not describe physical realizations of topological phases. In particular, this implies that the “Gaffnian” wave function can not be the ground state of a gapped fractional quantum Hall state.

  20. Conjugal Pairing in Escherichia Coli

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 13; Issue 8. Conjugal Pairing in Escherichia Coli. Joshua Lederberg. Classics Volume 13 Issue 8 August 2008 pp 793-794. Fulltext. Click here to view fulltext PDF. Permanent link: http://www.ias.ac.in/article/fulltext/reso/013/08/0793-0794 ...

  1. Bacteriophytochromes control conjugation in Agrobacterium fabrum.

    Science.gov (United States)

    Bai, Yingnan; Rottwinkel, Gregor; Feng, Juan; Liu, Yiyao; Lamparter, Tilman

    2016-08-01

    Bacterial conjugation, the transfer of single stranded plasmid DNA from donor to recipient cell, is mediated through the type IV secretion system. We performed conjugation assays using a transmissible artificial plasmid as reporter. With this assay, conjugation in Agrobacterium fabrum was modulated by the phytochromes Agp1 and Agp2, photoreceptors that are most sensitive in the red region of visible light. In conjugation studies with wild-type donor cells carrying a pBIN-GUSINT plasmid as reporter that lacked the Ti (tumor inducing) plasmid, no conjugation was observed. When either agp1(-) or agp2(-) knockout donor strains were used, plasmid DNA was delivered to the recipient, indicating that both phytochromes suppress conjugation in the wild type donor. In the recipient strains, the loss of Agp1 or Agp2 led to diminished conjugation. When wild type cells with Ti plasmid and pBIN-GUS reporter plasmid were used as donor, a high rate of conjugation was observed. The DNA transfer was down regulated by red or far-red light by a factor of 3.5. With agp1(-) or agp2(-) knockout donor cells, conjugation in the dark was about 10 times lower than with the wild type donor, and with the double knockout donor no conjugation was observed. These results imply that the phytochrome system has evolved to inhibit conjugation in the light. The decrease of conjugation under different temperature correlated with the decrease of phytochrome autophosphorylation. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. REVIEW ARTICLE Conjugated Hyperbilirubinaemia in Early Infancy ...

    African Journals Online (AJOL)

    REVIEW ARTICLE Conjugated Hyperbilirubinaemia in Early Infancy. AOK Johnson. Abstract. Conjugated hyperbilirubinaemia exists when the conjugated serum bilirubin level is more than 2 mg/dl or more than 20 per cent of the total serum bilirubin. It is always pathological in early infancy. The causes are many and diverse ...

  3. A physics-explicit model of bacterial conjugation shows the stabilizing role of the conjugative junction

    OpenAIRE

    Pastuszak, Jakub; Waclaw, Bartlomiej

    2017-01-01

    Conjugation is a process in which bacteria exchange DNA through a physical connection (conjugative junction) between mating cells. Despite its significance for processes such as the spread of antibiotic resistance, the role of physical forces in conjugation is poorly understood. Here we use computer models to show that the conjugative junction not only serves as a link to transfer the DNA but it also mechanically stabilises the mating pair which significantly increases the conjugation rate. W...

  4. Arabinose-derived ketones as catalysts for asymmetric epoxidation of alkenes.

    Science.gov (United States)

    Shing, Tony K M; Leung, Gulice Y C; Luk, To

    2005-09-02

    [reaction: see text] Readily available arabinose-derived ketones, containing a tunable butane-2,3-diacetal as the steric blocker, displayed increasing enantioselectivity (up to 90% ee) with the size of the acetal alkyl group in catalytic asymmetric epoxidation of trans-disubstituted and trisubstituted alkenes. The stereochemical communication between our ketone catalysts and the alkene substrates is mainly due to steric effect, and electronic effect involving pi-pi interaction between phenyl groups of substrate and of catalyst did not appear to be operative in our system.

  5. Asymmetric hydrogenation of ketones: Tactics to achieve high reactivity, enantioselectivity, and wide scope

    Science.gov (United States)

    Ohkuma, Takeshi

    2010-01-01

    Ru complexes with chiral diphosphines and amine-based ligands achieve high catalytic activity and enantioselectivity for the hydrogenation of ketones under neutral to slightly basic conditions. The chiral environment is controllable by changing the combination of these two ligands. A concerted six-membered transition state is proposed to be the origin of the high reactivity. The η6-arene/TsDPEN–Ru and MsDPEN–Cp*Ir catalysts effect the asymmetric reaction under slightly acidic conditions. A variety of chiral secondary alcohols are obtained in high enantiomeric excess. PMID:20228621

  6. Asymmetric electron and hole transport in a high-mobility n-type conjugated polymer

    NARCIS (Netherlands)

    Wetzelaer, Gert-Jan A. H.; Kuik, Martijn; Olivier, Yoann; Lemaur, Vincent; Cornil, Jerome; Fabiano, Simone; Loi, Maria Antonietta; Blom, Paul W. M.; Cornil, Jérôme

    2012-01-01

    Electron-and hole-transport properties of the n-type copolymer poly{[N, N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-dithiophene)} [P(NDI2OD-T2), PolyeraActivInk (TM) N2200] are investigated. Electron- and hole-only devices with Ohmic contacts are

  7. TAT Peptide and Its Conjugates: Proteolytic Stability

    OpenAIRE

    Grunwald, Jacob; Rejtar, Tomas; Sawant, Rupa; Wang, Zhouxi; Torchilin, Vladimir P.

    2009-01-01

    The proteolytic cleavage of TATp, TATp-PEG1000-PE conjugate (TATp-conjugate), and TATp as TATp-conjugate in mixed micelles made of TATp-conjugate and PEG5000-PE (2.5% mol of TATp-conjugate, TATp-Mic) were studied by HPLC with fluorescent detection using fluorenylmethyl chloroformate (FMOC) labeling and by MALDI-TOF MS analysis. The cleavage kinetics were analyzed in human blood plasma and in trypsin-containing phosphate buffered saline (PBS), pH 7.4, to simulate the proteolytic activity of hu...

  8. Small Ubiquitin-like Modifier (SUMO) Conjugation Impedes Transcriptional Silencing by the Polycomb Group Repressor Sex Comb on Midleg*

    OpenAIRE

    Smith, Matthew; Mallin, Daniel R.; Simon, Jeffrey A.; Courey, Albert J.

    2011-01-01

    The Drosophila protein Sex Comb on Midleg (Scm) is a member of the Polycomb group (PcG), a set of transcriptional repressors that maintain silencing of homeotic genes during development. Recent findings have identified PcG proteins both as targets for modification by the small ubiquitin-like modifier (SUMO) protein and as catalytic components of the SUMO conjugation pathway. We have found that the SUMO-conjugating enzyme Ubc9 binds to Scm and that this interaction, which requires the Scm C-te...

  9. Catalytic bioreactors and methods of using same

    Science.gov (United States)

    Worden, Robert Mark; Liu, Yangmu Chloe

    2017-07-25

    Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

  10. Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate.

    Science.gov (United States)

    North, Michael; Omedes-Pujol, Marta

    2010-11-03

    Propylene carbonate can be used as a green solvent for the asymmetric synthesis of cyanohydrin trimethylsilyl ethers from aldehydes and trimethylsilyl cyanide catalysed by VO(salen)NCS, though reactions are slower in this solvent than the corresponding reactions carried out in dichloromethane. A mechanistic study has been undertaken, comparing the catalytic activity of VO(salen)NCS in propylene carbonate and dichloromethane. Reactions in both solvents obey overall second-order kinetics, the rate of reaction being dependent on the concentration of both the aldehyde and trimethylsilyl cyanide. The order with respect to VO(salen)NCS was determined and found to decrease from 1.2 in dichloromethane to 1.0 in propylene carbonate, indicating that in propylene carbonate, VO(salen)NCS is present only as a mononuclear species, whereas in dichloromethane dinuclear species are present which have previously been shown to be responsible for most of the catalytic activity. Evidence from ⁵¹V NMR spectroscopy suggested that propylene carbonate coordinates to VO(salen)NCS, blocking the free coordination site, thus inhibiting its Lewis acidity and accounting for the reduction in catalytic activity. This explanation was further supported by a Hammett analysis study, which indicated that Lewis base catalysis made a much greater contribution to the overall catalytic activity of VO(salen)NCS in propylene carbonate than in dichloromethane.

  11. Modeling of asymmetrical boost converters

    Directory of Open Access Journals (Sweden)

    Eliana Isabel Arango Zuluaga

    2014-01-01

    Full Text Available The asymmetrical interleaved dual boost (AIDB is a fifth-order DC/DC converter designed to interface photovoltaic (PV panels. The AIDB produces small current harmonics to the PV panels, reducing the power losses caused by the converter operation. Moreover, the AIDB provides a large voltage conversion ratio, which is required to step-up the PV voltage to the large dc-link voltage used in grid-connected inverters. To reject irradiance and load disturbances, the AIDB must be operated in a closed-loop and a dynamic model is required. Given that the AIDB converter operates in Discontinuous Conduction Mode (DCM, classical modeling approaches based on Continuous Conduction Mode (CCM are not valid. Moreover, classical DCM modeling techniques are not suitable for the AIDB converter. Therefore, this paper develops a novel mathematical model for the AIDB converter, which is suitable for control-pur-poses. The proposed model is based on the calculation of a diode current that is typically disregarded. Moreover, because the traditional correction to the second duty cycle reported in literature is not effective, a new equation is designed. The model accuracy is contrasted with circuital simulations in time and frequency domains, obtaining satisfactory results. Finally, the usefulness of the model in control applications is illustrated with an application example.

  12. Catalytic Asymmetric Synthesis of 8-Oxabicyclooctanes by Intermolecular [5+2] Pyrylium Cycloadditions**

    Science.gov (United States)

    Witten, Michael R.

    2014-01-01

    Highly enantioselective intermolecular [5+2] cycloadditions of pyrylium ion intermediates with electron-rich alkenes are promoted by a dual catalyst system composed of an achiral thiourea and a chiral primary aminothiourea. The observed enantioselectivity is highly dependent on the substitution pattern of the 5π component, and the basis for this effect is analyzed using experimental and computational evidence. The resultant 8-oxabicyclo[3.2.1]octane derivatives possess a scaffold common in natural products and medicinally active compounds and are also versatile chiral building blocks for further manipulations. Several stereoselective complexity-generating transformations of the 8-oxabicyclooctane products are presented. PMID:24782332

  13. Primary amine/CSA ion pair: A powerful catalytic system for the asymmetric enamine catalysis

    KAUST Repository

    Liu, Chen

    2011-05-20

    A novel ion pair catalyst containing a chiral counteranion can be readily derived by simply mixing cinchona alkaloid-derived diamine with chiral camphorsulfonic acid (CSA). A mixture of 9-amino(9-deoxy)epi-quinine 8 and (-)-CSA was found to be the best catalyst with matching chirality, enabling the direct amination of α-branched aldehydes to proceed in quantitative yields and with nearly perfect enantioselectivities. A 0.5 mol % catalyst loading was sufficient to catalyze the reaction, and a gram scale enantioselective synthesis of biologically important α-methyl phenylglycine has been successfully demonstrated. © 2011 American Chemical Society.

  14. Catalytic Asymmetric C–H Insertions of Rhodium(II) Azavinyl Carbenes

    OpenAIRE

    Chuprakov, Stepan; Malik, Jamal A.; Zibinsky, Mikhail; Fokin, Valery V.

    2011-01-01

    A highly efficient enantioselective C–H insertion of azavinyl carbenes into unactivated alkanes has been developed. These transition metal carbenes are directly generated from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of chiral Rh(II) carboxylates and are used for C–H functionalization of alkanes to access a variety of β-chiral sulfonamides.

  15. Catalytic Asymmetric Ring-Opening Reactions of Aziridines with 3-Aryl-Oxindoles.

    Science.gov (United States)

    Wang, Linqing; Li, Dan; Yang, Dongxu; Wang, Kezhou; Wang, Jie; Wang, Pengxin; Su, Wu; Wang, Rui

    2016-03-04

    A highly enantioselective ring-opening alkylation reaction between 3-aryl-oxindole and N-(2-picolinoyl) aziridine has been realized for the first time. The reaction is efficiently mediated by a simple in-situ-generated magnesium catalyst and 3,3'-fluorinated-BINOL (BINOL=1,1'-binaphthalene-2,2'-diol) has been identified as a powerful chiral ligand. Notably, the fluorine atom on the chiral ligand plays a key role in providing the desired chiral 3-alkyl-3-aryl oxindoles with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Synthesis of Chiral Tertiary Boronic Esters: Phosphonate-Directed Catalytic Asymmetric Hydroboration of Trisubstituted Alkenes.

    Science.gov (United States)

    Chakrabarty, Suman; Takacs, James M

    2017-05-03

    Highly enantioselective rhodium-catalyzed hydroboration of allylic phosphonates by pinacolborane affords chiral tertiary boronic esters. The β-borylated phosphonates are readily converted to chiral β- and γ-hydroxyphosphonates and aminophosphonates and to phosphonates bearing a quaternary carbon stereocenter. The utility of the latter is illustrated by the synthesis of (S)-(+)-bakuchiol methyl ether.

  17. Catalytic asymmetric mannich-type reaction of N-alkylidene-α-aminoacetonitrile with ketimines.

    Science.gov (United States)

    Lin, Shaoquan; Kawato, Yuji; Kumagai, Naoya; Shibasaki, Masakatsu

    2015-04-20

    Optically active vicinal diamines are versatile chiral building blocks in organic synthesis. A soft Lewis acid/hard Brønsted base cooperative catalyst allows for an efficient stereoselective coupling of N-alkylidene-α-aminoacetonitrile and ketimines to access this class of compounds bearing consecutive tetra- and trisubstituted stereogenic centers. The strategic use of a soft Lewis basic thiophosphinoyl group for ketimines is the key to promoting the reaction, and aliphatic ketimines serve as suitable substrates with as little as 3 mol % catalyst loading. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Congenital asymmetric crying face: a case report

    Directory of Open Access Journals (Sweden)

    Semra Kara

    2011-12-01

    Full Text Available Congenital asymmetric crying face is an anomalia caused by unilateral absence or weakness of depressor anguli oris muscle The major finding of the disease is the absence or weakness in the outer and lower movement of the commissure during crying. The other expression muscles are normal and the face is symmetric at rest. The asymmetry in congenital asymmetric crying face is most evident during infancy but decreases by age. Congenital asymmetric crying face can be associated with cervicofacial, musclebone, respiratory, genitourinary and central nervous system anomalia. It is diagnosed by physical examination. This paper presents a six days old infant with Congenital asymmetric crying face and discusses the case in terms of diagnosis and disease features.

  19. Synthesis of asymmetrical multiantennary human milk oligosaccharides

    NARCIS (Netherlands)

    Prudden, Anthony R; Liu, Lin; Capicciotti, Chantelle J.; Wolfert, Margreet A; Wang, Shuo; Gao, Zhongwei; Meng, Lu; Moremen, Kelley W; Boons, Geert-Jan

    2017-01-01

    Despite mammalian glycans typically having highly complex asymmetrical multiantennary architectures, chemical and chemoenzymatic synthesis has almost exclusively focused on the preparation of simpler symmetrical structures. This deficiency hampers investigations into the biology of glycan-binding

  20. Asymmetric cryptography based on wavefront sensing.

    Science.gov (United States)

    Peng, Xiang; Wei, Hengzheng; Zhang, Peng

    2006-12-15

    A system of asymmetric cryptography based on wavefront sensing (ACWS) is proposed for the first time to our knowledge. One of the most significant features of the asymmetric cryptography is that a trapdoor one-way function is required and constructed by analogy to wavefront sensing, in which the public key may be derived from optical parameters, such as the wavelength or the focal length, while the private key may be obtained from a kind of regular point array. The ciphertext is generated by the encoded wavefront and represented with an irregular array. In such an ACWS system, the encryption key is not identical to the decryption key, which is another important feature of an asymmetric cryptographic system. The processes of asymmetric encryption and decryption are formulized mathematically and demonstrated with a set of numerical experiments.

  1. Stereogenic-Only-at-Metal Asymmetric Catalysts.

    Science.gov (United States)

    Zhang, Lilu; Meggers, Eric

    2017-09-19

    Chirality is an essential feature of asymmetric catalysts. This review summarizes asymmetric catalysts that derive their chirality exclusively from stereogenic metal centers. Reported chiral-at-metal catalysts can be divided into two classes, namely, inert metal complexes, in which the metal fulfills a purely structural role, so catalysis is mediated entirely through the ligand sphere, and reactive metal complexes. The latter are particularly appealing because structural simplicity (only achiral ligands) is combined with the prospect of particularly effective asymmetric induction (direct contact of the substrate with the chiral metal center). Challenges and solutions for the design of such reactive stereogenic-only-at-metal asymmetric catalysts are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Magnetically Modified Asymmetric Supercapacitors, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — This Small Business Innovation Research Phase I project is for the development of an asymmetric supercapacitor that will have improved energy density and cycle life....

  3. Conjugated Polymers for Energy Production

    DEFF Research Database (Denmark)

    Livi, Francesco

    for scalable PSCs fully printed under ambient conditions [Adv. Energy Mater. 2015, 5, 1402186]. PPDTBT resulted to be the conjugated polymer with the best photovoltaic performance within the 104 synthesized macromolecules. Therefore, further studies have been done on such material. The impact of side chain......This dissertation is aimed at developing materials for flexible, large area, ITO-free polymer solar cells (PSCs) fully printed under ambient conditions. A large screening of conjugated polymers, both novel and well-known materials, has been carried out in order to find suitable candidates.......The reactivity of DArP has been further studied and applied to the synthesis of fluorinated copolymers featuring thiophene, which are largely used materials for organic electronics. In particular, by moving the bromine functionality from one monomer to the other, a big impact on the reactivity has been observed...

  4. Organometallic B12-DNA conjugate

    DEFF Research Database (Denmark)

    Hunger, Miriam; Mutti, Elena; Rieder, Alexander

    2014-01-01

    Design, synthesis, and structural characterization of a B12-octadecanucleotide are presented herein, a new organometallic B12-DNA conjugate. In such covalent conjugates, the natural B12 moiety may be a versatile vector for controlled in vivo delivery of oligonucleotides to cellular targets...... with transcobalamin (TC), but not so efficient with the homologous glycoproteins intrinsic factor and haptocorrin. Binding of the B12 octadecanucleotide to TC suggests the capacity of the B12 moiety to serve as a natural vector for specific transport of single stranded, organometallic oligonucleotide loads from...... in humans and animals, through the endogenous B12 transport systems. Binding of the organometallic B12 octadecanucleotide to the three important human proteins of B12 transport was studied, to examine its structural suitability for the task of eventual in vivo oligonucleotide delivery. Binding was efficient...

  5. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric

    2017-01-01

    The decoupling technique is a fundamental tool in quantum information theory with applications ranging from quantum thermodynamics to quantum many body physics to the study of black hole radiation. In this work we introduce the notion of catalytic decoupling, that is, decoupling in the presence...... of an uncorrelated ancilla system. This removes a restriction on the standard notion of decoupling, which becomes important for structureless resources, and yields a tight characterization in terms of the max-mutual information. Catalytic decoupling naturally unifies various tasks like the erasure of correlations...

  6. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne

    2007-01-01

    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...

  7. Engineered Asymmetric Composite Membranes with Rectifying Properties.

    Science.gov (United States)

    Wen, Liping; Xiao, Kai; Sainath, Annadanam V Sesha; Komura, Motonori; Kong, Xiang-Yu; Xie, Ganhua; Zhang, Zhen; Tian, Ye; Iyoda, Tomokazu; Jiang, Lei

    2016-01-27

    Asymmetric composite membranes with rectifying properties are developed by grafting pH-stimulus-responsive materials onto the top layer of the composite structure, which is prepared by two novel block copolymers using a phase-separation technique. This engineered asymmetric composite membrane shows potential applications in sensors, filtration, and nanofluidic devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. STUDI TEKNOLOGI ASYMMETRIC DIGITAL SUBSCRIBER LINE

    OpenAIRE

    Syarif, Syafruddin

    2008-01-01

    ADSL is one of the xDSL variants are being developed. ADSL allows high-speed data transmission with asymmetric bandwidth to support the implementation of multimedia services on broadband network using telephone cable network that already exist. Is called asymmetric because bit rate from the downstream (central to the customer) is greater than the upstream direction (customer to central) or it can be said that bit rate of downstream direction is different than the upstream dir...

  9. Studi Teknologi Asymmetric Digital Subcriber Line

    OpenAIRE

    SYAFRUDDIN SYARIF, SYAFRUDDIN SYARIF

    2008-01-01

    - ADSL is one of the xDSL variants are being developed. ADSL allows high-speed data transmission with asymmetric bandwidth to support the implementation of multimedia services on broadband network using telephone cable network that already exist. Is called asymmetric because bit rate from the downstream (central to the customer) is greater than the upstream direction (customer to central) or it can be said that bit rate of downstream direction is different than the upstream direction. Bit ...

  10. Cs2CO3/[bmim]Br as an Efficient, Green, and Reusable Catalytic System for the Synthesis of N-Alkyl Derivatives of Phthalimide under Mild Conditions

    Directory of Open Access Journals (Sweden)

    Alireza Hasaninejad

    2008-01-01

    Full Text Available Aza-conjugate addition of phthalimide to α,β-unsaturated esters efficiently achieves in the presence of catalytic amount of Cs2CO3 and ionic liquid 1-butyl-3-methylimidazolium bromide ([bmim]Br under mild reaction conditions (70°C to afford N-alkyl phthalimides in high yields and relatively short reaction times.

  11. Characteristics of Braced Excavation under Asymmetrical Loads

    Directory of Open Access Journals (Sweden)

    Changjie Xu

    2013-01-01

    Full Text Available Numerous excavation practices have shown that large discrepancies exist between field monitoring data and calculated results when the conventional symmetry-plane method (with half-width is used to design the retaining structure under asymmetrical loads. To examine the characteristics of a retaining structure under asymmetrical loads, we use the finite element method (FEM to simulate the excavation process under four different groups of asymmetrical loads and create an integrated model to tackle this problem. The effects of strut stiffness and wall length are also investigated. The results of numerical analysis clearly imply that the deformation and bending moment of diaphragm walls are distinct on different sides, indicating the need for different rebar arrangements when the excavation is subjected to asymmetrical loads. This study provides a practical approach to designing excavations under asymmetrical loads. We analyze and compare the monitoring and calculation data at different excavation stages and find some general trends. Several guidelines on excavation design under asymmetrical loads are drawn.

  12. Theoretical insights into catalytic mechanism of protein arginine methyltransferase 1.

    Directory of Open Access Journals (Sweden)

    Ruihan Zhang

    Full Text Available Protein arginine methyltransferase 1 (PRMT1, the major arginine asymmetric dimethylation enzyme in mammals, is emerging as a potential drug target for cancer and cardiovascular disease. Understanding the catalytic mechanism of PRMT1 will facilitate inhibitor design. However, detailed mechanisms of the methyl transfer process and substrate deprotonation of PRMT1 remain unclear. In this study, we present a theoretical study on PRMT1 catalyzed arginine dimethylation by employing molecular dynamics (MD simulation and quantum mechanics/molecular mechanics (QM/MM calculation. Ternary complex models, composed of PRMT1, peptide substrate, and S-adenosyl-methionine (AdoMet as cofactor, were constructed and verified by 30-ns MD simulation. The snapshots selected from the MD trajectory were applied for the QM/MM calculation. The typical SN2-favored transition states of the first and second methyl transfers were identified from the potential energy profile. Deprotonation of substrate arginine occurs immediately after methyl transfer, and the carboxylate group of E144 acts as proton acceptor. Furthermore, natural bond orbital analysis and electrostatic potential calculation showed that E144 facilitates the charge redistribution during the reaction and reduces the energy barrier. In this study, we propose the detailed mechanism of PRMT1-catalyzed asymmetric dimethylation, which increases insight on the small-molecule effectors design, and enables further investigations into the physiological function of this family.

  13. Asymmetric Bessel-Gauss beams.

    Science.gov (United States)

    Kotlyar, V V; Kovalev, A A; Skidanov, R V; Soifer, V A

    2014-09-01

    We propose a three-parameter family of asymmetric Bessel-Gauss (aBG) beams with integer and fractional orbital angular momentum (OAM). The aBG beams are described by the product of a Gaussian function by the nth-order Bessel function of the first kind of complex argument, having finite energy. The aBG beam's asymmetry degree depends on a real parameter c≥0: at c=0, the aBG beam is coincident with a conventional radially symmetric Bessel-Gauss (BG) beam; with increasing c, the aBG beam acquires a semicrescent shape, then becoming elongated along the y axis and shifting along the x axis for c≫1. In the initial plane, the intensity distribution of the aBG beams has a countable number of isolated optical nulls on the x axis, which result in optical vortices with unit topological charge and opposite signs on the different sides of the origin. As the aBG beam propagates, the vortex centers undergo a nonuniform rotation with the entire beam about the optical axis (c≫1), making a π/4 turn at the Rayleigh range and another π/4 turn after traveling the remaining distance. At different values of the c parameter, the optical nulls of the transverse intensity distribution change their position, thus changing the OAM that the beam carries. An isolated optical null on the optical axis generates an optical vortex with topological charge n. A vortex laser beam shaped as a rotating semicrescent has been generated using a spatial light modulator.

  14. Hydrogen-Bond Directed Regioselective Pd-Catalyzed Asymmetric Allylic Alkylation: The Construction of Chiral α-Amino Acids with Vicinal Tertiary and Quaternary Stereocenters.

    Science.gov (United States)

    Wei, Xuan; Liu, Delong; An, Qianjin; Zhang, Wanbin

    2015-12-04

    A Pd-catalyzed asymmetric allylic alkylation of azlactones with 4-arylvinyl-1,3-dioxolan-2-ones was developed, providing "branched" chiral α-amino acids with vicinal tertiary and quaternary stereocenters, in high yields and with excellent selectivities. Mechanistic studies revealed that the formation of a hydrogen bond between the Pd-allylic complex and azlactone isomer is responsible for the excellent regioselectivities. This asymmetric alkylation can be carried out on a gram scale without a loss of catalytic efficiency, and the resulting product can be further transformed to a chiral azetidine in two simple steps.

  15. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    ... improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies ...

  16. Catalytic properties of niobium compounds

    International Nuclear Information System (INIS)

    Tanabe, K.; Iizuka, T.

    1983-04-01

    The catalytic activity and selectivity of niobium compounds including oxides, salts, organometallic compounds and others are outlined. The application of these compounds as catalysts to diversified reactions is reported. The nature and action of niobium catalysts are characteristic and sometimes anomalous, suggesting the necessity of basic research and the potential use as catalysts for important processes in the chemical industry. (Author) [pt

  17. Catalytic carboxyester hydrolysis by diaminodiphenols

    Indian Academy of Sciences (India)

    Administrator

    Two diaminodiphenols, 1 and 2, have been examined as catalysts for the hydrolysis of 4- nitrophenyl acetate (NA) and 4-nitrophenylphosphate (NP) in aqueous-acetonitrile (25% acetonitrile v/v) media at 35ºC, I = 1·0 mol dm–3. The compound 1 enhances the hydrolysis rate of NA more than 105 times. Its catalytic efficiency ...

  18. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so ...

  19. Modelling conjugation with stochastic differential equations.

    Science.gov (United States)

    Philipsen, K R; Christiansen, L E; Hasman, H; Madsen, H

    2010-03-07

    Conjugation is an important mechanism involved in the transfer of resistance between bacteria. In this article a stochastic differential equation based model consisting of a continuous time state equation and a discrete time measurement equation is introduced to model growth and conjugation of two Enterococcus faecium strains in a rich exhaustible media. The model contains a new expression for a substrate dependent conjugation rate. A maximum likelihood based method is used to estimate the model parameters. Different models including different noise structure for the system and observations are compared using a likelihood-ratio test and Akaike's information criterion. Experiments indicating conjugation on the agar plates selecting for transconjugants motivates the introduction of an extended model, for which conjugation on the agar plate is described in the measurement equation. This model is compared to the model without plate conjugation. The modelling approach described in this article can be applied generally when modelling dynamical systems. 2009 Elsevier Ltd. All rights reserved.

  20. Inclined asymmetric librations in exterior resonances

    Science.gov (United States)

    Voyatzis, G.; Tsiganis, K.; Antoniadou, K. I.

    2018-04-01

    Librational motion in Celestial Mechanics is generally associated with the existence of stable resonant configurations and signified by the existence of stable periodic solutions and oscillation of critical (resonant) angles. When such an oscillation takes place around a value different than 0 or π , the libration is called asymmetric. In the context of the planar circular restricted three-body problem, asymmetric librations have been identified for the exterior mean motion resonances (MMRs) 1:2, 1:3, etc., as well as for co-orbital motion (1:1). In exterior MMRs the massless body is the outer one. In this paper, we study asymmetric librations in the three-dimensional space. We employ the computational approach of Markellos (Mon Not R Astron Soc 184:273-281, https://doi.org/10.1093/mnras/184.2.273, 1978) and compute families of asymmetric periodic orbits and their stability. Stable asymmetric periodic orbits are surrounded in phase space by domains of initial conditions which correspond to stable evolution and librating resonant angles. Our computations were focused on the spatial circular restricted three-body model of the Sun-Neptune-TNO system (TNO = trans-Neptunian object). We compare our results with numerical integrations of observed TNOs, which reveal that some of them perform 1:2 resonant, inclined asymmetric librations. For the stable 1:2 TNO librators, we find that their libration seems to be related to the vertically stable planar asymmetric orbits of our model, rather than the three-dimensional ones found in the present study.

