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Sample records for asymmetric hydrovinylation ligands

  1. Ethylene in Organic Synthesis. A New Route to Anticholenergic Pyrrolidinoindolines, and Other Molecules with All Carbon-Quaternary Centers via Asymmetric Hydrovinylation

    Science.gov (United States)

    Lim, Hwan Jung; RajanBabu, T. V.

    2011-01-01

    The asymmetric hydrovinylation (1 mol % Ni-cat., 1 atm, ethylene, >98% ee) products from 1-methylenetetralines are readily converted into 3,3-disubstituted oxindoles, and subsequently to pyrrolidinoindolines. These hydrovinylation products are also useful for the syntheses of enantiopure benzomorphans. PMID:22103775

  2. Nickel-catalyzed enantioselective hydrovinylation of silyl-protected allylic alcohols:An efficient access to homoallylic alcohols with a chiral quaternary center

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Asymmetric hydrovinylation of silyl-protected allylic alcohols catalyzed by nickel complexes of chiral spiro phosphoramidite ligands was developed.A series of homoallylic alcohols with a chiral quaternary center were produced in high yields(up to 97%) and high enantioselectivities(up to 95% ee).The reaction provides an efficient method for preparing bifunctional compounds with a chiral quaternary carbon center.

  3. Asymmetric catalysis : ligand design and microwave acceleration

    OpenAIRE

    Bremberg, Ulf

    2000-01-01

    This thesis deals partly with the design and synthesis ofligands for use in asymmetric catalysis, and partly with theapplication of microwave heating on metal-based asymmetriccatalytic reactions. Enantiomerically pure pyridyl alcohols and bipyridylalcohols were synthesized from the chiral pool for future usein asymmetric catalysis. Lithiated pyridines were reacted withseveral chiral electrophiles, yielding diastereomeric mixturesthat could be separated without the use of resolutiontechniques....

  4. Development of chiral sulfoxide ligands for asymmetric catalysis.

    Science.gov (United States)

    Trost, Barry M; Rao, Meera

    2015-04-20

    Nitrogen-, phosphorus-, and oxygen-based ligands with chiral backbones have been the historic workhorses of asymmetric transition-metal-catalyzed reactions. On the contrary, sulfoxides containing chirality at the sulfur atom have mainly been used as chiral auxiliaries for diastereoselective reactions. Despite several distinct advantages over traditional ligand scaffolds, such as the proximity of the chiral information to the metal center and the ability to switch between S and O coordination, these compounds have only recently emerged as a versatile class of chiral ligands. In this Review, we detail the history of the development of chiral sulfoxide ligands for asymmetric catalysis. We also provide brief descriptions of metal-sulfoxide bonding and strategies for the synthesis of enantiopure sulfoxides. Finally, insights into the future development of this underutilized ligand class are discussed.

  5. Ethylene in Organic Synthesis. Repetitive Hydrovinylation of Alkenes for Highly Enantioselective Syntheses of Pseudopterosins

    Science.gov (United States)

    Mans, Daniel J.; Cox, G. Adam; RajanBabu, T. V.

    2011-01-01

    In this report we highlight the significant potential of ethylene as a reagent for the introduction of a vinyl group with excellent stereoselectivity at three different stages in the synthesis of a broad class of natural products, best exemplified by syntheses of pseudopterosins. The late-stage applications of the asymmetric hydrovinylation reaction further illustrate the compatibility of the catalyst with complex functional groups. We also show that depending on the choice of the catalyst, it is possible to either enhance or even completely reverse the inherent diastereoselectivity in the reactions of advanced chiral intermediates. This should enable the synthesis of diastereomeric analogs of several classes of medicinally relevant compounds that are not readily accessible by the existing methods, which depend on ‘substrate-control’ for the installation of many of the chiral centers, especially in molecules of this class. PMID:21449569

  6. Application of chiral thiazolidine ligands to asymmetric hydrosilation

    Institute of Scientific and Technical Information of China (English)

    李弘; 姚金水; 何炳林

    1997-01-01

    Seven chiral thiazolidines bound rhodium complexes were synthesized and their catalytic asymmetric hydrosilation properties were investigated It was found through investigation that the configuration of newly formed chiral centre C2 of substituted chiral thiazolidines prepared from L-cysteine or its esters has no effect on the final results of catalytic asymmetric hydrosilation.The direct reason for causing this phenomenon is reported by the present quantitative results for the first time:the rapid racemation of chiral center C2 of chiral thiazolidine ligands takes place under the catalysis of rhodium(Ⅰ) complex [Rh(COD)CI]2

  7. Rhodium catalyzed asymmetric Pauson-Khand reaction using SDP ligands

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The activity and enantiocontrol ability of the chiral catalysts prepared from spiro diphosphine ligands, SDP, and rhodium precursor were investigated in the asymmetric catalytic Pauson-Khand reaction. The results showed that SDP ligands were very effective in Rh-catalyzed Pauson-Khand reaction, and their complexes with rhodium could convert a variety of 1,6-enyne compounds into bicyclopentone derivatives under CO atmosphere in high yields with good enantioselectivities. The SbF6- was found to be a suitable counter anion of the catalyst, and 1,2-dichloroethane was the best choice of the solvent for Pauson-Khand reaction.

  8. Recent advances in catalytic asymmetric hydrogenation:Renaissance of the monodentate phosphorus ligands

    Institute of Scientific and Technical Information of China (English)

    GUO Hongchao; DING Kuiling; DAI Lixin

    2004-01-01

    The history for the development of chiral phosphorus ligands in catalytic asymmetric hydrogenation is briefly highlighted. This review focuses on the recent advances in the synthesis of the monodentate phosphorus ligands and their applications in catalytic asymmetric hydrogenation. The examples highlighted in this article clearly demonstrated the importance and advantages of monodentate phosphorus ligands, which had been ignored for 30 a and experienced a renaissance at the very beginning of this millennium, particularly in the area of asymmetric hydrogenation.

  9. A novel stereoselective synthesis of N-heterocycles by intramolecular hydrovinylation

    DEFF Research Database (Denmark)

    Bothe, Ulrich; Rudbeck, H. C.; Tanner, David Ackland;

    2001-01-01

    A novel method for the synthesis of bicyclic amines has been developed. Cyclisation of 1,6-dienes by intramolecular hydrovinylation in the presence of catalytic amounts of allylpalladium chloride dimer afforded bicyclic amines in one step. Added phosphines, silver salts, as well as the nature...... of the N-protecting group influenced the yield and selectivity of the reactions. Most strikingly, intramolecular hydrovinylation allowed the preparation of diastereomerically pure bicyclic amines as e.g. hexahydroindoles 2a-2d....

  10. Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis.

    Science.gov (United States)

    Ivry, Elisa; Ben-Asuly, Amos; Goldberg, Israel; Lemcoff, N Gabriel

    2015-03-01

    Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment.

  11. Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

    Directory of Open Access Journals (Sweden)

    Marina Rubina

    2014-07-01

    Full Text Available A novel class of chiral phosphanyl-oxazoline (PHOX ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to design a very efficient and highly selective catalytic system. Employment of the optimized ligands in the asymmetric arylation of cyclic olefins allowed for achieving high enantioselectivities and significantly suppressing product isomerization. Factors affecting the selectivity and the rate of the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands.

  12. Recent Advances in the Application of Chiral Phosphine Ligands in Pd-Catalysed Asymmetric Allylic Alkylation

    Directory of Open Access Journals (Sweden)

    Erika Martin

    2011-01-01

    Full Text Available One of the most powerful approaches for the formation of simple and complex chiral molecules is the metal-catalysed asymmetric allylic alkylation. This reaction has been broadly studied with a great variety of substrates and nucleophiles under different reaction conditions and it has promoted the synthesis of new chiral ligands to be evaluated as asymmetric inductors. Although the mechanism as well as the active species equilibria are known, the performance of the catalytic system depends on the fine tuning of factors such as type of substrate, nucleophile nature, reaction medium, catalytic precursor and type of ligand used. Particularly interesting are chiral phosphines which have proved to be effective asymmetric inductors in several such reactions. The present review covers the application of phosphine-donor ligands in Pd-catalysed asymmetric allylic alkylation in the last decade.

  13. Hybrid diphosphorus ligands in rhodium catalysed asymmetric hydroformylation

    NARCIS (Netherlands)

    Chikkali, S.H.; van der Vlugt, J.I.; Reek, J.N.H.

    2014-01-01

    This review aims to illustrate recent advances in the application of hybrid diphosphorus ligands for the Rh catalysed hydroformylation of alkenes, discussing the most prevalent classes of hybrid systems, i.e. phosphine-phosphinite, phosphine-phosphonite, phosphine-phosphite, phosphite-phosphoramidit

  14. A kinetic and structural investigation of DNA-Based asymmetric catalysis using first-generation ligands

    NARCIS (Netherlands)

    Rosati, Fiora; Boersma, Arnold J.; Klijn, Jaap E.; Meetsma, Auke; Feringa, Ben L.; Roelfes, Gerard

    2009-01-01

    The recently developed concept of DNA-based asymmetric catalysis involves the transfer of chirality from the DNA double helix in reactions using a noncovalently bound catalyst. To date, two generations of DNA-based catalysts have been reported that differ in the design of the ligand for the metal. H

  15. The asymmetric alkylation of dimethylhydrazones; intermolecular chirality transfer using sparteine as chiral ligand.

    Science.gov (United States)

    McSweeney, Christina M; Foley, Vera M; McGlacken, Gerard P

    2014-12-01

    The asymmetric alkylation of ketones represents a fundamental transformation in organic chemistry. Chiral auxiliaries have been used almost exclusively for this transformation. Herein we describe a strategy for the generation of enantiomerically enriched α-alkylated ketones up to an er of 83 : 17, using a chiral ligand protocol.

  16. NeoPHOX – a structurally tunable ligand system for asymmetric catalysis

    Science.gov (United States)

    Padevět, Jaroslav; Schrems, Marcus G; Scheil, Robin

    2016-01-01

    Summary A synthesis of new NeoPHOX ligands derived from serine or threonine has been developed. The central intermediate is a NeoPHOX derivative bearing a methoxycarbonyl group at the stereogenic center next to the oxazoline N atom. The addition of methylmagnesium chloride leads to a tertiary alcohol, which can be acylated or silylated to produce NeoPHOX ligands with different sterical demand. The new NeoPHOX ligands were tested in the iridium-catalyzed asymmetric hydrogenation and palladium-catalyzed allylic substitution. In both reactions high enantioselectivities were achieved, that were comparable to the enantioselectivities obtained with the up to now best NeoPHOX ligand derived from expensive tert-leucine. PMID:27559370

  17. Asymmetric transfer hydrogenation of ketones catalyzed by nickel complex with new PNO-type ligands

    Institute of Scientific and Technical Information of China (English)

    Zhen Rong Dong; Yan Yun Li; Shen Luan Yu; Guo Song Sun; Jing Xing Gao

    2012-01-01

    The new polydentate mixed-N,P,O chiral ligands have been synthesized by the condensation of bis(o-formylphenyl)-phenylphosphane and R-phenylglycinol in CHCl3,and fully characterized by IR,NMR and EIMS spectra.These ligands were employed with a simple Ni complex Ni(PPh8)2Cl2 in situ as catalytic systems for asymmetric transfer hydrogenation of ketones,and the corresponding optical alcohols were obtained with up to 84% ee under mild conditions.

  18. Synthesis of Novel C2-Symmetrical Bidentate Phosphoramidite Ligands for Rh-catalyzed Asymmetric Hydrogenation of β-(Acylamino)acrylates

    Institute of Scientific and Technical Information of China (English)

    Qing Heng ZENG; Xiang Ping HU; Xin Miao LIANG; Zhuo ZHENG

    2006-01-01

    Two new C2-symmetrical bidentate phosphoramidite ligands were synthesized and employed in the Rh-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates, up to 89% ee with full conversions was obtained.

  19. Metal-ligand binding affinity vs reactivity: qualitative studies in Rh(I)-catalyzed asymmetric ring-opening reactions.

    Science.gov (United States)

    Tsui, Gavin Chit; Dougan, Patrick; Lautens, Mark

    2013-06-01

    Rh(I)-catalyzed asymmetric ring opening (ARO) of oxabenzonorbornadiene is used as a model system to qualitatively study reactions involving multiple metal-ligand interactions. The key feature of this approach is the use of product ee as an indicator to quickly gain important information such as the relative ligand binding affinity and relative reactivity of catalysts.

  20. Rational design and asymmetric synthesis of potent and neurotrophic ligands for FK506-binding proteins (FKBPs).

    Science.gov (United States)

    Pomplun, Sebastian; Wang, Yansong; Kirschner, Alexander; Kozany, Christian; Bracher, Andreas; Hausch, Felix

    2015-01-01

    To create highly efficient inhibitors for FK506-binding proteins, a new asymmetric synthesis for pro-(S)-C(5) -branched [4.3.1] aza-amide bicycles was developed. The key step of the synthesis is an HF-driven N-acyliminium cyclization. Functionalization of the C(5)  moiety resulted in novel protein contacts with the psychiatric risk factor FKBP51, which led to a more than 280-fold enhancement in affinity. The most potent ligands facilitated the differentiation of N2a neuroblastoma cells with low nanomolar potency.

  1. Flexible and Asymmetric Ligand in Constructing Coordinated Complexes: Synthesis, Crystal Structures and Fluorescent Characterization

    Directory of Open Access Journals (Sweden)

    Jianhua Lin

    2010-12-01

    Full Text Available Flexible and asymmetric ligand L [L = 1-((pyridin-3-ylmethyl-1H-benzotriazole], is used as a basic backbone to construct complicated metal-organic frameworks. Two new polymers, namely, [Ag2(L2(NO32]n (1 and [Ag(L(ClO4]n (2, were synthesized and characterized by X-ray structure analysis and fluorescent spectroscopy. The complex 1 gives an “S” type double helical conformation, whereas complex 2 exhibits a 1D zigzag configuration. Different anions affect the silver coordination geometry and crystal packing topology.

  2. 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.