  1. The Tcp conjugation system of Clostridium perfringens.

    Science.gov (United States)

    Wisniewski, Jessica A; Rood, Julian I

    2017-05-01

    The Gram-positive pathogen Clostridium perfringens possesses a family of large conjugative plasmids that is typified by the tetracycline resistance plasmid pCW3. Since these plasmids may carry antibiotic resistance genes or genes encoding extracellular or sporulation-associated toxins, the conjugative transfer of these plasmids appears to be important for the epidemiology of C. perfringens-mediated diseases. Sequence analysis of members of this plasmid family identified a highly conserved 35kb region that encodes proteins with various functions, including plasmid replication and partitioning. The tcp conjugation locus also was identified in this region, initially based on low-level amino acid sequence identity to conjugation proteins from the integrative conjugative element Tn916. Genetic studies confirmed that the tcp locus is required for conjugative transfer and combined with biochemical and structural analyses have led to the development of a functional model of the Tcp conjugation apparatus. This review summarises our current understanding of the Tcp conjugation system, which is now one of the best-characterized conjugation systems in Gram-positive bacteria. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Chemistry of Oligonucleotibe-Gold Nanoparticle Conjugates

    National Research Council Canada - National Science Library

    Letsinger, Robert

    2003-01-01

    Conjugates prepared by immobilizing thiol-terminated oligonucleotides onto gold nanoparticles from stable colloidal solutions in aqueous media The oligo nucleotides can serve as linkers to organize...

  3. Modelling conjugation with stochastic differential equations

    DEFF Research Database (Denmark)

    Philipsen, Kirsten Riber; Christiansen, Lasse Engbo; Hasman, Henrik

    2010-01-01

    using a likelihood-ratio test and Akaike's information criterion. Experiments indicating conjugation on the agar plates selecting for transconjugants motivates the introduction of an extended model, for which conjugation on the agar plate is described in the measurement equation. This model is compared......Conjugation is an important mechanism involved in the transfer of resistance between bacteria. In this article a stochastic differential equation based model consisting of a continuous time state equation and a discrete time measurement equation is introduced to model growth and conjugation of two...

  4. Asymmetric biocatalysis with microbial enzymes and cells.

    Science.gov (United States)

    Wohlgemuth, Roland

    2010-06-01

    Microbial enzymes and cells continue to be important tools and nature's privileged chiral catalysts for performing asymmetric biocatalysis from the analytical small scale to the preparative and large scale in synthesis and degradation. The application of biocatalysts for preparing molecular asymmetry has achieved high efficiency, enantioselectivity and yield and is experiencing today a worldwide renaissance. Recent developments in the discovery, development and production of stable biocatalysts, in the design of new biocatalytic processes and in the product recovery and purification processes have made biocatalytic approaches using microbial cells and enzymes attractive choices for the synthesis of chiral compounds. The methodologies of kinetic resolution and kinetic asymmetric transformation, dynamic kinetic resolution and deracemization, desymmetrization, asymmetric synthesis with or without diastereo control and multi-step asymmetric biocatalysis are finding increasing applications in research. The ever-increasing use of hydrolytic enzymes has been accompanied by new applications of oxidoreductases, transferases and lyases. Isomerases, already used in large-scale processes, and ligases, are emerging as interesting biocatalysts for new synthetic applications. The production of a wide variety of industrial products by asymmetric biocatalysis has even become the preferred method of production. Copyright 2010 Elsevier Ltd. All rights reserved.

  5. A DFT based method for calculating the surface energies of asymmetric MoP facets

    Science.gov (United States)

    Tian, Xinxin; Wang, Tao; Fan, Lifang; Wang, Yuekui; Lu, Haigang; Mu, Yuewen

    2018-01-01

    MoP is a promising catalyst in heterogeneous catalysis. Understanding its surface stability and morphology is the first and essential step in exploring its catalytic properties. However, traditional surface energy calculation method does not work for the asymmetric termination of MoP. In this work, we reported a useful DFT based method to get the surface energies of asymmetric MoP facets. Under ideal condition, the (101) surface with mixed Mo/P termination is most stable, followed by the (100) surface, while the (001) surface is least stable. Wulff construction reveals the exposure of six surfaces on the MoP nanoparticle, where the (101) has the largest contribution. Atomistic thermodynamics results reveal the changes in surface stability orders with experimental conditions, and the (001)-P termination becomes more and more stable with increasing P chemical potential, which indicates its exposure is possible at defined conditions. Our results agree well with the previous experimental XRD and TEM data. We believe the reported method for surface energy calculation could be extended to other similar systems with asymmetric surface terminations.

  6. Catalytic enantioselective synthesis of chiral organic compounds of ultra-high purity of >99% ee.

    Science.gov (United States)

    Negishi, Ei-ichi; Xu, Shiqing

    2015-01-01

    Shortly after the discovery of Zr-catalyzed carboalumination of alkynes in 1978, we sought expansion of the scope of this reaction so as to develop its alkene version for catalytic asymmetric C-C bond formation, namely the ZACA (Zr-catalyzed asymmetric carboalumination of alkenes). However, this seemingly easy task proved to be quite challenging. The ZACA reaction was finally discovered in 1995 by suppressing three competitive side reactions, i.e., (i) cyclic carbometalation, (ii) β-H transfer hydrometalation, and (iii) alkene polymerization. The ZACA reaction has been used to significantly modernize and improve syntheses of various natural products including deoxypolypropionates and isoprenoids. This review focuses on our recent progress on the development of ZACA-lipase-catalyzed acetylation-transition metal-catalyzed cross-coupling processes for highly efficient and enantioselective syntheses of a wide range of chiral organic compounds with ultra-high enantiomeric purities.

  7. Vapor Phase Catalytic Ammonia Reduction

    Science.gov (United States)

    Flynn, Michael T.; Harper, Lynn D. (Technical Monitor)

    1994-01-01

    This paper discusses the development of a Vapor Phase Catalytic Ammonia Reduction (VPCAR) teststand and the results of an experimental program designed to evaluate the potential of the technology as a water purification process. In the experimental program the technology is evaluated based upon product water purity, water recovery rate, and power consumption. The experimental work demonstrates that the technology produces high purity product water and attains high water recovery rates at a relatively high specific power consumption. The experimental program was conducted in 3 phases. In phase I an Igepon(TM) soap and water mixture was used to evaluate the performance of an innovative Wiped-Film Rotating-Disk evaporator and associated demister. In phase II a phenol-water solution was used to evaluate the performance of the high temperature catalytic oxidation reactor. In phase III a urine analog was used to evaluate the performance of the combined distillation/oxidation functions of the processor.

  8. Multi-agent Bargaining under Asymmetric Information

    DEFF Research Database (Denmark)

    Asplund, Marcus; Genesove, David

    information aspect is due to partly unobserved individual valuations of an elevator. We tailor Hellwig (2003) to the features of the retrofitting problem and use this to predict which building characteristics should make it easier for owners to agree. Data from Copenhagen broadly support the model......It is well know that asymmetric information might lead to underprovision of public goods. To test the theoretical prediction, we study the decision to retrofit an elevator into an old apartment building, in which each owner has to agree on how the investment cost is split. The asymmetric......'s predictions. We use transaction data to estimate the market value of an elevator and conclude that for approximately 30-40 percent of the buildings without an elevator the aggregate increase in value exceeds the investment cost....

  9. Renewable resource management under asymmetric information

    DEFF Research Database (Denmark)

    Jensen, Frank; Andersen, Peder; Nielsen, Max

    2013-01-01

    Asymmetric information between fishermen and the regulator is important within fisheries. The regulator may have less information about stock sizes, prices, costs, effort, productivity and catches than fishermen. With asymmetric information, a strong analytical tool is principal-agent analysis....... In this paper, we study asymmetric information about productivity within a principal-agent framework and a tax on fishing effort is considered. It is shown that a second best optimum can be achieved if the effort tax is designed such that low-productivity agents rent is exhausted, while high-productivity agents...... receive an information rent. The information rent is equivalent to the total incentive cost. The incentive costs arise as we want to reveal the agent's type....

  10. Asymmetric synthesis II more methods and applications

    CERN Document Server

    Christmann, Mathias

    2012-01-01

    After the overwhelming success of 'Asymmetric Synthesis - The Essentials', narrating the colorful history of asymmetric synthesis, this is the second edition with latest subjects and authors. While the aim of the first edition was mainly to honor the achievements of the pioneers in asymmetric syntheses, the aim of this new edition was bringing the current developments, especially from younger colleagues, to the attention of students. The format of the book remained unchanged, i.e. short conceptual overviews by young leaders in their field including a short biography of the authors. The growing multidisciplinary research within chemistry is reflected in the selection of topics including metal catalysis, organocatalysis, physical organic chemistry, analytical chemistry, and its applications in total synthesis. The prospective reader of this book is a graduate or undergraduate student of advanced organic chemistry as well as the industrial chemist who wants to get a brief update on the current developments in th...

  11. Subgap Absorption in Conjugated Polymers

    Science.gov (United States)

    Sinclair, M.; Seager, C. H.; McBranch, D.; Heeger, A. J; Baker, G. L.

    1991-01-01

    Along with X{sup (3)}, the magnitude of the optical absorption in the transparent window below the principal absorption edge is an important parameter which will ultimately determine the utility of conjugated polymers in active integrated optical devices. With an absorptance sensitivity of materials. We have used PDS to measure the optical absorption spectra of the conjugated polymers poly(1,4-phenylene-vinylene) (and derivitives) and polydiacetylene-4BCMU in the spectral region from 0.55 eV to 3 eV. Our spectra show that the shape of the absorption edge varies considerably from polymer to polymer, with polydiacetylene-4BCMU having the steepest absorption edge. The minimum absorption coefficients measured varied somewhat with sample age and quality, but were typically in the range 1 cm{sup {minus}1} to 10 cm{sup {minus}1}. In the region below 1 eV, overtones of C-H stretching modes were observed, indicating that further improvements in transparency in this spectral region might be achieved via deuteration of fluorination.

  12. Inorganic membranes and catalytic reactors

    OpenAIRE

    Rangel, Maria do Carmo

    1997-01-01

    Membrane reactors are reviewed with emphasis in their applications in catalysis field. The basic principles of these systems are presented as well as a historical development. The several kinds of catalytic membranes and their preparations are discussed including the problems, needs and challenges to be solved in order to use these reactors in commercial processes. Some applications of inorganic membrane reactors are also shown. It was concluded that these systems have a great potential for i...

  13. Sensitization of spinal cord nociceptive neurons with a conjugate of substance P and cholera toxin.

    Science.gov (United States)

    Caudle, Robert M; Mannes, Andrew J; Keller, Jason; Perez, Federico M; Suckow, Shelby K; Neubert, John K

    2007-05-10

    Several investigators have coupled toxins to neuropeptides for the purpose of lesioning specific neurons in the central nervous system. By producing deficits in function these toxin conjugates have yielded valuable information about the role of these cells. In an effort to specifically stimulate cells rather than kill them we have conjugated the neuropeptide substance P to the catalytic subunit of cholera toxin (SP-CTA). This conjugate should be taken up selectively by neurokinin receptor expressing neurons resulting in enhanced adenylate cyclase activity and neuronal firing. The conjugate SP-CTA stimulates adenylate cyclase in cultured cells that are transfected with either the NK1 or NK2 receptor, but not the NK3 receptor. We further demonstrate that intrathecal injection of SP-CTA in rats induces the phosphorylation of the transcription factor cyclic AMP response element binding protein (CREB) and also enhances the expression of the immediate early gene c-Fos. Behaviorally, low doses of SP-CTA (1 microg) injected intrathecally produce thermal hyperalgesia. At higher doses (10 microg) peripheral sensitivity is suppressed suggesting that descending inhibitory pathways may be activated by the SP-CTA induced sensitization of spinal cord neurons. The finding that stimulation of adenylate cyclase in neurokinin receptor expressing neurons in the spinal cord produces thermal hyperalgesia is consistent with the known actions of these neurons. These data demonstrate that cholera toxin can be targeted to specific cell types by coupling the catalytic subunit to a peptide agonist for a g-protein coupled receptor. Furthermore, these results demonstrate that SP-CTA can be used as a tool to study sensitization of central neurons in vivo in the absence of an injury.

  14. Sensitization of spinal cord nociceptive neurons with a conjugate of substance P and cholera toxin

    Directory of Open Access Journals (Sweden)

    Perez Federico M

    2007-05-01

    Full Text Available Abstract Background Several investigators have coupled toxins to neuropeptides for the purpose of lesioning specific neurons in the central nervous system. By producing deficits in function these toxin conjugates have yielded valuable information about the role of these cells. In an effort to specifically stimulate cells rather than kill them we have conjugated the neuropeptide substance P to the catalytic subunit of cholera toxin (SP-CTA. This conjugate should be taken up selectively by neurokinin receptor expressing neurons resulting in enhanced adenylate cyclase activity and neuronal firing. Results The conjugate SP-CTA stimulates adenylate cyclase in cultured cells that are transfected with either the NK1 or NK2 receptor, but not the NK3 receptor. We further demonstrate that intrathecal injection of SP-CTA in rats induces the phosphorylation of the transcription factor cyclic AMP response element binding protein (CREB and also enhances the expression of the immediate early gene c-Fos. Behaviorally, low doses of SP-CTA (1 μg injected intrathecally produce thermal hyperalgesia. At higher doses (10 μg peripheral sensitivity is suppressed suggesting that descending inhibitory pathways may be activated by the SP-CTA induced sensitization of spinal cord neurons. Conclusion The finding that stimulation of adenylate cyclase in neurokinin receptor expressing neurons in the spinal cord produces thermal hyperalgesia is consistent with the known actions of these neurons. These data demonstrate that cholera toxin can be targeted to specific cell types by coupling the catalytic subunit to a peptide agonist for a g-protein coupled receptor. Furthermore, these results demonstrate that SP-CTA can be used as a tool to study sensitization of central neurons in vivo in the absence of an injury.

  15. Homogeneous asymmetric catalysis in fragrance chemistry.

    Science.gov (United States)

    Ciappa, Alessandra; Bovo, Sara; Bertoldini, Matteo; Scrivanti, Alberto; Matteoli, Ugo

    2008-06-01

    Opposite enantiomers of a chiral fragrance may exhibit different olfactory activities making a synthesis in high enantiomeric purity commercially and scientifically interesting. Accordingly, the asymmetric synthesis of four chiral odorants, Fixolide, Phenoxanol, Citralis, and Citralis Nitrile, has been investigated with the aim to develop practically feasible processes. In the devised synthetic schemes, the key step that leads to the formation of the stereogenic center is the homogeneous asymmetric hydrogenation of a prochiral olefin. By an appropriate choice of the catalyst and the reaction conditions, Phenoxanol, Citralis, and Citralis Nitrile were obtained in high enantiomeric purity, and odor profiles of the single enantiomers were determined.

  16. Asymmetric energy B factory at KEK

    International Nuclear Information System (INIS)

    Watanabe, Yasushi

    1994-01-01

    An introductory review is given on the project of the Asymmetric Energy B factory at KEK. First, the motivation for B factory is discussed. The most interesting and important topic there is the measurement of CP violation in other than the K-system. Thus, CP violation in the B decays is reviewed rather extensively, especially on how the angles of the unitarity triangle can be measured at an asymmetric energy B factory. Then the B factory project at KEK is briefly reviewed. (author)

  17. Direct catalytic enantio- and diastereoselective Mannich reaction of isocyanoacetates and ketimines.

    Science.gov (United States)

    Ortín, Irene; Dixon, Darren J

    2014-03-24

    A catalytic asymmetric synthesis of imidazolines with a fully substituted β-carbon atom by a Mannich-type addition/cyclization reaction of isocyanoacetate pronucleophiles and N-diphenylphosphinoyl ketimines has been developed. When a combination of a cinchona-derived aminophosphine precatalyst and silver oxide was employed as a binary catalyst system, good reactivity, high diastereoselectivities (up to 99:1 d.r.), and excellent enantioselectivities (up to 99% ee) were obtained for a range of substrates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Samarium(II) iodide-mediated intramolecular conjugate additions of alpha,beta-unsaturated lactones.

    Science.gov (United States)

    Molander, Gary A; St Jean, David J

    2002-05-31

    Samarium(II) iodide, in the presence of catalytic amounts of nickel(II) iodide, has been used to promote intramolecular conjugate additions of alkyl halides onto alpha,beta-unsaturated lactones. This process has been shown to be applicable to a number of alpha,beta-unsaturated lactones, including tetrasubstituted olefins, and has been demonstrated to be quite general for the formation of saturated bicyclic and tricyclic lactones. The method presented herein provides a mild, efficient process to form structurally complex lactones from simple precursors.

  19. DENDRIMER CONJUGATES FOR SELECTIVE OF PROTEIN AGGREGATES

    DEFF Research Database (Denmark)

    2004-01-01

    Dendrimer conjugates are presented, which are formed between a dendrimer and a protein solubilising substance. Such dendrimer conjugates are effective in the treatment of protein aggregate-related diseases (e.g. prion-related diseases). The protein solubilising substance and the dendrimer together...

  20. Parallel synthesis and screening of peptide conjugates.

    Science.gov (United States)

    Dirksen, Anouk; Madsen, Mark; Dello Iacono, Giuseppe; Matin, Marla J; Bacica, Michael; Stanković, Nebojša; Callans, Sherri; Bhat, Abhijit

    2014-06-18

    Peptide conjugates represent an emerging class of therapeutics. However, in contrast to that of small molecules and peptides, the discovery and optimization of peptide conjugates is low in throughput, resource intensive, time-consuming, and based on educated decisions rather than screening. A strategy for the parallel synthesis and screening of peptide conjugates is presented that (1) reduces variability in the conjugation steps; (2) provides a new method to rapidly and quantitatively measure conversion in crude conjugation mixtures; (3) introduces a purification step using an immobilized chemical scavenger that does not rely on protein-specific binding; and (4) is supported by robust analytical methods to characterize the large number of end products. Copper-free click chemistry is used as the chemoselective ligation method for conjugation and purification. The productivity in the generation and screening of peptide conjugates is significantly improved by applying this strategy as is demonstrated by the optimization of the anti-Angiopoietin-2 (Ang2) CovX-body, CVX-060, a peptide-antibody scaffold conjugate that has advanced in clinical trials for oncology indications.

  1. Tales of conjugation and sex pheromones

    Science.gov (United States)

    2011-01-01

    This review covers highlights of the author's experience becoming and working as a plasmid biologist. The account chronicles a progression from studies of ColE1 DNA in Escherichia coli to Gram-positive bacteria with an emphasis on conjugation in enterococci. It deals with gene amplification, conjugative transposons and sex pheromones in the context of bacterial antibiotic resistance. PMID:22016844

  2. Bio-Conjugates for Nanoscale Applications

    DEFF Research Database (Denmark)

    Villadsen, Klaus

    Bio-conjugates for Nanoscale Applications is the title of this thesis, which covers three different projects in chemical bio-conjugation research, namely synthesis and applications of: Lipidated fluorescent peptides, carbohydrate oxime-azide linkers and N-aryl O-R2 oxyamine derivatives. Lipidated...

  3. Preconditioning the modified conjugate gradient method ...

    African Journals Online (AJOL)

    In this paper, the convergence analysis of the conventional conjugate Gradient method was reviewed. And the convergence analysis of the modified conjugate Gradient method was analysed with our extension on preconditioning the algorithm. Convergence of the algorithm is a function of the condition number of M-1A.

  4. Singularities and Conjugate Points in FLRW Spacetimes

    NARCIS (Netherlands)

    Lam, Huibert het; Prokopec, Tom

    2017-01-01

    Conjugate points play an important role in the proofs of the singularity theorems of Hawking and Penrose. We examine the relation between singularities and conjugate points in FLRW spacetimes with a singularity. In particular we prove a theorem that when a non-comoving, non-spacelike geodesic in a

  5. CONJUGATED BLOCK-COPOLYMERS FOR ELECTROLUMINESCENT DIODES

    NARCIS (Netherlands)

    Hilberer, A; Gill, R.E; Herrema, J.K; Malliaras, G.G; Wildeman, J.; Hadziioannou, G

    In this article we review results obtained in our laboratory on the design and study of new light-emitting polymers. We are interested in the synthesis and characterisation of block copolymers with regularly alternating conjugated and non conjugated sequences. The blocks giving rise to luminescence

  6. The Conjugate Acid-Base Chart.

    Science.gov (United States)

    Treptow, Richard S.

    1986-01-01

    Discusses the difficulties that beginning chemistry students have in understanding acid-base chemistry. Describes the use of conjugate acid-base charts in helping students visualize the conjugate relationship. Addresses chart construction, metal ions, buffers and pH titrations, and the organic functional groups and nonaqueous solvents. (TW)

  7. Crystallization and preliminary crystallographic studies of the Pasteurella multocida toxin catalytic domain

    Energy Technology Data Exchange (ETDEWEB)

    Miyazawa, Masayuki [Research Institute for Microbial Diseases, Osaka University, 3-1 Yamada-oka, Suita-shi, Osaka 565-0871 (Japan); Kitadokoro, Kengo [Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan); Kamitani, Shigeki; Shime, Hiroaki; Horiguchi, Yasuhiko, E-mail: horiguti@biken.osaka-u.ac.jp [Research Institute for Microbial Diseases, Osaka University, 3-1 Yamada-oka, Suita-shi, Osaka 565-0871 (Japan)

    2006-09-01

    The C-terminal catalytic domain of P. multocida toxin, which is the virulence factor of the organism in P. multocida, has been expressed, purified and subsequently crystallized using the sitting-drop vapour-diffusion technique. The C-terminal catalytic domain of Pasteurella multocida toxin, which is the virulence factor of the organism in P. multocida, has been expressed, purified and subsequently crystallized using the sitting-drop vapour-diffusion technique. Native diffraction data to 1.9 Å resolution were obtained at the BL44XU beamline of SPring-8 from a flash-frozen crystal at 100 K. The crystals belong to space group C2, with unit-cell parameters a = 111.0, b = 150.4, c = 77.1 Å, β = 105.5°, and are likely to contain one C-PMT (726 residues) per asymmetric unit.

  8. Block copolymer hollow fiber membranes with catalytic activity and pH-response

    KAUST Repository

    Hilke, Roland

    2013-08-14

    We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes. © 2013 American Chemical Society.

  9. Atropisomeric chiral dienes in asymmetric catalysis: C(2) -symmetric (Z,Z)-2,3-bis[1-(diphenylphosphinyl)ethylidene]tetralin as a highly active Lewis base organocatalyst.

    Science.gov (United States)

    Ogasawara, Masamichi; Kotani, Shunsuke; Nakajima, Hikaru; Furusho, Haruka; Miyasaka, Mitsuru; Shimoda, Yasushi; Wu, Wei-Yi; Sugiura, Masaharu; Takahashi, Tamotsu; Nakajima, Makoto

    2013-12-16

    Diene catalysts with a twist: The title C2 -symmetric tetralin-fused 1,3-butadiene derivative is atropisomeric and can be resolved into the two helical enantiomers. The optically pure compound showed excellent enantioselectivity as well as unusually high catalytic activity as a chiral Lewis basic organocatalyst in the asymmetric allylation of various aldehydes with β-substituted allyltrichlorosilanes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Approximate error conjugation gradient minimization methods

    Science.gov (United States)

    Kallman, Jeffrey S

    2013-05-21

    In one embodiment, a method includes selecting a subset of rays from a set of all rays to use in an error calculation for a constrained conjugate gradient minimization problem, calculating an approximate error using the subset of rays, and calculating a minimum in a conjugate gradient direction based on the approximate error. In another embodiment, a system includes a processor for executing logic, logic for selecting a subset of rays from a set of all rays to use in an error calculation for a constrained conjugate gradient minimization problem, logic for calculating an approximate error using the subset of rays, and logic for calculating a minimum in a conjugate gradient direction based on the approximate error. In other embodiments, computer program products, methods, and systems are described capable of using approximate error in constrained conjugate gradient minimization problems.

  11. A novel one-pot de-blocking and conjugation reaction step leads to process intensification in the manufacture of PEGylated insulin IN-105.

    Science.gov (United States)

    Hazra, Partha; Chatterjee, Amarnath; Shabandri, Qais; Adhikary, Laxmi; Dave, Nitesh; Buddha, Madhavan

    2012-10-01

    Bio-catalytic in vitro multistep reactions can be combined in a single step in one pot by optimizing multistep reactions under identical reaction condition. Using this analogy, the process of making PEGylated insulin, IN-105, was simplified. Instead of taking the purified active insulin bulk powder as the starting material for the conjugation step, an insulin process intermediate, partially purified insulin ester, was taken as starting material. Process intensification (PI) was established by performing a novel de-blocking (de-esterification) of the partially purified insulin ester and conjugation at B-29 Lys residue of B chain with a short-chain methoxy polyethylene glycol (mPEG) in a single-pot reactor. The chromatographic profile at the end of the reaction was found similar irrespective of whether both the reactions were performed sequentially or simultaneously. The conjugated product of interest, IN-105 (conjugation at LysB(29)), was purified from the heterogeneous mixture of conjugated products. The new manufacturing process was deduced to be more simplified and economical in making the insulin conjugates as several downstream purification steps could be circumvented. The physicochemical characteristics of IN-105 manufactured through this economic process was found to be indifferent from the product formed through the traditional process where the conjugation starting material was purified from bulk insulin.

  12. Asymmetric transition disks: Vorticity or eccentricity?

    NARCIS (Netherlands)

    Ataiee, S.; Pinilla, P.; Zsom, A.; Dullemond, C.P.; Dominik, C.; Ghanbari, J.

    2013-01-01

    Context. Transition disks typically appear in resolved millimeter observations as giant dust rings surrounding their young host stars. More accurate observations with ALMA have shown several of these rings to be in fact asymmetric: they have lopsided shapes. It has been speculated that these rings

  13. MHD stability of vertically asymmetric tokamak equilibria

    International Nuclear Information System (INIS)

    Dalhed, H.E.; Grimm, R.C.; Johnson, J.L.

    1981-03-01

    The ideal MHD stability properties of a special class of vertically asymmetric tokamak equilibria are examined. The calculations confirm that no major new physical effects are introduced and the modifications can be understood by conventional arguments. The results indicate that significant departures from up-down symmetry can be tolerated before the reduction in β becomes important for reactor operation

  14. Organocatalytic asymmetric transfer hydrogenation of imines

    NARCIS (Netherlands)

    de Vries, Johannes G.; Mrsic, Natasa; Mršić, Nataša

    2011-01-01

    The asymmetric organocatalytic transfer hydrogenation of imines can be accomplished in good yields with high enantioselectivities through the use of BINOL-derived phosphoric acids as catalysts and Hantzsch esters or benzothiazoles as the hydride source. The same method can also be applied to the

  15. Asymmetric Hydrogenation of 3-Substituted Pyridinium Salts

    NARCIS (Netherlands)

    Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent

    2016-01-01

    The use of an equivalent amount of an organic base leads to high enantiomeric excess in the asymmetric hydrogenation of N-benzylated 3-substituted pyridinium salts into the corresponding piperidines. Indeed, in the presence of Et3N, a Rh-JosiPhos catalyst reduced a range of pyridinium salts with ee

  16. Modelling asymmetric growth in crowded plant communities

    DEFF Research Database (Denmark)

    Damgaard, Christian

    2010-01-01

    -asymmetric growth part, where growth is assumed to be proportional to a power function of the size of the individual, and a term that reduces the relative growth rate as a decreasing function of the individual plant size and the competitive interactions from other plants in the neighbourhood....

  17. Mixed gas plasticization phenomena in asymmetric membranes

    NARCIS (Netherlands)

    Visser, Tymen

    2006-01-01

    This thesis describes the thorough investigation of mixed gas transport behavior of asymmetric membranes in the separation of feed streams containing plasticizing gases in order to gain more insights into the complicated behavior of plasticization. To successfully employ gas separation membranes in

  18. Asymmetrical Representation of Gender in Amharic | Leyew ...

    African Journals Online (AJOL)

    Asymmetrical Representation of Gender in Amharic. ... In gender linguistics, it is customary to observe the correlation between language and socially constructed gender roles. Language users show male and female language ... and novels written in Amharic). Key words: Language, Society, Gender, Pragmatics, Correlation ...

  19. Palladium catalysed asymmetric alkylation of benzophenone Schiff ...

    Indian Academy of Sciences (India)

    Asymmetric alkyl substitution of various benzophenone Schiff base substrates under biphasic conditions proceeded using optically active Palladium(II) complexes. The corresponding products were obtained in high yields but with moderate enantiomeric excess (ee). Addition of specific ionic liquids to the reaction medium ...

  20. The Asymmetric Predictive Effects of Investor Sentiment

    DEFF Research Database (Denmark)

    Lutz, Chandler

    that the relationship between sentiment and returns is asymmetric: during bear markets, high sentiment predicts low future returns for the cross-section of speculative stocks and the market overall while the relationship during bull markets is weak and often insignicant. Thus, the results suggest that sophisticated...

  1. The Asymmetric Effects of Investor Sentiment

    DEFF Research Database (Denmark)

    Lutz, Chandler

    2016-01-01

    are asymmetric: During peak-to-trough periods of investor sentiment (sentiment contractions), high sentiment predicts low future returns for the cross section of speculative stocks and for the market overall, whereas the relationship between sentiment and future returns is positive but relatively weak during...

  2. Motion in an Asymmetric Double Well

    OpenAIRE

    Brizard, Alain J.; Westland, Melissa C.

    2016-01-01

    The problem of the motion of a particle in an asymmetric double well is solved explicitly in terms of the Weierstrass and Jacobi elliptic functions. While the solution of the orbital motion is expressed simply in terms of the Weierstrass elliptic function, the period of oscillation is more directly expressed in terms of periods of the Jacobi elliptic functions.

  3. Spectral inequalities for the quantum asymmetric top

    Energy Technology Data Exchange (ETDEWEB)

    Bourget, Alain; McMillen, Tyler [Department of Mathematics, California State University (Fullerton), McCarthy Hall 154, Fullerton, CA 92834 (United States)], E-mail: abourget@fullerton.edu, E-mail: tmcmillen@fullerton.edu

    2009-03-06

    We consider the spectrum of the quantum asymmetric top. Unlike in the case when two or three moments of inertia are equal, when the moments of inertia are distinct all degeneracy in the spectrum of the operator is removed. We derive inequalities for the spectra based on recent results on the interlacing of Van Vleck zeros.

  4. Computing modal dispersion characteristics of radially Asymmetric ...

    African Journals Online (AJOL)

    We developed a matrix theory that applies to with non-circular/circular but concentric layers fibers. And we compute the dispersion characteristics of radially unconventional fiber, known as Asymmetric Bragg fiber. An attempt has been made to determine how the modal characteristics change as circular Bragg fiber is ...

  5. Charge asymmetric cosmic rays as a probe of flavor violating asymmetric dark matter

    Energy Technology Data Exchange (ETDEWEB)

    Masina, Isabella [Dipartimento di Fisica, Università di Ferrara and INFN Sez. di Ferrara, Via Saragat 1, I-44100 Ferrara (Italy); Sannino, Francesco, E-mail: masina@fe.infn.it, E-mail: sannino@cp3-origins.net [CP3-Origins and DIAS, University of Southern Denmark, Campusvej 55, DK-5230 Odense M (Denmark)

    2011-09-01

    The recently introduced cosmic sum rules combine the data from PAMELA and Fermi-LAT cosmic ray experiments in a way that permits to neatly investigate whether the experimentally observed lepton excesses violate charge symmetry. One can in a simple way determine universal properties of the unknown component of the cosmic rays. Here we attribute a potential charge asymmetry to the dark sector. In particular we provide models of asymmetric dark matter able to produce charge asymmetric cosmic rays. We consider spin zero, spin one and spin one-half decaying dark matter candidates. We show that lepton flavor violation and asymmetric dark matter are both required to have a charge asymmetry in the cosmic ray lepton excesses. Therefore, an experimental evidence of charge asymmetry in the cosmic ray lepton excesses implies that dark matter is asymmetric.

  6. Unique Helicase Determinants in the Essential Conjugative TraI Factor from Salmonella enterica Serovar Typhimurium Plasmid pCU1

    Energy Technology Data Exchange (ETDEWEB)

    McLaughlin, Krystle J.; Nash, Rebekah P.; Redinbo, Mathew R. (UNC)

    2014-06-16

    The widespread development of multidrug-resistant bacteria is a major health emergency. Conjugative DNA plasmids, which harbor a wide range of antibiotic resistance genes, also encode the protein factors necessary to orchestrate the propagation of plasmid DNA between bacterial cells through conjugative transfer. Successful conjugative DNA transfer depends on key catalytic components to nick one strand of the duplex DNA plasmid and separate the DNA strands while cell-to-cell transfer occurs. The TraI protein from the conjugative Salmonella plasmid pCU1 fulfills these key catalytic roles, as it contains both single-stranded DNA-nicking relaxase and ATP-dependent helicase domains within a single, 1,078-residue polypeptide. In this work, we unraveled the helicase determinants of Salmonella pCU1 TraI through DNA binding, ATPase, and DNA strand separation assays. TraI binds DNA substrates with high affinity in a manner influenced by nucleic acid length and the presence of a DNA hairpin structure adjacent to the nick site. TraI selectively hydrolyzes ATP, and mutations in conserved helicase motifs eliminate ATPase activity. Surprisingly, the absence of a relatively short (144-residue) domain at the extreme C terminus of the protein severely diminishes ATP-dependent strand separation. Collectively, these data define the helicase motifs of the conjugative factor TraI from Salmonella pCU1 and reveal a previously uncharacterized C-terminal functional domain that uncouples ATP hydrolysis from strand separation activity.

  7. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)

    1995-12-31

    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  8. Catalytic Organometallic Reactions of Ammonia

    Science.gov (United States)

    Klinkenberg, Jessica L.

    2012-01-01

    Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

  9. Studies of Catalytic Model Systems

    DEFF Research Database (Denmark)

    Holse, Christian

    of the Cu/ZnO nanoparticles is highly relevant to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boost the catalytic activity. The dynamical behavior of the nanoparticles under reducing and oxidizing environments were studied by means of ex situ X...... as the nanoparticles are reduced. The Cu/ZnO nanoparticles are tested on a  µ-reactor platform and prove to be active towards methanol synthesis, making it an excellent model system for further investigations into activity depended morphology changes....

  10. Catalytic Combustion of Ethyl Acetate

    OpenAIRE

    ÖZÇELİK, Tuğba GÜRMEN; ATALAY, Süheyda; ALPAY, Erden

    2014-01-01

    The catalytic combustion of ethyl acetate over prepared metal oxide catalysts was investigated. CeO, Co2O3, Mn2O3, Cr2O3, and CeO-Co2O3 catalysts were prepared on monolith supports and they were tested. Before conducting the catalyst experiments, we searched for the homogeneous gas phase combustion reaction of ethyl acetate. According to the homogeneous phase experimental results, 45% of ethyl acetate was converted at the maximum reactor temperature tested (350 °C). All the prepare...

  11. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  12. TAT peptide and its conjugates: proteolytic stability.

    Science.gov (United States)

    Grunwald, Jacob; Rejtar, Tomas; Sawant, Rupa; Wang, Zhouxi; Torchilin, Vladimir P

    2009-08-19

    The proteolytic cleavage of TATp, TATp-PEG(1000)-PE conjugate (TATp-conjugate), and TATp as TATp-conjugate in mixed micelles made of TATp-conjugate and PEG(5000)-PE (2.5% mol of TATp-conjugate, TATp-Mic) were studied by HPLC with fluorescent detection using fluorenylmethyl chloroformate (FMOC) labeling and by MALDI-TOF MS analysis. The cleavage kinetics were analyzed in human blood plasma and in trypsin-containing phosphate buffered saline (PBS), pH 7.4, to simulate the proteolytic activity of human plasma. The trypsinolysis of free TATp, TATp-conjugate, and TATp-Mic revealed that the main initial fragmentation is an endocleavage at the carboxyl terminus resulting in an Arg-Arg (RR) dimer. The trypsinolysis followed pseudo-first-order kinetics. The cleavage of the free TATp was relatively fast with a half-life of a few minutes (t(1/2) ∼ 3.5 min). The TATp-conjugate showed more stability with about a 3-fold increase in half-life (t(1/2) ∼ 10 min). TATp in TATp-Mic was highly protected against proteolysis with an over 100-fold increase in half-life (t(1/2) ∼ 430 min). The shielding of TATp by PEG moieties in the proposed TATp-Mic is of great importance for its potential use as a cell-penetrating moiety for multifunctional "smart" drug delivery systems with detachable PEG.

  13. Photo-catalytic properties of doped or substituted polyaniline-coated Fe3O4 nanoparticles

    Science.gov (United States)

    Zhang, Fan; Song, Weijie; Zhao, Zongshan; Cheng, Yang

    2014-10-01

    In this work, doped and substituted polyaniline (PANI)-coated Fe3O4 nanoparticles were synthesized. The diameter of Fe3O4 core was 430 nm, and the thickness of PANI shell was 20 nm. Their photo-catalytic properties for methyl orange were investigated under natural light illumination. The photo-catalytic activity sequence of three doped PANI/Fe3O4 nanoparticles is as follows: iodine doping > without doping > graphite powder doping. This should be due to the difference of structure, conductivity, and band gap resulting from the dopants. The photo-catalytic activity of five substituted PANI/Fe3O4 nanoparticles followed the order of poly(1,2-diaminobenzene) > poly( o-toluidine) > poly(1,3-diaminobenzene) > PANI > polydiphenylamine. The effects of steric hindrance, activated ability, and conjugation of the substituents on the photo-catalytic properties were discussed. The ESR results suggested that O2 and H2O2 dissolved in the solutions were important factors on the photo-degradation, and the ·OH generated via h+-mediated pathway was the key oxidizing substance.

  14. Palladium-Catalyzed Asymmetric Quaternary Stereocenter Formation

    NARCIS (Netherlands)

    Gottumukkala, Aditya L.; Matcha, Kiran; Lutz, Martin; de Vries, Johannes G.; Minnaard, Adriaan J.

    2012-01-01

    An efficient palladium catalyst is presented for the formation of benzylic quaternary stereocenters by conjugate addition of arylboronic acids to a variety of beta,beta-disubstituted carbocyclic, heterocyclic, and acyclic enones. The catalyst is readily prepared from PdCl2, PhBOX, and AgSbF6, and

  15. Palladium-catalyzed asymmetric quaternary stereocenter formation

    NARCIS (Netherlands)

    Gottumukkala, A.L.; Matcha, K.; Lutz, M.|info:eu-repo/dai/nl/304828971; de Vries, J.G.; Minnaard, A.J.

    2012-01-01

    An efficient palladium catalyst is presented for the formation of benzylic quaternary stereocenters by conjugate addition of arylboronic acids to a variety of β,β-disubstituted carbocyclic, heterocyclic, and acyclic enones. The catalyst is readily prepared from PdCl2, PhBOX, and AgSbF6, and provides

  16. Preparation of Mesoporous SBA-16 Silica-Supported Biscinchona Alkaloid Ligand for the Asymmetric Dihydroxylation of Olefins

    Directory of Open Access Journals (Sweden)

    Shaheen M. Sarkar

    2014-01-01

    Full Text Available Optically active cinchona alkaloid was anchored onto mesoporous SBA-16 silica and the as-prepared complex was used as a heterogeneous chiral ligand of osmium tetraoxide for the asymmetric dihydroxylation of olefins. The prepared catalytic system provided 90–93% yield of vicinal diol with 92–99% enantioselectivity. The ordered mesoporous SBA-16 silica was found to be a valuable support for the cinchona alkaloid liganded osmium catalyst system which is frequently used in chemical industries and research laboratories for olefin functionalization.

  17. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  18. [Covalent stretokinase-polyethylene glycol conjugates with increased stability and decreased side effects].

    Science.gov (United States)

    Aĭsina, R B; Mukhametova, L I; Tiupa, D V; Gershkovich, K B; Gulin, D A; Varfolomeev, S D

    2014-01-01

    By variation of incubation time of streptokinase (SK) with activated polyethylene glycol (M 2 and 5 kDa, PEG2 and PEG5) it was obtained covalent SK-PEG2 and SK-PEG5 conjugates with different modification degrees of amino groups of protein and their properties were studied in vitro as compared with free SK. It was shown, that maximal stable and retaining 80% fibrinolytic activity SK-PEG2 and SK-PEG5 conjugates are formed when the modification degrees of amino groups of protein are 54 and 52%, respectively. At interaction of the given conjugates with equimolar plasminogen concentration it were formed the plasmin (Pm)·SK-PEG2 and Pm·SK-PEG5 activator complexes, the maximal amidase activity of which is equal to activity of unmodified Pm·SK complex. It was found, that the catalytic efficiency of plasminogen activation (kPg/KPg) by Pm·SK-PEG2 complex is some higher (2.84 min(-1) μM(-1)) and by Pm·SK-PEG5 complex is lower (1.17 min(-1) μM(-1)), than that by unmodified Pm·SK complex (2.1 min(-1) μM(-1)). Investigation of lysis kinetics of human plasma clots and depletion of plasminogen and fibrinogen in plasma under the action of free SK and SK-PEG2 and SK-PEG5 conjugates showed, that the latter's have high thrombolytic activity (89 and 72%, respectively) and cause 3.5-4 fold lower side effects, than free SK. Obtained by us SK-PEG2 and SK-PEG5 conjugates with increased stability and decreased side effects may be used in the therapy of thrombotic disorders.

  19. Multicomponent Synthesis of Cyclic Depsipeptide Mimics by Ugi Reaction Including Cyclic Hemiacetals Derived from Asymmetric Organocatalysis.

    Science.gov (United States)

    de la Torre, Alexander F; Rivera, Daniel G; Concepción, Odette; Echemendia, Radell; Correa, Arlene G; Paixão, Márcio W

    2016-02-05

    The synthesis of novel cyclic depsipeptide mimics by means of an organocatalytic conjugate addition, leading to chiral cyclic hemiacetals, followed by a multicomponent reaction with α-amino acids and isocyanides, is described. The initial organocatalytic step is employed for the asymmetric derivatization of α,β-unsaturated aldehydes to 4,5-disubstituted 2-hydroxytetrahydropyrans, which are next used as chiral bifunctional substrates on the Ugi five-center three-component reaction, giving rise to nine-membered-ring lactones. This sequential approach proved to be suitable for the rapid generation of molecular complexity through the combination of aliphatic, dipeptidic, glucosidic, and lipidic isocyanides with several amino acids, thus giving access to amido-, glyco-, and lipo-depsipeptide scaffolds featuring natural product-like structures.

  20. Asymmetric epoxidation of cis/trans-β-methylstyrene catalysed by immobilised Mn(salen) with different linkages: heterogenisation of homogeneous asymmetric catalysis.

    Science.gov (United States)

    Zhang, Haidong; Zou, Yu; Wang, Yi-Meng; Shen, Yu; Zheng, Xuxu

    2014-06-16

    Immobilised Mn(salen) catalysts with two different linkages were studied in the asymmetric epoxidation of cis/trans-β-methylstyrene using NaClO as oxidant. The immobilised Mn(salen) complexes inside nanopores can lead to different catalytic behaviour compared with that of homogeneous Jacobsen catalyst. The rigidity of the linkage was found to be a key factor affecting the catalytic performance of immobilised catalysts. The immobilised catalyst with a rigid linkage exhibited comparable chemical selectivity, enantioselectivity and cis/trans ratio of product formation to that obtained with homogeneous Jacobsen catalysts. In contrast, the immobilised catalyst with a flexible linkage gave remarkably lower chemical selectivity, enantioselectivity and inverted cis/trans ratio compared with the results obtained with the homogeneous Jacobsen catalyst and the immobilised catalyst with rigid linkage. Thus, for immobilised Mn(salen) catalysts, a rigid linkage connecting active centres to the support is essential to obtain activity and enantioselectivity as high as those obtained in homogeneous systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Catalytic converters in the fireplace

    International Nuclear Information System (INIS)

    Kouki, J.

    1995-01-01

    In addition to selecting the appropriate means of heating and using dry fuel, the amount of harmful emissions contained by flue gases produced by fireplaces can be reduced by technical means. One such option is to use an oxidising catalytic converter. Tests at TTS Institute's Heating Studies Experimental Station have focused on two such converters (dense and coarse) mounted in light-weight iron heating stoves. The ability of the dense catalytic converter to oxidise carbon monoxide gases proved to be good. The concentration of carbon monoxide in the flue gases was reduced by as much as 90 %. Measurements conducted by VTT (Technical Research Centre of Finland) showed that the conversion of other gases, e.g. of methane, was good. The exhaust resistance caused by the dense converter was so great as to necessitate the mounting of a fluegas evacuation fan in the chimney for the purpose of creating sufficient draught. When relying on natural draught, the dense converter requires a chimney of at least 7 metres and a by-pass connection while the fire is being lit. In addition, the converter will have to be constructed to be less dense and this will mean that it's capability to oxidise non-combusted gases will be reduced. The coarse converter did not impair the draught but it's oxidising property was insufficient. With the tests over, the converter was not observed to have become blocked up by impurities

  2. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  3. Conjugated Polymers and Oligomers: Structural and Soft Matter Aspects

    DEFF Research Database (Denmark)

    conjugated polymer backbone, water soluble conjugated polyelectrolytes and surfactants, conjugated molecules and biomolecules and DNA and the advanced use of synchrotron radiation and electron microscopy to find out structural details in conjugated molecule films and devices as well as under ambient...

  4. Oligonucleotides conjugated to short lysine chains.

    Science.gov (United States)

    Winkler, Johannes; Urban, Ernst; Noe, Christian R

    2005-01-01

    A new method for synthesizing oligonucleotide peptide conjugates by an in-line approach is presented. A phosphorothioate oligonucleotide with the sequence of bcl-2 targeted Oblimersen by employing a modified 2'-amino-2'-desoxy-uridine nucleotide bearing a succinyl linker at the 2' position was prepared. The carboxyl group was protected for solid-phase synthesis as the benzyl ester. Ester cleavage was afforded by a phase transfer reaction using palladium nanoparticles as catalyst and cyclohexadiene as hydrogen donor. Short tails of up to three lysyl residues were conjugated to the oligonucleotide by an inverse stepwise peptide synthesis. The conjugates were characterized by HPLC, mass spectrometry, and circular dichroism. Influence of lysyl tails on CD spectra were minimal. Melting profiles revealed only minimal destabilizing effects on duplexes by conjugation of peptides.

  5. Stochastic differential equations used to model conjugation

    DEFF Research Database (Denmark)

    Philipsen, Kirsten Riber; Christiansen, Lasse Engbo

    be split into measurement noise and system noise. The system noise is used to compensate for those biological processes not explicitly described by the model. Many authors model conjugation by a simple mass action model first proposed by Levin et al. (1979). Also Michaelis-Menten dependence...... by an experiment conducted with E. faecium. In addition, we suggest that a 3rd order time-delay must be included in the model to account for the delay before a newly conjugated plasmid is expressed. A ML estimate of the parameters based on experimental data is found using the software CTSM. The conjugation rate......Stochastic differential equations (SDEs) are used to model horizontal transfer of antibiotic resis- tance by conjugation. The model describes the concentration of donor, recipient, transconjugants and substrate. The strength of the SDE model over the traditional ODE models is that the noise can...

  6. Deciphering conjugative plasmid permissiveness in wastewater microbiomes

    DEFF Research Database (Denmark)

    Jacquiod, Samuel Jehan Auguste; Brejnrod, Asker Daniel; Milani, Stefan Morberg

    2017-01-01

    Wastewater treatment plants (WWTPs) are designed to robustly treat polluted water. They are characterized by ceaseless flows of organic, chemical and microbial matter, followed by treatment steps before environmental release. WWTPs are hotspots of horizontal gene transfer between bacteria via...... conjugative plasmids, leading to dissemination of potentially hazardous genetic material such as antimicrobial resistance genes (AMRGs). While current focus is on the threat of AMRGs spreading and their environmental maintenance, conjugative plasmid transfer dynamics within and between bacterial communities...... still remains largely uncharted. Furthermore, current in vitro methods used to assess conjugation in complex microbiomes do not include in situ behaviours of recipient cells, resulting in partial understanding of transfers. We investigated the in vitro conjugation capacities of WWTP microbiomes from...

  7. Design and Application of Antimicrobial Peptide Conjugates

    Directory of Open Access Journals (Sweden)

    Andre Reinhardt

    2016-05-01

    Full Text Available Antimicrobial peptides (AMPs are an interesting class of antibiotics characterized by their unique antibiotic activity and lower propensity for developing resistance compared to common antibiotics. They belong to the class of membrane-active peptides and usually act selectively against bacteria, fungi and protozoans. AMPs, but also peptide conjugates containing AMPs, have come more and more into the focus of research during the last few years. Within this article, recent work on AMP conjugates is reviewed. Different aspects will be highlighted as a combination of AMPs with antibiotics or organometallic compounds aiming to increase antibacterial activity or target selectivity, conjugation with photosensitizers for improving photodynamic therapy (PDT or the attachment to particles, to name only a few. Owing to the enormous resonance of antimicrobial conjugates in the literature so far, this research topic seems to be very attractive to different scientific fields, like medicine, biology, biochemistry or chemistry.

  8. Bianisotropic metamaterials based on twisted asymmetric crosses

    International Nuclear Information System (INIS)

    Reyes-Avendaño, J A; Sampedro, M P; Juárez-Ruiz, E; Pérez-Rodríguez, F

    2014-01-01

    The effective bianisotropic response of 3D periodic metal-dielectric structures, composed of crosses with asymmetrically-cut wires, is investigated within a general homogenization theory using the Fourier formalism and the form-factor division approach. It is found that the frequency dependence of the effective permittivity for a system of periodically-repeated layers of metal crosses exhibits two strong resonances, whose separation is due to the cross asymmetry. Besides, bianisotropic metamaterials, having a base of four twisted asymmetric crosses, are proposed. The designed metamaterials possess negative refractive index at frequencies determined by the cross asymmetry, the gap between the arms of adjacent crosses lying on the same plane, and the type of Bravais lattice. (papers)

  9. Asymmetric hypsarrhythmia: clinical electroencephalographic and radiological findings.

    Science.gov (United States)

    Drury, I; Beydoun, A; Garofalo, E A; Henry, T R

    1995-01-01

    Twenty-six children (16 boys and 10 girls) with hypsarrhythmia and infantile spasms (IS) were studied at the University of Michigan EEG Laboratory in a 4-year period. Six (2 boys, 4 girls), had asymmetric hypsarrhythmia with a preponderance of both slowing and epileptiform activity over one hemisphere. All 6 had the symptomatic form of IS, 4 with dysplastic conditions, 1 with porencephaly from a cerebral infarct, and 1 with hypoxicischemic encephalopathy. Five children had focal abnormalities on either physical examination or imaging studies. Four had the highest amplitude slowing and most epileptiform activity ipsilateral to the lesion, in 1, it was contralateral. Asymmetric hypsarrhythmia constituted 23% of cases with hypsarrhythmia examined at our EEG laboratory. The significant success in surgical therapy for some children with IS indicates the importance of identifying focal hemispheric abnormalities even if they are not apparent clinically. EEG may suggest focal changes not detected clinically or radiologically.

  10. Improved DFIG Capability during Asymmetrical Grid Faults

    DEFF Research Database (Denmark)

    Zhou, Dao; Blaabjerg, Frede

    2015-01-01

    In the wind power application, different asymmetrical types of the grid fault can be categorized after the Y/d transformer, and the positive and negative components of a single-phase fault, phase-to-phase fault, and two-phase fault can be summarized. Due to the newly introduced negative and even...... the natural component of the Doubly-Fed Induction Generator (DFIG) stator flux during the fault period, their effects on the rotor voltage can be investigated. It is concluded that the phase-to-phase fault has the worst scenario due to its highest introduction of the negative stator flux. Afterwards......, the capability of a 2 MW DFIG to ride through asymmetrical grid faults can be estimated at the existing design of the power electronics converter. Finally, a control scheme aimed to improve the DFIG capability is proposed and the simulation results validate its feasibility....

  11. Energetic Tuning in Spirocyclic Conjugated Polymers

    OpenAIRE

    Hugo Bronstein; Frank D. King

    2016-01-01

    Precise control of the energy levels in a conjugated polymer is the key to allowing their exploitation in optoelectronic devices. The introduction of spirocycles into conjugated polymers has traditionally been used to enhance their solid state microstructure. Here we present a highly novel method of energetic tuning through the use of electronically active spirocyclic systems. By modifying the size and oxidation state of a heteroatom in an orthogonal spirocycle we demonstrate energetic fine t...

  12. Two-zone double phase conjugate mirror

    Science.gov (United States)

    Belić, M. R.; Vujić, D.; Sandfuchs, O.; Kaiser, F.

    2001-10-01

    An analysis of photorefractive (PR) oscillators consisting of two facing four-wave mixing regions is carried out. The threshold and operation conditions of different phase conjugate mirrors are discussed with the help of the grating action method. In particular, the threshold and the operation of the two-zone double phase conjugate mirror (DPCM) is compared with other related PR oscillators, the interconnected ring, and different connected DPCM.

  13. Rapid modification of retroviruses using lipid conjugates

    International Nuclear Information System (INIS)

    Mukherjee, Nimisha G; Le Doux, Joseph M; Andrew Lyon, L

    2009-01-01

    Methods are needed to manipulate natural nanoparticles. Viruses are particularly interesting because they can act as therapeutic cellular delivery agents. Here we examine a new method for rapidly modifying retroviruses that uses lipid conjugates composed of a lipid anchor (1,2-distearoyl-sn-glycero-3-phosphoethanolamine), a polyethylene glycol chain, and biotin. The conjugates rapidly and stably modified retroviruses and enabled them to bind streptavidin. The implication of this work for modifying viruses for gene therapy and vaccination protocols is discussed.

  14. Syntheses of conjugated polymers for photonics

    Czech Academy of Sciences Publication Activity Database

    Výprachtický, Drahomír; Cimrová, Věra; Kmínek, Ivan; Pavlačková, Petra

    2010-01-01

    Roč. 295, č. 1 (2010), s. 94-99 ISSN 1022-1360. [Prague Meetings on Macromolecules /73./ New Frontiers in Macromolecular Science: From Macromolecular Concepts of Living Matter to Polymers for Better Quality of Life. Prague, 05.07.2009-09.07.2009] R&D Projects: GA MŠk(CZ) 1M06031 Institutional research plan: CEZ:AV0Z40500505 Keywords : cis and trans isomers * conjugated polymer * conjugated polyelectrolyte Subject RIV: BM - Solid Matter Physics ; Magnetism

  15. Isospin dependent properties of asymmetric nuclear matter

    OpenAIRE

    Chowdhury, P. Roy; Basu, D. N.; Samanta, C.

    2009-01-01

    The density dependence of nuclear symmetry energy is determined from a systematic study of the isospin dependent bulk properties of asymmetric nuclear matter using the isoscalar and the isovector components of density dependent M3Y interaction. The incompressibility $K_\\infty$ for the symmetric nuclear matter, the isospin dependent part $K_{asy}$ of the isobaric incompressibility and the slope $L$ are all in excellent agreement with the constraints recently extracted from measured isotopic de...

  16. Magnetic properties of strongly asymmetric nuclear matter

    International Nuclear Information System (INIS)

    Kutschera, M.; Wojcik, W.

    1988-01-01

    We investigate stability of neutron matter containing a small proton admixture with respect to spin fluctuations. We establish conditions under which strongly asymmetric nuclear matter could acquire a permanent magnetization. It is shown that if the protons are localized, the system becomes unstable to spin fluctuations for arbitrarily weak proton-neutron spin interactions. For non-localized protons there exists a threshold value of the spin interaction above which the system can develop a spontaneous polarization. 12 refs., 2 figs. (author)

  17. Asymmetric inheritance of cytoophidia in Schizosaccharomyces pombe

    OpenAIRE

    Zhang, Jing; Hulme, Lydia; Liu, Ji-Long

    2014-01-01

    ABSTRACT A general view is that Schizosaccharomyces pombe undergoes symmetric cell division with two daughter cells inheriting equal shares of the content from the mother cell. Here we show that CTP synthase, a metabolic enzyme responsible for the de novo synthesis of the nucleotide CTP, can form filamentous cytoophidia in the cytoplasm and nucleus of S. pombe cells. Surprisingly, we observe that both cytoplasmic and nuclear cytoophidia are asymmetrically inherited during cell division. Our t...

  18. Asymmetric flow events in a VEER 1000

    International Nuclear Information System (INIS)

    Horak, W.C.; Kennett, R.J.; Shier, W.; Guppy, J.G.

    1992-07-01

    This paper describes the simulation of asymmetric loss of flow events in Russian designed VVER-1000 reactors using the RETRAN-02 Mod4 computer code. VVER-1000 reactors have significant differences from United States pressurized water reactors including multi-level emergency response systems and plant operation at reduced power levels with one or more main circulation pumps inoperable. The results of these simulations are compared to similar analyses done by the designers for the Rovno plant

  19. Asymmetric k-Center with Minimum Coverage

    DEFF Research Database (Denmark)

    Gørtz, Inge Li

    2008-01-01

    In this paper we give approximation algorithms and inapproximability results for various asymmetric k-center with minimum coverage problems. In the k-center with minimum coverage problem, each center is required to serve a minimum number of clients. These problems have been studied by Lim et al. [A....... Lim, B. Rodrigues, F. Wang, Z. Xu, k-center problems with minimum coverage, Theoret. Comput. Sci. 332 (1–3) (2005) 1–17] in the symmetric setting....