  3. Bifunctional Enantioselective Ligands of Chiral BINOL Derivatives for Asymmetric Addition of Alkynylzinc to Aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZOU Xiao-Wei; ZHENG Li-Fei; WU Ling-Lin; ZONG Li-Li; CHENG Yi-Xiang

    2008-01-01

    Four analogous binaphthyl compounds (R)-3a-3d containing (R)-3,3'-bis(2-pyridyl) groups were synthesized by the conjugation of (R)-2,2'-dimethoxy-1,1'-binaphthyl-3,3'-diboronic acid [(R)-2] with 2-bromopyridine,2-bromo-5-methylpyridine, 2-chloro-4-fluoropyridine and 2-chloro-3-(trifluoromethyl)pyridine via Pd-catalyzed Suzuki reactions, respectively.The application of the four chiral ligands in combination with Et2Zn and Ti(Oi-Pr)4 to the asymmetric addition of phenylacetylene to various aldehydes has been studied.The results show that (R)-3a and (R)-3b are not good catalysts for the alkynylzinc addition to aldehydes, (R)-3d shows good enantioselectivity only for the alkynylzinc addition to aliphatic aldehydes, and (R)-3c exhibits excellent enantioselectivity for phenylethynylzinc addition to both aromatic and aliphatic aldehydes.All the four chiral ligands produced the opposite configuration of the propargylic alcohols to that of the chiral ligands.

  4. Synthesis of novel chiral N, P-containing multidentate ligands and their applications in asymmetric transfer hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Shen Luan Yu; Yan Yun Li; Zhen Rong Dong; Juan Ni Zhang; Qi Li; Jing Xing Gao

    2011-01-01

    Novel chiral PN4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis(o-formylphenyl)phenylphosphane and various chiral amino-sulfonamides. Their structures were fully characterized by IR, EI-MS and NMR. The catalytic systems, prepared in situ from the multidentate ligands and iridium(I) complexes, showed high activity in asymmetric transfer hydrogenation of propiophenone in 2-propanol solution, leading to corresponding optical alcohol with up to 75% ee.

  5. Controlling stereochemical outcomes of asymmetric processes by catalyst remote molecular functionalizations: chiral diamino-oligothiophenes (DATs) as ligands in asymmetric catalysis.

    Science.gov (United States)

    Albano, Vincenzo Giulio; Bandini, Marco; Barbarella, Giovanna; Melucci, Manuela; Monari, Magda; Piccinelli, Fabio; Tommasi, Simona; Umani-Ronchi, Achille

    2006-01-11

    The synthesis, characterization, and structure-guided application of a new class of highly versatile chiral C(2)-symmetric diamine-oligothiophene ligands in Pd-catalyzed asymmetric transformations are presented. Experimental investigations of the intimate role of pendant pi-conjugate oligothiophenes in determining the catalytic activity of the corresponding chiral Pd complexes are described. Their unusual behavior opens up new routes toward the logical design of finely tuned organometallic catalysts by remote structural functionalizations.

  6. Scope and limitations of chiral bis(oxazoline) ligands in the copper-catalysed asymmetric cyclopropanation of trisubstituted alkenes

    DEFF Research Database (Denmark)

    Østergaard, N.; Jensen, Jakob Feldthusen; Tanner, David Ackland

    2001-01-01

    A series of derivatives of 3-methyl-2-buten-1-ol has been used to test the scope and limitations of the copper-catalysed asymmetric cyclopropanation of trisubstituted alkenes by ethyl diazoacetate in the presence of C-2-symmetric bis(oxazoline) ligands. In the best case, a trans/cis ratio of 91...

  7. A highly efficient and recoverable bi-cinchona alkaloid ligand for the catalytic asymmetric aminohydroxylation of olefins

    Directory of Open Access Journals (Sweden)

    SHENGYONG ZHANG

    2006-10-01

    Full Text Available A new freely recyclable bi-cinchona alkaloid ligand has been developed for the homogeneous catalytic asymmetric aminohydroxylation (AA of olefins. It can be easily recovered by precipitation and reused for 5 times without any significant loss in its catalytic efficiency in AA reactions.

  8. Development of Ar-BINMOL-Derived Atropisomeric Ligands with Matched Axial and sp(3) Central Chirality for Catalytic Asymmetric Transformations.

    Science.gov (United States)

    Xu, Zheng; Xu, Li-Wen

    2015-10-01

    Recently, academic chemists have renewed their interest in the development of 1,1'-binaphthalene-2,2'-diol (BINOL)-derived chiral ligands. Six years ago, a working hypothesis, that the chirality matching of hybrid chirality on a ligand could probably lead to high levels of stereoselective induction, prompted us to use the axial chirality of BINOL derivatives to generate new stereogenic centers within the same molecule with high stereoselectivity, obtaining as a result sterically favorable ligands for applications in asymmetric catalysis. This Personal Account describes our laboratory's efforts toward the development of a novel class of BINOL-derived atropisomers bearing both axial and sp(3) central chirality, the so-called Ar-BINMOLs, for asymmetric synthesis. Furthermore, on the basis of the successful application of Ar-BINMOLs and their derivatives in asymmetric catalysis, the search for highly efficient and enantioselective processes also compelled us to give special attention to the BINOL-derived multifunctional ligands with multiple stereogenic centers for use in catalytic asymmetric reactions.

  9. Synthesis of novel chiral tridentate Schiff-base ligands and their applications in catalytic asymmetric Henry reaction.

    Science.gov (United States)

    Qiang, Gen-Rong; Shen, Tian-Hua; Zhou, Xiao-Cong; An, Xiao-Xia; Song, Qing-Bao

    2014-12-01

    A series of chiral tridentate Schiff-bases were prepared and used as ligands in the catalytic asymmetric Henry reaction. Under the optimal conditions, a variety of arylaldehydes were smoothly converted into corresponding adducts with high yields (up to 98%) and excellent enantioselectivities (up to 97% ee).

  10. New chiral diamino-bis(tert-thiophene): an effective ligand for Pd- and Zn-catalyzed asymmetric transformations.

    Science.gov (United States)

    Bandini, Marco; Melucci, Manuela; Piccinelli, Fabio; Sinisi, Riccardo; Tommasi, Simona; Umani-Ronchi, Achille

    2007-11-21

    Enantiomerically pure diamino-bis(tert-thiophene) proved to be a valuable and flexible chiral ligand for Pd- and Zn-catalyzed transformations, allowing for high levels of stereocontrol in asymmetric allylic alkylation (ee up to 99%) and hydrosilylations of prochiral carbonyls (ee up to 97%).

  11. A comparative Study of C2-Symmetric Bis(aziridine) Ligands in Some Transition Metal-Mediated Asymmetric Transformations

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Johansson, Fredrik; Harden, Adrian;

    1998-01-01

    A comparative study has been made of the performance of differently substituted Ca-symmetric bis(aziridine) ligands in a variety of metal-mediated asymmetric reactions. The metals studied were osmium (dihydroxylation), palladium (allylic alkylation) and copper (cyclopropanation and aziridination......), the ligands being chosen so as to allow evaluation of both electronic and steric effects. The electronic effects were most pronounced for complexes of palladium, which seem to bind rather loosely to this type of ligand. For the other metals, steric effects play a more important role. (C) 1998 Elsevier Science...

  12. Copper-, palladium-, and platinum-containing complexes of an asymmetric dinucleating ligand.

    Science.gov (United States)

    Halvagar, Mohammad Reza; Neisen, Benjamin; Tolman, William B

    2013-01-18

    The coordination chemistry of an asymmetric dinucleating hexadentate ligand LH(2) comprising neutral alkyltriamine and potentially dianionic dicarboxamido-pyridyl donor sets with copper, palladium, and platinum has been explored. Monometallic, dicopper, and heterodinuclear Cu-Pd and -Pt complexes have been prepared and characterized, including by NMR, EPR, UV-vis, and IR spectroscopy and X-ray crystallography. For example, the monometallic complexes [(LH(2))MCl]X (M = Cu, X = OTf; M = Pd or Pt, X = Cl) were prepared, wherein the metal(II) ions are coordinated to the triamine portion and the pyridyldicarboxamide is unperturbed. Treatment of LH(2) with [MesCu](x) (Mes = mesityl) provided a monocopper(I) complex, again with the metal coordinated only to the trialkylamine donor set. Reaction of [(LH(2))CuCl]OTf with NaOMe resulted in an unexpected migration of the copper(II)-chloride fragment to the pyridyldicarboxamide site to yield Na[LCuCl], from which a dicopper complex LCu(2)Cl(2) and mixed-metal complexes LCu(Cl)M(Cl) (M = Pd, Pt) were prepared by addition of CuCl(2) or MCl(2), respectively. The heterodinuclear complexes were also prepared by addition of CuCl(2) to [(LH(2))MCl]Cl.

  13. 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.

  14. Rh-Catalyzed Asymmetric Hydrogenation of a-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine- Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    HU Juan, WANG Dao-yong, ZHENG Zhuo, HU Xiang-ping J. Mol. Catal. (China) 2012, 26(6), 487 ~492 Chiral phosphine-phosphoramidite ligand, ( So, S,, )-2b, was found to be highly efficient in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates, in which excellent enantioselectivities (up to 〉99% ee) and high catalyticactivity ( S/C up to 5000) were achieved.

  15. Synthesis of solution-phase phosphoramidite and phosphite ligand libraries and their in situ screening in the rhodium-catalyzed asymmetric addition of arylboronic acids

    NARCIS (Netherlands)

    Jagt, Richard B. C.; Toullec, Patrick Y.; Schudde, Ebe P.; de Vries, Johannes G.; Feringa, Ben L.; Minnaard, Adriaan J.

    2007-01-01

    Herein, we report the automated parallel synthesis of solution-phase libraries of phosphoramidite ligands for the development of enantioselective catalysts. The ligand libraries are screened in situ in the asymmetric rhodium-catalyzed addition of arylboronic acids to aldehydes and imines. It is show

  16. Synthesis, characterization and thermal study of some transition metal complexes of an asymmetrical tetradentate Schiff base ligand

    Directory of Open Access Journals (Sweden)

    ACHUT S. MUNDE

    2010-03-01

    Full Text Available Complexes of Cu(II, Ni(II, Co(II, Mn(II and Fe(III with an asymmetric tetradentate Schiff base ligand derived from dehydroacetic acid, 4-methyl-o-phenylenediamine and salicylic aldehyde were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV–Vis, IR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a dibasic tetadentate ligand towards the central metal ion with an ONNO donor atoms sequence. From the microanalytical data, the stoichiometry of the complexes 1:1 (metal:ligand was found. The physico-chemical data suggested square planar geometry for the Cu(II and Ni(II complexes and octahedral geometry for the Co(II, Mn(II and Fe(III complexes. The thermal behaviour (TGA/DTA of the complexes was studied and kinetic parameters were determined by Horowitz–Metzger and Coats–Redfern methods. The powder X-ray diffraction data suggested a monoclinic crystal system for the Co(II, Mn(II and Fe(III complexes. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma viride.

  17. Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

    Science.gov (United States)

    Yamamoto, Kosuke; Shimizu, Takashi; Igawa, Kazunobu; Tomooka, Katsuhiko; Hirai, Go; Suemune, Hiroshi; Usui, Kazuteru

    2016-11-01

    A series of novel optically active [5]helicene-derived phosphine ligands (L1, with a 7,8-dihydro[5]helicene core structure- and L2, with a fully aromatic [5]helicene core structure) were synthesized. Despite their structural similarities, L1 and L2 exhibit particularly different characteristics in their use as chiral ligands. L1 was highly effective in the asymmetric allylation of indoles with 1,3-diphenylallyl acetate (up to 99% ee), and in the etherification of alcohols (up to 96% ee). In contrast, L2 was highly effective in the stereocontrol of helical chirality in Suzuki-Miyaura coupling (SMC) reaction (up to 99% ee). Density functional theory analysis was employed to propose a model that accounts for the origin of the enantioselectivity in these reactions.

  18. Ureaphosphanes as hybrid, anionic or supramolecular bidentate ligands for asymmetric hydrogenation reactions

    NARCIS (Netherlands)

    Meeuwissen, J.; Detz, R.; Sandee, A. J.; de Bruin, B.; Siegler, M. A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    We report the coordination behavior of ureaphosphane ligand 1-[2-(diphenylphosphanyl)ethyl]-3-phenylurea (L1) towards different rhodium precursor complexes. Depending on the nature of the anion and the ligand/metal ratio, L1 acts either as a hybrid P,O-coordinating chelate, as an anionic P,N-coordin

  19. Fructose derived pyridyl alcohol ligands: synthesis and application in the asymmetric diethylzinc addition to aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHOU, Yong-Gui; DAI, Li-Xin; HOU, Xue-Long

    2000-01-01

    Easily available chiral ketones were employed for the synthesis of optically active pyridyl alcohols, which were applied in the asymmetric diethylzinc addition to aldehydes, up to 89.4%e.e. was obtained using D-fructose-derived pyridyl alcohol.

  20. Imidazole-based Potential Bi- and Tridentate Nitrogen Ligands: Synthesis, Characterization and Application in Asymmetric Catalysis

    Directory of Open Access Journals (Sweden)

    Jiří Kulhánek

    2008-09-01

    Full Text Available Twelve new imidazole-based potential bi- and tridentate ligands were synthesized and characterized. Whereas in the first series the α-amino acid and imidazole moieties were linked by an amino bond, in the second series the tridentate ligands, containing two imidazole groups, were separated by an amide bond. The first series was obtained by the reductive amination of 2-phenylimidazole-4-carboxaldehyde with α-amino acid esters. The tridentate ligands were prepared from 2-phenylimidazole-4-carboxylic acid and chiral amines. In the Henry reaction, the amines were revealed as a more reactive species than the less nucleophilic amides, however the enantiomeric excesses were generally poor.

  1. Asymmetric Transfer Hydrogenation of Prochiral Ketones in Aqueous Media with New Water-Soluble Chiral Vicinal Diamine as Ligand

    Institute of Scientific and Technical Information of China (English)

    ZHU Jin; MA Ya-Ping; LIU Hui; CHEN Li; CUI Xin; DENG Jin-Gen

    2003-01-01

    @@ As a consequence of the increasing demand for atom economy and environmental friendly methods, the water soluble ligands and their metal complexes are of great interest in catalytic synthesis because of simpler product sepa ration and the possibility of recycling. [1] Unique reactivity and selectivity are often observed in aqueous reactions. [2]Recently, we have developed a new water-soluble chiral vicinal diamine and synthesized its mono-N-tosylated derivative for the first time. The application of its mono-N-tosylated derivative in catalytic asymmetric transfer hydrogenation of prochiral ketones was examined in aqueous media. High activity (up to > 99 % conv. ) and good enatioselectivity ( up to 98% ee ) were achieved for most of prochiral aromatic ketones in organic solvent free system. [3

  2. Instant Ligand Libraries. Parallel Synthesis of Monodentate Phosphoramidites and in Situ Screening in Asymmetric Hydrogenation

    NARCIS (Netherlands)

    Lefort, Laurent; Boogers, Jeroen A.F.; Vries, André H.M. de; Vries, Johannes G. de

    2004-01-01

    Chiral phosphoramidites have been identified as excellent ligands for various metal-catalyzed enantioselective transformations. Taking advantage of their easy preparation and modular nature, we designed a fully automated protocol for the parallel preparation of a library of 32 phosphoramidites and i

  3. Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO2 Reduction.