  20. Asymmetric volatility connectedness on the forex market

    Czech Academy of Sciences Publication Activity Database

    Baruník, Jozef; Kočenda, Evžen; Vácha, Lukáš

    2017-01-01

    Roč. 77, č. 1 (2017), s. 39-56 ISSN 0261-5606 R&D Projects: GA ČR(CZ) GA16-14179S Institutional support: RVO:67985556 Keywords : volatility * connectedness * asymmetric effects Subject RIV: AH - Economics OBOR OECD: Finance Impact factor: 1.853, year: 2016 http://library.utia.cas.cz/separaty/2017/E/barunik-0478477.pdf

  1. Climate Change, Procrastination and Asymmetric Power

    OpenAIRE

    Korkut Alp Ertürk; Jason Whittle

    2015-01-01

    This paper argues that policy conclusions of the economics of climate change literature based on “integrated assessment models” (IAM) fails to take into account the intricacies of collective action. Specifically, IAMs do not account for how asymmetric power between developed and undeveloped countries changes the former's pay off matrix with respect to mitigation and adaptation strategies. Using a simple one-sided prisoner's dilemma model, the paper illustrates how developed countries' power t...

  2. Asymmetric unemployment rate dynamics in Australia

    OpenAIRE

    Gunnar Bardsen; Stan Hurn; Zoe McHugh

    2011-01-01

    The unemployment rate in Australia is modelled as an asymmetric and nonlinear function of aggregate demand, productivity, real interest rates, the replacement ratio and the real exchange rate. If changes in unemployment are big, the management of of demand, real interest rates and the replacement ratio will be good instruments to start bringing it down. The model is developed by exploiting recent developments in automated model-selection procedures.

  3. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

    2018-01-01

    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope...... of the reaction. Particularly, a formation of configurationally labile aminal centers with alkyl substituents has been a formidable challenge due to the enamine/imine equilibrium of electrophilic substrates. Herein, we report enantioselective nucleophilic addition reactions of potassium phthalimides to Boc-protected...

  4. Conjugation in Gram-Positive Bacteria.

    Science.gov (United States)

    Goessweiner-Mohr, Nikolaus; Arends, Karsten; Keller, Walter; Grohmann, Elisabeth

    2014-08-01

    Conjugative transfer is the most important means of spreading antibiotic resistance and virulence factors among bacteria. The key vehicles of this horizontal gene transfer are a group of mobile genetic elements, termed conjugative plasmids. Conjugative plasmids contain as minimum instrumentation an origin of transfer (oriT), DNA-processing factors (a relaxase and accessory proteins), as well as proteins that constitute the trans-envelope transport channel, the so-called mating pair formation (Mpf) proteins. All these protein factors are encoded by one or more transfer (tra) operons that together form the DNA transport machinery, the Gram-positive type IV secretion system. However, multicellular Gram-positive bacteria belonging to the streptomycetes appear to have evolved another mechanism for conjugative plasmid spread reminiscent of the machinery involved in bacterial cell division and sporulation, which transports double-stranded DNA from donor to recipient cells. Here, we focus on the protein key players involved in the plasmid spread through the two different modes and present a new secondary structure homology-based classification system for type IV secretion protein families. Moreover, we discuss the relevance of conjugative plasmid transfer in the environment and summarize novel techniques to visualize and quantify conjugative transfer in situ.

  5. Asymmetric threat data mining and knowledge discovery

    Science.gov (United States)

    Gilmore, John F.; Pagels, Michael A.; Palk, Justin

    2001-03-01

    Asymmetric threats differ from the conventional force-on- force military encounters that the Defense Department has historically been trained to engage. Terrorism by its nature is now an operational activity that is neither easily detected or countered as its very existence depends on small covert attacks exploiting the element of surprise. But terrorism does have defined forms, motivations, tactics and organizational structure. Exploiting a terrorism taxonomy provides the opportunity to discover and assess knowledge of terrorist operations. This paper describes the Asymmetric Threat Terrorist Assessment, Countering, and Knowledge (ATTACK) system. ATTACK has been developed to (a) data mine open source intelligence (OSINT) information from web-based newspaper sources, video news web casts, and actual terrorist web sites, (b) evaluate this information against a terrorism taxonomy, (c) exploit country/region specific social, economic, political, and religious knowledge, and (d) discover and predict potential terrorist activities and association links. Details of the asymmetric threat structure and the ATTACK system architecture are presented with results of an actual terrorist data mining and knowledge discovery test case shown.

  6. Predicting tensorial electrophoretic effects in asymmetric colloids

    Science.gov (United States)

    Mowitz, Aaron J.; Witten, T. A.

    2017-12-01

    We formulate a numerical method for predicting the tensorial linear response of a rigid, asymmetrically charged body to an applied electric field. This prediction requires calculating the response of the fluid to the Stokes drag forces on the moving body and on the countercharges near its surface. To determine the fluid's motion, we represent both the body and the countercharges using many point sources of drag known as Stokeslets. Finding the correct flow field amounts to finding the set of drag forces on the Stokeslets that is consistent with the relative velocities experienced by each Stokeslet. The method rigorously satisfies the condition that the object moves with no transfer of momentum to the fluid. We demonstrate that a sphere represented by 1999 well-separated Stokeslets on its surface produces flow and drag force like a solid sphere to 1% accuracy. We show that a uniformly charged sphere with 3998 body and countercharge Stokeslets obeys the Smoluchowski prediction [F. Morrison, J. Colloid Interface Sci. 34, 210 (1970), 10.1016/0021-9797(70)90171-2] for electrophoretic mobility when the countercharges lie close to the sphere. Spheres with dipolar and quadrupolar charge distributions rotate and translate as predicted analytically to 4% accuracy or better. We describe how the method can treat general asymmetric shapes and charge distributions. This method offers promise as a way to characterize and manipulate asymmetrically charged colloid-scale objects from biology (e.g., viruses) and technology (e.g., self-assembled clusters).

  7. Asymmetric wettability of nanostructures directs leidenfrost droplets.

    Science.gov (United States)

    Agapov, Rebecca L; Boreyko, Jonathan B; Briggs, Dayrl P; Srijanto, Bernadeta R; Retterer, Scott T; Collier, C Patrick; Lavrik, Nickolay V

    2014-01-28

    Leidenfrost phenomena on nano- and microstructured surfaces are of great importance for increasing control over heat transfer in high power density systems utilizing boiling phenomena. They also provide an elegant means to direct droplet motion in a variety of recently emerging fluidic systems. Here, we report the fabrication and characterization of tilted nanopillar arrays (TNPAs) that exhibit directional Leidenfrost water droplets under dynamic conditions, namely on impact with Weber numbers ≥40 at T ≥ 325 °C. The directionality for these droplets is opposite to the direction previously exhibited by macro- and microscale Leidenfrost ratchets where movement against the tilt of the ratchet was observed. The batch fabrication of the TNPAs was achieved by glancing-angle anisotropic reactive ion etching of a thermally dewet platinum mask, with mean pillar diameters of 100 nm and heights of 200-500 nm. In contrast to previously implemented macro- and microscopic Leidenfrost ratchets, our TNPAs induce no preferential directional movement of Leidenfrost droplets under conditions approaching steady-state film boiling, suggesting that the observed droplet directionality is not a result of the widely accepted mechanism of asymmetric vapor flow. Using high-speed imaging, phase diagrams were constructed for the boiling behavior upon impact for droplets falling onto TNPAs, straight nanopillar arrays, and smooth silicon surfaces. The asymmetric impact and directional trajectory of droplets was exclusive to the TNPAs for impacts corresponding to the transition boiling regime, linking asymmetric surface wettability to preferential directionality of dynamic Leidenfrost droplets on nanostructured surfaces.

  8. Heterogeneous catalytic degradation of polyacrylamide solution | Hu ...

    African Journals Online (AJOL)

    Modified with trace metal elements, the catalytic activity of Fe2O3/Al2O3 could be changed greatly. Among various trace metal elements, Fe2O3/Al2O3 catalysts modified with Co and Cu showed great increase on catalytic activity. International Journal of Engineering, Science and Technology, Vol. 2, No. 7, 2010, pp. 110- ...

  9. Catalytic gasification of dry and wet biomass

    NARCIS (Netherlands)

    van Rossum, G.; Potic, B.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria

    2009-01-01

    Catalytic gasification of dry biomass and of wet biomass streams in hot compressed water are reviewed and discussed as potential technologies for the production of synthesis gas, hydrogen- and methane-rich gas. Next to literature data also new experimental results from our laboratory on catalytic

  10. Non-catalytic recuperative reformer

    Science.gov (United States)

    Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

    2015-12-22

    A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

  11. Electrochemical promotion of catalytic reactions

    Science.gov (United States)

    Imbihl, R.

    2010-05-01

    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  12. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  13. Asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with a new trifluoromethoxylation reagent

    Science.gov (United States)

    Guo, Shuo; Cong, Fei; Guo, Rui; Wang, Liang; Tang, Pingping

    2017-06-01

    Fluorinated organic compounds are becoming increasingly important in pharmaceuticals, agrochemicals and materials science. The introduction of trifluoromethoxy groups into new drugs and agrochemicals has attracted much attention due to their strongly electron-withdrawing nature and high lipophilicity. However, synthesis of trifluoromethoxylated organic molecules is difficult owing to the decomposition of trifluoromethoxide anion and β-fluoride elimination from transition-metal-trifluoromethoxide complexes, and no catalytic enantioselective trifluoromethoxylation reaction has been reported until now. Here, we present an example of an asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with trifluoromethyl arylsulfonate (TFMS) as a new trifluoromethoxylation reagent. Compared to other trifluoromethoxylation reagents, TFMS is easily prepared and thermally stable with good reactivity. In addition, this reaction is operationally simple, scalable and proceeds under mild reaction conditions. Furthermore, broad scope and good functional group compatibility has been demonstrated by application of the method to the bromotrifluoromethoxylation of double bonds in natural products and natural product derivatives.

  14. Gold(I)-Mediated Thiourea Organocatalyst Activation: A Synergic Effect for Asymmetric Catalysis.

    Science.gov (United States)

    Izaga, Anabel; Herrera, Raquel P; Gimeno, M Concepción

    2017-04-07

    Several group 11 metal complexes with chiral thiourea organocatalysts have been prepared and tested as organocatalysts. The promising results on the influence of metal-assisted thiourea organocatalysts in the asymmetric Friedel-Crafts alkylation of indole with nitrostyrene are described. Better results with the metal complexes have been achieved because of the cooperative effects between the chiral thiourea and the metal. The synergic effect between both species is higher than the effect promoted by each one separately, especially for gold(I). These outcomes are attributed to a pioneering gold(I) activation of the thiourea catalysts, affording a more acidic and rigid catalytic complex than that provided by the thiourea alone. Furthermore, the use of the gold-thiourea organocatalyst allows reducing the catalyst loading to 1-3 mol %. This contribution could become an important starting point for further investigations opening a new line of research overlooked so far in the literature.

  15. Diesel engine catalytic combustor system. [aircraft engines

    Science.gov (United States)

    Ream, L. W. (Inventor)

    1984-01-01

    A low compression turbocharged diesel engine is provided in which the turbocharger can be operated independently of the engine to power auxiliary equipment. Fuel and air are burned in a catalytic combustor to drive the turbine wheel of turbine section which is initially caused to rotate by starter motor. By opening a flapper value, compressed air from the blower section is directed to catalytic combustor when it is heated and expanded, serving to drive the turbine wheel and also to heat the catalytic element. To start, engine valve is closed, combustion is terminated in catalytic combustor, and the valve is then opened to utilize air from the blower for the air driven motor. When the engine starts, the constituents in its exhaust gas react in the catalytic element and the heat generated provides additional energy for the turbine section.

  16. The evolution of catalytic function

    Science.gov (United States)

    Maurel, Marie-Christine; Ricard, Jacques

    2006-03-01

    It is very likely that the main driving force of enzyme evolution is the requirement to improve catalytic and regulatory efficiency which results from the intrinsic performance as well as from the spatial and functional organization of enzymes in living cells. Kinetic co-operativity may occur in simple monomeric proteins if they display “slow” conformational transitions, at the cost of catalytic efficiency. Oligomeric enzymes on the other hand can be both efficient and co-operative. We speculate that the main reason for the emergence of co-operative oligomeric enzymes is the need for catalysts that are both cooperative and efficient. As it is not useful for an enzyme to respond to a change of substrate concentration in a complex kinetic way, the emergence of symmetry has its probable origin in a requirement for “functional simplicity”. In a living cell, enzyme are associated with other macromolecules and membranes. The fine tuning of their activity may also be reached through mutations of the microenvironment. Our hypothesis is that these mutations are related to the vectorial transport of molecules, to achieve the hysteresis loops of enzyme reactions generated by the coupling of reaction and diffusion, through the co-operativity brought about by electric interactions between a charged substrate and a membrane, and last but not least, through oscillations. As the physical origins of these effects are very simple and do not require complex molecular devices, it is very likely that the functional advantage generated by the spatial and functional organization of enzyme molecules within the cell have appeared in prebiotic catalysis or very early during the primeval stages of biological evolution. We shall began this paper by presenting the nature of the probable earliest catalysts in the RNA world.

  17. Magnetic resonance imaging of differential compartmental function of horizontal rectus extraocular muscles during conjugate and converged ocular adduction.

    Science.gov (United States)

    Demer, Joseph L; Clark, Robert A

    2014-08-15

    Activity in horizontal rectus extraocular muscles (EOMs) was investigated by magnetic resonance imaging (MRI) of humans during asymmetric convergence to a monocularly aligned target at 15-cm distance or monocular fixation of afocal targets placed over a wide range of conjugate abduction through adduction. Cross sections and posterior partial volumes (PPVs) of EOMs were determined from quasi-coronal image planes and were separately analyzed in the inferior vs. superior compartments, defined by lines bisecting their maximum vertical dimensions. Both inferior and superior compartments of medial (MR) and lateral (LR) rectus exhibited contractile changes in PPV and maximum cross section for both asymmetric convergence and a comparable range of conjugate adduction. Both LR compartments, and the inferior MR compartment, exhibited similar decreases in contractility correlating with relaxation during both convergence and conjugate adduction. In contrast, the superior MR compartment exhibited roughly three times the contractility in conjugate adduction as in similar-magnitude convergence. In the aligned eye that did not move during convergence, summed contractility in all compartments of MR and LR exhibited corelaxation consistent with published EOM force measurements in this paradigm (Miller JM, Bockisch CJ, Pavlovski DS. J Neurophysiol 87: 2421-2433, 2002; Miller JM, Davison RC, Gamlin PD. J Neurophysiol 105: 2863-2873, 2011). The superior MR compartment also exhibited significantly greater contractility than the other compartments over the maximum achievable horizontal globe rotation from abduction to adduction. These findings suggest that the superior MR compartment is controlled differentially from the inferior compartment and suggest that its activity is reduced during convergence as a component of generally altered extraocular mechanics. Copyright © 2014 the American Physiological Society.

  18. One-Step Protein Conjugation to Upconversion Nanoparticles.

    Science.gov (United States)

    Lu, Jie; Chen, Yinghui; Liu, Deming; Ren, Wei; Lu, Yiqing; Shi, Yu; Piper, James; Paulsen, Ian; Jin, Dayong

    2015-10-20

    The emerging upconversion nanoparticles offer a fascinating library of ultrasensitive luminescent probes for a range of biotechnology applications from biomarker discovery to single molecule tracking, early disease diagnosis, deep tissue imaging, and drug delivery and therapies. The effective bioconjugation of inorganic nanoparticles to the molecule-specific proteins, free of agglomeration, nonspecific binding, or biomolecule deactivation, is crucial for molecular recognition of target molecules or cells. The current available protocols require multiple steps which can lead to low probe stability, specificity, and reproducibility. Here we report a simple and rapid protein bioconjugation method based on a one-step ligand exchange using the DNAs as the linker. Our method benefits from the robust DNA-protein conjugates as well as from multiple ions binding capability. Protein can be preconjugated via an amino group at the 3' end of a synthetic DNA molecule, so that the 5' end phosphoric acid group and multiple phosphate oxygen atoms in the phosphodiester bonds are exposed to replace the oleic acid ligands on the surface of upconversion nanoparticles due to their stronger chelating capability to lanthanides. We demonstrated that our method can efficiently pull out the upconversion nanoparticles from organic solvent into an aqueous phase. The upconversion nanoparticles then become hydrophilic, stable, and specific biomolecules recognition. This allows us to successfully functionalize the upconversion nanoparticles with horseradish peroxidise (HRP) for catalytic colorimetric assay and for streptavidin (SA)-biotin immunoassays.

  19. Nanoarmored Enzymes for Organic Enzymology: Synthesis and Characterization of Poly(2-Alkyloxazoline)-Enzyme Conjugates.

    Science.gov (United States)

    Leurs, Melanie; Tiller, Joerg C

    2017-01-01

    The properties of enzymes can be altered significantly by modification with polymers. Numerous different methods are known to obtain such polymer-enzyme conjugates (PECs). However, there is no universal method to render enzymes into PECs that are fully soluble in organic solvents. Here, we present a method, which achieves such high degree of modification of proteins that the majority of modified enzymes will be soluble in organic solvents. This is achieved by preparing poly(2-alkyloxazoline)s (POx) with an NH 2 end group and coupling this functional polymer via pyromellitic acid dianhydride onto the amino groups of the respective protein. The resulting PECs are capable of serving as surfactants for unmodified proteins, rendering the whole mixture organosoluble. Depending on the nature of the POx and the molecular weight and the nature of the enzyme, the PECs are soluble in chloroform or even toluene. Another advantage of this method is that the poly(2-alkyloxazoline) can be activated with the coupling agent and used for the enzyme conjugation without further purification. The POx-enzyme conjugates generated by this modification strategy show modulated catalytic activity in both, aqueous and organic, systems. © 2017 Elsevier Inc. All rights reserved.

  20. TcpM: a novel relaxase that mediates transfer of large conjugative plasmids from Clostridium perfringens.

    Science.gov (United States)

    Wisniewski, Jessica A; Traore, Daouda A; Bannam, Trudi L; Lyras, Dena; Whisstock, James C; Rood, Julian I

    2016-03-01

    Conjugative transfer of toxin and antibiotic resistance plasmids in Clostridium perfringens is mediated by the tcp conjugation locus. Surprisingly, neither a relaxase gene nor an origin of transfer (oriT) has been identified on these plasmids, which are typified by the 47 kb tetracycline resistance plasmid pCW3. The tcpM gene (previously called intP) encodes a potential tyrosine recombinase that was postulated to be an atypical relaxase. Mutagenesis and complementation studies showed that TcpM was required for wild-type transfer of pCW3 and that a tyrosine residue, Y259, was essential for TcpM activity, which was consistent with the need for a relaxase-mediated hydrophilic attack at the oriT site. Other catalytic residues conserved in tyrosine recombinases were not required for TcpM activity, suggesting that TcpM was not a site-specific recombinase. Mobilization studies led to the identification of the oriT site, which was located in the 391 bp intergenic region upstream of tcpM. The oriT site was localized to a 150 bp region, and gel mobility shift studies showed that TcpM could bind to this region. Based on these studies we postulate that conjugative transfer of pCW3 involves the atypical relaxase TcpM binding to and processing the oriT site to initiate plasmid transfer. © 2015 John Wiley & Sons Ltd.

  1. Cretaceous to Recent Assymetrical Subsidence of South American and West African Conjugate Margins

    Science.gov (United States)

    Kenning, J.; Mann, P.

    2017-12-01

    Two divergent interpretations have been proposed for South American rifted-passive margins: the "mirror hypothesis" proposes that the rifted margins form symmetrically from pure shear of the lithosphere while upper-plate-lower plate models propose that the rifted margins form asymmetrically by simple shear. Models based on seismic reflection and refraction imaging and comparison of conjugate, rifted margins generally invoke a hybrid stretching process involving elements of both end member processes along with the effects of mantle plumes active during the rift and passive margin phases. We use subsidence histories of 14, 1-7 km-deep exploration wells located on South American and West African conjugate pairs now separated by the South Atlantic Ocean, applying long-term subsidence to reveal the symmetry or asymmetry of the underlying, conjugate, rift processes. Conjugate pairs characterize the rifted margin over a distance of 3500 km and include: Colorado-South Orange, Punta Del Este-North Orange, South Pelotas-Lüderitz and the North Pelotas-Walvis Basins. Of the four conjugate pairs, more rapid subsidence on the South American plate is consistently observed with greater initial rift and syn-rift subsidence rates of >60m/Ma (compared to 100 m/Ma are observed offshore South Africa between approximately 120-80 Ma, compatible with onset of the post-rift thermal sag phase. During this period the majority of burial is completed and rates remain low at Argentina/Uruguay displays more gradual subsidence throughout the Cretaceous, consistently averaging a moderate 15-30m/Ma. By the end of this stage there is a subsequent increase to 25-60 m/Ma within the last 20 Ma, interpreted to reflect lithospheric loading due to increased sedimentation rates during the Cenozoic. This increase in subsidence rate is not seen in the African conjugate section where the majority of sediments bypassed the highly aggraded Cretaceous shelf. Initially greater on the Brazilian margin compared to

  2. [Acid-base catalysis of chiral Pd complexes: development of novel asymmetric reactions].

    Science.gov (United States)

    Hamashima, Yoshitaka

    2005-10-01

    Using a unique character of the chiral palladium complexes 1 and 2, several types of novel catalytic asymmetric reactions have been developed. In contrast to the conventional Pd(0)-catalyzed reactions, these complexes function as an acid-base catalyst. Thus active methine compounds were activated to form chiral palladium enolates, which underwent the enantioselective Michael reaction and Mannich-type reaction with up to 99% ee. Interestingly, these palladium enolates acted cooperatively with a strong protic acid activating the electrophiles, formed concomitantly during the formation of the enolates, whereby the C-C bond-forming reaction was promoted. In addition, this palladium enolate chemistry was also applicable to the electrophilic asymmetric fluorination reactions, and thus various carbonyl compounds including beta-ketoesters, beta-ketophosphonates, and oxindoles were fluorinated in a highly enantioselective manner (up to 98% ee). It is advantageous that these reactions were carried out in environmentally friendly alcoholic solvents such as ethanol, and exclusion of air and moisture is not necessary.

  3. An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM for Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Ketones

    Directory of Open Access Journals (Sweden)

    Norio Miyaura

    2012-12-01

    Full Text Available A new bidentate phosphoramidite (N-Me-BIPAM based on Shibasaki’s N-linked BINOL was synthesized. This ligand appears to be highly effective for rhodium-catalyzed asymmetric conjugated addition of arylboronic acids to α,β-unsaturated enones. The reaction of ortho-substituted arylboronic acid with acyclic and cyclic enones provides the corresponding products in good yields and enantioselectivities.

  4. Opening of the Central Atlantic Ocean: Implications for Geometric Rifting and Asymmetric Initial Seafloor Spreading after Continental Breakup

    Science.gov (United States)

    Klingelhoefer, F.; Biari, Y.; Sahabi, M.; Funck, T.; Benabdellouahed, M.; Schnabel, M.; Reichert, C. J.; Gutscher, M. A.; Bronner, A.; Austin, J. A., Jr.

    2017-12-01

    The structure of conjugate passive margins provides information about rifting styles, the initial phases of the opening of an ocean and the formation of its associated sedimentary basins. The study of the deep structure of conjugate passive continental margins combined with precise plate kinematic reconstructions can provide constraints on the mechanisms of rifting and formation of initial oceanic crust. In this study the Central Atlantic conjugate margins are compared, based on compilation of wide-angle seismic profiles from the NW-Africa Nova Scotian and US passive margins. Plate cinematic reconstructions were used to place the profiles in the position at opening and at the M25 magnetic anomaly. The patterns of volcanism, crustal thickness, geometry, and seismic velocities in the transition zone. suggest symmetric rifting followed by asymmetric oceanic crustal accretion. Conjugate profiles in the southern Central Atlantic image differences in the continental crustal thickness. While profiles on the eastern US margin are characterized by thick layers of magmatic underplating, no such underplate was imaged along the NW-African continental margin. It has been proposed that these volcanic products form part of the CAMP (Central Atlantic Magmatic Province). In the north, two wide-angle seismic profiles acquired in exactly conjugate positions show that the crustal geometry of the unthinned continental crust and the necking zone are nearly symmetric. A region including seismic velocities too high to be explained by either continental or oceanic crust is imaged along the Nova Scotia margin off Eastern Canada, corresponding on the African side to an oceanic crust with slightly elevated velocities. These might result from asymmetric spreading creating seafloor by faulting the existing lithosphere on the Canadian side and the emplacement of magmatic oceanic crust including pockets of serpentinite on the Moroccan margin. A slightly elevated crustal thickness along the

  5. Catalytic Wittig and aza-Wittig reactions

    Directory of Open Access Journals (Sweden)

    Zhiqi Lao

    2016-11-01

    Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

  6. Catalytic Wittig and aza-Wittig reactions.

    Science.gov (United States)

    Lao, Zhiqi; Toy, Patrick H

    2016-01-01

    This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

  7. Asymmetric Cache Coherency: Policy Modifications to Improve Multicore Performance

    OpenAIRE

    Shield, John; Diguet, Jean-Philippe; Gogniat, Guy

    2012-01-01

    International audience; Asymmetric coherency is a new optimisation method for coherency policies to support non-uniform work- loads in multicore processors. Asymmetric coherency assists in load balancing a workload and this is applica- ble to SoC multicores where the applications are not evenly spread among the processors and customization of the coherency is possible. Asymmetric coherency is a policy change, and consequently our designs re- quire little or no additional hardware over an exis...

  8. Observation of asymmetric electromagnetic field profiles in chiral metamaterials

    Science.gov (United States)

    Hisamoto, Nobuyuki; Ueda, Tetsuya; Sawada, Kei; Tomita, Satoshi

    2018-02-01

    We experimentally observe asymmetric electromagnetic field profiles along two-dimensional chiral metamaterials. The asymmetric field profiles depending on the chirality and the operation frequency have been reproduced well by the numerical simulation. Around a chiral meta-atom, distribution of a Poynting vector is found to be shifted asymmetrically. These results are explained in terms of an analogy with the side-jump mechanism in the electronic anomalous Hall systems.

  9. Cross-conjugation and quantum interference: a general correlation?

    DEFF Research Database (Denmark)

    Valkenier, Hennie; Guedon, Constant M.; Markussen, Troels

    2014-01-01

    -conjugation patterns, but identical lengths, i.e. an anthracene (linear conjugation), an anthraquinone (cross-conjugation), and a dihydroanthracene (broken conjugation) derivative. To benchmark reliable trends, conductance experiments on these series have been performed by various techniques. Here, we compare data...... characterized by beta = 0.37 +/- 0.03 angstrom(-1) (CP-AFM). Remarkably, for the second series, we do not only find that the linearly conjugated anthracene-containing wire is the most conductive, but also that the cross-conjugated anthraquinone-containing wire is less conductive than the broken...

  10. Population dynamics with symmetric and asymmetric harvesting

    Directory of Open Access Journals (Sweden)

    J. Ali

    2009-10-01

    Here $\\lambda, a, b, c$ and $L$ are positive constants with $0asymmetric harvesting case. Our objective is to study the existence of positive solutions and also discuss the effects of harvesting. We will develop appropriate quadrature methods via which we will establish our results.

  11. Asymmetric acoustic transmission in graded beam

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Li, E-mail: lj94172350@hotmail.com [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Wu, Jiu Hui, E-mail: ejhwu@mail.xjtu.edu.cn [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Guan, Dong; Lu, Kuan [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Gao, Nansha [School of Marine Science and Technology, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Songhua, Cao [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China)

    2016-12-01

    We demonstrate the dynamic effective material parameters and vibration performance of a graded beam. The structure of the beam was composed of several unit cells with different fill factors. The dispersion relations and energy band structures of each unit cell were calculated using the finite element method (FEM). The dynamic effective material parameters in each unit cell of the graded beam were determined by the dispersion relations and energy band structures. Longitudinal wave propagation was investigated using a numerical method and FEM. The results show that the graded beam allows asymmetric acoustic transmission over a wide range of frequencies.

  12. Asymmetric Laser Radiant Cooling in Storage Rings

    CERN Document Server

    Bulyak, E V; Zimmermann, F

    2011-01-01

    Laser pulses with small spatial and temporal dimensions can interact with a fraction of the electron bunches circulating in Compton storage rings. We studied synchrotron dynamics of such bunches when laser photons scatter off from the electrons with energy higher than the synchronous energy. In this case of ‘asymmetric cooling', as shown theoretically, the stationary energy spread is much smaller than under conditions of regular scattering; the oscillations are damped faster. Coherent oscillations of large amplitude may be damped in one synchrotron period, which makes this method feasible for injection the bunches into a ring in the longitudinal phase space. The theoretical results are validated with simulations.

  13. Asymmetrical transverse structures in nonlinear interferometers

    CERN Document Server

    Romanov, O G

    2003-01-01

    The work presents a novel type of optical instability, which leads to the spontaneous formation of a stationary or pulsating asymmetrical structure in the problem of interaction between two counterpropagating waves in a ring cavity with Kerr-like nonlinearity. Linear stability analysis of interferometer transmission stationary states enabled: (1) to mark out typical bifurcations for this system: self- and cross-modulational instabilities, (2) to determine the range of parameters for which the symmetry breaking of transverse structures and complex temporal behaviour of the light field could be observed. The predictions of linear stability analysis have been verified with numerical modelling of coupled-modes equations.

  14. A protic ionic liquid as an atom economical solution for palladium catalyzed asymmetric allylic alkylation.

    Science.gov (United States)

    Guerrero-Ríos, Itzel; Ortiz-Ramírez, Alfonso H; van Leeuwen, Piet W N M; Martin, Erika

    2018-03-12

    The asymmetric allylic alkylation of rac-1,3-diphenyl-3-acetoxyprop-1-ene (I) catalysed by palladium and diverse phosphorus containing ligands [(S)-BINAP, (R,R)-Chiraphite and (R,R)-Et-Duphos] in an ionic liquid [HDBU][OAc] was successfully performed, achieving full conversions and up to 96% ee of the (S)-product when (R,R)-Et-Duphos was used as a ligand. The reaction could be performed using an equimolar amount of substrate, malonate and base DBU, in which case the total products sum to the desired alkylated product and the ionic pair [HDBU][OAc]; this system thus produces its own IL solvent as the only co-product. These catalytic systems were active in recycling experiments for up to four cycles, albeit with a loss of activity due to the poor retention of palladium in the ionic liquid. The catalytic performance of each Pd/ligand system was optimized by varying the ratio of the substrate and malonate. Systems based on [HDBU][OAc] were found to be the best.

  15. Ruthenium complexes with chiral tetradentate PNNP ligands: asymmetric catalysis from the viewpoint of inorganic chemistry.

    Science.gov (United States)

    Mezzetti, Antonio

    2010-09-14

    This is a personal account of the application of ruthenium complexes containing chiral tetradentate ligands with a P(2)N(2) ligand set (PNNP) as catalyst precursors for enantioselective "atom transfer" reactions. Therewith are meant reactions that involve bond formation between a metal-coordinated molecule and a free reagent. The reactive fragment (e.g. carbene) is transferred either from the metal to the non-coordinated substrate (e.g. olefin) or from the free reagent (e.g. F(+)) to the metal-bound substrate (e.g.beta-ketoester), depending on the class of catalyst (monocationic, Class A; or dicationic, Class B). The monocationic five-coordinate species [RuCl(PNNP)](+) and the six-coordinate complexes [RuCl(L)(PNNP)](+) (L = Et(2)O, H(2)O) of Class A catalyse asymmetric epoxidation, cyclopropanation (carbene transfer from the metal to the free olefin), and imine aziridination. Alternatively, the dicationic complexes [Ru(L-L)(PNNP)](2+) (Class B), which contain substrates that act as neutral bidentate ligands L-L (e.g., beta-ketoesters), catalyse Michael addition, electrophilic fluorination, and hydroxylation reactions. Additionally, unsaturated beta-ketoesters form dicationic complexes of Class B that catalyse Diels-Alder reactions with acyclic dienes to produce tetrahydro-1-indanones and estrone derivatives. Excellent enantioselectivity has been achieved in several of the catalytic reactions mentioned above. The study of key reaction intermediates (both in the solid state and in solution) has revealed significant mechanistic aspects of the catalytic reactions.

  16. Phase conjugate Michelson interferometer for optical logic

    Science.gov (United States)

    Khoury, Jed

    2017-05-01

    The interference theory is developed for of the phase conjugate Michelson interferometer in which its ordinary mirrors are replaced by a single externally pumped phase conjugate mirror. According to the theory, it was found that for an interferometer with two equal arms, the path length difference depends solely on the initial alignment of the two input beams, and the vertical alignment readout. Small vertical misalignments in the readout beam by mrad causes a huge change in the phase difference in the phase between the two interferometer arms beam. The phase difference is proportional to the interferometer arm lengths. The overlap between the phase conjugate beams is not affected by the interferometer beam alignment. The interferometer is proposed for nondestructive testing and the design all optical logic and associated fuzzy logic for ultrafast optical pattern recognition.

  17. Tight-binding treatment of conjugated polymers

    DEFF Research Database (Denmark)

    Lynge, Thomas Bastholm

    This PhD thesis concerns conjugated polymers which constitute a constantly growing research area. Today, among other things, conjugated polymers play a role in plastic based solar cells, photodetectors and light emitting diodes, and even today such plastic-based components constitute an alternative...... of tomorrow. This thesis specifically treats the three conjugated polymers trans-polyacetylene (tPA), poly(para-phenylene) (PPP) and poly(para-phe\\-nylene vinylene) (PPV). The present results, which are derived within the tight-binding model, are divided into two parts. In one part, analytic results...... are derived for the optical properties of the polymers expressed in terms of the optical susceptibility both in the presence and in the absence of a static electric field. In the other part, the cumputationally efficient Density Functional-based Tight-Binding (DFTB) model is applied to the description...

  18. Conjugate Meningococcal Vaccines Development: GSK Biologicals Experience

    Directory of Open Access Journals (Sweden)

    Jacqueline M. Miller

    2011-01-01

    Full Text Available Meningococcal diseases are serious threats to global health, and new vaccines specifically tailored to meet the age-related needs of various geographical areas are required. This paper focuses on the meningococcal conjugate vaccines developed by GSK Biologicals. Two combined conjugate vaccines were developed to help protect infants and young children in countries where the incidence of meningococcal serogroup C or serogroup C and Y disease is important: Hib-MenC-TT vaccine, which offers protection against Haemophilus influenzae type b and Neisseria meningitidis serogroup C diseases, is approved in several countries; and Hib-MenCY-TT vaccine, which adds N. meningitidis serogroup Y antigen, is currently in the final stages of development. Additionally, a tetravalent conjugate vaccine (MenACWY-TT designed to help protect against four meningococcal serogroups is presently being evaluated for global use in all age groups. All of these vaccines were shown to be highly immunogenic and to have clinically acceptable safety profiles.

  19. Nonlinear conjugate gradient methods in micromagnetics

    Directory of Open Access Journals (Sweden)

    J. Fischbacher

    2017-04-01

    Full Text Available Conjugate gradient methods for energy minimization in micromagnetics are compared. The comparison of analytic results with numerical simulation shows that standard conjugate gradient method may fail to produce correct results. A method that restricts the step length in the line search is introduced, in order to avoid this problem. When the step length in the line search is controlled, conjugate gradient techniques are a fast and reliable way to compute the hysteresis properties of permanent magnets. The method is applied to investigate demagnetizing effects in NdFe12 based permanent magnets. The reduction of the coercive field by demagnetizing effects is μ0ΔH = 1.4 T at 450 K.

  20. Conjugate Meningococcal Vaccines Development: GSK Biologicals Experience

    Science.gov (United States)

    Miller, Jacqueline M.; Mesaros, Narcisa; Van Der Wielen, Marie; Baine, Yaela

    2011-01-01

    Meningococcal diseases are serious threats to global health, and new vaccines specifically tailored to meet the age-related needs of various geographical areas are required. This paper focuses on the meningococcal conjugate vaccines developed by GSK Biologicals. Two combined conjugate vaccines were developed to help protect infants and young children in countries where the incidence of meningococcal serogroup C or serogroup C and Y disease is important: Hib-MenC-TT vaccine, which offers protection against Haemophilus influenzae type b and Neisseria meningitidis serogroup C diseases, is approved in several countries; and Hib-MenCY-TT vaccine, which adds N. meningitidis serogroup Y antigen, is currently in the final stages of development. Additionally, a tetravalent conjugate vaccine (MenACWY-TT) designed to help protect against four meningococcal serogroups is presently being evaluated for global use in all age groups. All of these vaccines were shown to be highly immunogenic and to have clinically acceptable safety profiles. PMID:21991444

  1. Serogroup A meningococcal conjugate vaccines in Africa.

    Science.gov (United States)

    Kristiansen, Paul A; Jørgensen, Hannah J; Caugant, Dominique A

    2015-01-01

    Serogroup A meningococcal epidemics have been a recurrent public health problem, especially in resource-poor countries of Africa. Recently, the administration in mass vaccination campaigns of a single dose of the monovalent meningococcal conjugate vaccine, MenAfriVac, to the 1-29 year-old population of sub-Saharan Africa has prevented epidemics of meningitis caused by serogroup A Neisseria meningitidis. This strategy has also been shown to provide herd protection of the non-vaccinated population. Development of meningococcal conjugate vaccines covering other serogroups and enhanced use of the pneumococcal and Haemophilus influenzae type b conjugate vaccines must be pursued to fully control bacterial meningitis in sub-Saharan Africa.

  2. Conjugate gradient algorithms using multiple recursions

    Energy Technology Data Exchange (ETDEWEB)

    Barth, T.; Manteuffel, T.

    1996-12-31

    Much is already known about when a conjugate gradient method can be implemented with short recursions for the direction vectors. The work done in 1984 by Faber and Manteuffel gave necessary and sufficient conditions on the iteration matrix A, in order for a conjugate gradient method to be implemented with a single recursion of a certain form. However, this form does not take into account all possible recursions. This became evident when Jagels and Reichel used an algorithm of Gragg for unitary matrices to demonstrate that the class of matrices for which a practical conjugate gradient algorithm exists can be extended to include unitary and shifted unitary matrices. The implementation uses short double recursions for the direction vectors. This motivates the study of multiple recursion algorithms.

  3. CO-releasing molecule (CORM) conjugate systems.

    Science.gov (United States)

    Kautz, Anna Christin; Kunz, Peter C; Janiak, Christoph

    2016-11-15

    The development of CORMs (CO-releasing molecules) as a prodrug for CO administration in living organisms has attracted significant attention. CORMs offer the promising possibility of a safe and controllable release of CO in low amounts triggered by light, ligands, enzymes, etc. For the targeting of specific tissues or diseases and to prevent possible side effects from metals and other residues after CO release, these CORMs are attached to biocompatible systems, like peptides, polymers, nanoparticles, dendrimers, protein cages, non-wovens, tablets, and metal-organic frameworks. We discuss in this review the known CORM carrier conjugates, in short CORM conjugates, with covalently-bound or incorporated CORMs for medicinal and therapeutic applications. Most conjugates are nontoxic, show increasing half-lives of CO release, and make use of the EPR-effect, but still show problems because of a continuous background of CO release and the absence of an on/off-switch for the CO release.

  4. Auxin as an inducer of asymmetrical division generating the subsidiary cells in stomatal complexes of Zea mays.

    Science.gov (United States)

    Livanos, Pantelis; Giannoutsou, Eleni; Apostolakos, Panagiotis; Galatis, Basil

    2015-01-01

    The data presented in this work revealed that in Zea mays the exogenously added auxins indole-3-acetic acid (IAA) and 1-napthaleneacetic acid (NAA), promoted the establishment of subsidiary cell mother cell (SMC) polarity and the subsequent subsidiary cell formation, while treatment with auxin transport inhibitors 2,3,5-triiodobenzoic acid (TIBA) and 1-napthoxyacetic acid (NOA) specifically blocked SMC polarization and asymmetrical division. Furthermore, in young guard cell mother cells (GMCs) the PIN1 auxin efflux carriers were mainly localized in the transverse GMC faces, while in the advanced GMCs they appeared both in the transverse and the lateral ones adjacent to SMCs. Considering that phosphatidyl-inositol-3-kinase (PI3K) is an active component of auxin signal transduction and that phospholipid signaling contributes in the establishment of polarity, treatments with the specific inhibitor of the PI3K LY294002 were carried out. The presence of LY294002 suppressed polarization of SMCs and prevented their asymmetrical division, whereas combined treatment with exogenously added NAA and LY294002 restricted the promotional auxin influence on subsidiary cell formation. These findings support the view that auxin is involved in Z. mays subsidiary cell formation, probably functioning as inducer of the asymmetrical SMC division. Collectively, the results obtained from treatments with auxin transport inhibitors and the appearance of PIN1 proteins in the lateral GMC faces indicate a local transfer of auxin from GMCs to SMCs. Moreover, auxin signal transduction seems to be mediated by the catalytic function of PI3K.

  5. Conjugation of silica nanoparticles with cellulose acetate/polyethylene glycol 300 membrane for reverse osmosis using MgSO4 solution.

    Science.gov (United States)

    Sabir, Aneela; Shafiq, Muhammad; Islam, Atif; Jabeen, Faiza; Shafeeq, Amir; Ahmad, Adnan; Zahid Butt, Muhammad Taqi; Jacob, Karl I; Jamil, Tahir

    2016-01-20

    Thermally-induced phase separation (TIPS) method was used to synthesize polymer matrix (PM) membranes for reverse osmosis from cellulose acetate/polyethylene glycol (CA/PEG300) conjugated with silica nanoparticles (SNPs). Experimental data showed that the conjugation of SNPs changed the surface properties as dense and asymmetric composite structure. The results were explicitly determined by the permeability flux and salt rejection efficiency of the PM-SNPs membranes. The effect of SNPs conjugation on MgSO4 salt rejection was more significant in magnitude than on permeation flux i.e. 2.38 L/m(2)h. FTIR verified that SNPs were successfully conjugated on the surface of PM membrane. DSC of PM-SNPs shows an improved Tg from 76.2 to 101.8 °C for PM and PM-S4 respectively. Thermal stability of the PM-SNPs membranes was observed by TGA which was significantly enhanced with the conjugation of SNPs. The micrographs of SEM and AFM showed the morphological changes and increase in the valley and ridges on membrane surface. Experimental data showed that the PM-S4 (0.4 wt% SNPs) membrane has maximum salt rejection capacity and was selected as an optimal membrane. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Conjugated Polymers as Actuators: Modes of Actuation

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2004-01-01

    The physical and chemical properties of conjugated polymers often depend very strongly on the degree of doping with anions or cations. The movement of ions in and out of the polymer matrix as it is redox cycled is also accompanied by mechanical changes. Both the volume and the stiffness can exhibit...... significant differences between the oxidized and reduced states. These effects form the basis of the use of conjugated polymers as actuators (or “artificial muscles”) controllable by a small (1-10 V) voltage. Three basic modes of actuation (bending, linear extension and stiffness change) have been proposed...

  7. Functionalized conjugated polyelectrolytes design and biomedical applications

    CERN Document Server

    Wang, Shu

    2014-01-01

    Functionalized Conjugated Polyelectrolytes presents a comprehensive review of these polyelectrolytes and their biomedical applications. Basic aspects like molecular design and optoelectronic properties are covered in the first chapter. Emphasis is placed on the various applications including sensing (chemical and biological), disease diagnosis, cell imaging, drug/gene delivery and disease treatment. This book explores a multi-disciplinary topic of interest to researchers working in the fields of chemistry, materials, biology and medicine. It also offers an integrated perspective on both basic research and application issues. Functionalized conjugated polyelectrolyte materials, which have already drawn considerable interest, will become a major new direction for biomedicine development.

  8. Conjugated polymers as actuators: modes of actuation

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2007-01-01

    The physical and chemical properties of conjugated polymers often depend very strongly on the degree of doping with anions or cations. The movement of ions in and out of the polymer matrix as it is redox cycled is also accompanied by mechanical changes. Both the volume and the stiffness can exhibit...... significant differences between the oxidized and reduced states. These effects form the basis of the use of conjugated polymers as actuators (or “artificial muscles”) controllable by a small (1-10 V) voltage. Three basic modes of actuation (bending, linear extension and stiffness change) have been proposed...

  9. De-conjugation behavior of conjugated estrogens in the raw sewage, activated sludge and river water.

    Science.gov (United States)

    Kumar, Vimal; Johnson, Andrew C; Nakada, Norihide; Yamashita, Naoyuki; Tanaka, Hiroaki

    2012-08-15

    The fate and behavior of estrone-3-sulfate (E1-3S), estradiol-3-sulfate (E2-3S), estrone-3-glucuronide (E1-3G) and estradiol-3-glucuronide (E2-3G) were studied in raw sewage, activated sludge and river water using microcosms. The glucuronide conjugates had a half-life of 0.4h in raw sewage, yielding 40-60% of their free estrogens. Field observations at three activated sludge processes suggested complete transformation of the glucuronide conjugates in the sewer. In river water glucuronide conjugates half-lives extended to over 2d yielding 60-100% of their free parent estrogens. Transformation of the sulfate conjugates in raw sewage and river water was slow with little formation of the parent estrogens. Sulfate conjugates could readily be detected in sewage influent in the field studies. In activated sludge the sulfate conjugates had half-lives of 0.2h with the transient formation of 10-55% of the free parent estrogens. Field studies indicated transformation of sulfate conjugates across the sewage treatment, although a proportion escaped into the effluent. These results broadly support the view that glucuronide conjugates will be entirely transformed within the sewer largely to their parent estrogens. The sulfate conjugates may persist in raw sewage and river water but are transformable in activated sludge and, in the case of E2-3S, reform a high proportion of the parent estrogen. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Kinetic basis for the conjugation of auxin by a GH3 family indole-acetic acid-amido synthetase.

    Science.gov (United States)

    Chen, Qingfeng; Westfall, Corey S; Hicks, Leslie M; Wang, Shiping; Jez, Joseph M

    2010-09-24

    The GH3 family of acyl-acid-amido synthetases catalyze the ATP-dependent formation of amino acid conjugates to modulate levels of active plant hormones, including auxins and jasmonates. Initial biochemical studies of various GH3s show that these enzymes group into three families based on sequence relationships and acyl-acid substrate preference (I, jasmonate-conjugating; II, auxin- and salicylic acid-conjugating; III, benzoate-conjugating); however, little is known about the kinetic and chemical mechanisms of these enzymes. Here we use GH3-8 from Oryza sativa (rice; OsGH3-8), which functions as an indole-acetic acid (IAA)-amido synthetase, for detailed mechanistic studies. Steady-state kinetic analysis shows that the OsGH3-8 requires either Mg(2+) or Mn(2+) for maximal activity and is specific for aspartate but accepts asparagine as a substrate with a 45-fold decrease in catalytic efficiency and accepts other auxin analogs, including phenyl-acetic acid, indole butyric acid, and naphthalene-acetic acid, as acyl-acid substrates with 1.4-9-fold reductions in k(cat)/K(m) relative to IAA. Initial velocity and product inhibition studies indicate that the enzyme uses a Bi Uni Uni Bi Ping Pong reaction sequence. In the first half-reaction, ATP binds first followed by IAA. Next, formation of an adenylated IAA intermediate results in release of pyrophosphate. The second half-reaction begins with binding of aspartate, which reacts with the adenylated intermediate to release IAA-Asp and AMP. Formation of a catalytically competent adenylated-IAA reaction intermediate was confirmed by mass spectrometry. These mechanistic studies provide insight on the reaction catalyzed by the GH3 family of enzymes to modulate plant hormone action.

  11. Evolutionary stability in the asymmetric volunteer's dilemma.

    Directory of Open Access Journals (Sweden)

    Jun-Zhou He

    Full Text Available It is often assumed that in public goods games, contributors are either strong or weak players and each individual has an equal probability of exhibiting cooperation. It is difficult to explain why the public good is produced by strong individuals in some cooperation systems, and by weak individuals in others. Viewing the asymmetric volunteer's dilemma game as an evolutionary game, we find that whether the strong or the weak players produce the public good depends on the initial condition (i.e., phenotype or initial strategy of individuals. These different evolutionarily stable strategies (ESS associated with different initial conditions, can be interpreted as the production modes of public goods of different cooperation systems. A further analysis revealed that the strong player adopts a pure strategy but mixed strategies for the weak players to produce the public good, and that the probability of volunteering by weak players decreases with increasing group size or decreasing cost-benefit ratio. Our model shows that the defection probability of a "strong" player is greater than the "weak" players in the model of Diekmann (1993. This contradicts Selten's (1980 model that public goods can only be produced by a strong player, is not an evolutionarily stable strategy, and will therefore disappear over evolutionary time. Our public good model with ESS has thus extended previous interpretations that the public good can only be produced by strong players in an asymmetric game.

  12. An asymmetric B factory based on PEP

    International Nuclear Information System (INIS)

    1991-02-01

    In this report we describe a design for a high-luminosity Asymmetric B Factory to be built in the PEP tunnel on the SLAC site. This proposal, a collaborative effort SLAC, LBL, and LLNL, is the culmination of more than two years of effort aimed at the design and construction of an asymmetric e + e - collider capable of achieving a luminosity of L = 3 x 10 33 cm -2 s -1 . The configuration adopted utilizes two storage rings, and electron ring operating at 9 GeV and a positron ring at 3.1 GeV, each with a circumference of 2200 m. The high-energy ring is an upgrade of the PEP storage ring at SLAC; all PEP magnets and most power supplies will be reused. The upgrade consists primarily of replacing the PEP vacuum chamber and RF system with newly designed versions optimized for the high-current environment of the B Factory. The low-energy ring will be newly constructed and will be situated atop the high-energy ring in the PEP tunnel. Utilities already installed in the PEP tunnel are largely sufficient to operate the two B Factory storage rings

  13. [Asymmetric hypertrophy of the masticatory muscles].

    Science.gov (United States)

    Arzul, L; Corre, P; Khonsari, R H; Mercier, J-M; Piot, B

    2012-06-01

    Hypertrophy of the masticatory muscles most commonly affects the masseter. Less common cases of isolated or associated temporalis hypertrophy are also reported. Parafunctional habits, and more precisely bruxism, can favor the onset of the hypertrophy. This condition is generally idiopathic and can require both medical and/or surgical management. A 29-year-old patient was referred to our department for an asymmetric swelling of the masticatory muscles. Physical examination revealed a bilateral hypertrophy of the masticatory muscles, predominantly affecting the right temporalis and the left masseter. Major bruxism was assessed by premature dental wearing. The additional examinations confirmed the isolated muscle hypertrophy. Benign asymmetric hypertrophy of the masticatory muscles promoted by bruxism was diagnosed. Treatment with injections of type A botulinum toxin was conducted in association with a splint and relaxation. Its effectiveness has been observed at six months. Few cases of unilateral or bilateral temporalis hypertrophy have been reported, added to the more common isolated masseter muscles hypertrophy. The diagnosis requires to rule out secondary hypertrophies and tumors using Magnetic Resonance Imaging. The condition is thought to be favoured by parafunctional habits such as bruxism. The conservative treatment consists in reducing the volume of the masticatory muscles using intramuscular injections of type A botulinum toxin. Other potential conservative treatments are wearing splints and muscle relaxant drugs. Surgical procedures aiming to reduce the muscle volume and/or the bone volume (mandibular gonioplasty) can be proposed. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  14. Asymmetric inheritance of cytoophidia in Schizosaccharomyces pombe

    Directory of Open Access Journals (Sweden)

    Jing Zhang

    2014-10-01

    Full Text Available A general view is that Schizosaccharomyces pombe undergoes symmetric cell division with two daughter cells inheriting equal shares of the content from the mother cell. Here we show that CTP synthase, a metabolic enzyme responsible for the de novo synthesis of the nucleotide CTP, can form filamentous cytoophidia in the cytoplasm and nucleus of S. pombe cells. Surprisingly, we observe that both cytoplasmic and nuclear cytoophidia are asymmetrically inherited during cell division. Our time-lapse studies suggest that cytoophidia are dynamic. Once the mother cell divides, the cytoplasmic and nuclear cytoophidia independently partition into one of the two daughter cells. Although the two daughter cells differ from one another morphologically, they possess similar chances of inheriting the cytoplasmic cytoophidium from the mother cell, suggesting that the partition of cytoophidium is a stochastic process. Our findings on asymmetric inheritance of cytoophidia in S. pombe offer an exciting opportunity to study the inheritance of metabolic enzymes in a well-studied model system.

  15. Asymmetric disassembly and robustness in declining networks

    Science.gov (United States)

    Saavedra, Serguei; Reed-Tsochas, Felix; Uzzi, Brian

    2008-01-01

    Mechanisms that enable declining networks to avert structural collapse and performance degradation are not well understood. This knowledge gap reflects a shortage of data on declining networks and an emphasis on models of network growth. Analyzing >700,000 transactions between firms in the New York garment industry over 19 years, we tracked this network's decline and measured how its topology and global performance evolved. We find that favoring asymmetric (disassortative) links is key to preserving the topology and functionality of the declining network. Based on our findings, we tested a model of network decline that combines an asymmetric disassembly process for contraction with a preferential attachment process for regrowth. Our simulation results indicate that the model can explain robustness under decline even if the total population of nodes contracts by more than an order of magnitude, in line with our observations for the empirical network. These findings suggest that disassembly mechanisms are not simply assembly mechanisms in reverse and that our model is relevant to understanding the process of decline and collapse in a broad range of biological, technological, and financial networks. PMID:18936489

  16. D mesons in asymmetric nuclear matter

    International Nuclear Information System (INIS)

    Mishra, Amruta; Mazumdar, Arindam

    2009-01-01

    We calculate the in-medium D and D meson masses in isospin-asymmetric nuclear matter in an effective chiral model. The D and D mass modifications arising from their interactions with the nucleons and the scalar mesons in the effective hadronic model are seen to be appreciable at high densities and have a strong isospin dependence. These mass modifications can open the channels of the decay of the charmonium states (Ψ ' ,χ c ,J/Ψ) to DD pairs in dense hadronic matter. The isospin asymmetry in the doublet D=(D 0 ,D + ) is seen to be particularly appreciable at high densities and should show in observables such as their production and flow in asymmetric heavy-ion collisions in the compressed baryonic matter experiments in the future facility of FAIR, GSI. The results of the present work are compared to calculations of the D(D) in-medium masses in the literature using the QCD sum rule approach, quark meson coupling model, and coupled channel approach as well as to those from studies of quarkonium dissociation using heavy-quark potentials from lattice QCD at finite temperatures

  17. Asymmetric Cell Divisions in the Epidermis

    Science.gov (United States)

    Poulson, Nicholas D.; Lechler, Terry

    2012-01-01

    Generation of three-dimensional tissue with distinct cell types is required for the development of all organs. On its own, mitotic spindle orientation allows tissues to change in length or shape. In combination with intrinsic or extrinsic cues this can also be coupled to the generation of diverse cell fates - a process known as asymmetric cell division (ACD). Understanding ACD’s has been greatly aided by studies in invertebrate model systems, where genetics and live imaging have provided the basis for much of what we know. ACD’s also drive the development and differentiation of the epidermis in mammals. While similar to the invertebrate models, the epidermis is distinct in balancing symmetric and asymmetric divisions to yield a tissue of the correct surface area and thickness. Here we review the roles of spindle orientation in driving both morphogenesis and cell fate decisions. We highlight the epidermis as a unique model system to study not only basic mechanisms of ACD, but also to study their regulation during development. PMID:22449491

  18. Asymmetric facial skin viscoelasticity during climacteric aging

    Science.gov (United States)

    Piérard, Gérald E; Hermanns-Lê, Trinh; Gaspard, Ulysse; Piérard-Franchimont, Claudine

    2014-01-01

    Background Climacteric skin aging affects certain biophysical characteristics of facial skin. The purpose of the present study was to assess the symmetric involvement of the cheeks in this stage of the aging process. Methods Skin viscoelasticity was compared on both cheeks in premenopausal and post-menopausal women with indoor occupational activities somewhat limiting the influence of chronic sun exposure. Eighty-four healthy women comprising 36 premenopausal women and 48 early post-menopausal women off hormone replacement therapy were enrolled in two groups. The tensile characteristics of both cheeks were tested and compared in each group. A computerized suction device equipped with a 2 mm diameter hollow probe was used to derive viscoelasticity parameters during a five-cycle procedure of 2 seconds each. Skin unfolding, intrinsic distensibility, biological elasticity, and creep extension were measured. Results Both biological elasticity and creep extension were asymmetric on the cheeks of the post-menopausal women. In contrast, these differences were more discrete in the premenopausal women. Conclusion Facial skin viscoelasticity appeared to be asymmetric following menopause. The possibility of asymmetry should be taken into account in future studies of the effects of hormone replacement therapy and any antiaging procedure on the face in menopausal women. PMID:24748810

  19. Asymmetric DSL Technology of Signal Transmission

    Directory of Open Access Journals (Sweden)

    Dražen Kovačević

    2005-05-01

    Full Text Available Asymmetric flow of information is the key feature of theADSL (Asymmetric Digital Subscriber Loop technology, i.e.higher data transmission rate towards the user than from theuser towards the network. Characteristic is the short messagesending by the user with a certain request to the se!Ver. These!Ver responds to the request by a significantly longer messageof various electronic forms (data, digitized speech, pictures orvideo. Therefore, this technology is most often used by smalland medium users. ADSL is currently the only commerciallyavailable DSL technology which is still experiencing the breakthroughon the seiVice market. It enables faster access to theInternet, LAN (Local Area Network, videoconferencing, VoD(Video on Demand and interactive multimedia. In order tostandardize such se/Vices, the !TU (International TelecommunicationsUnion G. 992.1 (standardized DMT-discrete multi-tone line coding technology and ANSJ (American NationalStandards Institution Tl.413-95!98 are used for ADSL. DMT(Discrete Multi Tone, as the more popular one, uses the linecoding technique, which splits a certain frequency range intoseveral sub-channels. Most of these sub-channels are used forupstream and downstream transmission of speech and data,whereas some are used as pilot signals or kept in rese/Ve. Suchmodulation technique expands the frequency spectrum, allowingthe usage ofbroadband se/Vices per one pair of wires. In thisway the sharing of speech and data se/Vice transmission is realized.