    Science.gov (United States)

    Spall, Steven J P; Keane, Theo; Tory, Joanne; Cocker, Dean C; Adams, Harry; Fowler, Hannah; Meijer, Anthony J H M; Hartl, František; Weinstein, Julia A

    2016-12-19

    Manganese tricarbonyl bromide complexes incorporating IP (2-(phenylimino)pyridine) derivatives, [MnBr(CO)3(IP)], are demonstrated as a new group of catalysts for CO2 reduction, which represent the first example of utilization of (phenylimino)pyridine ligands on manganese centers for this purpose. The key feature is the asymmetric structure of the redox-noninnocent ligand that permits independent tuning of its steric and electronic properties. The α-diimine ligands and five new Mn(I) compounds have been synthesized, isolated in high yields, and fully characterized, including X-ray crystallography. Their electrochemical and electrocatalytic behavior was investigated using cyclic voltammetry and UV-vis-IR spectroelectrochemistry within an OTTLE cell. Mechanistic investigations under an inert atmosphere have revealed differences in the nature of the reduction products as a function of steric bulk of the ligand. The direct ECE (electrochemical-chemical-electrochemical) formation of a five-coordinate anion [Mn(CO)3(IP)](-), a product of two-electron reduction of the parent complex, is observed in the case of the bulky DIPIMP (2-[((2,6-diisopropylphenyl)imino)methyl]pyridine), TBIMP (2-[((2-tert-butylphenyl)imino)methyl]pyridine), and TBIEP (2-[((2-tert-butylphenyl)imino)ethyl]pyridine) derivatives. This process is replaced for the least sterically demanding IP ligand in [MnBr(CO)3(IMP)] (2-[(phenylimino)methyl]pyridine) by the stepwise formation of such a monoanion via an ECEC(E) mechanism involving also the intermediate Mn-Mn dimer [Mn(CO)3(IMP)]2. The complex [MnBr(CO)3(IPIMP)] (2-[((2-diisopropylphenyl)imino)methyl]pyridine), which carries a moderately electron donating, moderately bulky IP ligand, shows an intermediate behavior where both the five-coordinate anion and its dimeric precursor are jointly detected on the time scale of the spectroelectrochemical experiments. Under an atmosphere of CO2 the studied complexes, except for the DIPIMP derivative, rapidly

  4. Asymmetric catalysis mediated by the ligand sphere of octahedral chiral-at-metal complexes.

    Science.gov (United States)

    Gong, Lei; Chen, Liang-An; Meggers, Eric

    2014-10-06

    Due to the relationship between structure and function in chemistry, access to novel chemical structures ultimately drives the discovery of novel chemical function. In this light, the formidable utility of the octahedral geometry of six-coordinate metal complexes is founded in its stereochemical complexity combined with the ability to access chemical space that might be unavailable for purely organic compounds. In this Minireview we wish to draw attention to inert octahedral chiral-at-metal complexes as an emerging class of metal-templated asymmetric "organocatalysts" which exploit the globular, rigid nature and stereochemical options of octahedral compounds and promise to provide new opportunities in the field of catalysis.

  5. Palladium-catalyzed, asymmetric Baeyer–Villiger oxidation of prochiral cyclobutanones with PHOX ligands

    KAUST Repository

    Petersen, Kimberly S.

    2011-06-01

    Described in this report is a general method for the conversion of prochiral 3-substituted cyclobutanones to enantioenriched γ-lactones through a palladium-catalyzed Baeyer-Villiger oxidation using phosphinooxazoline ligands in up to 99% yield and 81% ee. Lactones of enantiopurity ≥93% could be obtained through a single recrystallization step. Importantly, 3,3-disubtituted cyclobutanones produced enantioenriched lactones containing a β-quaternary center. © 2011 Elsevier Ltd. All rights reserved.

  6. Phosphino hydrazones as suitable ligands in the asymmetric Suzuki-Miyaura cross-coupling.

    Science.gov (United States)

    Ros, Abel; Estepa, Beatriz; Bermejo, Antonio; Alvarez, Eleuterio; Fernández, Rosario; Lassaletta, José M

    2012-05-18

    Phosphino hydrazones derived from C(2)-symmetric hydrazines exhibit excellent catalytic activity and provide good enantioselectivities in the asymmetric Suzuki-Miyaura cross-coupling to axially chiral biaryls, in particular for the most challenging reactions of monocyclic, functionalized aryl bromides and triflates. X-ray analysis of preformed [Pd(P/N)Cl(2)] precatalysts [(P/N) = phosphino hydrazone] revealed a strong n-π conjugation in the hydrazone moiety, identified by a high planarity degree at the pyrrolidine N(sp(3)) atom, that makes rotations around N-N bonds inconsequential. The complexes are also characterized by an envelope-like conformation with the Pd atom placed at the opposite side to the 2-phenyl group on the nearest stereogenic center of the pyrrolidine group. The isolation and structural analysis of oxidative addition intermediates indicate that the configurational stability of Pd-C(Ar) bonds is dependent on the substitution pattern in the aryl bromide.

  7. A new copper(II) Schiff base complex containing asymmetrical tetradentate N2O2 Schiff base ligand: Synthesis, characterization, crystal structure and DFT study

    Science.gov (United States)

    Grivani, Gholamhossein; Baghan, Sara Husseinzadeh; Vakili, Mohammad; Khalaji, Aliakbar Dehno; Tahmasebi, Vida; Eigner, Václav; Dušek, Michal

    2015-02-01

    A new copper (II) Schiff base complex, CuL1, was prepared from the reaction of asymmetrical Schiff base ligand of L1 and Cu(OAC)2 (L1 = salicylidene imino-ethylimino-pentan-2-one). The Schiff base ligand, L1, and its copper (II) complex, CuL1, have been characterized by elemental analysis (CHN) and FT-IR and UV-vis spectroscopy. In addition, 1H NMR was employed for characterization of the ligand. Thermogrametric analysis of the CuL1 reveals its thermal stability and its decomposition pattern shows that it is finally decomposed to the copper oxide (CuO). The crystal structure of CuL1 was determined by the single crystal X-ray analysis. The CuL1 complex crystallizes in the monoclinic system, with space group P21/n and distorted square planar coordination around the metal ion. The Schiff base ligand of L1 acts as a chelating ligand and coordinates via two nitrogen and two oxygen atoms to the copper (II) ion with C1 symmetry. The structure of the CuL1 complex was also studied theoretically at different levels of DFT and basis sets. According to calculated results the Csbnd O bond length of the salicylate fragment is slightly higher than that in the acetylacetonate fragment of ligand, which could be interpreted by resonance increasing between phenyl and chelated rings in ligand in relative to the acetylacetonate fragment.

  8. Synthesis, spectral, photolysis and electrochemical studies of mononuclear copper(II) complex with a new asymmetric tetradentate ligand: application as copper nanoparticle precursor.

    Science.gov (United States)

    Habibi, Mohammad Hossein; Mikhak, Maryam

    2012-10-01

    A copper(II) complex with asymmetric tetradentate Schiff base ligand, obtained by the single condensation of 1,2-diaminopropane with 2-hydroxy-5-methoxy benzaldehyde was prepared. The ligand and complex were characterized by their IR, UV-Vis, FT-IR, NMR spectra and CV. Crystal structures of the mononuclear copper complex have been obtained by X-ray diffraction studies which revealed to be distorted square planner coordination geometry. The spectral data confirm coordination of ligand to copper ion center. The redox properties of complex at different scan rates exhibit grossly similar features consisting of an electrochemically pseudo-reversible Cu(II)/Cu(I) reduction at ca. -0.97 V and pseudo-reversible Cu(I)/Cu(II) oxidation at ca. -0.81 V. The copper nanoparticles with average size of 73 nm were formed by thermal reduction of copper complex in the presence of triphenylphosphine.

  9. Synthesis, spectral, photolysis and electrochemical studies of mononuclear copper(II) complex with a new asymmetric tetradentate ligand: Application as copper nanoparticle precursor

    Science.gov (United States)

    Habibi, Mohammad Hossein; Mikhak, Maryam

    2012-10-01

    A copper(II) complex with asymmetric tetradentate Schiff base ligand, obtained by the single condensation of 1,2-diaminopropane with 2-hydroxy-5-methoxy benzaldehyde was prepared. The ligand and complex were characterized by their IR, UV-Vis, FT-IR, NMR spectra and CV. Crystal structures of the mononuclear copper complex have been obtained by X-ray diffraction studies which revealed to be distorted square planner coordination geometry. The spectral data confirm coordination of ligand to copper ion center. The redox properties of complex at different scan rates exhibit grossly similar features consisting of an electrochemically pseudo-reversible Cu(II)/Cu(I) reduction at ca. -0.97 V and pseudo-reversible Cu(I)/Cu(II) oxidation at ca. -0.81 V. The copper nanoparticles with average size of 73 nm were formed by thermal reduction of copper complex in the presence of triphenylphosphine.

  10. Zn(II), Ni(II), Cu(II) and Pb(II) complexes of tridentate asymmetrical Schiff base ligands: Synthesis, characterization, properties and biological activity

    Science.gov (United States)

    Şahin, Mustafa; Koçak, Nuriye; Erdenay, Damla; Arslan, Uğur

    2013-02-01

    New asymmetrical tridentate Schiff base ligands were synthesized using 1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-hydroxy-1-napthaldehyde, 9-anthracenecarboxaldehyde. Schiff base ligands and their metal complexes were synthesised and characterized by using FT-IR, 1H NMR, 13C NMR, UV-Vis, XRD, ESR, elemental analysis and fluorescence studies. The antimicrobial activity of the ligands and their metal complexes were studied against Staphylococcus aureus ATCC 29213, S. aureus ATCC 25923, Streptococcus mutans RSHM 676, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853. The determination of the antibacterial activity was done using the broth microdilution methods. In general, it has been determined that the studied compounds have MIC values similar to Gram-positive and Gram-negative bacteria. It has been found that Ni, Pb, Zn derivatives of HL1A and ZnL2A has lower MIC values than ampicillin for P. aeruginosa ATCC 27853 strain.

  11. A Helical Polyphenylacetylene Having Amino Alcohol Moieties Without Chiral Side Groups as a Chiral Ligand for the Asymmetric Addition of Diethylzinc to Benzaldehyde.

    Science.gov (United States)

    Liu, Lijia; Long, Qing; Aoki, Toshiki; Zhang, Geng; Kaneko, Takashi; Teraguchi, Masahiro; Zhang, Chunhong; Wang, Yudan

    2015-08-01

    One-handed helical polyphenylacetylenes having achiral amino alcohol moieties, but no chiral side groups, were synthesized by the helix-sense-selective copolymerization of an achiral phenylacetylene having an amino alcohol side group with a phenylacetylene having two hydroxyl groups. Since the resulting helical copolymers were successfully utilized as chiral ligands for the enantioselective alkylation of benzaldehyde with diethylzinc, we can conclude that the main-chain chirality based on the one-handed helical conformation is useful for the chiral catalysis of an asymmetric reaction for the first time. The enantioselectivities of the reaction were controlled by the optical purities of the helical polymer ligands. In addition, the polymer ligands could be easily recovered by precipitation after the reaction.

  12. SYNERGISTIC EFFECTS OF HEMILABILE COORDINATION AND COUNTERIONS IN HOMOGENEOUS CATALYSIS: NEW TUNABLE MONOPHOSPHINE LIGANDS FOR HYDROVINYLATION REACTIONS. (R826120)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  13. Synthesis, characterization and crystal structure of four new asymmetric triazene ligands: An example of linear HII complex with H... secondary bonding interactions

    Indian Academy of Sciences (India)

    Mohammad Reza Melardi; Fatemeh Baber Shamsi Mogoii; Ayoob Babaii Sajirani; Jafar Attar Gharamaleki; Behrouz Notash; Mohammad Kazem Rofouei

    2015-12-01

    In this work, the asymmetric ligands [1-(phenyl)-3-(2-nitro-4-methylphenyl)]triazene (1), [1-(4-methylphenyl)-3-(2-nitro-4-methylphenyl)]triazene (2), [1-(4-ethylphenyl)-3-(2-nitro-4-methylphenyl)]triazene (3) and [1-(4-ethoxyphenyl)-3-(2-nitro-4-methylphenyl)]triazene (4), were synthesized. The reaction of the ligand (3) with HgCl2 in methanol resulted in the formation of the [HgL2] complex, (5). All compounds were characterized by means of CHN analysis, FT-IR, 1H NMR, 13C NMR spectroscopy. In addition, the crystal structures of the ligands (2) to (4) were investigated by single crystal X-ray analysis. In the solid state, all ligands exhibited trans conformation about the –N=N– double bond. The HgII complex (5) crystallized in monoclinic system with 2/ space group. The triazene ligand was found to be deprotonated prior to coordination and acts as monodentate ligand. The HgII which lies on inversion center (site symmetry $\\bar{1}$), is surrounded by two N atoms from L ligands forming a linear geometry. The other two Hg–N bonds are relatively longer and can only be regarded as weak secondary bonds. Also, Hg-3-arene -interactions are present in this compound. Hydrogen bonds, · · · and C–H· · · stacking interactions help in the stabilization of the resulted frameworks. These C–H· · · edge-to-face interactions are present with H· · · distance of 3.00 Å.

  14. Synthesis of novel chiral phosphine-triazine ligand derived from α-phenylethylamine for Pd-catalyzed asymmetric allylic alkylation

    Institute of Scientific and Technical Information of China (English)

    Jia Di Huang; Xiang Ping Hu; Zhuo Zheng

    2008-01-01

    A novel chiral phosphine-triazine ligand was synthesized from chiral model reaction of Pd-catalyzed allylic alkylation of rac-l,3-diphenylprop-2-en-l-yl pivalate with dimethyl malonate, good enantioselectivity (90% e.e.) was obtained by using this ligand.

  15. A comparison of MOP-phosphonite ligands and their applications in Rh(i)- and Pd(ii)-catalysed asymmetric transformations.