  20. MOBILE COMPLEX FOR CATALYTIC THERMAL WASTE TREATMENT

    Directory of Open Access Journals (Sweden)

    Vedi V.E.

    2012-12-01

    Full Text Available The design and purpose of the basic units of the mobile waste processing complex “MPK” are described. Experimental data of catalytic purification of exhaust gases are presented. Experimental data on catalytic clearing of final gases of a designed mobile incinerator plant are shown. It is defined, that concentrating of parasitic bridging in waste gases of the complex are considerably smaller, rather than allowed by normative documents.

  1. Design of iron atom modified thiophene-linked metalloporphyrin 2D conjugated microporous polymer as CO2reduction photocatalyst.

    Science.gov (United States)

    Chen, Chongyang; Tang, Chao; Xu, Weiwei; Li, Youyong; Xu, Lai

    2018-03-23

    Herein, by means of density functional theory (DFT) calculations, we designed a new type of thiophene-linked porphyrin unit and incorporated it into an extended 2D conjugated microporous polymer (CMP) to serve as a CO2 reduction catalyst. This newly designed catalyst combines the advantages of molecular catalysis, heterogeneous catalysis, high structural stability and tunable electronic properties. A series of metal atoms (Fe, Mg, Mn, and Cu) were introduced into the center of the porphyrin ring to modify its capacity for reducing CO2. Our transition state (TS) search calculations revealed that the Fe-modified CMP possessed the highest catalytic activity toward CO2 reduction. The plausible reduction pathway was also determined. The band structure and frontier orbital distribution calculations further demonstrated its semimetallic property and higher stimulated transition probability, both of which are critical factors for photocatalytic performance. We hope that our design could provide meaningful guidance for other relevant CO2 catalytic reactions.

  2. Conjugation fidelity of double phase-conjugate mirrors in photorefractive materials with two-center transport.

    Science.gov (United States)

    Geri, I; Ozkul, C

    1996-11-01

    The temporal evolution of double phase-conjugate mirrors (DPCM's) in photorefractive materials such as BaTiO(3):Co:Fe is studied by use of the plane-wave expansion method. The buildup time of DPCM and its conjugation fidelity are compared with those of photorefractive materials with a single-center transport. Numerical simulations show that one can decrease the threshold value of the coupling strength required for the DPCM operation with a high conjugation fidelity by doping the BaTiO(3) crystals weakly with Co in comparison with undoped crystals.

  3. Efficient Xerographic Photoreceptors from Conjugated Polymers and Polymer Blends

    National Research Council Canada - National Science Library

    Zhang, Xuejun, Ph.D

    1998-01-01

    Bilayer xerographic photoreceptors in which pi-conjugated polymers and binary conjugated polymer blends are used as the charge generation layer have been fabricated, evaluated, and shown to be highly efficient...

  4. Deep seismic studies of conjugate profiles from the Nova Scotia - Moroccan and the Liguro-Provencal margin pairs

    Science.gov (United States)

    Klingelhoefer, F.; Biari, Y.; Sahabi, M.; Aslanian, D.; Philippe, S.; Schnabel, M.; Moulin, M.; Louden, K. E.; Funck, T.; Reichert, C. J.

    2014-12-01

    The structure of conjugate passive margins provides information about rifting styles, opening of an ocean and formation of it's associated sedimentary basins. In order to distinguish between tectonic inheritance and structures directly related to rifting of passive margins conjugate profiles have to be acquired on margins on diverse locations and different ages. In this study we use new and existing reflection and wide-angle seismic data from two margin pairs, the 200 Ma year old Nova-Scotia - Morocco margin pair and the only 20 Ma Gulf of Lions - Sardinia margin pair. On both margin pairs wide-angle seismic data combined with reflection seismic data were acquired on conjugate profiles on sea and extended on land. Forward modelling of the deep crustal structure along the four transects indicates that a high velocity zone (HVZ) (> 7.2 km/s) is present at the base of the lower crust on all four margins along the ocean-continental transition zone (OCT). This may represent either exhumed upper mantle material or injection of upper mantle material into proto-oceanic crust at the onset of sea-floor spreading. However the width of the HVZ might strongly differ between conjugates, which may be the result of tectonic inheritance, for example the presence of ancient subduction zones or orogens. Both margin pairs show a similar unthinned continental crustal thickness. Crustal thinning and upper-to-lower crustal thickness vary between margin pairs, but remain nearly symmetric on conjugate profiles and might therefore depend on the structure and mechanical properties of the original continental crust. For the Mediterranean margin pair, the oceanic crust is similar on both sides, with a thickness of only 4-5 km. For the Atlantic margin pair, oceanic crustal thickness is higher on the Moroccan Margin, a fact that can be explained by either asymmetric spreading or by the volcanic underplating, possibly originating from the Canary Hot Spot.

  5. Crystallization of the Atg12–Atg5 conjugate bound to Atg16 by the free-interface diffusion method

    Energy Technology Data Exchange (ETDEWEB)

    Noda, Nobuo N.; Fujioka, Yuko [Department of Structural Biology, Graduate School of Pharmaceutical Sciences, Hokkaido University, N-21, W-11, Kita-ku, Sapporo 001-0021 (Japan); Ohsumi, Yoshinori [Division of Molecular Cell Biology, National Institute for Basic Biology, Myodaiji, Okazaki 444-8585 (Japan); Inagaki, Fuyuhiko, E-mail: finagaki@pharm.hokudai.ac.jp [Department of Structural Biology, Graduate School of Pharmaceutical Sciences, Hokkaido University, N-21, W-11, Kita-ku, Sapporo 001-0021 (Japan)

    2008-05-01

    The Atg12–Atg5 conjugate was prepared by in vivo reconstitution and was crystallized with Atg16 using the free-interface diffusion method. Autophagy mediates the bulk degradation of cytoplasmic components in lysosomes/vacuoles. Five autophagy-related (Atg) proteins are involved in a ubiquitin-like protein conjugation system. Atg12 is conjugated to its sole target, Atg5, by two enzymes, Atg7 and Atg10. The Atg12–Atg5 conjugates form a multimeric complex with Atg16. Formation of the Atg12–Atg5–Atg16 ternary complex is crucial for the functions of these proteins on autophagy. Here, the expression, purification and crystallization of the Atg12–Atg5 conjugate bound to the N-terminal region of Atg16 (Atg16N) are reported. The Atg12–Atg5 conjugates were formed by co-expressing Atg5, Atg7, Atg10 and Atg12 in Eschericia coli. The Atg12–Atg5–Atg16N ternary complex was formed by mixing purified Atg12–Atg5 conjugates and Atg16N, and was further purified by gel-filtration chromatography. Crystallization screening was performed by the free-interface diffusion method. Using obtained microcrystals as seeds, large crystals for diffraction data collection were obtained by the sitting-drop vapour-diffusion method. The crystal contained one ternary complex per asymmetric unit, and diffracted to 2.6 Å resolution.

  6. Functional analysis of the conjugation system from Clostridium perfringens

    OpenAIRE

    Wisniewski, Jessica Ann

    2017-01-01

    In Clostridium perfringens, toxins that cause histotoxic and gastrointestinal diseases have been identified on a family of large conjugative plasmids. The tcp transfer locus was initially identified on the prototype conjugative plasmid, pCW3. This locus has been shown to mediate conjugative plasmid transfer and studies on several of the Tcp proteins have identified their role in plasmid transfer. In general less is known about the mechanism of conjugative transfer in Gram positive bacteria, n...

  7. Application of a new amidophosphite ligand to Rh-catalyzed asymmetric hydrogenation of β-dehydroamino acid derivatives in supercritical carbon dioxide: activation effect of protic Co-solvents.

    Science.gov (United States)

    Lyubimov, Sergey E; Rastorguev, Eugenie A; Davankov, Vadim A

    2011-09-01

    New chiral amidophosphite ligand was synthesized and tested in the Rh-catalyzed asymmetric hydrogenation of (Z)-β-(acylamino)acrylates in protic solvents and supercritical carbon dioxide (scCO(2) ) The catalytic performance is affected greatly by the acidity of the solvents. Better enantioselectivity (up to 88% ee) was achieved in scCO(2) containing 1,1,1,3,3,3-hexafluoro-2-propanol, compared to neat protic solvents. Copyright © 2011 Wiley-Liss, Inc.

  8. Adsorbent catalytic nanoparticles and methods of using the same

    Energy Technology Data Exchange (ETDEWEB)

    Slowing, Igor Ivan; Kandel, Kapil

    2017-01-31

    The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

  9. Efficient Supercapacitor Energy Storage Using Conjugated Microporous Polymer Networks Synthesized from Buchwald-Hartwig Coupling.

    Science.gov (United States)

    Liao, Yaozu; Wang, Haige; Zhu, Meifang; Thomas, Arne

    2018-01-15

    Supercapacitors have received increasing interest as energy storage devices due to their rapid charge-discharge rates, high power densities, and high durability. In this work, novel conjugated microporous polymer (CMP) networks are presented for supercapacitor energy storage, namely 3D polyaminoanthraquinone (PAQ) networks synthesized via Buchwald-Hartwig coupling between 2,6-diaminoanthraquinone and aryl bromides. PAQs exhibit surface areas up to 600 m 2 g -1 , good dispersibility in polar solvents, and can be processed to flexible electrodes. The PAQs exhibit a three-electrode specific capacitance of 576 F g -1 in 0.5 m H 2 SO 4 at a current of 1 A g -1 retaining 80-85% capacitances and nearly 100% Coulombic efficiencies (95-98%) upon 6000 cycles at a current density of 2 A g -1 . Asymmetric two-electrode supercapacitors assembled by PAQs show a capacitance of 168 F g -1 of total electrode materials, an energy density of 60 Wh kg -1 at a power density of 1300 W kg -1 , and a wide working potential window (0-1.6 V). The asymmetric supercapacitors show Coulombic efficiencies up to 97% and can retain 95.5% of initial capacitance undergo 2000 cycles. This work thus presents novel promising CMP networks for charge energy storage. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Homogenous Pd-catalyzed asymmetric hydrogenation of unprotected indoles: scope and mechanistic studies.

    Science.gov (United States)

    Duan, Ying; Li, Lu; Chen, Mu-Wang; Yu, Chang-Bin; Fan, Hong-Jun; Zhou, Yong-Gui

    2014-05-28

    An efficient palladium-catalyzed asymmetric hydrogenation of a variety of unprotected indoles has been developed that gives up to 98% ee using a strong Brønsted acid as the activator. This methodology was applied in the facile synthesis of biologically active products containing a chiral indoline skeleton. The mechanism of Pd-catalyzed asymmetric hydrogenation was investigated as well. Isotope-labeling reactions and ESI-HRMS proved that an iminium salt formed by protonation of the C═C bond of indoles was the significant intermediate in this reaction. The important proposed active catalytic Pd-H species was observed with (1)H NMR spectroscopy. It was found that proton exchange between the Pd-H active species and solvent trifluoroethanol (TFE) did not occur, although this proton exchange had been previously observed between metal hydrides and alcoholic solvents. Density functional theory calculations were also carried out to give further insight into the mechanism of Pd-catalyzed asymmetric hydrogenation of indoles. This combination of experimental and theoretical studies suggests that Pd-catalyzed hydrogenation goes through a stepwise outer-sphere and ionic hydrogenation mechanism. The activation of hydrogen gas is a heterolytic process assisted by trifluoroacetate of Pd complex via a six-membered-ring transition state. The reaction proceeds well in polar solvent TFE owing to its ability to stabilize the ionic intermediates in the Pd-H generation step. The strong Brønsted acid activator can remarkably decrease the energy barrier for both Pd-H generation and hydrogenation. The high enantioselectivity arises from a hydrogen-bonding interaction between N-H of the iminium salt and oxygen of the coordinated trifluoroacetate in the eight-membered-ring transition state for hydride transfer, while the active chiral Pd complex is a typical bifunctional catalyst, effecting both the hydrogenation and hydrogen-bonding interaction between the iminium salt and the coordinated

  11. Women experiencing the intergenerationality of conjugal violence

    Directory of Open Access Journals (Sweden)

    Gilvânia Patrícia do Nascimento Paixão

    2015-10-01

    Full Text Available Objective: to analyze the family relationship, in childhood and adolescence, of women who experience conjugal violence.Method: qualitative study. Interviews were held with 19 women, who were experiencing conjugal violence, and who were resident in a community in Salvador, Bahia, Brazil. The project was approved by the Research Ethics Committee (N. 42/2011.Results: the data was organized using the Discourse of the Collective Subject, identifying the summary central ideas: they witnessed violence between their parents; they suffered repercussions from the violence between their parents: they were angry about the mother's submission to her partner; and they reproduced the conjugal violence. The discourse showed that the women witnessed, in childhood and adolescence, violence between their parents, and were injured both physically and psychologically. As a result of the mother's submission, feelings of anger arose in the children. However, in the adult phase of their own lives, they noticed that their conjugal life resembled that of their parents, reproducing the violence.Conclusion: investment is necessary in strategies designed to break inter-generational violence, and the health professionals are important in this process, as it is a phenomenon with repercussions in health. Because they work in the Family Health Strategy, which focuses on the prevention of harm and illness, health promotion and interdepartmentality, the nurses are essential in the process of preventing and confronting this phenomenon.

  12. Women experiencing the intergenerationality of conjugal violence.

    Science.gov (United States)

    Paixão, Gilvânia Patrícia do Nascimento; Gomes, Nadirlene Pereira; Diniz, Normélia Maria Freire; Carvalho e Lira, Margaret Ollinda de Souza; Carvalho, Milca Ramaiane da Silva; da Silva, Rudval Souza

    2015-01-01

    to analyze the family relationship, in childhood and adolescence, of women who experience conjugal violence. qualitative study. Interviews were held with 19 women, who were experiencing conjugal violence, and who were resident in a community in Salvador, Bahia, Brazil. The project was approved by the Research Ethics Committee (N. 42/2011). the data was organized using the Discourse of the Collective Subject, identifying the summary central ideas: they witnessed violence between their parents; they suffered repercussions from the violence between their parents: they were angry about the mother's submission to her partner; and they reproduced the conjugal violence. The discourse showed that the women witnessed, in childhood and adolescence, violence between their parents, and were injured both physically and psychologically. As a result of the mother's submission, feelings of anger arose in the children. However, in the adult phase of their own lives, they noticed that their conjugal life resembled that of their parents, reproducing the violence. investment is necessary in strategies designed to break inter-generational violence, and the health professionals are important in this process, as it is a phenomenon with repercussions in health. Because they work in the Family Health Strategy, which focuses on the prevention of harm and illness, health promotion and interdepartmentality, the nurses are essential in the process of preventing and confronting this phenomenon.

  13. Unsymmetrical extended -conjugated zinc phthalocyanine for ...

    Indian Academy of Sciences (India)

    We have designed and synthesized a new unsymmetrical zinc phthalocyanine based on `push-pull' and extended -conjugation concept, PCH008. The new sensitizer was fully characterized by CHN anlysis, UV-Vis., fluorescence spectroscopies and cyclic voltammetry. The new sensitizer which upon anchoring onto ...

  14. Compositions for directed alignment of conjugated polymers

    Science.gov (United States)

    Kim, Jinsang; Kim, Bong-Gi; Jeong, Eun Jeong

    2016-04-19

    Conjugated polymers (CPs) achieve directed alignment along an applied flow field and a dichroic ratio of as high as 16.67 in emission from well-aligned thin films and fully realized anisotropic optoelectronic properties of CPs in field-effect transistor (FET).

  15. Theoretical study of conjugated porphyrin polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Lynge, T.B.; Kristensen, P.K.

    2005-01-01

    for these applications. From a theoretical analysis of excitons in long metalloporphyrin chains, we demonstrate that the binding energy is much lower than in usual conjugated polymers. Our calculated absorption spectra are in good agreement with measurements. (c) 2004 Elsevier B.V. All rights reserved....

  16. preconditioning the modified conjugate gradient method

    African Journals Online (AJOL)

    Admin

    The conventional conjugate method (CGM) was originally developed by Hestenes and. Stiefel (1952) as a method of solution for linear systems. Fletcher and Reeves (1964) built the necessary underlying theory for a successful application of the method to quadratic functional and developed its convergence properties.

  17. Ciprofloxacin conjugated zinc oxide nanoparticle: A camouflage ...

    Indian Academy of Sciences (India)

    excellent antibacterial activity against clinically isolated multidrug resistant bacterial strains of Escherichia coli,. Staphylococcus aureus and ... Keywords. Zinc oxide nanoparticles; ciprofloxacin; chemical conjugation; antibacterial property. 1. Introduction ... Nanoparticles of TiO2, ZnO, silver, etc. are commonly known for their ...

  18. Bacillus thuringiensis Conjugation in Simulated Microgravity

    Science.gov (United States)

    Beuls, Elise; van Houdt, Rob; Leys, Natalie; Dijkstra, Camelia; Larkin, Oliver; Mahillon, Jacques

    2009-10-01

    Spaceflight experiments have suggested a possible effect of microgravity on the plasmid transfer among strains of the Gram-positive Bacillus thuringiensis, as opposed to no effect recorded for Gram-negative conjugation. To investigate these potential effects in a more affordable experimental setup, three ground-based microgravity simulators were tested: the Rotating Wall Vessel (RWV), the Random Positioning Machine (RPM), and a superconducting magnet. The bacterial conjugative system consisted in biparental matings between two B. thuringiensis strains, where the transfer frequencies of the conjugative plasmid pAW63 and its ability to mobilize the nonconjugative plasmid pUB110 were assessed. Specifically, potential plasmid transfers in a 0-g position (simulated microgravity) were compared to those obtained under 1-g (normal gravity) condition in each device. Statistical analyses revealed no significant difference in the conjugative and mobilizable transfer frequencies between the three different simulated microgravitational conditions and our standard laboratory condition. These important ground-based observations emphasize the fact that, though no stimulation of plasmid transfer was observed, no inhibition was observed either. In the case of Gram-positive bacteria, this ability to exchange plasmids in weightlessness, as occurs under Earth's conditions, should be seen as particularly relevant in the scope of spread of antibiotic resistances and bacterial virulence.

  19. Conjugated Polymer Actuators: Prospects and Limitations

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2007-01-01

    Actuators constructed with a conjugated polymer as the active part have been predicted to have a number of highly desirable properties: Large mechanical strength, high power density, i.e. high actuation speeds possible, sufficient maximum strain values, high reversibility and safe, low voltages (1...

  20. Immunogenicity of novel sulfadimethoxide conjugates | Chen ...

    African Journals Online (AJOL)

    Immunogenicity of novel sulfadimethoxide conjugates. L Chen, J Su, X Zhang, L Li, X He. Abstract. Sulfadimethoxine (SDM) is an antibiotic commonly added to animal feeds. Anti-SDM antibodies are useful for the detection of residual SDM in foods, feeds and biological fluids by ELISA. In this study, we show that SDM is ...

  1. Theory of periodic conjugate heat transfer

    CERN Document Server

    Zudin, Yuri B

    2016-01-01

    This book presents the theory of periodic conjugate heat transfer in detail. It offers a simplified description of the interaction between a solid body and a fluid as a boundary value problem of the heat conduction equation for the solid body.

  2. Meningococcal conjugate vaccines: optimizing global impact

    Directory of Open Access Journals (Sweden)

    Terranella A

    2011-09-01

    Full Text Available Andrew Terranella1,2, Amanda Cohn2, Thomas Clark2 1Epidemic Intelligence Service, Division of Applied Sciences, Scientific Education and Professional Development Program Office, 2Meningitis and Vaccine Preventable Diseases Branch, National Center for Immunization and Respiratory Diseases, Centers for Disease Control and Prevention, Atlanta, GA, USA Abstract: Meningococcal conjugate vaccines have several advantages over polysaccharide vaccines, including the ability to induce greater antibody persistence, avidity, immunologic memory, and herd immunity. Since 1999, meningococcal conjugate vaccine programs have been established across the globe. Many of these vaccination programs have resulted in significant decline in meningococcal disease in several countries. Recent introduction of serogroup A conjugate vaccine in Africa offers the potential to eliminate meningococcal disease as a public health problem in Africa. However, the duration of immune response and the development of widespread herd immunity in the population remain important questions for meningococcal vaccine programs. Because of the unique epidemiology of meningococcal disease around the world, the optimal vaccination strategy for long-term disease prevention will vary by country. Keywords: conjugate vaccine, meningitis, meningococcal vaccine, meningococcal disease

  3. One-pot synthesis of conjugated trienes

    Czech Academy of Sciences Publication Activity Database

    Šebesta, Petr; Jahn, Ullrich

    2009-01-01

    Roč. 103, č. 11 (2009), s. 990-990 ISSN 0009-2770. [Pokroky v organické, bioorganické a farmaceutické chemii /44./. 27.11.2009-29.11.2009, Liblice] Institutional research plan: CEZ:AV0Z40550506 Keywords : pheromones * Suzuki coupling * conjugated trienes Subject RIV: CC - Organic Chemistry

  4. Determinants of pneumococcal conjugate vaccine uptake among ...

    African Journals Online (AJOL)

    Subjects: The respondents were the parents/guardians of children less than two years of age attending immunisation services at KNH and those admitted in the peadiatric wards with pneumonia. Results: The study established that the determinants of uptake of Pneumococcal Conjugate Vaccine are age(OR 5.8, CI 1.4-23.4, ...

  5. Stabilizing cations in the backbones of conjugated polymers

    NARCIS (Netherlands)

    Voortman, Thomas P.; de Gier, Hilde D.; Havenith, Remco W. A.; Chiechi, Ryan C.

    2014-01-01

    We synthesized a cross-conjugated polymer containing ketones in the backbone and converted it to a linearly conjugated, cationic polyarylmethine via a process we call "spinless doping" to create a new class of materials, conjugated polyions. This process involves activating the ketones with a Lewis

  6. DA conjugated polymers containing substituted thiophene, 1, 3, 4 ...

    Indian Academy of Sciences (India)

    ... electron-accepting (A) 1,3,4- oxadiazole unit and non-conjugation linkers. The conjugated segment in P1-P3 contains only five aromatic rings resulting in short conjugation length, but has an alternate D-A arrangement which significantly enhances the intramolecular charge transfer (ICT) interaction within the segment.

  7. Rapid asymmetrical evolution of Saccharomyces cerevisiae wine yeasts.

    Science.gov (United States)

    Ambrona, Jesús; Vinagre, Antonia; Ramírez, Manuel

    2005-12-01

    Genetic instability causes very rapid asymmetrical loss of heterozygosity (LOH) at the cyh2 locus and loss of killer K2 phenotype in some wine yeasts under the usual laboratory propagation conditions or after long freeze-storage. The direction of this asymmetrical evolution in heterozygous cyh2(R)/CYH2(S) hybrids is determined by the mechanism of asymmetrical LOH. However, the speed of the process is affected by the differences in cell viability between the new homozygous yeasts and the original heterozygous hybrid cells. The concomitant loss of ScV-M2 virus in the LOH process may increase cell viability of cyh2(R)/cyh2(R) yeasts and so favour asymmetrical evolution. The presence of active killer K2 toxin, however, abolishes the asymmetrical evolution of the hybrid populations. This phenomenon may cause important sudden phenotype changes in industrial and pathogenic yeasts. Copyright 2005 John Wiley & Sons, Ltd.

  8. Subcopula-based measure of asymmetric association for contingency tables.

    Science.gov (United States)

    Wei, Zheng; Kim, Daeyoung

    2017-10-30

    For the analysis of a two-way contingency table, a new asymmetric association measure is developed. The proposed method uses the subcopula-based regression between the discrete variables to measure the asymmetric predictive powers of the variables of interest. Unlike the existing measures of asymmetric association, the subcopula-based measure is insensitive to the number of categories in a variable, and thus, the magnitude of the proposed measure can be interpreted as the degree of asymmetric association in the contingency table. The theoretical properties of the proposed subcopula-based asymmetric association measure are investigated. We illustrate the performance and advantages of the proposed measure using simulation studies and real data examples. Copyright © 2017 John Wiley & Sons, Ltd.

  9. Contributions to the theory of catalytic titrations-III Neutralization catalytic titrations.

    Science.gov (United States)

    Gaál, F F; Abramović, B F

    1985-07-01

    Neutralization catalytic titrations of weak monoprotic adds and bases with both volumetric and coulometric addition of the titrant (strong base/acid) have been simulated by taking into account the equilibrium concentration of the catalyst during the titration. The influence of several factors on the shape of the simulated catalytic titration curve has been investigated and is discussed.

  10. Behavior of forced asymmetric oscillators at resonance

    Directory of Open Access Journals (Sweden)

    C. Fabry

    2000-12-01

    Full Text Available This article collects recent results concerning the behavior at resonance of forced oscillators driven by an asymmetric restoring force, with or without damping. This synthesis emphasizes the key role played by a function denoted by $Phi_{alpha,eta,p}$, which is, up to a sign reversal of its argument, a correlation product of the forcing term $p$ and of a function representing a free oscillation for theundamped equation. The theoretical results are accompanied by graphical representations illustrating the behavior of the damped and undamped oscillators. In particular, the damped oscillator is considered, with a forcing term whose frequency is close to the frequency of the free oscillations. For that problem, frequency-response curves are studied, both theoretically and through numerical computations, revealing a hysteresis phenomenon, when $Phi_{alpha,eta,p}$ is of constant sign.

  11. The Asymmetric Effects of Investor Sentiment

    DEFF Research Database (Denmark)

    Lutz, Chandler

    investors only act as corrective force during certain time periods. We also show that our index predicts implied volatility, media pessimism, and mutual fund flows. Overall, our findings are consistent with both the theories and anecdotal accounts of investor sentiment in the stock market.......We use the returns on lottery-like stocks to construct a novel index for investor sentiment in the stock market. This new measure is closely related to previously developed sentiment indicators, but more accurately tracks speculative episodes over the sample period. Using our index, we find...... that the relationship between sentiment and returns is asymmetric: during bear markets, high sentiment predicts low future returns for the cross-section of speculative stocks and the market overall while the relationship during bull markets is weak and often insignificant. Thus, the results suggest that sophisticated...

  12. Asymmetric pair distribution functions in catalysts

    DEFF Research Database (Denmark)

    Clausen, B. S.; Nørskov, Jens Kehlet

    2000-01-01

    it has been realized that often there is a need to use an improved EXAFS data analysis compared to the simple harmonic approach which works well for well-defined bulk structures. This is due to the fact that catalysts contain highly dispersed or disordered structures with pair distribution functions...... of asymmetric pair distribution functions for nano-sized particles and how they influence the structural parameters obtained from the standard data analysis. An alternative method, which takes into account deviations from the Gaussian pair distribution function typically used in the analysis of EXAFS spectra......, will be described. The method is based on an analysis of the pair distribution functions derived from molecular dynamics simulations of small metal particles and its reliability is demonstrated by comparing structural parameters obtained from independent X-ray diffraction experiments....

  13. Isospin dependent properties of asymmetric nuclear matter

    Science.gov (United States)

    Chowdhury, P. Roy; Basu, D. N.; Samanta, C.

    2009-07-01

    The density dependence of nuclear symmetry energy is determined from a systematic study of the isospin dependent bulk properties of asymmetric nuclear matter using the isoscalar and isovector components of the density dependent M3Y interaction. The incompressibility K∞ for the symmetric nuclear matter, the isospin dependent part Kasy of the isobaric incompressibility, and the slope L are all in excellent agreement with the constraints recently extracted from measured isotopic dependence of the giant monopole resonances in even-A Sn isotopes, from the neutron skin thickness of nuclei, and from analyses of experimental data on isospin diffusion and isotopic scaling in intermediate energy heavy-ion collisions. This work provides a fundamental basis for the understanding of nuclear matter under extreme conditions and validates the important empirical constraints obtained from recent experimental data.

  14. Do Daily Retail Gasoline Prices adjust Asymmetrically?

    International Nuclear Information System (INIS)

    Bettendorf, L.; Van der Geest, S.; Kuper, G.

    2005-04-01

    This paper analyzes adjustments in the Dutch retail gasoline prices. We estimate an error correction model on changes in the daily retail price for gasoline (taxes excluded) for the period 1996-2004 taking care of volatility clustering by estimating an EGARCH model. It turns out the volatility process is asymmetrical: an unexpected increase in the producer price has a larger effect on the variance of the producer price than an unexpected decrease. We do not find strong evidence for amount asymmetry. However, there is a faster reaction to upward changes in spot prices than to downward changes in spot prices. This implies timing or pattern asymmetry. This asymmetry starts three days after the change in the spot price and lasts for four days

  15. An asymmetric B Factory based on PEP

    International Nuclear Information System (INIS)

    Hutton, A.; Zisman, M.S.

    1990-06-01

    The study of rare and CP-violating B meson decays is well suited to a high-luminosity e + e - collider. For studying certain decay processes there are also substantial benefits associated with asymmetric beam energies, which give a moving center of mass for the B mesons. We describe a design for a 9 GeV x 3.1 GeV B Factory in the PEP tunnel that would operate initially at a luminosity of 3 x 10 33 cm -2 s -1 . Technical problems include issues related to high currents (e.g., beam instabilities, feedback systems, lifetime degradation and detector radiation power dissipation) and those related to the hetero-energetic beams (e.g., beam separation, beam-beam interaction and detector requirements). Issues requiring R ampersand D effort are identified. 8 refs., 2 figs., 2 tabs

  16. Mass asymmetric fission barriers for 75Br

    Science.gov (United States)

    Delis, D. N.; Blumenfeld, Y.; Bowman, D. R.; Colonna, N.; Hanold, K.; Jing, K.; Justice, M.; Meng, J. C.; Peaslee, G. F.; Wozniak, G. J.; Moretto, L. G.