    Science.gov (United States)

    Fleming, James T; Wills, Corinne; Waddell, Paul G; Harrington, Ross W; Higham, Lee J

    2016-10-04

    Six chiral MOP-phosphonites have been synthesised and compared via experimental and computational methods in an effort to quantify their differing structural and electronic profiles. They were found to be electron-poor ligands in comparison to their arylphosphine analogues and have a larger trans influence in square planar Pt(ii) complexes. Four [Rh(L(P))(η(2):η(2)-cod)Cl] complexes were synthesised and characterised by NMR, HRMS and X-ray crystallography. Two [Rh(L(P))2]BF4 complexes were prepared where one ligand acts as a chelating P,C-π-donor; detailed NMR studies demonstrated a hemilabile η(6)-coordination mode, which in one case was confirmed by X-ray crystallography. Rh(i) complexes were used as catalysts in asymmetric hydrogenation and hydroformylation reactions and in the addition of phenyl boronic acid to an isatin. Pd(ii) complexes were successfully employed in asymmetric Suzuki-Miyaura cross-coupling reactions yielding binaphthyl products. Two [Pd(L(P))2Cl2] complexes were synthesised and characterised by X-ray crystallography, both adopting cis orientations, with one of the complexes crystallising as two pseudo-polymorphs.

  16. Structures of human thymidylate synthase R163K with dUMP, FdUMP and glutathione show asymmetric ligand binding.

    Science.gov (United States)

    Gibson, Lydia M; Celeste, Lesa R; Lovelace, Leslie L; Lebioda, Lukasz

    2011-01-01

    Thymidylate synthase (TS) is a well validated target in cancer chemotherapy. Here, a new crystal form of the R163K variant of human TS (hTS) with five subunits per asymmetric part of the unit cell, all with loop 181-197 in the active conformation, is reported. This form allows binding studies by soaking crystals in artificial mother liquors containing ligands that bind in the active site. Using this approach, crystal structures of hTS complexes with FdUMP and dUMP were obtained, indicating that this form should facilitate high-throughput analysis of hTS complexes with drug candidates. Crystal soaking experiments using oxidized glutathione revealed that hTS binds this ligand. Interestingly, the two types of binding observed are both asymmetric. In one subunit of the physiological dimer covalent modification of the catalytic nucleophile Cys195 takes place, while in another dimer a noncovalent adduct with reduced glutathione is formed in one of the active sites.

  17. New chiral phosphinephosphinite ligands: Application to stereoselective synthesis of a key intermediate of 1{beta}-methyl carbapenems by Rh(I)-catalyzed asymmetric hydroformylation

    Energy Technology Data Exchange (ETDEWEB)

    Saito, Takao; Yoshida, Akifumi; Matsumura, Kazuhiko [Takasago International Corp., Kanagawa (Japan)] [and others

    1995-12-31

    Transition metal catalyzed asymmetric hydroformylation is an attractive and highly useful homologation process for organic synthesis. Recently, the authors reported that the Rh(I) complexes of phosphinephosphite BINAPHOS are highly efficient catalysts for enantioselective hydroformylation of a variety of olefins. This time, the authors have designed and synthesized new chiral phosphinephosphinite ligands having binaphthyl backbone, (R)-2-diarylphosphino-2{prime}-diarylphosphinoxy-1,1{prime}-binaphthy1 (hereafter abbreviated (R)-BIPNITE). The Rh(I) complexes of these ligands are effective catalysts for the asymmetric hydroformylation of 4-vinylazetidin-2-one to give the corresponding oxo-aldehyde 3{beta} as the major product in very high diastereoselectivities and in good regioselectivities. Interestingly, modifications of the aryl substituents in phosphine and phosphinite moieties afforded higher selectivities. Aldehyde 3{beta} was easily oxidized with NaClO{sub 2} to 4, a key intermediate of 1{beta}-methyl carbapenems. Thus, the present method provides a new practical route to a versatile key intermediate for the synthesis of carbapenem antibiotics.

  18. Simultaneous recognition of a carboxylate-containing ligand and an intramolecular surrogate ligand in the crystal structure of an asymmetric vancomycin dimer

    Energy Technology Data Exchange (ETDEWEB)

    Loll, P.J.; Bevivino, A.E.; Korty, B.D.; Axelsen, P.H. [Univ. of Pennsylvania School of Medicine, Philadelphia, PA (United States)

    1997-02-19

    Vancomycin is one of the most important and commonly used antibiotics in hospitals. Despite numerous investigations, however, it is not clear how vancomycin recognizes its site of action in the bacterial cell wall. The increasing incidence of bacterial resistance to vancomycin makes it imperative to understand these recognition determinants so that alternative agents may be developed. Herein we report the first crystal structure of vancomycin. The structure resolves a long-standing controversy about carboxylate recognition by vancomycin, suggests a possible cooperative mechanism linking ligand binding and dimerization, and demonstrates the operation of a novel intramolecular flap which occupies the binding site in the absence of ligand. 45 refs., 5 figs., 1 tab.

  19. Self-assembled copper(II) metallacycles derived from asymmetric Schiff base ligands: efficient hosts for ADP/ATP in phosphate buffer.

    Science.gov (United States)

    Kumar, Amit; Pandey, Rampal; Kumar, Ashish; Gupta, Rakesh Kumar; Dubey, Mrigendra; Mohammed, Akbar; Mobin, Shaikh M; Pandey, Daya Shankar

    2015-10-21

    Novel asymmetric Schiff base ligands 2-{[3-(3-hydroxy-1-methyl-but-2-enylideneamino)-2,4,6-trimethylphenylimino]-methyl}-phenol (H2L(1)) and 1-{[3-(3-hydroxy-1-methyl-but-2-enylideneamino)-2,4,6-trimethylphenylimino]-methyl}-naphthalen-2-ol (H2L(2)) possessing dissimilar N,O-chelating sites and copper(ii) metallacycles (CuL(1))4 (1) and (CuL(2))4 (2) based on these ligands have been described. The ligands and complexes have been thoroughly characterized by satisfactory elemental analyses, and spectral (IR, (1)H, (13)C NMR, ESI-MS, UV/vis) and electrochemical studies. Structures of H2L(2) and 1 have been unambiguously determined by X-ray single crystal analyses. The crystal structure of H2L(2) revealed the presence of two distinct N,O-chelating sites on dissimilar cores (naphthalene and β-ketoaminato groups) offering a diverse coordination environment. Metallacycles 1 and 2 having a cavity created by four Cu(ii) centres coordinated in a homo- and heteroleptic fashion with respective ligands act as efficient hosts for adenosine-5'-diphosphate (ADP) and adenosine-5'-triphosphate (ATP) respectively, over other nucleoside polyphosphates (NPPs). The disparate sensitivity of these metallacycles toward ADP and ATP has been attributed to the size of the ligands assuming diverse dimensions and spatial orientations. These are attuned for π-π stacking and electrostatic interactions suitable for different guest molecules under analogous conditions, metallacycle 1 offers better orientation for ADP, while 2 for ATP. The mechanism of the host-guest interaction has been investigated by spectral and electrochemical studies and supported by molecular docking studies.

  20. Allelic mutations of KITLG, encoding KIT ligand, cause asymmetric and unilateral hearing loss and Waardenburg syndrome type 2

    NARCIS (Netherlands)

    Zazo Seco, C. (Celia); Serrão De Castro, L. (Luciana); J.W.I. van Nierop; Morín, M. (Matías); Jhangiani, S. (Shalini); Verver, E.J.J. (Eva J.J.); M. Schraders (Margit); Maiwald, N. (Nadine); Wesdorp, M. (Mieke); H. Venselaar (Hanka); L. Spruijt (Liesbeth); Oostrik, J. (Jaap); J. Schoots (Jeroen); J. van Reeuwijk (Jeroen); Lelieveld, S.H. (Stefan H.); P.L.M. Huygen (Patrick); Insenser, M. (María); R.J. Admiraal (Ronald); Pennings, R.J.E. (Ronald J.E.); E.H. Hoefsloot (Lies); A. Arias-Vásquez (Alejandro); J. de Ligt (Joep); H.G. Yntema; Jansen, J.H. (Joop H.); D. Muzny (Donna); G. Huls (Gerwin); M.M. van Rossum; Lupski, J.R. (James R.); Moreno-Pelayo, M.A. (Miguel Angel); Kunst, H.P.M. (Henricus P.M.); H. Kremer (Hannie)

    2015-01-01

    textabstractLinkage analysis combined with whole-exome sequencing in a large family with congenital and stable non-syndromic unilateral and asymmetric hearing loss (NS-UHL/AHL) revealed a heterozygous truncating mutation, c.286-303delinsT (p.Ser96Ter), in KITLG. This mutation co-segregated with NS-U

  1. Synthesis of New Ligand 1,2-Bis { di[( R ,R) -1,3,2-oxzaphosphlidine ] phosphino} ethane with C2 -symmetric Axis and Application in Rh-catalyzed Asymmetric Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    GONG Da-chun; ZHOU Hua; WEI Ping; OUYANG Ping-kai

    2007-01-01

    New ligand 1,2-bis{ di[(R,R)-1,3,2-oxzaphosphlidine ] phosphino } ethane [ (R, R)-BDOPPEs 1, 2, 3 and 4 ] with C2-symmetric axis and bearing nitrogen and oxygen were synthesized from readily available optically active amino alcohols. Rh complexes with these ligands were highly enantioselective catalysts for asymmetric hydrogenation of N-benzoyldehydroamino acid derivatives and α-functionalized ketones in 99% e. e. and 98% e. e. , respectively.This new class of (R,R)-BDOPPEs 1, 2, 3 and 4 gave much more effectivity and enantionselectivity than their corresponding non-C2-asymmetric aminophosphine phosphinite.

  2. Synthesis of iridium and rhodium complexes with new chiral phosphine-NHC ligands based on 1,1'-binaphthyl framework and their application in asymmetric hydrogenation.

    Science.gov (United States)

    Gu, Peng; Zhang, Jun; Xu, Qin; Shi, Min

    2013-10-07

    The first series of chiral phosphine-imidazole carbene ligands based on a 1,1'-binaphthyl framework were synthesized from (R)-2-amine-2'-(diphenylphosphino)-1,1'-binaphthyl (1) in a four-step pathway. After deprotonation of these phosphine-imidazolium salts with LiO(t)Bu, and subsequent complexation with [Ir(COD)Cl]2 and anion exchange with NaBArF, phosphine-carbene chelated iridium complexes (R)-6a and (R)-6b were obtained. Their structures have been characterized by NMR and X-ray diffraction analysis. The NHC-phosphine rhodium complex (R)-6c has been also obtained by a similar synthetic method. These iridium complexes have been applied to catalyze the asymmetric hydrogenation of alkenes to give the corresponding products in moderate to excellent conversion (up to 99%) and moderate enantioselectivities under mild conditions (up to 61% ee).

  3. Ruthenium and osmium complexes of hemilabile chiral monophosphinite ligands derived from 1D-pinitol or 1D-chiro-inositol as catalysts for asymmetric hydrogenation reactions.

    Science.gov (United States)

    Slade, Angela T; Lensink, Cornelis; Falshaw, Andrew; Clark, George R; Wright, L James

    2014-12-07

    The monophosphinite ligands, 1D-1,2;5,6-di-O-cyclopentylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P1), 1D-1,2;5,6-di-O-isopropylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P2), 1D-1,2;5,6-di-O-cyclohexylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P3), and 1D-1,2;5,6-di-O-cyclopentylidene-3-O-ethyl-4-O-diphenylphosphino-chiro-inositol (D-P4), can be conveniently prepared from the chiral natural products 1D-pinitol or 1D-chiro-inositol. On treatment of toluene solutions of RuCl2(PPh3)3 with two mole equivalents of the ligands D-PY (Y = 1-4) the complexes RuCl2(D-P1)2 (1), RuCl2(D-P2)2 (4), RuCl2(D-P3)2 (5), or RuCl2(D-P4)2 (6), respectively, are formed. Similarly, treatment of OsCl2(PPh3)3 with D-P1 gives OsCl2(D-P1)2 (7). The single crystal X-ray structure determination of 1 reveals that each D-P1 ligand coordinates to ruthenium through phosphorus and the oxygen atom of the methoxyl group. Treatment of 1 with excess LiBr or LiI results in metathesis of the chloride ligands and RuBr2(D-P1)2 (2) or RuI2(D-P1)2 (3), respectively, are formed. Exposure of a solution of 1 to carbon monoxide results in the very rapid formation of RuCl2(CO)2(D-P1)2 (8), thereby demonstrating the ease with which the oxygen donors are displaced from the metal and hence the hemilabile nature of the two bidentate D-P1 ligands in 1. Preliminary studies indicate that 1-7 act as catalysts for the asymmetric hydrogenation reactions of acetophenone and 3-quinuclidinone to give the corresponding alcohols in generally high conversions but low enantiomeric excesses.

  4. Asymmetric Ruthenium(II and Osmium(II Complexes with New Bidentate Polyquinoline Ligands. Synthesis and NMR Characterization

    Directory of Open Access Journals (Sweden)

    Antonino Mamo

    2010-03-01

    Full Text Available A series of Ru(II and Os(II tris-chelate complexes with new bidentate 2-pyridylquinoline ligands have been synthesized and fully characterized by EA,1H-NMR and FAB-MS techniques. The new ligands are: L1 = 4-p-methoxyphenyl-6-bromo-2-(2′- pyridylquinoline (mphbr-pq and L2 = 4-p-hydroxyphenyl-6-bromo-2-(2′-pyridyl-quinoline (hphbr-pq. The complexes studied are: [Ru(bpy2L1](PF62 (C1, [Ru(bpy2L2](PF62 (C2, [Os(bpy2L1](PF62 (C3, [Os(bpy2L2](PF62 (C4 (bpy = 2,2′-bipyridine, [Ru(dmbpy2L1](PF62 (C5, [Ru(dmbpy2L2](PF62 (C6, [Os(dmbpy2L1](PF62 (C7, and [Os(dmbpy2L2](PF62 (C8 (dmbpy = 4,4′-dimethyl-2,2′-bipyridine. Moreover, new functionalized complexes C9-C12 were obtained by the basecatalyzed direct alkylation of C2, C4, C6, and C8 with 6-bromo-1-hexene. The complete assignment of the 1H-NMR spectra for the two new ligands (L1 and L2, and their Ru(II or Os(II complexes has been accomplished using a combination of one- and two-dimensional NMR techniques. The JH,H values have been determined for the majority of the resonances.

  5. Asymmetric ruthenium(II) and osmium(II) complexes with new bidentate polyquinoline ligands. Synthesis and NMR characterization.