    1991-11-01

    Fragments with atomic numbers covering nearly the entire range of the mass-asymmetry coordinate (4 < Z < 27) were observed from the 5.0, 6.2, 6.9, 8.0, 10.2 and 12.7 MeV/A 63Cu + 12C reactions. Energy spectra and angular distributions show the presence of projectile-like and target-like components along with an isotropic component. The isotropic component appears as a Coulomb ring in the invariant cross-section plots indicating the presence of a binary compound nucleus decay which is confirmed by the coincidence data. Excitation functions were constructed for each Z value and a nearly complete set of mass-asymmetric barriers has been extracted for 75Br. There is excellent agreement between the experimentally determined barriers and the finite-range model predictions.

  17. Baryon destruction by asymmetric dark matter

    International Nuclear Information System (INIS)

    Davoudiasl, Hooman; Morrissey, David E.; Tulin, Sean; Sigurdson, Kris

    2011-01-01

    We investigate new and unusual signals that arise in theories where dark matter is asymmetric and carries a net antibaryon number, as may occur when the dark matter abundance is linked to the baryon abundance. Antibaryonic dark matter can cause induced nucleon decay by annihilating visible baryons through inelastic scattering. These processes lead to an effective nucleon lifetime of 10 29 -10 32 yrs in terrestrial nucleon decay experiments, if baryon number transfer between visible and dark sectors arises through new physics at the weak scale. The possibility of induced nucleon decay motivates a novel approach for direct detection of cosmic dark matter in nucleon decay experiments. Monojet searches (and related signatures) at hadron colliders also provide a complementary probe of weak-scale dark-matter-induced baryon number violation. Finally, we discuss the effects of baryon-destroying dark matter on stellar systems and show that it can be consistent with existing observations.

  18. PEP-II: An asymmetric B factory

    International Nuclear Information System (INIS)

    1993-06-01

    In this report, the authors have described an updated conceptual design for the high-luminosity Asymmetric B Factory (PEP-II) to be built in the PEP tunnel culmination of more than four years of effort aimed at the design and construction of an asymmetric e + e - collider capable of achieving a luminosity of L = 3 x 10 33 cm -2 s -1 . All aspects of the conceptual design were scrutinized in March 1991 by a DOE technical review committee chaired by Dr. L. Edward Temple. The design was deemed feasible and capable of achieving its physics goals. Furthermore, the cost estimate, schedule, and management plan for the project were fully endorsed by the committee. This updated conceptual design report captures the technical progress since the March 1991 review and reflects the lower cost estimate corresponding to the improved design. Although the PEP-II design has continued to evolve, no technical scope changes have been made that invalidate the conclusion of the DOE review. The configuration adopted utilizes two storage rings, an electron ring operating at 9 GeV and a positron ring at 3.1 GeV, each with a circumference of 2200 m. The high-energy ring is an upgrade of the PEP storage ring at SLAC; all PEP magnets and most power supplies will be reused. The upgrade consists primarily of replacing the PEP vacuum chamber and RF system with newly designed versions optimized for the high-current environment of PEP-II. The low-energy ring will be newly constructed and will be situated atop the high-energy ring in the PEP tunnel. Utilities already installed in the PEP tunnel are largely sufficient to operate the two PEP-II storage rings

  19. Asymmetric collimation in breast cancer irradiation

    International Nuclear Information System (INIS)

    Isin, G.; Uzal, D.; Oezyar, E.; Arslan, G.; Akyol, F.; Atahan, I. L.

    1995-01-01

    Many methods have been devised to achieve an ideal match of the anterior supraclavicular field (SCV) caudal edge and the cephalad edges of the tangential fields. A non divergent SCV field edge is easily achieved using a half beam block. A number of methods are used to achieve a non divergent edge from the tangential beams including blocking, table angulation, collimator angulation in combination, and half beam blocking, collimator angulation. Using asymmetric collimation technique it is possible to achieve a perfect match-line at the junction of SCV and tangential fields. Via the longitudinal X-jaws, caudal edge of the SCV field and the cephalad margin of the tangential fields is defined. All three fields use one isocenter and thus a single set-up point by abutting beam-split fields at the match plane. The transverse Y jaws are used to beam-split the medial and lateral tangential fields at the chest wall level and define the lateral and medial edges of the SCV field. This technique eliminates lifting heavy half beam block, and the use of single isocenter is time-saving during set-up procedure. Computerized water phantom was utilized in dosimetric evaluations in this nonstandard technique. The match-line is clinically confirmed with verification film for each patient at first treatment. Our treatment planning system, Theraplan - Version 5B, is capable of asymmetric field planning. The 3-D treatment planning is performed at the central axis plane. Angle of tangential fields and source-skin distance at the set-up point is confirmed by 3D treatment planning

  20. Carbohydrate protease conjugates: Stabilized proteases for peptide synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Wartchow, C.A.; Wang, Peng; Bednarski, M.D.; Callstrom, M.R. [Ohio State Univ., Columbus, OH (United States)]|[Lawrence Berkeley Lab., CA (United States)

    1995-12-31

    The synthesis of oligopeptides using stable carbohydrate protease conjugates (CPCs) was examined in acetonitrile solvent systems. CPC[{alpha}-chymotrypsin] was used for the preparation of peptides containing histidine, phenylalanine, tryptophan in the P{sub 1} position in 60-93% yield. The CPC[{alpha}-chymotrypsin]-catalyzed synthesis of octamer Z-Gly-Gly-Phe-Gly-Gly-Phe-Gly-Gly-OEt from Z-Gly-Gly-Phe-Gly-Gly-Phe-OMe was achieved in 71% yield demonstrating that synthesis peptides containing both hydrophylic and hydrophobic amino acids. The P{sub 2} specificity of papain for aromatic residues was utilized for the 2 + 3 coupling of Z-Tyr-Gly-OMe to H{sub 2}N-Gly-Phe-Leu-OH to generate the leucine enkephalin derivative in 79% yield. Although papain is nonspecific for the hydrolysis of N-benzyloxycarbonyl amino acid methyl esters in aqueous solution, the rates of synthesis for these derivitives with nucleophile leucine tert-butyl ester differed by nearly 2 orders of magnitude. CPC[thermolysin] was used to prepare the aspartame precursor Z-Asp-Phe-OMe in 90% yield. The increased stability of CPCs prepared from periodate-modified poly(2-methacryl- amido-2-deoxy-D-glucose), poly(2-methacrylamido-2-deoxy-D-galactose), and poly(5-methacryl-amido-5-deoxy-D-ribose), carbohydrate materials designed to increase the aldehyde concentration in aqueous solution, suggests that the stability of CPCs is directly related to the aldehyde concentration of the carbohydrate material. Periodate oxidation of poly(2-methacrylamido-2-deoxy-D-glucose) followed by covalent attachment to {alpha}-chymotrypsin gave a CPC with catalytic activity in potassium phosphate buffer at 90{degrees}C for 2 h. 1 fig., 1 tab., 40 refs.

  1. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

    2016-11-18

    The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au25(SR)18, Au28(SR)20, Au38(SR)24, Au99(SR)42, Au144(SR)60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

  2. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    W. R. Laster; E. Anoshkina

    2008-01-31

    Under the sponsorship of the U. S. Department of Energy's National Energy Technology Laboratory, Siemens Westinghouse has conducted a three-year program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine application in IGCC. The program is defined in three phases: Phase 1 - Implementation Plan, Phase 2 - Validation Testing and Phase 3 - Field Testing. Both Phase 1 and Phase 2 of the program have been completed. In IGCC power plants, the gas turbine must be capable of operating on syngas as a primary fuel and an available back-up fuel such as natural gas. In this program the Rich Catalytic Lean (RCLTM) technology is being developed as an ultra low NOx combustor. In this concept, ultra low NOx is achieved by stabilizing a lean premix combustion process by using a catalytic reactor to oxidize a portion of the fuel, increasing the temperature of fuel/air mixture prior to the main combustion zone. In Phase 1, the feasibility of the catalytic concept for syngas application has been evaluated and the key technology issues identified. In Phase II the technology necessary for the application of the catalytic concept to IGCC fuels was developed through detailed design and subscale testing. Phase III (currently not funded) will consist of full-scale combustor basket testing on natural gas and syngas.

  3. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    Laster, W. R.; Anoshkina, E.

    2008-01-31

    Under the sponsorship of the U. S. Department of Energy’s National Energy Technology Laboratory, Siemens Westinghouse has conducted a three-year program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine application in IGCC. The program is defined in three phases: Phase 1- Implementation Plan, Phase 2- Validation Testing and Phase 3 – Field Testing. Both Phase 1 and Phase 2 of the program have been completed. In IGCC power plants, the gas turbine must be capable of operating on syngas as a primary fuel and an available back-up fuel such as natural gas. In this program the Rich Catalytic Lean (RCLTM) technology is being developed as an ultra low NOx combustor. In this concept, ultra low NOx is achieved by stabilizing a lean premix combustion process by using a catalytic reactor to oxidize a portion of the fuel, increasing the temperature of fuel/air mixture prior to the main combustion zone. In Phase 1, the feasibility of the catalytic concept for syngas application has been evaluated and the key technology issues identified. In Phase II the technology necessary for the application of the catalytic concept to IGCC fuels was developed through detailed design and subscale testing. Phase III (currently not funded) will consist of full-scale combustor basket testing on natural gas and syngas.

  4. Conjugated Polymers and Oligomers: Structural and Soft Matter Aspects

    DEFF Research Database (Denmark)

    This book identifies modern topics and current trends of structural and soft matter aspects of conjugated polymers and oligomers. Each chapter recognizes an active research line where structural perspective dominates research and therefore the book covers fundamental aspects of persistent...... conjugated polymer backbone, water soluble conjugated polyelectrolytes and surfactants, conjugated molecules and biomolecules and DNA and the advanced use of synchrotron radiation and electron microscopy to find out structural details in conjugated molecule films and devices as well as under ambient...... and extreme conditions....

  5. Vitexin inhibits polyubiquitin synthesis by the ubiquitin-conjugating enzyme E2-25K.

    Science.gov (United States)

    Helms, Kimberli M; Wilson, Randall C; Ogungbe, Ifedayo V; Setzer, William N; Twigg, Pamela D

    2011-10-01

    An extract of bark from the tropical rainforest plant Byrsonima crassifolia was screened for inhibition of diubiquitin formation by the human ubiquitin-conjugating enzyme E2-25K. Activity assays with both the full-length enzyme and a truncated, active catalytic UBC domain revealed that the extract contained inhibitory properties. Separation of the extract into individual components and additional screens identified vitexin as the active inhibitor. An IC50 for vitexin was calculated to be approximately 0.5 mM. Molecular modeling simulations were used to predict the mode of inhibition and NMR spectra were used to confirm the binding site of vitexin to E2-25K.

  6. SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps

    KAUST Repository

    Falivene, Laura

    2016-06-27

    Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.

  7. Symmetry in Cascade Chirality-Transfer Processes: A Catalytic Atroposelective Direct Arylation Approach to BINOL Derivatives.

    Science.gov (United States)

    Wang, Jin-Zheng; Zhou, Jin; Xu, Chang; Sun, Hongbin; Kürti, László; Xu, Qing-Long

    2016-04-27

    Herein we disclose a scalable organocatalytic direct arylation approach for the regio- and atroposelective synthesis of non-C2-symmetric 2,2'-dihydroxy-1,1'-binaphthalenes (BINOLs). In the presence of catalytic amounts of axially chiral phosphoric acids, phenols and naphthols are coupled with iminoquinones via a cascade process that involves sequential aminal formation, sigmatropic rearrangement, and rearomatization to afford enantiomerically enriched BINOL derivatives in good to excellent yields. Our studies suggest that the (local) symmetry of the initially formed aminal intermediate has a dramatic impact on the level of enantioinduction in the final product. Aminals with a plane of symmetry give rise to BINOL derivatives with significantly lower enantiomeric excess than unsymmetrical ones featuring a stereogenic center. Presumably asymmetric induction in the sigmatropic rearrangement step is significantly more challenging than during aminal formation. Sigmatropic rearrangement of the enantiomerically enriched aminal and subsequent rearomatization transfers the central chirality into axial chirality with high fidelity.

  8. Electro Catalytic Oxidation (ECO) Operation

    Energy Technology Data Exchange (ETDEWEB)

    Morgan Jones

    2011-03-31

    The power industry in the United States is faced with meeting many new regulations to reduce a number of air pollutants including sulfur dioxide, nitrogen oxides, fine particulate matter, and mercury. With over 1,000 power plants in the US, this is a daunting task. In some cases, traditional pollution control technologies such as wet scrubbers and SCRs are not feasible. Powerspan's Electro-Catalytic Oxidation, or ECO{reg_sign} process combines four pollution control devices into a single integrated system that can be installed after a power plant's particulate control device. Besides achieving major reductions in emissions of sulfur dioxide (SO{sub 2}), nitrogen oxides (NOx), fine particulate matter (PM2.5) and mercury (Hg), ECO produces a highly marketable fertilizer, which can help offset the operating costs of the process system. Powerspan has been operating a 50-MW ECO commercial demonstration unit (CDU) at FirstEnergy Corp.'s R.E. Burger Plant near Shadyside, Ohio, since February 2004. In addition to the CDU, a test loop has been constructed beside the CDU to demonstrate higher NOx removal rates and test various scrubber packing types and wet ESP configurations. Furthermore, Powerspan has developed the ECO{reg_sign}{sub 2} technology, a regenerative process that uses a proprietary solvent to capture CO{sub 2} from flue gas. The CO{sub 2} capture takes place after the capture of NOx, SO{sub 2}, mercury, and fine particulate matter. Once the CO{sub 2} is captured, the proprietary solution is regenerated to release CO{sub 2} in a form that is ready for geological storage or beneficial use. Pilot scale testing of ECO{sub 2} began in early 2009 at FirstEnergy's Burger Plant. The ECO{sub 2} pilot unit is designed to process a 1-MW flue gas stream and produce 20 tons of CO{sub 2} per day, achieving a 90% CO{sub 2} capture rate. The ECO{sub 2} pilot program provided the opportunity to confirm process design and cost estimates, and prepare for large

  9. Highly Dense Isolated Metal Atom Catalytic Sites

    DEFF Research Database (Denmark)

    Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

    2015-01-01

    -ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation......Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X...

  10. Catalytic Organic Transformations Mediated by Actinide Complexes

    Directory of Open Access Journals (Sweden)

    Isabell S. R. Karmel

    2015-10-01

    Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

  11. Synthesis of gold and silver nanoparticle S-ovalbumin protein conjugates by in situ conjugation process

    Science.gov (United States)

    Joshi, Deepti; Soni, R. K.

    2015-05-01

    Pure gold and silver nanoparticle (NP) generation and their conjugation with protein S-ovalbumin using in situ conjugation process have been reported. The in situ conjugation involves nanosecond pulse laser ablation of pure metal target in the protein S-ovalbumin solution. Transmission electron microscopy (TEM) and UV-Visible absorption results show decrease in mean NP size along with narrow particle size distribution on ablation in S-ovalbumin solution as compared to ablation in water for both Au and Ag NPs. Also, the NP size reduction was found to be dependent on the concentration of S-ovalbumin. For AuNPs, spherical NPs of mean size 4 nm with particle size distribution 2-6 nm were obtained at 300 nM S-ovalbumin concentration. Further, it has been observed that the resultant in situ-conjugated colloid gold and silver NP solutions were quite stable even in the presence of NaCl at physiological salt concentration (0.15 M). On post-laser irradiation (532 nm, 15 mJ) for 20 min, 9 nm red shift in surface plasmon resonance peak (SPR), along with increased broadening towards longer wavelength, was observed in the AuNPs-S-ovalbumin sample. Further increase in the time of irradiation showed shift in AuNPs-S-ovalbumin SPR towards lower wavelength. On laser irradiation (532 nm, 15 mJ) for 20 min, no significant change was observed in the line shape of the plasmon absorption band of the AgNPs-S-ovalbumin conjugate. FTIR spectra revealed that S-ovalbumin peptide backbone and secondary structure remain unchanged on laser irradiation during in situ conjugation process. Thus, integrity of S-ovalbumin does not get affected, and no degradation of S-ovalbumin takes place on laser-induced in situ conjugation. Raman results confirm that both Au and Ag NPs interact with S-ovalbumin via thiol-bearing cysteine residues of the disulfide bond.

  12. Porous media for catalytic renewable energy conversion

    Science.gov (United States)

    Hotz, Nico

    2012-05-01

    A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

  13. Asymmetric fluorination of α-branched cyclohexanones enabled by a combination of chiral anion phase-transfer catalysis and enamine catalysis using protected amino acids.

    Science.gov (United States)

    Yang, Xiaoyu; Phipps, Robert J; Toste, F Dean

    2014-04-09

    We report a study involving the successful merger of two separate chiral catalytic cycles: a chiral anion phase-transfer catalysis cycle to activate Selectfluor and an enamine activation cycle, using a protected amino acid as organocatalyst. We have demonstrated the viability of this approach with the direct asymmetric fluorination of α-substituted cyclohexanones to generate quaternary fluorine-containing stereocenters. With these two chiral catalytic cycles operating together in a matched sense, high enantioselectivites can be achieved, and we envisage that this dual catalysis method has the potential to be more broadly applicable, given the breadth of enamine catalysis. It also represents a rare example of chiral enamine catalysis operating successfully on α-branched ketones, substrates commonly inert to this activation mode.

  14. Thermal and catalytic pyrolysis of plastic waste

    Directory of Open Access Journals (Sweden)

    Débora Almeida

    2016-02-01

    Full Text Available Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolites can be used as catalysts in catalytic pyrolysis and influence the final products obtained.

  15. Catalytic Wastewater Treatment Using Pillared Clays

    Science.gov (United States)

    Perathoner, Siglinda; Centi, Gabriele

    After introduction on the use of solid catalysts in wastewater treatment technologies, particularly advanced oxidation processes (AOPs), this review discussed the use of pillared clay (PILC) materials in three applications: (i) wet air catalytic oxidation (WACO), (ii) wet hydrogen peroxide catalytic oxidation (WHPCO) on Cu-PILC and Fe-PILC, and (iii) behavior of Ti-PILC and Fe-PILC in the photocatalytic or photo-Fenton conversion of pollutants. Literature data are critically analyzed to evidence the main direction to further investigate, in particularly with reference to the possible practical application of these technologies to treat industrial, municipal, or agro-food production wastewater.

  16. Catalytic gasification of oil-shales

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)

    2012-07-01

    Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

  17. General classes of double phase conjugation.

    Science.gov (United States)

    Sternklar, S

    1995-02-01

    The double phase-conjugate mirror (DPCM) is a stimulated four-wave mixing effect, mediated by either a chi(3) mechanism or a photorefractive effect. The type of grating that operates in the DPCM can be a transmission or reflection grating, depending on the wave-mixing configuration. Any combination of nonlinearity and grating geometry is possible, so that four general DPCM classes emerge. An analytic solution of the last unsolved class, the photorefractive reflection DPCM, is presented. With these results, general observations concerning the four categories of double phase conjugation are made. An important conclusion is that the type of grating geometry and its associated boundary conditions dictate many of the basic features of the DPCM, regardless of the nonlinearity involved.

  18. Stochastic Spectral and Conjugate Descent Methods

    KAUST Repository

    Kovalev, Dmitry

    2018-02-11

    The state-of-the-art methods for solving optimization problems in big dimensions are variants of randomized coordinate descent (RCD). In this paper we introduce a fundamentally new type of acceleration strategy for RCD based on the augmentation of the set of coordinate directions by a few spectral or conjugate directions. As we increase the number of extra directions to be sampled from, the rate of the method improves, and interpolates between the linear rate of RCD and a linear rate independent of the condition number. We develop and analyze also inexact variants of these methods where the spectral and conjugate directions are allowed to be approximate only. We motivate the above development by proving several negative results which highlight the limitations of RCD with importance sampling.

  19. Antibody conjugate radioimmunotherapy of superficial bladder cancer

    International Nuclear Information System (INIS)

    Perkins, Alan; Hopper, Melanie; Murray, Andrea; Frier, Malcolm; Bishop, Mike

    2002-01-01

    The administration of antibody conjugates for cancer therapy is now proving to be of clinical value. We are currently undertaking a programme of clinical studies using the monoclonal antibody C 595 (gG3) which reacts with the MUC1 glycoprotein antigen that is aberrantly expressed in a high proportion of bladder tumours. Radio immuno conjugates of the C 595 antibody have been produced with high radiolabelling efficiency and immuno reactivity using Tc-99 m and In-111 for diagnostic imaging, and disease staging and the cytotoxic radionuclides Cu-67 and Re-188 for therapy of superficial bladder cancer. A Phase I/II therapeutic trail involving the intravesical administration of antibody directly into the bladder has now begun. (author)

  20. High-Voltage, Asymmetric-Waveform Generator

    Science.gov (United States)

    Beegle, Luther W.; Duong, Tuan A.; Duong, Vu A.; Kanik, Isik

    2008-01-01

    The shapes of waveforms generated by commercially available analytical separation devices, such as some types of mass spectrometers and differential mobility spectrometers are, in general, inadequate and result in resolution degradation in output spectra. A waveform generator was designed that would be able to circumvent these shortcomings. It is capable of generating an asymmetric waveform, having a peak amplitude as large as 2 kV and frequency of several megahertz, which can be applied to a capacitive load. In the original intended application, the capacitive load would consist of the drift plates in a differential-mobility spectrometer. The main advantage to be gained by developing the proposed generator is that the shape of the waveform is made nearly optimum for various analytical devices requiring asymmetric-waveform such as differential-mobility spectrometers. In addition, this waveform generator could easily be adjusted to modify the waveform in accordance with changed operational requirements for differential-mobility spectrometers. The capacitive nature of the load is an important consideration in the design of the proposed waveform generator. For example, the design provision for shaping the output waveform is based partly on the principle that (1) the potential (V) on a capacitor is given by V=q/C, where C is the capacitance and q is the charge stored in the capacitor; and, hence (2) the rate of increase or decrease of the potential is similarly proportional to the charging or discharging current. The proposed waveform generator would comprise four functional blocks: a sine-wave generator, a buffer, a voltage shifter, and a high-voltage switch (see Figure 1). The sine-wave generator would include a pair of operational amplifiers in a feedback configuration, the parameters of which would be chosen to obtain a sinusoidal timing signal of the desired frequency. The buffer would introduce a slight delay (approximately equal to 20 ns) but would otherwise

  1. SOLAR CONSTRAINTS ON ASYMMETRIC DARK MATTER

    International Nuclear Information System (INIS)

    Lopes, Ilídio; Silk, Joseph

    2012-01-01

    The dark matter content of the universe is likely to be a mixture of matter and antimatter, perhaps comparable to the measured asymmetric mixture of baryons and antibaryons. During the early stages of the universe, the dark matter particles are produced in a process similar to baryogenesis, and dark matter freezeout depends on the dark matter asymmetry and the annihilation cross section (s-wave and p-wave annihilation channels) of particles and antiparticles. In these η-parameterized asymmetric dark matter (ηADM) models, the dark matter particles have an annihilation cross section close to the weak interaction cross section, and a value of dark matter asymmetry η close to the baryon asymmetry η B . Furthermore, we assume that dark matter scattering of baryons, namely, the spin-independent scattering cross section, is of the same order as the range of values suggested by several theoretical particle physics models used to explain the current unexplained events reported in the DAMA/LIBRA, CoGeNT, and CRESST experiments. Here, we constrain ηADM by investigating the impact of such a type of dark matter on the evolution of the Sun, namely, the flux of solar neutrinos and helioseismology. We find that dark matter particles with a mass smaller than 15 GeV, a spin-independent scattering cross section on baryons of the order of a picobarn, and an η-asymmetry with a value in the interval 10 –12 -10 –10 , would induce a change in solar neutrino fluxes in disagreement with current neutrino flux measurements. This result is also confirmed by helioseismology data. A natural consequence of this model is suppressed annihilation, thereby reducing the tension between indirect and direct dark matter detection experiments, but the model also allows a greatly enhanced annihilation cross section. All the cosmological ηADM scenarios that we discuss have a relic dark matter density Ωh 2 and baryon asymmetry η B in agreement with the current WMAP measured values, Ω DM h 2 = 0

  2. Asymmetric Branching in Biological Resource Distribution Networks

    Science.gov (United States)

    Brummer, Alexander Byers

    There is a remarkable relationship between an organism's metabolic rate (resting power consumption) and the organism's mass. It may be a universal law of nature that an organism's resting metabolic rate is proportional to its mass to the power of 3/4. This relationship, known as Kleiber's Law, appears to be valid for both plants and animals. This law is important because it implies that larger organisms are more efficient than smaller organisms, and knowledge regarding metabolic rates are essential to a multitude of other fields in ecology and biology. This includes modeling the interactions of many species across multiple trophic levels, distributions of species abundances across large spatial landscapes, and even medical diagnostics for respiratory and cardiovascular pathologies. Previous models of vascular networks that seek to identify the origin of metabolic scaling have all been based on the unrealistic assumption of perfectly symmetric branching. In this dissertation I will present a theory of asymmetric branching in self-similar vascular networks (published by Brummer et al. in [9]). The theory shows that there can exist a suite of vascular forms that result in the often observed 3/4 metabolic scaling exponent of Kleiber's Law. Furthermore, the theory makes predictions regarding major morphological features related to vascular branching patterns and their relationships to metabolic scaling. These predictions are suggestive of evolutionary convergence in vascular branching. To test these predictions, I will present an analysis of real mammalian and plant vascular data that shows: (i) broad patterns in vascular networks across entire animal kingdoms and (ii) within these patterns, plant and mammalian vascular networks can be uniquely distinguished from one another (publication in preparation by Brummer et al.). I will also present results from a computational study in support of point (i). Namely, that asymmetric branching may be the optimal strategy to

  3. High temperature solid state catalytic isotope exchange with deuterium and tritium

    International Nuclear Information System (INIS)

    Zolotarev, Yu.A.; Kozik, V.S.; Dorokhova, E.M.; Zaitsev, D.A., Myasoedov, N.F.; Rozenberg, S.G.

    1992-01-01

    A method for synthesizing tritium- or deuterium-labeled amino acids, peptides and biogenic amines through high temperature solid state catalytic isotope exchange (HSCIE) is proposed. The dependence of the degree of isotope exchange in HSCIE on the structure of the compound, the reactivity of hydrogen at different carbon atoms and the conditions of the process has been examined. If HSCIE is performed in the temperature range of 373 to 413 K, the selectivity of isotopic label incorporation comes to 70% or higher. When the tritium label is introduced into peptides, they retain the configuration of asymmetric atoms, even upon the substitution of tritium for hydrogen at the α-carbon atoms of the amino acid residues. HSCIE at 453-513 K leads to an even distribution of the isotopic label over the organic compound molecule. The results of 3 H NMR spectroscopy highlighting the distribution of the tritium label in the organic compound molecules are presented. The configuration of asymmetric atoms in amino acids is preserved to a high extent upon 80-90% substitution of isotopes for hydrogen atoms. (author) 13 refs.; 4 figs.;

  4. Direct Catalytic Asymmetric Mannich Reaction with Dithiomalonates as Excellent Mannich Donors: Organocatalytic Synthesis of (R)-Sitagliptin.

    Science.gov (United States)

    Bae, Han Yong; Kim, Mun Jong; Sim, Jae Hun; Song, Choong Eui

    2016-08-26

    In this study, dithiomalonates (DTMs) were demonstrated to be exceptionally efficient Mannich donors in terms of reactivity and stereoselectivity in cinchona-based-squaramide-catalyzed enantioselective Mannich reactions of diverse imines or α-amidosulfones as imine surrogates. Owing to the superior reactivity of DTMs as compared to conventional malonates, the catalyst loading could be reduced to 0.1 mol % without the erosion of enantioselectivity (up to 99 % ee). Furthermore, by the use of a DTM, even some highly challenging primary alkyl α-amidosulfones were smoothly converted into the desired adducts with excellent enantioselectivity (up to 97 % ee), whereas the use of a malonate or monothiomalonate resulted in no reaction under identical conditions. The synthetic utility of the chiral Mannich adducts obtained from primary alkyl substrates was highlighted by the organocatalytic, coupling-reagent-free synthesis of the antidiabetic drug (-)-(R)-sitagliptin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Catalytic Asymmetric Synthesis of 3-Indolyl Methanamines Using Unprotected Indoles and N-Boc Imines under Basic Conditions.

    Science.gov (United States)

    Arai, Takayoshi; Kakino, Junki

    2016-12-05

    A chiral imidazolidine-containing NCN/Pd-OTf catalyst (C4) promoted the nucleophilic addition of unprotected indoles to N-Boc imines. Using sulfinyl amines as the N-Boc imine precursors, the combined use of C4 with K 2 CO 3 activated the NH indoles to give chiral 3-indolyl methanamines with up to 98 % ee. Compared with conventional acid-catalyzed Friedel-Crafts reactions, this reaction proceeds under mildly basic conditions and is advantageous for the use of acid-sensitive substrates. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Towards an integrated model of bacterial conjugation.