    Science.gov (United States)

    Mamo, Antonino; Aureliano, Alessandro; Recca, Antonino

    2010-03-05

    A series of Ru(II) and Os(II) tris-chelate complexes with new bidentate 2-pyridylquinoline ligands have been synthesized and fully characterized by EA,1H-NMR and FAB-MS techniques. The new ligands are: L1 = 4-p-methoxyphenyl-6-bromo-2-(2'- pyridyl)quinoline (mphbr-pq) and L2 = 4-p-hydroxyphenyl-6-bromo-2-(2'-pyridyl)-quinoline (hphbr-pq). The complexes studied are: [Ru(bpy)2L1](PF6)2 (C1), [Ru(bpy)2L2](PF6)2 (C2), [Os(bpy)2L1](PF6)2 (C3), [Os(bpy)2L2](PF6)2 (C4) (bpy = 2,2'-bipyridine), [Ru(dmbpy)2L1](PF6)2 (C5), [Ru(dmbpy)2L2](PF6)2 (C6), [Os(dmbpy)2L1](PF6)2 (C7), and [Os(dmbpy)2L2](PF6)2 (C8) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine). Moreover, new functionalized complexes C9-C12 were obtained by the base-catalyzed direct alkylation of C2, C4, C6, and C8 with 6-bromo-1-hexene. The complete assignment of the 1H-NMR spectra for the two new ligands (L1 and L2), and their Ru(II) or Os(II) complexes has been accomplished using a combination of one- and two-dimensional NMR techniques. The JH,H values have been determined for the majority of the resonances.

  6. Monomeric Cu(Ⅱ) Complex Containing Chiral Phase-transfer Catalyst as Ligand and Its Asymmetrically Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

    QU Zhi-Rong; XIONG Ren-Gen

    2008-01-01

    The thermal treatment of CuCl2 with N-(4'-vinylbenzyl)cinchonidinitim chloride(L1)afforded a monomeric discrete homochiral copper(Ⅱ)complex N-4'-(vinylbenzyl)cinchonidinium trichlorocoprate(Ⅱ)(1).Their applications to the enantioselectively catalytic alkylation reaction of N-(diphenylmethylidene)glycine tert-butyl ester(3)show that the higher ee value observed in catalyst 1 than that in the corresponding free ligand L1 is probably due to the rigidity enhancement after the coordination of N atom of quinoline ring to the copper ion.

  7. Synthesis, spectroscopic characterization and antimicrobial activity of binuclear metal complexes of a new asymmetrical Schiff base ligand: DNA binding affinity of copper(II) complexes.

    Science.gov (United States)

    Shebl, Magdy

    2014-01-03

    The 1:1 condensation of o-acetoacetylphenol and 1,2-diaminopropane under condition of high dilution gives the mono-condensed Schiff base, (E)-3-(1-aminopropan-2-ylimino)-1-(2-hydroxyphenyl)butan-1-one. The mono-condensed Schiff base has been used for further condensation with isatin to obtain the new asymmetrical dicompartmental Schiff base ligand, (E)-3-(2-((E)-4-(2-hydroxyphenyl)-4-oxobutan-2-ylideneamino) propylimino)indolin-2-one (H3L) with a N2O3 donor set. Reactions of the ligand with metal salts give a series of new binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H and (13)C NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The analytical and spectroscopic tools showed that the complexes can be formulated as: [(HL)(VO)2(SO4)(H2O)]·4H2O, [(HL)Fe2Cl4(H2O)3]·EtOH, [(HL)Fe2(ox)Cl2(H2O)3]·2H2O, [(L)M2(OAc)(H2O)m]·nH2O; M=Co, Ni or Cu, m=4, 0 and n=2, 3, [(HL)Cu2Cl]Cl·6H2O and [(L)(UO2)2(OAc)(H2O)3]·6H2O. The metal complexes exhibited octahedral geometrical arrangements except copper complexes that exhibited tetrahedral geometries and uranyl complex in which the metal ion is octa-coordinated. The Schiff base and its metal complexes were evaluated for antimicrobial activity against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli) and fungi (Candida albicans and Aspergillus flavus). The ligand and some of its complexes were found to be biologically active. The DNA-binding properties of the copper complexes (6 and 7) have been investigated by electronic absorption, fluorescence and viscosity measurements. The results obtained indicate that these complexes bind to DNA via an intercalation binding mode with an intrinsic binding constant, Kb of 1.34×10(4) and 2.5×10(4) M(-1), respectively.

  8. 糖基含磷配体在不对称氢化反应中的应用%Application of Sugar-Based Phosphorus Ligands in Asymmetric Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    崔朋雷; 刘卉敏; 果秀敏; 张冬暖; 王彦恩; 王春

    2013-01-01

    There is a very important application for the asymmetric hydrogenation in the actual industrial production. Sugar is chiral natural product which widely exists in the nature. More and more attention was paid to the research of the chiral sugar's synthesis and application. Sugar derivatives, as chiral ligands, were widely used in asymmetric reactions and the relative research became a very active area in organic chemistry. The recent progress of sugar-based phosphorus-containing ligands that used in asymmetric hydrogenation is reviewed.%不对称氢化反应在实际工业生产中有非常重要的应用.糖类是广泛存在于自然界的手性天然产物,手性糖类化合物的合成与应用研究日益受到人们的关注,以糖类衍生物作为手性配体用于不对称反应已成为有机化学中非常活跃的研究领域.综述了糖基含磷配体用于不对称氢化反应的最新研究进展.

  9. Study on the Asymmetric Aminohydroxylation of Olefins Catalyzed by a Free Recoverable and Reusable Ligand%可回收手性配体催化烯烃不对称氨羟化反应研究

    Institute of Scientific and Technical Information of China (English)

    南鹏娟; 陈晶; 孙晓莉

    2011-01-01

    A reusable free cinchona alkaloid derivative ligand was applied to asymmetric aminohydroxylation (AA) of 5 five methyl cinnamates with 91%-96% e.e. and 52%-72% yields. In the AA reaction of methyl cinnamates,this ligand can be easily recovered and reused without any significant loss in its catalytic efficiency by two defferent methods. this ligand was applied to the catalytic asymmetric aminohydroxylation to produce enantioselective α-aminoacid esters.%一种可重复使用的非支载型金鸡纳生物碱衍生物配体与金属锇形成原位催化剂用于催化5种肉桂酸甲酯类烯烃的不对称氨羟化(AA)反应,表现了好的对映选择性(91%~96%)和反应活性(52%~72%).在以对甲基肉桂酸甲酯为底物的AA反应中,采用了两种不同的回收方法,均能有效地进行配体的回收和再利用,配体的催化活性和对映选择性基本保持不变.该手性配体用于催化AA反应,可以制备光学活性的α-氨基酸酯类化合物.

  10. In Pursuit of an Ideal C-C Bond-Forming Reaction: Development and Applications of the Hydrovinylation of Olefins.

    Science.gov (United States)

    Rajanbabu, T V

    2009-01-01

    Attempts to introduce the highly versatile vinyl group into other organic molecules in a chemo-, regio- and stereoselective fashion via catalytic activation of ethylene provided challenging opportunities to explore new ligand and salt effects in homogeneous catalysis. This review provides a personal account of the development of enantioselective reactions involving ethylene.

  11. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Montalvo-Gonzalez, Ruben [Universidad Autonoma de Nayarit, Tepic, Nay (Mexico). Unidad Academica de Ciencias Quimico Biologicas y Farmaceuticas; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy, E-mail: somanatha@sundown.sdsu.ed [Instituto Tecnologico de Tijuana, B.C. (Mexico). Centro de Graduados e Investigacion

    2010-07-01

    Two C{sub 2}-symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh{sup III}(Cp{sup *}) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  12. Synthesis, Characterization, and Crystal Structure of a Novel Copper(II) Complex with an Asymmetric Coordinated 2,2'-Bipyridine Derivative: A Model for the Associative Complex in the Ligand-Substitution Reactions of [Cu(tren)L](2+)?

    Science.gov (United States)

    Lu Zl, Zhong-lin; Duan Cy, Chun-ying; Tian Yp, Yu-peng; You Xz, Xiao-zeng; Huang Xy, Xiao-ying

    1996-04-10

    The titled compound, (tris(2-aminoethyl)amine)(4,5-diazafluoren-9-one) copper(II) perchlorate, [Cu(C(6)H(18)N(4))(C(11)H(6)N(2)O)(ClO(4))(2)], 1, has been designed, synthesized, and characterized. The electronic and ESR spectra are very different from those of [Cu(tren)L](2+) complexes where L is monodentate ligand. The X-ray analysis revealed that the complex crystallizes in the monoclinic space group P2(1)/c, with a = 10.726(6) Å, b = 14.921(7) Å, c = 14.649(4) Å, beta = 95.13(3) degrees, and Z = 4. The copper(II) ion is coordinated by four nitrogen atoms from tris(2-aminoethyl)amine (tren) and two nitrogen atoms from 4,5-diazafluoren-9-one (dzf) to form an unusual six-coordinate (4 + 1 + 1') geometry. The structure is very rare, and to our knowledge, it is the first example of an asymmetric bidentate phenanthroline derivative metal complex. The structure could be used as a model of the associative complex in the ligand-exchange and ligand-substitution reactions of [Cu(tren)L](2+) and the catalytic mechanisms of enzymes involving copper sites. From the electronic and variable-temperature ESR spectra in solution, the possible mechanism of these reactions has also been proposed. As a comparison, the complex [Cu(tren)(ImH)(ClO(4))(2)], 2, was also synthesized and characterized, where ImH is imidazole.

  13. New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones

    Directory of Open Access Journals (Sweden)

    Fuentes José A

    2012-12-01

    Full Text Available Abstract Enantioselective hydrogenation of ketones is a key reaction in organic chemistry. In the past, we have attempted to deal with some unsolved challenges in this arena by introducing chiral tridentate phosphine-diamine/Ru catalysts. New catalysts and new applications are presented here, including the synthesis of phosphine-amino-alcohol P,N,OH ligands derived from (R,S-1-amino-2-indanol, (S,S-1-amino-2-indanol and a new chiral P,N,N ligand derived from (R,R-1,2-diphenylethylenediamine. Ruthenium pre-catalysts of type [RuCl2(L(DMSO] were isolated and then examined in the hydrogenation of ketones. While the new P,N,OH ligand based catalysts are poor, the new P,N,N system gives up to 98% e.e. on substrates that do not react at all with most catalysts. A preliminary attempt at realising a new delta lactone synthesis by organocatalytic Michael addition between acetophenone and acrylonitrile, followed by asymmetric hydrogenation of the nitrile functionalised ketone is challenging in part due to the Michael addition chemistry, but also since Noyori pressure hydrogenation catalysts gave massively reduced reactivity relative to their performance for other acetophenone derivatives. The Ru phosphine-diamine system allowed quantitative conversion and around 50% e.e. The product can be converted into a delta lactone by treatment with KOH with complete retention of enantiomeric excess. This approach potentially offers access to this class of chiral molecules in three steps from the extremely cheap building blocks acrylonitrile and methyl-ketones; we encourage researchers to improve on our efforts in this potentially useful but currently flawed process.

  14. 2-(Methylamido)pyridine-Borane: A Tripod κ(3)-N,H,H Ligand in Trigonal Bipyramidal Rhodium(I) and Iridium(I) Complexes with an Asymmetric Coordination of Its BH3 Group.

    Science.gov (United States)

    Brugos, Javier; Cabeza, Javier A; García-Álvarez, Pablo; Kennedy, Alan R; Pérez-Carreño, Enrique; Van der Maelen, Juan F

    2016-09-06

    The complexes [M(κ(3)-N,H,H-mapyBH3)(cod)] (M = Rh, Ir; HmapyBH3 = 2-(methylamino)pyridine-borane; cod = 1,5-cyclooctadiene), which contain a novel anionic tripod ligand coordinated to the metal atom through the amido N atom and through two H atoms of the BH3 group, were prepared by treating the corresponding [M2(μ-Cl)2(cod)2] (M = Rh, Ir) precursor with K[mapyBH3]. X-ray diffraction studies and a theoretical Quantum Theory of Atoms in Molecules analysis of their electron density confirmed that the metal atoms of both complexes are in a very distorted trigonal bipyramidal coordination environment, in which two equatorial sites are asymmetrically spanned by the H-B-H fragment. While both 3c-2e BH-M interactions are more κ(1)-H (terminal σ coordination of the B-H bond) than κ(2)-H,B (agostic-type coordination of the B-H bond), one BH-M interaction is more agostic than the other, and this difference is more marked in the iridium complex than in the rhodium one. This asymmetry is not evident in solution, where the cod ligand and the BH3 group of these molecules participate in two concurrent dynamic processes of low activation energies (variable-temperature NMR and density functional theory studies), namely, a rotation of the cod ligand that interchanges its two alkene fragments (through a square pyramidal transition state) and a rotation of the BH3 group about the B-N bond that equilibrates the three B-H bonds (through a square planar transition state). While the cod rotation has similar activation energy in 2 and 3, the barrier to the BH3 group rotation is higher in the iridium complex than in the rhodium one.

  15. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Harden, Adrian; Wyatt, Paul

    1996-01-01

    A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines)]. In the b......A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines...

  16. Rh2 (S-1,2-NTTL)4 : A novel Rh2 (S-PTTL)4 analog with lower ligand symmetry for asymmetric synthesis of chiral cyclopropylphosphonates.

    Science.gov (United States)

    Adly, Frady G; Maddalena, Johncarlo; Ghanem, Ashraf

    2014-11-01

    A new series of dirhodium(II) tetracarboxylate was derived from N-1,2-naphthaloyl-(S)-amino acid ligands. In terms of enantioselectivity, Rh2 (S-1,2-NTTL)4 () derived from N-1,2-naphthaloyl-(S)-tert-leucine, was the best-performing catalyst among the new series in the enantioselective synthesis of cyclopropylphosphonate derivatives (up to >99% enantiomeric excess). A predictive model was proposed to justify the observed high enantiomeric induction exhibited by Rh2 (S-1,2-NTTL)4 with donor-acceptor phosphonate carbenoids.

  17. Syntheses, crystal structures and DNA-binding studies of Cu(II) and Zn(II) complexes bearing asymmetrical aroylhydrazone ligand

    Science.gov (United States)

    Li, Yueqin; Yang, Zhiwei; Zhou, Minya; He, Jing; Wang, Xuehong; Wu, Yanlong; Wang, Zhuye

    2017-02-01

    Zn(II) and Cu(II) complexes with benzophenone benzoyl hydrazone (HBBH) and benzophenone salicylylhydrazone (HBSH) have been synthesized and characterized by different physico-chemical and spectroscopic techniques (UV-vis, IR and NMR). The molecular structures of these complexes [Zn(BBH)2, Cu(BBH)2 and Cu(BSH)2Cl2H2O] have also been determined by single X-ray diffraction technique. In Zn(BBH)2 and Cu(BBH)2 complexes, each ligand coordinates to metal through enol tautomeric form by azomethine-N and carbonylate-O resulting a 4-coordinate distorted tetrahedral geometry. While in Cu(BSH)2Cl2H2O, each ligand coordinates to metal through keto tautomeric form resulting distorted octahedral geometry in which two chlorine atoms occupy the axial positions. The DNA interaction propensity of the complexes with Herring sperm DNA, studied at physiological pH by spectrophotometric, spectrofluorometric, viscometric techniques and cyclic voltammetry, revealed intercalation as the possible binding mode. Fascinatingly, Cu(BSH)2Cl2H2O was found to exhibit greater binding strength than the others. A strong hyperchromism effect and a slight red shift were exhibited by all complexes. The intrinsic binding constants are of moderate values and are about 3.28 × 104 M-1, 4.73 × 104 M-1 and 5.80 × 104 M-1, respectively. Cyclic voltammetry studies of the complexes binding with DNA indicate quasireversible oxidation and reduction potentials. The results suggest that the binding affinity of complexes lies in the order Cu(BSH)2Cl2H2O > Cu(BBH)2 > Zn(BBH)2.

  18. Asymmetric Synthesis and Binding Study of New Long-Chain HPA-12 Analogues as Potent Ligands of the Ceramide Transfer Protein CERT.

    Science.gov (United States)

    Ďuriš, Andrej; Daïch, Adam; Santos, Cécile; Fleury, Laurence; Ausseil, Frédéric; Rodriguez, Frédéric; Ballereau, Stéphanie; Génisson, Yves; Berkeš, Dušan

    2016-05-01

    A series of 12 analogues of the Cer transfer protein (CERT) antagonist HPA-12 with long aliphatic chains were prepared as their (1R,3S)-syn and (1R,3R)-anti stereoisomers from pivotal chiral oxoamino acids. The enantioselective access to these intermediates as well as their ensuing transformation relied on a practical crystallization-induced asymmetric transformation (CIAT) process. Sonogashira coupling followed by triple bond reduction and thiophene ring hydrodesulfurization (HDS) into the corresponding alkane moieties was then implemented to complete the synthetic routes delivering the targeted HPA-12 analogues in concise 4- to 6-step reaction sequences. Ten compounds were evaluated regarding their ability to bind to the CERT START domain by using the recently developed time-resolved FRET-based homogeneous (HTR-FRET) binding assay. The introduction of a lipophilic appendage on the phenyl moiety led to an overall 10- to 1000-fold enhancement of the protein binding, with the highest effect being observed for a n-hexyl residue in the meta position. The importance of the phenyl ring for the activity was indicated by the reduced potency of the 3-deoxyphytoceramide aliphatic analogues. The 1,3-syn stereoisomers were systematically more potent than their 1,3-anti analogues. In silico studies were used to rationalized these trends, leading to a model of protein recognition coherent with the stronger binding of (1R,3S)-syn HPAs.

  19. Structural, spectroscopic, and electrochemical behavior of trans-phenolato cobalt(III) complexes of asymmetric NN'O ligands as archetypes for metallomesogens.

    Science.gov (United States)

    Shakya, Rajendra; Imbert, Camille; Hratchian, Hrant P; Lanznaster, Mauricio; Heeg, Mary Jane; McGarvey, Bruce R; Allard, Marco; Schlegel, H Bernhard; Verani, Claudio N

    2006-06-07

    In order to understand and predict structural, redox, magnetic, and optical properties of more complex and potentially mesogenic electroactive compounds such as [Co(III)(L(t-BuLC))2]ClO4 (1), five archetypical complexes of general formula [Co(III)(L(RA))2]ClO4, where R = H (2), tert-butyl (3), methoxy (4), nitro (5), and chloro (6), were obtained and studied by means of several spectrometric, spectroscopic, and electrochemical methods. The complexes 2, 4, and 6 were characterized by single-crystal X-ray diffraction, and show the metal center in an approximate D2h symmetry. Experimental results support the fact that the electron donating or withdrawing nature of the phenolate-appended substituents changes dramatically the redox and spectroscopic properties of these compounds. The 3d6 electronic configuration of the metal ion dominates the overall geometry adopted by these compounds with the phenolate rings occupying trans positions to one another. Formation of phenoxyl radicals has been observed for 1, 3, and 6, but irreversible ligand oxidation takes place upon bulk electrolysis. These data were compared to detailed B3LYP/6-31G (d)-level computational calculations and have been used to account for the results observed. A comparison between compound 1 and archetype 3, validates the approach of using archetypical models to study metal-containing soft materials.

  20. Monoterpenos di-hidroxilados e hidróxi-nitrogenados 1,2 e 1,3 como ligantes quirais em reação de reformatsky assimétrica 1,2- and 1,3-dihydroxylated and hydroxynitrogenated monoterpenes as chiral ligands in the asymmetric reformatsky reaction

    Directory of Open Access Journals (Sweden)

    Carlos Magno R. Ribeiro

    2008-01-01

    Full Text Available This study describes the use of three (--alpha-pinene derivatives, one diol-1,2 [(--(1R, 2R, 3S, 5R-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol 4] and two piridine-hydroxy derivatives [(+-(1R,2S,3R,5S-2,6,6-trimethyl-3-(2-pyridinylmethylbicyclo[3.1.1]heptan-3-ol 7 and (--(1R,2S,3R,5S-2,6,6-trimethyl-3-[2-(2-pyridinyl ethyl]bicyclo[3.1.1]heptan-3-ol 8]; one diol-1,3 [(--(1S,2R,5S-2-(1-hydroxy-1-methylethyl-5-methylcyclohexanol 5] derived from (+-isopulegol 2 and one diol-1,3 [(+-(1R,2R,5R-2-(1-hydroxy-1-methylethyl-5-methylcyclohexanol 6] derived from (+-neo-isopulegol 3, as ligands in the asymmetric Reformatsky reaction. The best enantiomeric excess of beta-hydroxy ester obtained in the Reformatsky asymmetric reaction was 18% using ligand 6, and the chemical yield of the reactions was 65% on average.

  1. 1,2- and 1,3-dihydroxylated and hydroxynitrogenated monoterpenes as chiral ligands in the asymmetric reformatsky reaction; Monoterpenos di-hidroxilados e hidroxi-nitrogenados 1,2 e 1,3 como ligantes quirais em reacao de reformatsky assimetrica

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Carlos Magno R.; Morita, Cristina M.; Maia, Monica P. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Inst. de Quimica. Dept. de Quimica Organica]. E-mail: gqocmrr@vm.uff.br

    2008-07-01

    This study describes the use of three (-)-{alpha}-pinene derivatives, one diol-1,2 [(-)- (1R, 2R, 3S, 5R)-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol 4] and two pyridine-hydroxy derivatives [(+)-(1R,2S,3R,5S)-2,6,6- trimethyl-3-(2-pyridinylmethyl)bicyclo[3.1.1]heptane-3-ol 7 and (-)-(1R,2S,3R,5S)-2,6,6-trimethyl-3-[2-(2-pyridinyl) ethyl]bicyclo[3.1.1]heptane-3-ol 8]; one diol-1,3 [(-)-(1S,2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol 5] derived from (+)-isopulegol 2 and one diol-1,3 [(+)-(1R,2R,5R)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol 6] derived from (+)-neoisopulegol 3, as ligands in the asymmetric Reformatsky reaction. The best enantiomeric excess of {beta}-hydroxy ester obtained in the Reformatsky asymmetric reaction was 18% using ligand 6, and the chemical yield of the reactions was 65% on average. (author)

  2. ASYMMETRIC HYDROSILYLATION CATALYZED BY POLYMER—SUPPORTED THIAZOLIDINE RHODIUM CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    LEIYanohui; LIHong; 等

    1999-01-01

    Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalysts was conducted.Almost the same optical yields have been obtained when comb-shaped polymeric ligands and their corresponding monomer complexed rhodium cataltysts were used to asymmetric hydrosilylation of acetophenone.Optical yield of chiral 1-methylbenzyl alcohol reaches as high as 71.5%.Temperature dependence of enantioselective hydrosilylation of acetophenone was discussed.

  3. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG XiaoMing

    2001-01-01

    @@ Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.

  4. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

    Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.  ……

  5. 苯乙胺衍生的手性膦-亚磷酰胺酯配体在Rh-催化α-烯醇酯膦酸酯的不对称氢化反应中的应用%Rh-Catalyzed Asymmetric Hydrogenation of α-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine-Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)

    胡娟; 王道永; 郑卓; 胡向平

    2012-01-01

    A series of phosphine-phosphoramidite ligands derived from commercially available,inexpensive chiral 1-phenylethylamine were employed in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates.The results indicated that the ligand(Sc,Sa)-2b bearing a Me-group on amino moiety exhibited similar enantioselectivity but superior catalytic activity to(Rc,Ra)-THNAPhos.Excellent enantioselectivities(up to 99% ee) and high catalytic activity(S/C up to 5 000) have been achieved in the hydrogenation of various β-alkyl and β-aryl substituted substrates,demonstrating the high potential of this phosphine-phosphoramidite ligand in the preparation of optically active α-hydroxyphosphonates%将苯乙胺衍生的手性膦-亚磷酰胺酯配体应用在Rh-催化α-烯醇酯膦酸酯的不对称氢化反应中,考察了配体结构及反应条件对反应结果的影响,并在优化的条件下研究了各种底物的适用范围,产物的对映选择性最高〉99%ee.

  6. Ruthenium(II) and osmium(II) polypyridyl complexes of an asymmetric pyrazinyl- and pyridinyl-containing 1,2,4-triazole based ligand. Connectivity and physical properties of mononuclear complexes

    NARCIS (Netherlands)

    Browne, Wesley R.; O’Connor, Christine M.; Hughes, Helen P.; Hage, Ronald; Walter, Olaf; Doering, Manfred; Gallagher, John F.; Vos, Johannes G.

    2002-01-01

    The synthesis, purification and characterisation of two coordination isomers of ruthenium(II) and osmium (II) complexes containing the ligand 3-(pyrazin-2'-yl)-5-(pyridin-2"-yl)-1,2,4-triazole (Hppt) are described. The X-ray and molecular structure of the complex [Ru(bipy)(2) (ppt)] PF6.CH3OH (1a) i

  7. 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

  8. 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.

  9. Privileged chiral ligands and catalysts

    CERN Document Server

    Zhou, Qi-Lin

    2011-01-01

    This ultimate ""must have"" and long awaited reference for every chemist working in the field of asymmetric catalysis starts with the core structure of the catalysts, explaining why a certain ligand or catalyst is so successful. It describes in detail the history, the basic structural characteristics, and the applications of these ""privileged catalysts"". A novel concept that gives readers a much deeper insight into the topic.

  10. Looking for a synergic effect between NHCs and chiral P-ligands.

    Science.gov (United States)

    Toselli, Nicolas; Martin, David; Buono, Gérard

    2008-04-03

    The issue of the added value of NHCs in asymmetric catalysis with respect to trusted chiral P-ligands was addressed: considering a prototypical asymmetric allylic alkylation reaction as a model, the association of a priori inhibiting and achiral NHCs with modular P-ligand resulted in enhancement of er up to 508% and increased rates.

  11. Copper(II) coordination chain complex with the 2,5-bis(2-pyridyl)-1,3,4-thiadiazole ligand and an asymmetric μ2-1,1-azido double-bridged: Synthesis, crystal structure and magnetic properties

    Science.gov (United States)

    Laachir, Abdelhakim; Guesmi, Salaheddine; Saadi, Mohamed; El Ammari, Lahcen; Mentré, Olivier; Vezin, Hervé; Colis, Silviu; Bentiss, Fouad

    2016-11-01

    A new asymmetric μ2-1,1-azido double bridged cooper (II), with 2,5-bis(2-pyridyl)-1,3,4-thiadiazole (L), has been synthesized and characterized using single crystal X-ray diffraction, FT-IR, UV-Visible spectroscopic and magnetic measurements. The asymmetric unit of the title compound contains half molecule of formula, C12H8CuN10S, which crystallizes in the triclinic system, space group P 1 bar , with a = 6.5916 (4)Å, b = 10.6905 (7) Å, c = 11.5037 (7) Å, α = 106.508 (3)°, β = 105.538 (3)°, γ = 90.233 (4)°, V = 745.99 (8) Å3 and Z = 2. The structure consists of two [CuN5] prismatic polyhedra linked together by edge-sharing to build up a [Cu2N8] dimer arranged in chain. The connectivity along the chain is performed by Nsbnd N edge sharing between dimers. In the crystal, the molecules are linked together by Csbnd H⋯N hydrogen bonds and by π---π interactions between parallel pyridyl rings of neighboring molecules. The interpretation of FT-IR and UV-Vis spectra is consistent with the crystal structure determined by X-ray diffraction. The magnetic properties of the complex confirm the picture of an alternated … Cu-J1-Cu ….J2 … Cu-J1-Cu … magnetic chains. We found in the dimers weak antiferromagnetic exchange interactions J1/k = -5.9 (1) k and between them J2/k = -2.3 k.

  12. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG XuMu

    2001-01-01

    @@ Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals

  13. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG; XuMu

    2001-01-01

    Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals  ……

  14. Ligand placement based on prior structures: the guided ligand-replacement method

    Energy Technology Data Exchange (ETDEWEB)

    Klei, Herbert E. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Bristol-Myers Squibb, Princeton, NJ 08543-4000 (United States); Moriarty, Nigel W., E-mail: nwmoriarty@lbl.gov; Echols, Nathaniel [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Terwilliger, Thomas C. [Los Alamos National Laboratory, Los Alamos, NM 87545-0001 (United States); Baldwin, Eric T. [Bristol-Myers Squibb, Princeton, NJ 08543-4000 (United States); Natural Discovery LLC, Princeton, NJ 08542-0096 (United States); Pokross, Matt; Posy, Shana [Bristol-Myers Squibb, Princeton, NJ 08543-4000 (United States); Adams, Paul D. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); University of California at Berkeley, Berkeley, CA 94720-1762 (United States)

    2014-01-01

    A new module, Guided Ligand Replacement (GLR), has been developed in Phenix to increase the ease and success rate of ligand placement when prior protein-ligand complexes are available. The process of iterative structure-based drug design involves the X-ray crystal structure determination of upwards of 100 ligands with the same general scaffold (i.e. chemotype) complexed with very similar, if not identical, protein targets. In conjunction with insights from computational models and assays, this collection of crystal structures is analyzed to improve potency, to achieve better selectivity and to reduce liabilities such as absorption, distribution, metabolism, excretion and toxicology. Current methods for modeling ligands into electron-density maps typically do not utilize information on how similar ligands bound in related structures. Even if the electron density is of sufficient quality and resolution to allow de novo placement, the process can take considerable time as the size, complexity and torsional degrees of freedom of the ligands increase. A new module, Guided Ligand Replacement (GLR), was developed in Phenix to increase the ease and success rate of ligand placement when prior protein–ligand complexes are available. At the heart of GLR is an algorithm based on graph theory that associates atoms in the target ligand with analogous atoms in the reference ligand. Based on this correspondence, a set of coordinates is generated for the target ligand. GLR is especially useful in two situations: (i) modeling a series of large, flexible, complicated or macrocyclic ligands in successive structures and (ii) modeling ligands as part of a refinement pipeline that can automatically select a reference structure. Even in those cases for which no reference structure is available, if there are multiple copies of the bound ligand per asymmetric unit GLR offers an efficient way to complete the model after the first ligand has been placed. In all of these applications, GLR

  15. The applications of Schiff bases in Ti-catalyzed asymmetric alkynylation of aldehydes

    Institute of Scientific and Technical Information of China (English)

    Xian Jia; Lu Yin; Xuan Zhao; Xing Shu Li

    2007-01-01

    Sciff bases 1 and 2, which were derived from chiral aminoalcohols, were used as ligands in Ti-catalyzed asymmetric alkynylation of aldehydes. Good enantioselectivities (up to 88% ee) and high chemical yields (80-90 %) were obtained.