    Science.gov (United States)

    Cabezón, Elena; Ripoll-Rozada, Jorge; Peña, Alejandro; de la Cruz, Fernando; Arechaga, Ignacio

    2015-01-01

    Bacterial conjugation is one of the main mechanisms for horizontal gene transfer. It constitutes a key element in the dissemination of antibiotic resistance and virulence genes to human pathogenic bacteria. DNA transfer is mediated by a membrane-associated macromolecular machinery called Type IV secretion system (T4SS). T4SSs are involved not only in bacterial conjugation but also in the transport of virulence factors by pathogenic bacteria. Thus, the search for specific inhibitors of different T4SS components opens a novel approach to restrict plasmid dissemination. This review highlights recent biochemical and structural findings that shed new light on the molecular mechanisms of DNA and protein transport by T4SS. Based on these data, a model for pilus biogenesis and substrate transfer in conjugative systems is proposed. This model provides a renewed view of the mechanism that might help to envisage new strategies to curb the threating expansion of antibiotic resistance. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permission@oup.com.

  7. Cancer Chemopreventive Ability of Conjugated Linolenic Acids

    Directory of Open Access Journals (Sweden)

    Kazuo Miyashita

    2011-11-01

    Full Text Available Conjugated fatty acids (CFA have received increased interest because of their beneficial effects on human health, including preventing cancer development. Conjugated linoleic acids (CLA are such CFA, and have been reviewed extensively for their multiple biological activities. In contrast to other types of CFAs including CLA that are found at low concentrations (less than 1% in natural products, conjugated linolenic acids (CLN are the only CFAs that occur in higher quantities in natural products. Some plant seeds contain a considerably high concentration of CLN (30 to 70 wt% lipid. Our research group has screened CLN from different plant seed oils to determine their cancer chemopreventive ability. This review describes the physiological functions of CLN isomers that occur in certain plant seeds. CLN are able to induce apoptosis through decrease of Bcl-2 protein in certain human cancer cell lines, increase expression of peroxisome proliferator-activated receptor (PPAR-γ, and up-regulate gene expression of p53. Findings in our preclinical animal studies have indicated that feeding with CLN resulted in inhibition of colorectal tumorigenesis through modulation of apoptosis and expression of PPARγ and p53. In this review, we summarize chemopreventive efficacy of CLN against cancer development, especially colorectal cancer.

  8. Conjugation, characterization and toxicity of lipophosphoglycan-polyacrylic acid conjugate for vaccination against leishmaniasis.

    Science.gov (United States)

    Topuzogullari, Murat; Cakir Koc, Rabia; Dincer Isoglu, Sevil; Bagirova, Melahat; Akdeste, Zeynep; Elcicek, Serhat; Oztel, Olga N; Yesilkir Baydar, Serap; Canim Ates, Sezen; Allahverdiyev, Adil M

    2013-06-03

    Research on the conjugates of synthetic polyelectrolytes with antigenic molecules, such as proteins, peptides, or carbohydrates, is an attractive area due to their highly immunogenic character in comparison to classical adjuvants. For example, polyacrylic acid (PAA) is a weak polyelectrolyte and has been used in several biomedical applications such as immunological studies, drug delivery, and enzyme immobilization. However, to our knowledge, there are no studies that document immune-stimulant properties of PAA in Leishmania infection. Therefore, we aimed to develop a potential vaccine candidate against leishmaniasis by covalently conjugating PAA with an immunologically vital molecule of lipophosphoglycan (LPG) found in Leishmania parasites. In the study, LPG and PAA were conjugated by a multi-step procedure, and final products were analyzed with GPC and MALDI-TOF MS techniques. In cytotoxicity experiments, LPG-PAA conjugates did not indicate toxic effects on L929 and J774 murine macrophage cells. We assume that LPG-PAA conjugate can be a potential vaccine candidate, and will be immunologically characterized in further studies to prove its potential.

  9. Heterogeneous Catalytic Oligomerization of Ethylene

    Science.gov (United States)

    Jan, Oliver Dennis

    increased with temperature, with 17 wt.% observed at 190ºC. Higher reaction temperatures led to the formation of odd-numbered oligomers primarily due to acid-catalyzed cracking reactions. In the range of space velocities tested, a moderate WHSV of 2.0 hr-1 resulted in a local maximum of 10.6 wt.% of liquid hydrocarbon yield. A moderate nickel loading of 3.4 wt.% also resulted in the highest liquid yield out of the three loadings tested (10.6 wt.%). The variation in nickel loading revealed the importance of having a synergistic balance of nickel and acid sites on the catalyst to maximize ethylene conversion and maintain high liquid hydrocarbon yield. Lastly, we used supercritical ethylene as both a solvent and as a reactant for ethylene oligomerization over two silica-alumina type catalysts: Ni-Hbeta and Ni-Al-SBA-15. Specifically, the effect of pressure and temperature on the overall conversion and product selectivity were evaluated in the range from 0 to 65 bar and 30 to 120ºC. At subcritical conditions, the ethylene conversion reached a plateau of around 50%. By increasing the pressure past the critical point of ethylene, the conversion drastically increased to 71%. The increased conversion can be attributed to the solubility of certain oligomers, namely butene, in supercritical ethylene that promotes desorption from catalytic active site before further oligomerization. We also tested a mesoporous catalyst, Ni-Al-SBA-15 and observed conversion trends analogous to that of Ni-Hbeta. At supercritical conditions, ethylene oligomerization over Ni-Al-SBA-15 was more selective towards the butene product, with nearly 74 wt.% butenes observed. The catalyst activity increased with temperature from 30ºC to 120ºC. The experiment conducted at 30ºC showed very little activity and ethylene conversion, however it effectively heavy molecular weight species from the catalyst. This condition, albeit being not effective for ethylene oligomerization, could be implemented as an in

  10. Computation in Dynamically Bounded Asymmetric Systems

    Science.gov (United States)

    Rutishauser, Ueli; Slotine, Jean-Jacques; Douglas, Rodney

    2015-01-01

    Previous explanations of computations performed by recurrent networks have focused on symmetrically connected saturating neurons and their convergence toward attractors. Here we analyze the behavior of asymmetrical connected networks of linear threshold neurons, whose positive response is unbounded. We show that, for a wide range of parameters, this asymmetry brings interesting and computationally useful dynamical properties. When driven by input, the network explores potential solutions through highly unstable ‘expansion’ dynamics. This expansion is steered and constrained by negative divergence of the dynamics, which ensures that the dimensionality of the solution space continues to reduce until an acceptable solution manifold is reached. Then the system contracts stably on this manifold towards its final solution trajectory. The unstable positive feedback and cross inhibition that underlie expansion and divergence are common motifs in molecular and neuronal networks. Therefore we propose that very simple organizational constraints that combine these motifs can lead to spontaneous computation and so to the spontaneous modification of entropy that is characteristic of living systems. PMID:25617645

  11. Unitarity Constraints on Asymmetric Freeze-In

    Energy Technology Data Exchange (ETDEWEB)

    Hook, Anson; /SLAC

    2011-08-15

    This paper considers unitarity and CPT constraints on asymmetric freeze-in, the use of freeze-in to store baryon number in a dark sector. In this scenario, Sakharov's out of equilibrium condition is satisfied by placing the visible and hidden sectors at different temperatures while a net visible baryon number is produced by storing negative baryon number in a dark sector. It is shown that unitarity and CPT lead to unexpected cancellations. In particular, the transfer of baryon number cancels completely at leading order. This note has shown that if two sectors are in thermal equilibrium with themselves, but not with each other, then the leading effect transferring conserved quantities between the two sectors is of order the the weak coupling connecting them to the third power. When freeze-in is used to produce a net baryon number density, the leading order effect comes from {Omicron}({lambda}{sup 3}) diagrams where the intermediate state that goes on-shell has a different visible baryon number than the final state visible baryon number. Models in which the correct baryon number is generated with freeze-in as the dominant source of abundance, typically require {lambda} {approx}> 10{sup -6} and m{sub bath} {approx}> TeV. m{sub bath} is the mass of the visible particle which communicates with the hidden sector. The lower window is potentially observable at the LHC.

  12. Asymmetric iterative blind deconvolution of multiframe images

    Science.gov (United States)

    Biggs, David S. C.; Andrews, Mark

    1998-10-01

    Imaging through a stochastically varying distorting medium, such as a turbulent atmosphere, requires multiple short-exposure frames to ensure maximum resolution of object features. Restoration methods are used to extract the common underlying object from the speckle images, and blind deconvolution techniques are required as typically there is little prior information available about either the image or individual PSFs. A method is presented for multiframe restoration based on iterative blind deconvolution, which alternates between restoring the image and PSF estimates. A maximum-likelihood approach is employed via the Richardson-Lucy (RL) method which automatically ensures positively and conservation of the total number of photons. The restoration is accelerated by applying a vector sequence is treated as a 3D volume of data and processed to produce a 3D stack of PSFs and a single 2D image of the object. The problem of convergence to an undesirable solution, such as a delta function, is addressed by weighting the number of image or PSF iterations according to how quickly each is converging, this leads to the asymmetrical nature of the algorithm. Noise artifacts are suppressed by using a dampened RL algorithm to prevent over fitting of the corrupted data. Results are presented for real single frame and simulated multiframe speckle imaging.

  13. Asymmetric sensory reweighting in human upright stance.

    Directory of Open Access Journals (Sweden)

    David Logan

    Full Text Available To investigate sensory reweighting as a fundamental property of sensor fusion during standing, we probed postural control with simultaneous rotations of the visual scene and surface of support. Nineteen subjects were presented with pseudo-random pitch rotations of visual scene and platform at the ankle to test for amplitude dependencies in the following conditions: low amplitude vision: high amplitude platform, low amplitude vision: low amplitude platform, and high amplitude vision: low amplitude platform. Gain and phase of frequency response functions (FRFs to each stimulus were computed for two body sway angles and a single weighted EMG signal recorded from seven muscles. When platform stimulus amplitude was increased while visual stimulus amplitude remained constant, gain to vision increased, providing strong evidence for inter-modal reweighting between vision and somatosensation during standing. Intra-modal reweighting of vision was also observed as gains to vision decreased as visual stimulus amplitude increased. Such intra-modal and inter-modal amplitude dependent changes in gain were also observed in muscular activity. Gains of leg segment angle and muscular activity relative to the platform, on the other hand, showed only intra-modal reweighting. That is, changing platform motion amplitude altered the responses to both visual and support surface motion whereas changing visual scene motion amplitude did not significantly affect responses to support surface motion, indicating that the sensory integration scheme between somatosensation (at the support surface and vision is asymmetric.

  14. Asymmetric Dark Matter and Dark Radiation

    International Nuclear Information System (INIS)

    Blennow, Mattias; Martinez, Enrique Fernandez; Mena, Olga; Redondo, Javier; Serra, Paolo

    2012-01-01

    Asymmetric Dark Matter (ADM) models invoke a particle-antiparticle asymmetry, similar to the one observed in the Baryon sector, to account for the Dark Matter (DM) abundance. Both asymmetries are usually generated by the same mechanism and generally related, thus predicting DM masses around 5 GeV in order to obtain the correct density. The main challenge for successful models is to ensure efficient annihilation of the thermally produced symmetric component of such a light DM candidate without violating constraints from collider or direct searches. A common way to overcome this involves a light mediator, into which DM can efficiently annihilate and which subsequently decays into Standard Model particles. Here we explore the scenario where the light mediator decays instead into lighter degrees of freedom in the dark sector that act as radiation in the early Universe. While this assumption makes indirect DM searches challenging, it leads to signals of extra radiation at BBN and CMB. Under certain conditions, precise measurements of the number of relativistic species, such as those expected from the Planck satellite, can provide information on the structure of the dark sector. We also discuss the constraints of the interactions between DM and Dark Radiation from their imprint in the matter power spectrum

  15. Climate policy, asymmetric information and firm survival

    International Nuclear Information System (INIS)

    Hagem, C.

    2001-02-01

    The purpose of this paper is to compare the effect of different domestic climate policy instruments under asymmetric information when the regulator wants to secure the survival of a specific firm. It is a well-known result from economic theory that emission taxes lead to a cost-effective distribution of abatement across polluters. However, if the regulator wants to ensure the survival of a specific firm, it may need to design policy instruments that reduce the firm's cost of complying with an emission tax regime. The climate policy instruments considered in this paper are tradable emission permits with distribution of free permits, emission taxes in combination with a fixed subsidy, and two types of voluntary agreements. It demonstrates first that if distributing free tradable permits shall have a preventing effect, the allocation of permits has to be made contingent on production. It further shows that a voluntary agreement where a specific abatement target is set by the regulator can prevent a shutdown but leads to lower welfare than the use of emission taxes in combination with a fixed subsidy. And finally it illustrates that a voluntary agreement designed as a menu of abatement contracts increases social welfare compared to an emission tax regime

  16. Network effects on coordination in asymmetric games.

    Science.gov (United States)

    Broere, Joris; Buskens, Vincent; Weesie, Jeroen; Stoof, Henk

    2017-12-05

    Network structure can have an important effect on the behavior of players in an iterated 2 × 2 game. We study the effect of network structure on global and local behavior in asymmetric coordination games using best response dynamics. We find that global behavior is highly dependent on network topology. Random (Erdös-Rényi) networks mostly converge to homogeneous behavior, but the higher the clustering in the network the more heterogeneous the behavior becomes. Behavior within the communities of the network is almost exclusively homogeneous. The findings suggest that clustering of networks facilitates self-organization of uniform behavior within clusters, but heterogeneous behavior between clusters. At the local level we find that some nodes are more important in determining the equilibrium behavior than other nodes. Degree centrality is for most networks the main predictor for the behavior and nodes with an even degree have an advantage over nodes with an uneven degree in dictating the behavior. We conclude that the behavior is difficult to predict for (Erdös-Rényi) networks and that the network imposes the behavior as a function of clustering and degree heterogeneity in other networks.

  17. Asymmetric translation between multiple representations in chemistry

    Science.gov (United States)

    Lin, Yulan I.; Son, Ji Y.; Rudd, James A., II

    2016-03-01

    Experts are more proficient in manipulating and translating between multiple representations (MRs) of a given concept than novices. Studies have shown that instruction using MR can increase student understanding of MR, and one model for MR instruction in chemistry is the chemistry triplet proposed by Johnstone. Concreteness fading theory suggests that presenting concrete representations before abstract representations can increase the effectiveness of MR instruction; however, little work has been conducted on varying the order of different representations during instruction and the role of concreteness in assessment. In this study, we investigated the application of concreteness fading to MR instruction and assessment in teaching chemistry. In two experiments, undergraduate students in either introductory psychology courses or general chemistry courses were given MR instruction on phase changes using different orders of presentation and MR assessment questions based on the representations in the chemistry triplet. Our findings indicate that the order of presentation based on levels of concreteness in MR chemistry instruction is less important than implementation of comprehensive MR assessments. Even after MR instruction, students display an asymmetric understanding of the chemical phenomenon on the MR assessments. Greater emphasis on MR assessments may be an important component in MR instruction that effectively moves novices toward more expert MR understanding.

  18. Experimental study of asymmetric heart valve prototype

    Science.gov (United States)

    Vukicevic, M.; Fortini, S.; Querzoli, G.; Cenedese, A.; Pedrizzetti, G.

    2011-11-01

    The mechanical heart valves (MHVs) are extremely important medical devices, commonly used for diseased heart valves replacement. Despite the long term of use and constant design refinement, the MHVs are very far from ideal and their performance is very diverse from that of the native ones. It has been approved that small variations in geometry of valvular leaflets influence the significant change in the intraventricular vortical flow, known as one of the most important factors for the overall functionality of the heart. We have experimentally examined the home-made heart valve prototypes, exclusively modeled for the mitral valve replacement. The performance and energetic properties of the prototypes have been compared with those in the presence of standard MHVs. The analysis was based on the testing of intraventricular fluid dynamics, usually missing criteria for the quality of the valve performance. It has been shown that the asymmetric prototype, with unequal leaflets and D-shaped orifice produces flow patterns and energetic properties close to those found in the healthy subjects. Thus, the break of symmetry in the standard bi-leaflet MHV prosthesis, at least from the fluid dynamics point of view, is worthwhile to be considered for the design of MHVs for the mitral valve replacement.

  19. Collaborative hierarchy maintains cooperation in asymmetric games.

    Science.gov (United States)

    Antonioni, Alberto; Pereda, María; Cronin, Katherine A; Tomassini, Marco; Sánchez, Angel

    2018-03-29

    The interplay of social structure and cooperative behavior is under much scrutiny lately as behavior in social contexts becomes increasingly relevant for everyday life. Earlier experimental work showed that the existence of a social hierarchy, earned through competition, was detrimental for the evolution of cooperative behaviors. Here, we study the case in which individuals are ranked in a hierarchical structure based on their performance in a collective effort by having them play a Public Goods Game. In the first treatment, participants are ranked according to group earnings while, in the second treatment, their rankings are based on individual earnings. Subsequently, participants play asymmetric Prisoner's Dilemma games where higher-ranked players gain more than lower ones. Our experiments show that there are no detrimental effects of the hierarchy formed based on group performance, yet when ranking is assigned individually we observe a decrease in cooperation. Our results show that different levels of cooperation arise from the fact that subjects are interpreting rankings as a reputation which carries information about which subjects were cooperators in the previous phase. Our results demonstrate that noting the manner in which a hierarchy is established is essential for understanding its effects on cooperation.

  20. Asymmetric evaluation promotes cooperation in network population

    Science.gov (United States)

    Shen, Chen; Li, Xiaoping; Shi, Lei; Deng, Zhenghong

    2017-05-01

    The evolution of cooperation remains a fundamental challenge in human society. Many previous studies investigated these questions via spatial reciprocity, where players obtain their payoffs by interacting with their direct neighbors. It has also been verified that environmental factors can influence the evolution of cooperation theoretically and empirically. In reality, however, individuals may have the limit knowledge about their indirect neighbors. Inspired by this fact, we consider an asymmetric fitness calculation mechanism, which only integrates the environment factors into the focal player, to explore the evolution of cooperation. Here, the environmental factor is defined as the average payoff of all individual neighbors, which is regulated by a tunable parameter u. Through numerical simulation, we find that, compared with the traditional version (u = 0), that the cooperation level can be greatly enhanced when u is positive. Interestingly, the larger the value of u, the higher the level of cooperation. Finally, to explore the generality of this finding, we have tested the results on different topologies.

  1. CATALYTIC SPECTROPHOTOMETRIC DETERMINATION OF Mn(II ...

    African Journals Online (AJOL)

    Preferred Customer

    The aim of the present study was to develop a new precise and accurate catalytic spectrophotometric ... manganese sulfate monohydrate (Merck, Darmstadt, Germany) in water and diluted to 250 mL. The working .... and potassium hydrogen phthalate-HCl buffer solutions, the slope of calibration graph was unsatisfactory.

  2. Catalytic models developed through social work

    DEFF Research Database (Denmark)

    Jensen, Mogens

    2015-01-01

    of adolescents placed in out-of-home care and is characterised using three situated cases as empirical data. Afterwards the concept of catalytic processes is briefly presented and then applied in an analysis of pedagogical treatment in the three cases. The result is a different conceptualisation of the social...

  3. Fluid catalytic cracking : Feedstocks and reaction mechanism

    NARCIS (Netherlands)

    Dupain, X.

    2006-01-01

    The Fluid Catalytic Cracking (FCC) process is one of the key units in a modern refinery. Traditionally, its design is primarily aimed for the production of gasoline from heavy oil fractions, but as co-products also diesel blends and valuable gasses (e.g. propene and butenes) are formed in

  4. Catalytic dehydrogenations of ethylbenzene to styrene

    NARCIS (Netherlands)

    Nederlof, C.

    2012-01-01

    This research work on the catalytic dehydrogenation of ethylbenzene (EB) to styrene (ST) had a primary goal of developing improved catalysts for dehydrogenation processes both in CO2 as well as with O2 that can compete with the conventional dehydrogenation process in steam. In order to achieve this

  5. Synthesis, spectroscopic characterization and catalytic oxidation ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3. Synthesis, spectroscopic characterization and catalytic oxidation properties of ONO/ONS donor Schiff base ruthenium(III) complexes containing PPh3/AsPh3. Priyarega M Muthu Tamizh R Karvembu R Prabhakaran K Natarajan. Volume 123 Issue 3 May ...

  6. DEALUMINATION OF MORDENITE ZEOLITE AND ITS CATALYTIC ...

    African Journals Online (AJOL)

    The xylene mixtures result from the catalytic reforming of petroleum NAFTA and the isomers of xylenes are usually obtained from this mixture by separation. After separation of o-isomers and p-isomers, the remainder richer in m-xylene, needs to be subjected to isomerization [2]. Xylene isomerization has received growing ...

  7. Novel Metal Nanomaterials and Their Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Jiaqing Wang

    2015-09-01

    Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

  8. Catalytic site interactions in yeast OMP synthase

    DEFF Research Database (Denmark)

    Hansen, Michael Riis; Barr, Eric W.; Jensen, Kaj Frank

    2014-01-01

    45 (2006) 5330-5342]. This behavior was investigated in the yeast enzyme by mutations in the conserved catalytic loop and 5-phosphoribosyl-1-diphosphate (PRPP) binding motif. Although the reaction is mechanistically sequential, the wild-type (WT) enzyme shows parallel lines in double reciprocal...

  9. THEORETICAL STUDY OF CATALYTIC HYDROGENATION OF ...

    African Journals Online (AJOL)

    Preferred Customer

    Catalytic hydrotreating process is a technique of purification of the crude oil with the aim of the improvement of the quality and the stability of fuels and lubricants. This is performed by the destruction of heterocyclic compounds and by the saturation of unsaturated hydrocarbons under the effect of the hydrogen pressure in ...

  10. Catalytic Converters Maintain Air Quality in Mines

    Science.gov (United States)

    2014-01-01

    At Langley Research Center, engineers developed a tin-oxide based washcoat to prevent oxygen buildup in carbon dioxide lasers used to detect wind shears. Airflow Catalyst Systems Inc. of Rochester, New York, licensed the technology and then adapted the washcoat for use as a catalytic converter to treat the exhaust from diesel mining equipment.

  11. Electrochemical Promotion of Catalytic Reactions Using

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cleemann, Lars Nilausen

    2007-01-01

    This paper presents the results of a study on electrochemical promotion (EP) of catalytic reactions using Pt/C/polybenzimidazole(H3PO4)/Pt/C fuel cell performed by the Energy and Materials Science Group (Technical University of Denmark) during the last 6 years[1-4]. The development of our...

  12. Crystallization and first data collection of the putative transfer protein TraN from the Gram-positive conjugative plasmid pIP501

    International Nuclear Information System (INIS)

    Goessweiner-Mohr, Nikolaus; Fercher, Christian; Abajy, Mohammad Yaser; Grohmann, Elisabeth; Keller, Walter

    2012-01-01

    The successful purification, crystallization and first data collection to 1.8 Å resolution of the putative transfer protein TraN from the Gram-positive conjugative plasmid pIP501 are reported. Conjugative plasmid transfer is the most important route for the spread of resistance and virulence genes among bacteria. Consequently, bacteria carrying conjugative plasmids are a substantial threat to human health, especially hospitalized patients. Whilst detailed information about the process has been obtained for Gram-negative type-4 secretion systems, little is known about the corresponding mechanisms in Gram-positive (G+) bacteria. The successful purification and crystallization of the putative transfer protein TraN from the G+ conjugative model plasmid pIP501 of Enterococcus faecalis are presented. Native crystals diffracted to 1.8 Å resolution on a synchrotron beamline. The crystals belonged to space group P2 1 , with unit-cell parameters a = 32.88, b = 54.94, c = 57.71 Å, β = 91.89° and two molecules per asymmetric unit

  13. Polarization dependent switching of asymmetric nanorings with a circular field

    Directory of Open Access Journals (Sweden)

    Nihar R. Pradhan

    2016-01-01

    Full Text Available We experimentally investigated the switching from onion to vortex states in asymmetric cobalt nanorings by an applied circular field. An in-plane field is applied along the symmetric or asymmetric axis of the ring to establish domain walls (DWs with symmetric or asymmetric polarization. A circular field is then applied to switch from the onion state to the vortex state, moving the DWs in the process. The asymmetry of the ring leads to different switching fields depending on the location of the DWs and direction of applied field. For polarization along the asymmetric axis, the field required to move the DWs to the narrow side of the ring is smaller than the field required to move the DWs to the larger side of the ring. For polarization along the symmetric axis, establishing one DW in the narrow side and one on the wide side, the field required to switch to the vortex state is an intermediate value.

  14. Asymmetric MRI Systems: Shim and RF Coil Designs

    National Research Council Canada - National Science Library

    Crozier, S

    2001-01-01

    We have recently introduced the concept of asymmetric clinical MRI systems. The potential advantages of these systems include a reduced perception of claustrophobia by patients and better physician access to the patient...

  15. Asymmetric wave transmission in a diatomic acoustic/elastic metamaterial

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bing; Tan, K. T., E-mail: ktan@uakron.edu [Department of Mechanical Engineering, The University of Akron, Akron, Ohio 44325-3903 (United States)

    2016-08-21

    Asymmetric acoustic/elastic wave transmission has recently been realized using nonlinearity, wave diffraction, or bias effects, but always at the cost of frequency distortion, direction shift, large volumes, or external energy. Based on the self-coupling of dual resonators, we propose a linear diatomic metamaterial, consisting of several small-sized unit cells, to realize large asymmetric wave transmission in low frequency domain (below 1 kHz). The asymmetric transmission mechanism is theoretically investigated, and numerically verified by both mass-spring and continuum models. This passive system does not require any frequency conversion or external energy, and the asymmetric transmission band can be theoretically predicted and mathematically controlled, which extends the design concept of unidirectional transmission devices.

  16. Asymmetric continuum extreme processes in solids and fluids

    CERN Document Server

    Teisseyre, Roman

    2014-01-01

    This book deals with a class of basic deformations in asymmetric continuum theory. It describes molecular deformations and transport velocities in fluids, strain deformations in solids as well as the molecular transport, important in fracture processes.

  17. Optimal multicopy asymmetric Gaussian cloning of coherent states

    Science.gov (United States)

    Fiurášek, Jaromír; Cerf, Nicolas J.

    2007-05-01

    We investigate the asymmetric Gaussian cloning of coherent states which produces M copies from N input replicas in such a way that the fidelity of each copy may be different. We show that the optimal asymmetric Gaussian cloning can be performed with a single phase-insensitive amplifier and an array of beam splitters. We obtain a simple analytical expression characterizing the set of optimal asymmetric Gaussian cloning machines and prove the optimality of these cloners using the formalism of Gaussian completely positive maps and semidefinite programming techniques. We also present an alternative implementation of the asymmetric cloning machine where the phase-insensitive amplifier is replaced with a beam splitter, heterodyne detector, and feedforward.

  18. Optimal multicopy asymmetric Gaussian cloning of coherent states

    International Nuclear Information System (INIS)

    Fiurasek, Jaromir; Cerf, Nicolas J.

    2007-01-01

    We investigate the asymmetric Gaussian cloning of coherent states which produces M copies from N input replicas in such a way that the fidelity of each copy may be different. We show that the optimal asymmetric Gaussian cloning can be performed with a single phase-insensitive amplifier and an array of beam splitters. We obtain a simple analytical expression characterizing the set of optimal asymmetric Gaussian cloning machines and prove the optimality of these cloners using the formalism of Gaussian completely positive maps and semidefinite programming techniques. We also present an alternative implementation of the asymmetric cloning machine where the phase-insensitive amplifier is replaced with a beam splitter, heterodyne detector, and feedforward

  19. Vertical Control and Parallel Trade under Asymmetric Information

    Directory of Open Access Journals (Sweden)

    Alessandro Avenali

    2015-05-01

    profits from the manufacturer to the wholesaler. Therefore, in R&D-intensive industries, such as pharmaceuticals, policy makers should anticipate the likely consequences of PT under asymmetric information on the long-run incentives to innovate.

  20. Subglottic cysts and asymmetrical subglottic narrowing on neck radiograph

    International Nuclear Information System (INIS)

    Holinger, L.D.; Torium, D.M.; Anandappa, E.C.

    1988-01-01

    The congenital subglottic hemangioma typically appears as an asymmetric subglottic narrowing or mass on frontal neck radiograph. Therefore, soft tissue neck radiography has been advocated as a definitive non-operative approach for diagnosing these lesions. However, we have noted similar asymmetric subglottic narrowing in patients with acquired subglottic cysts. These retention cysts occur following long-term intubation in the neonate. The mechanism probably involves subglottic fibrosis which obstructs glands with subsequent cyst formation. Acquired subglottic cysts typically appear as an asymmetric narrowing on frontal or lateral soft tissue neck radiographs. These lesions may produce airway compromise but are effectively treated by forceps or laser removal. Acquired subglottic cysts must be included in the differential diagnosis of asymmetric subglottic narrowing. The definitive diagnosis is made by direct laryngoscopy, not soft tissue neck radiograph. (orig.)