  16. Synthesis and application of chiral N,N′-dialkylated cyclohexanediamine for asymmetric hydrogenation of aryl ketones

    Institute of Scientific and Technical Information of China (English)

    Meng Lin Ma; Chuan Hong Ren; Ya Jing Lv; Hua Chen; Xian Jun Li

    2011-01-01

    Chiral N,N′-dialkylated cyclohexanediamine derived ligands have been synthesized and used in the asymmetric hydrogenation of aryl ketones. Optically active alcohols with up to 90% enantiomeric excess were obtained in high yields.

  17. Monodentate phosphoramidites : A breakthrough in rhodium-catalysed asymmetric hydrogenation of olefins

    NARCIS (Netherlands)

    Berg, Michel van den; Minnaard, Adriaan J.; Haak, Robert M.; Leeman, Michel; Schudde, Ebe P.; Meetsma, Auke; de Vries, Andre H.M.; Maljaars, C. Elizabeth P.; Willans, Charlotte E.; Hyett, David; Boogers, Jeroen A.F.; Henderickx, Hubertus; Feringa, Ben L.

    2003-01-01

    Monodentate phosphoramidites based on BINOL or substituted BINOL are excellent ligands for the rhodium-catalysed asymmetric hydrogenation of olefins. Very high enantioselectivities were obtained with MonoPhos (7a) the simplest member of this class, a ligand that is prepared in a single step from BIN

  18. Preparation of New Chiral Ferroceny Phosphine Ligands and Their Application to Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    S.Fukuzawa

    2007-01-01

    1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl phosphine ligands have already been reported,it is still an challenging subject tocreate new ferrocenyl phosphine ligands in order to cover asymmetric reactions in which conventional ligands do not effectively work[1].We happned to discover that 1,5-dilithiation of o-TMS blocked ferrocene 1 pr...

  19. 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.

  20. Asymmetric synthesis of gem-diaryl substituted cyclic sulfamidates and sulfamides by rhodium-catalyzed arylation of cyclic ketimines.

    Science.gov (United States)

    Nishimura, Takahiro; Ebe, Yusuke; Fujimoto, Hiroto; Hayashi, Tamio

    2013-06-18

    Asymmetric addition of arylboronates to aryl-substituted cyclic ketimines proceeded in the presence of a rhodium catalyst coordinated with a chiral diene ligand to give high yields of sulfamidates and sulfamides with high enantioselectivity (up to 99% ee).

  1. Asymmetrical international attitudes

    NARCIS (Netherlands)

    Van Oudenhoven, JP; Askevis-Leherpeux, F; Hannover, B; Jaarsma, R; Dardenne, B

    2002-01-01

    In general, attitudes towards nations have a fair amount of reciprocity: nations either like each other are relatively indifferent to each other or dislike each other Sometimes, however international attitudes are asymmetrical. In this study, we use social identity theory in order to explain asymmet

  2. 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.

  3. Asymmetric catalysis with helical polymers

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    2011-01-01

    Inspired by nature, the use of helical biopolymer catalysts has emerged over the last years as a new approach to asymmetric catalysis. In this Concept article the various approaches and designs and their application in asymmetric catalysis will be discussed.

  4. Structural Basis of Cooperative Ligand Binding by the Glycine Riboswitch

    OpenAIRE

    Butler, Ethan B.; Xiong, Yong; Wang, Jimin; Strobel, Scott A.

    2011-01-01

    The glycine riboswitch regulates gene expression through the cooperative recognition of its amino acid ligand by a tandem pair of aptamers. A 3.6Å crystal structure of the tandem riboswitch from the glycine permease operon of Fusobacterium nucleatum reveals the glycine binding sites and an extensive network of interactions, largely mediated by asymmetric A-minor contacts, that serve to communicate ligand binding status between the aptamers. These interactions provide a structural basis for ho...

  5. Asymmetric information and economics

    Science.gov (United States)

    Frieden, B. Roy; Hawkins, Raymond J.

    2010-01-01

    We present an expression of the economic concept of asymmetric information with which it is possible to derive the dynamical laws of an economy. To illustrate the utility of this approach we show how the assumption of optimal information flow leads to a general class of investment strategies including the well-known Q theory of Tobin. Novel consequences of this formalism include a natural definition of market efficiency and an uncertainty principle relating capital stock and investment flow.

  6. Asymmetric extractions in orthodontics

    OpenAIRE

    Camilo Aquino Melgaço; Mônica Tirre de Souza Araújo

    2012-01-01

    INTRODUCTION: Extraction decisions are extremely important in during treatment planning. In addition to the extraction decision orthodontists have to choose what tooth should be extracted for the best solution of the problem and the esthetic/functional benefit of the patient. OBJECTIVE: This article aims at reviewing the literature relating the advantages, disadvantages and clinical implications of asymmetric extractions to orthodontics. METHODS: Keywords were selected in English and Portugue...

  7. DIFLUORPHOS and SYNPHOS in asymmetric catalysis: Synthetic applications

    Indian Academy of Sciences (India)

    Sebastien Prevost; Tahar Ayad; Jean-Pierre Genet; Phannarath Phansavath; Virginie Ratovelomanana-Vidal

    2014-03-01

    Enantiomerically pure diphosphines play an important role in various homogeneous metalcatalyzed asymmetric reactions. Over the last few years, our group has been involved in the design and synthesis of atropisomeric ligands named SYNPHOS and DIFLUORPHOS with complementary stereoelectronic properties. This paper shows the high catalytic performances of DIFLUORPHOS, SYNPHOS and SYNPHOS analogues for some C-H and C-C bond forming processes as well as for the synthesis of biorelevant targets.

  8. Synthesis of antidepressant duloxetine via asymmetric transfer hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Shan Zhen He; Xue Ming Li; Jia Dai; Ming Yan

    2008-01-01

    Antidepressant duloxetine (1) was prepared via asymmetric transfer hydrogenation of 3-(dimethylamino)-1-(thiophen-2-yl)propan-1-one (3). The Ru(Ⅱ), Rh(Ⅲ) and Ir(Ⅲ) complexes of several chiral ligands were examined as the catalyst and(S,S)-N-tosyl-1,2-diphenyl ethylenediamine (TsDPEN)-Ru(Ⅱ) complex was found to provide good yield and excellent enantios-electivity.

  9. 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.

  10. Asymmetric extractions in orthodontics

    Directory of Open Access Journals (Sweden)

    Camilo Aquino Melgaço

    2012-04-01

    Full Text Available INTRODUCTION: Extraction decisions are extremely important in during treatment planning. In addition to the extraction decision orthodontists have to choose what tooth should be extracted for the best solution of the problem and the esthetic/functional benefit of the patient. OBJECTIVE: This article aims at reviewing the literature relating the advantages, disadvantages and clinical implications of asymmetric extractions to orthodontics. METHODS: Keywords were selected in English and Portuguese and the EndNote 9 program was used for data base search in PubMed, Web of Science (WSc and LILACS. The selected articles were case reports, original articles and prospective or retrospective case-control studies concerning asymmetrical extractions of permanent teeth for the treatment of malocclusions. CONCLUSION: According to the literature reviewed asymmetric extractions can make some specific treatment mechanics easier. Cases finished with first permanent molars in Class II or III relationship in one or both sides seem not to cause esthetic or functional problems. However, diagnosis knowledge and mechanics control are essential for treatment success.

  11. P-chiral phosphine-sulfonate/palladium-catalyzed asymmetric copolymerization of vinyl acetate with carbon monoxide.

    Science.gov (United States)

    Nakamura, Akifumi; Kageyama, Takeharu; Goto, Hiroki; Carrow, Brad P; Ito, Shingo; Nozaki, Kyoko

    2012-08-01

    Utilization of palladium catalysts bearing a P-chiral phosphine-sulfonate ligand enabled asymmetric copolymerization of vinyl acetate with carbon monoxide. The obtained γ-polyketones have head-to-tail and isotactic polymer structures. The origin of the regio- and stereoregularities was elucidated by stoichiometric reactions of acylpalladium complexes with vinyl acetate. The present report for the first time demonstrates successful asymmetric coordination-insertion (co)polymerization of vinyl acetate.

  12. Unravelling Thiol’s Role in Directing Asymmetric Growth of Au Nanorod–Au Nanoparticle Dimers

    KAUST Repository

    Huang, Jianfeng

    2015-12-15

    Asymmetric nanocrystals have practical significance in nanotechnologies but present fundamental synthetic challenges. Thiol ligands have proven effective in breaking the symmetric growth of metallic nanocrystals but their exact roles in the synthesis remain elusive. Here, we synthesized an unprecedented Au nanorod-Au nanoparticle (AuNR-AuNP) dimer structure with the assistance of a thiol ligand. On the basis of our experimental observations, we unraveled for the first time that the thiol could cause an inhomogeneous distribution of surface strains on the seed crystals as well as a modulated reduction rate of metal precursors, which jointly induced the asymmetric growth of monometallic dimers. © 2015 American Chemical Society.

  13. 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

  14. Asymmetric flow networks

    OpenAIRE

    Olaizola Ortega, María Norma; Valenciano Llovera, Federico

    2012-01-01

    This paper provides a new model of network formation that bridges the gap between the two benchmark models by Bala and Goyal, the one-way flow model, and the two-way flow model, and includes both as particular extreme cases. As in both benchmark models, in what we call an "asymmetric flow" network a link can be initiated unilaterally by any player with any other, and the flow through a link towards the player who supports it is perfect. Unlike those models, in the opposite direction there is ...

  15. Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

    KAUST Repository

    Benhamou, Laure

    2014-01-13

    PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

  16. Catalytic Enantioselective Aryl Transfer to Aldehydes Using Chiral 2,2’-Bispyrrolidine-Based Salan Ligands

    Directory of Open Access Journals (Sweden)

    Yixiang Cheng

    2011-04-01

    Full Text Available Chiral C2-symmetric diamines have emerged as versatile auxiliaries or ligands in numerous asymmetric transformations. Chiral 2,2’-bispyrrolidine-based salan ligands were prepared and applied to the asymmetric aryl transfer to aldehydes with arylboronic acids as the source of transferable aryl groups. The corresponding diarylmethanols were obtained in high yields with moderate to good enantioselectivitives of up to 83% ee.

  17. Enantiopure inherently chiral calix[4]arene derivatives containing quinolin-2-yl-methanol moiety:Synthesis and application in the catalytic asymmetric addition of diethylzinc to benzaldehyde

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A series of novel N,O-type chiral ligands derived from enantiopure inherently chiral calix[4]arenes containing quinolin-2-yl-methanol moiety in the cone or partialcone conformation have been synthe-sized and characterized. Moreover,they have been applied to the catalytic asymmetric addition of diethylzinc to benzaldehyde,which represents the first example that the inherently chiral calixarene can be used as the chiral ligands for the catalytic asymmetric synthesis.

  18. Additive Effects on Asymmetric Catalysis.

    Science.gov (United States)

    Hong, Liang; Sun, Wangsheng; Yang, Dongxu; Li, Guofeng; Wang, Rui

    2016-03-23

    This review highlights a number of additives that can be used to make asymmetric reactions perfect. Without changing other reaction conditions, simply adding additives can lead to improved asymmetric catalysis, such as reduced reaction time, improved yield, or/and increased selectivity.

  19. The asymmetric sandwich theorem

    CERN Document Server

    Simons, Stephen

    2011-01-01

    We discuss the asymmetric sandwich theorem, a generalization of the Hahn-Banach theorem. As applications, we derive various results on the existence of linear functionals that include bivariate, trivariate and quadrivariate generalizations of the Fenchel duality theorem. Most of the results are about affine functions defined on convex subsets of vector spaces, rather than linear functions defined on vector spaces. We consider both results that use a simple boundedness hypothesis (as in Rockafellar's version of the Fenchel duality theorem) and also results that use Baire's theorem (as in the Robinson-Attouch-Brezis version of the Fenchel duality theorem). This paper also contains some new results about metrizable topological vector spaces that are not necessarily locally convex.

  20. 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.

  1. Asymmetric organic/metal(oxide) hybrid nanoparticles: synthesis and applications.

    Science.gov (United States)

    He, Jie; Liu, Yijing; Hood, Taylor C; Zhang, Peng; Gong, Jinlong; Nie, Zhihong

    2013-06-21

    Asymmetric particles (APs) with broken centrosymmetry are of great interest, due to the asymmetric surface properties and diverse functionalities. In particular, organic/metal(oxide) APs naturally combine the significantly different and complementary properties of organic and inorganic species, leading to their unique applications in various fields. In this review article, we highlighted recent advances in the synthesis and applications of organic/metal(oxide) APs. This type of APs is grounded on chemical or physical interactions between metal(oxide) NPs and organic small molecular or polymeric ligands. The synthetic methodologies were summarized in three categories, including the selective surface modifications, phase separation of mixed ligands on the surface of metal(oxide) NPs, and direct synthesis of APs. We further discussed the unique applications of organic/metal(oxide) APs in self-assembly, sensors, catalysis, and biomedicine, as a result of the distinctions between asymmetrically distributed organic and inorganic components. Finally, challenges and future directions are discussed in an outlook section.

  2. Directional Notch trafficking in Sara endosomes during asymmetric cell division in the spinal cord.

    Science.gov (United States)

    Kressmann, Sabine; Campos, Claudia; Castanon, Irinka; Fürthauer, Maximilian; González-Gaitán, Marcos

    2015-03-01

    Asymmetric division of neural precursor cells contributes to the generation of a variety of neuronal types. Asymmetric division is mediated by the asymmetric inheritance of fate determinants by the two daughter cells. In vertebrates, asymmetric fate determinants, such as Par3 and Mib, are only now starting to be identified. Here we show that, during mitosis of neural precursors in zebrafish, directional trafficking of Sara endosomes to one of the daughters can function as such a determinant. In asymmetric lineages, where one daughter cell becomes a neuron (n cell) whereas the other divides again to give rise to two neurons (p cell), we found that the daughter that inherits most of the Sara endosomes acquires the p fate. Sara endosomes carry an endocytosed pool of the Notch ligand DeltaD, which is thereby itself distributed asymmetrically. Sara and Notch are both essential for cell fate assignation within asymmetric lineages. Therefore, the Sara endosome system determines the fate decision between neuronal differentiation and mitosis in asymmetric lineages and thereby contributes to controlling the number of neural precursors and differentiated neurons during neurogenesis in a vertebrate.

  3. Rhodium-catalyzed asymmetric ring opening of azabenzonorbornadiene with substituted piperazine nucleophiles

    Institute of Scientific and Technical Information of China (English)

    Lei Xie; Ding Qiao Yang; Shuang Qi Zhao; Huan Wang; Li Hua Liang; Ren Shi Luo

    2007-01-01

    We have developed an asymmetric ring opening reaction of azabenzonorbornadiene with substituted piperazine. By increasing the amount of catalyst (from 2.5 to 5%) and ligands (5 to 10%) as well as addition of ammonium iodide, the products can be obtained in high yield and the reaction time shortened dramatically, but the ee values were rather low.

  4. Synthesis of Versatile Building Blocks through Asymmetric Hydrogenation of Functionalized Itaconic Acid Mono-Esters

    NARCIS (Netherlands)

    Hekking, Koen F.W.; Lefort, Laurent; Vries, André H.M. de; Delft, Floris L. van; Schoemaker, Hans E.; Vries, Johannes G. de; Rutjes, Floris P.J.T.

    2008-01-01

    The rhodium-catalyzed asymmetric hydrogenation of several β-substituted itaconic acid mono-esters, using a library of monodentate phosphoramidite and phosphite ligands is described. Two β-alkyl-substituted substrates were readily hydrogenated by the rhodium complex Rh(COD)2BF4 in combination with (S

  5. Copper-catalyzed asymmetric allylic substitution reactions with organozinc and Grignard reagents

    NARCIS (Netherlands)

    Geurts, Koen; Fletcher, Stephen P.; van Zijl, Anthoni W.; Minnaard, Adriaan J.; Feringa, Ben L.; Bignall, H. E.; Jauncey, D. L.; Lovell, J. E. J.; Tzioumis, A. K.; Kedziora-Chudczer, L. L.; MacQuart, J. P.; Tingay, S. J.; Rayner, D. P.; Clay, R. W.

    2008-01-01

    Asymmetric allylic alkylations (AAAs) are among the most powerful C-C bond-forming reactions. We present a brief overview of copper-catalyzed AAAs with organometallic reagents and discuss our own contributions to this field. Work with zinc reagents and phosphoramidite ligands provided a framework fo

  6. Asymmetric Gepner Models (Revisited)

    CERN Document Server

    Gato-Rivera, B

    2010-01-01

    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 th...

  7. Magnetically Modified Asymmetric Supercapacitors Project

    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....

  8. 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

  9. On Asymmetric Quantum MDS Codes

    CERN Document Server

    Ezerman, Martianus Frederic; Ling, San

    2010-01-01

    Assuming the validity of the MDS Conjecture, the weight distribution of all MDS codes is known. Using a recently-established characterization of asymmetric quantum error-correcting codes, linear MDS codes can be used to construct asymmetric quantum MDS codes with $d_{z} \\geq d_{x}\\geq 2$ for all possible values of length $n$ for which linear MDS codes over $\\F_{q}$ are known to exist.

  10. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    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...... 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...

  11. The Combinatorial Approach to Asymmetric Hydrogenation: More Miles out of Monophos

    Institute of Scientific and Technical Information of China (English)

    Johannes G. de Vries

    2005-01-01

    @@ 1Introduction In custom manufacturing time-to-market is of overriding importance. Thus, asymmetric hydrogenation will be applied only if an appropriate catalyst can be found in a very short period of time. For this reason we have build up a full-scale capability for High Throughput Experimentation, encompassing several robot systems. As ligand synthesis was the last remaining barrier we have explored, together with the University of Groningen, the use of simple monodentate ligands, such as MonoPhosTM. These ligands can be synthesised in two chemical steps, from BINOL, PCl3 and an amine.Surprisingly, very high enantioselectivities can be obtained in the asymmetric hydrogenation of α-and β-dehydro-amino acids and esters, aromatic enamides, itaconic acid and ester[1]. See Scheme 1 and 2(at page 830).

  12. Mechanistic Insights into Homogeneous and Heterogeneous Asymmetric Iron Catalysis

    Science.gov (United States)

    Sonnenberg, Jessica

    Our group has been focused on replacing toxic and expensive precious metal catalysts with iron for the synthesis of enantiopure compounds for industrial applications. During an investigation into the mechanism of asymmetric transfer hydrogenation with our first generation iron-(P-N-N-P) catalysts we found substantial evidence for zero-valent iron nanoparticles coated in chiral ligand acting as the active site. Extensive experimental and computational experiments were undertaken which included NMR, DFT, reaction profile analysis, substoichiometric poisoning, electron microscope imaging, XPS and multiphasic analysis, all of which supported the fact that NPs were the active species in catalysis. Reversibility of this asymmetric reaction on the nanoparticle surface was then probed using oxidative kinetic resolution of racemic alcohols, yielding modest enantiopurity and high turnover frequencies (TOF) for a range of aromatic alcohols. Efficient dehydrogenation of ammonia-borane for hydrogen evolution and the formation of B-N oligomers was also shown using the NP system, yielding highly active systems, with a maximum TOF of 3.66 H2/s-1 . We have also begun to focus on the development of iron catalysts for asymmetric direct hydrogenation of ketones using hydrogen gas. New chiral iron-(P-N-P) catalysts were developed and shown to be quite active and selective for a wide range of substrates. Mechanistic investigations primarily using NMR and DFT indicated that a highly active trans-dihydride species was being formed during catalyst activation. Lastly, a new library of chiral P-N-P and P-NH-P ligands were developed, as well as their corresponding iron complexes, some of which show promise for the development of future generations of active asymmetric direct hydrogenation catalysts.

  13. 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.

  14. Structural Basis of Cooperative Ligand Binding by the Glycine Riboswitch

    Energy Technology Data Exchange (ETDEWEB)

    E Butler; J Wang; Y Xiong; S Strobel

    2011-12-31

    The glycine riboswitch regulates gene expression through the cooperative recognition of its amino acid ligand by a tandem pair of aptamers. A 3.6 {angstrom} crystal structure of the tandem riboswitch from the glycine permease operon of Fusobacterium nucleatum reveals the glycine binding sites and an extensive network of interactions, largely mediated by asymmetric A-minor contacts, that serve to communicate ligand binding status between the aptamers. These interactions provide a structural basis for how the glycine riboswitch cooperatively regulates gene expression.

  15. Nonlinear effects in asymmetric catalysis.

    Science.gov (United States)

    Satyanarayana, Tummanapalli; Abraham, Susan; Kagan, Henri B

    2009-01-01

    There is a need for the preparation of enantiomerically pure compounds for various applications. An efficient approach to achieve this goal is asymmetric catalysis. The chiral catalyst is usually prepared from a chiral auxiliary, which itself is derived from a natural product or by resolution of a racemic precursor. The use of non-enantiopure chiral auxiliaries in asymmetric catalysis seems unattractive to preparative chemists, since the anticipated enantiomeric excess (ee) of the reaction product should be proportional to the ee value of the chiral auxiliary (linearity). In fact, some deviation from linearity may arise. Such nonlinear effects can be rich in mechanistic information and can be synthetically useful (asymmetric amplification). This Review documents the advances made during the last decade in the use of nonlinear effects in the area of organometallic and organic catalysis.

  16. Asymmetric distances for binary embeddings.

    Science.gov (United States)

    Gordo, Albert; Perronnin, Florent; Gong, Yunchao; Lazebnik, Svetlana

    2014-01-01

    In large-scale query-by-example retrieval, embedding image signatures in a binary space offers two benefits: data compression and search efficiency. While most embedding algorithms binarize both query and database signatures, it has been noted that this is not strictly a requirement. Indeed, asymmetric schemes that binarize the database signatures but not the query still enjoy the same two benefits but may provide superior accuracy. In this work, we propose two general asymmetric distances that are applicable to a wide variety of embedding techniques including locality sensitive hashing (LSH), locality sensitive binary codes (LSBC), spectral hashing (SH), PCA embedding (PCAE), PCAE with random rotations (PCAE-RR), and PCAE with iterative quantization (PCAE-ITQ). We experiment on four public benchmarks containing up to 1M images and show that the proposed asymmetric distances consistently lead to large improvements over the symmetric Hamming distance for all binary embedding techniques.

  17. Asymmetric catalysis in organic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Reilly, S.D.; Click, D.R.; Grumbine, S.K.; Scott, B.L.; Watkins, J.G.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of the project was to prepare new catalyst systems, which would perform chemical reactions in an enantioselective manner so as to produce only one of the possible optical isomers of the product molecule. The authors have investigated the use of lanthanide metals bearing both diolate and Schiff-base ligands as catalysts for the enantioselective reduction of prochiral ketones to secondary alcohols. The ligands were prepared from cheap, readily available starting materials, and their synthesis was performed in a ''modular'' manner such that tailoring of specific groups within the ligand could be carried out without repeating the entire synthetic procedure. In addition, they have developed a new ligand system for Group IV and lanthanide-based olefin polymerization catalysts. The ligand system is easily prepared from readily available starting materials and offers the opportunity to rapidly prepare a wide range of closely related ligands that differ only in their substitution patterns at an aromatic ring. When attached to a metal center, the ligand system has the potential to carry out polymerization reactions in a stereocontrolled manner.

  18. Phosphinoureas: cooperative ligands in rhodium-catalyzed hydroformylation? On the possibility of a ligand-assisted reductive elimination of the aldehyde

    NARCIS (Netherlands)

    Meeuwissen, J.; Sandee, A.J.; de Bruin, B.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    We report the synthesis of a novel type of phosphinourea ligand, its coordination chemistry with rhodium, its use in the asymmetric hydroformylation of styrene, and investigations on the hydroformylation reaction mechanism. Complex studies on the 2:1 complex of phosphinourea to [Rh(acac)(CO)(2)] sho

  19. Phosphinoureas: cooperative ligands in rhodium-catalyzed hydroformylation? on the possibility of a ligand-assisted reductive elimination of the aldehyde

    NARCIS (Netherlands)

    Meeuwissen, J.; Sandee, A. J.; de Bruin, B.; Siegler, M. A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    We report the synthesis of a novel type of phosphinourea ligand, its coordination chemistry with rhodium, its use in the asymmetric hydroformylation of styrene, and investigations on the hydroformylation reaction mechanism. Complex studies on the 2:1 complex of phosphinourea to [Rh(acac)(CO)2] showe

  20. Synthesis of New Chiral Bis(BINOL) Substituted 2,2'-Bipyridine Ligands

    Institute of Scientific and Technical Information of China (English)

    BAI,Xiao-Li; GAO,Lian-Xun

    2004-01-01

    @@ Chiral 2,2'-bipyridines have been reported to be highly efficient catalysts and useful building blocks of supramolecular.[1,2] Chirality of bipyridines was introduced by chiral substituents. Because 1,1'-binaphthyl (BINOL) and its derivatives belong to the most important components of asymmetric catalysts, we would like to synthesize 5,5'-and 6,6'-positions substituted chiral bipyridine-type ligands, the chiral moieties of ligands originate from enationpure 1, 1'-binapthyl units.

  1. Asymmetric carbon-carbon bond forming reactions catalyzed by chiral titanium complexes. Efficient synthesis of optically active secondary alcohols; Kiraru na chitan shokubai ni yoru fuseitanso-tanso ketsugo keisei. Kogaku kassei dainikyu arukoru no gosei

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, M. [Yamaguchi Univ., Yamaguchi (Japan). Faculty of Science

    1996-02-01

    For asymmetric metal complex catalysts with high catalytic activity and ability for recognizing asymmetry, it is most important to choose center metals and design asymmetric organic ligands. When the authors began to study on the title reactions, combination of titanium alkoxides as center metals and chiral Schiff bases as organic ligands was unknown, although two moieties had been used independently for asymmetric reactions with excellent results. Asymmetric silylcyanation of aldehydes and enantio-selective addition of diketone to aldehydes are introduced, that have been achieved by authors using titanium complexes of the above combination. In the silylcyanation, reactivity is remarkably improved, compared with a single catalyst of titanium isopropoxide. Cyanohydrin of R from was obtained preferentially with salicyladehyde, particularly having 3-tert butyl group, in an asymmetric yield of 85 % ee. In the latter addition reaction, 5-hydroxy-3-ketoesters were obtained from benzaldehyde in an asymmetric yield as high as 91 % ee. 9 refs., 2 figs.

  2. Ligand modeling and design

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B.P. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used in the cost-effective removal of specific radionuclides from nuclear waste streams. Organic ligands with metal ion specificity are critical components in the development of solvent extraction and ion exchange processes that are highly selective for targeted radionuclides. The traditional approach to the development of such ligands involves lengthy programs of organic synthesis and testing, which in the absence of reliable methods for screening compounds before synthesis, results in wasted research effort. The author`s approach breaks down and simplifies this costly process with the aid of computer-based molecular modeling techniques. Commercial software for organic molecular modeling is being configured to examine the interactions between organic ligands and metal ions, yielding an inexpensive, commercially or readily available computational tool that can be used to predict the structures and energies of ligand-metal complexes. Users will be able to correlate the large body of existing experimental data on structure, solution binding affinity, and metal ion selectivity to develop structural design criteria. These criteria will provide a basis for selecting ligands that can be implemented in separations technologies through collaboration with other DOE national laboratories and private industry. The initial focus will be to select ether-based ligands that can be applied to the recovery and concentration of the alkali and alkaline earth metal ions including cesium, strontium, and radium.

  3. Mechanistic insights on cooperative asymmetric multicatalysis using chiral counterions.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-08-15

    Cooperative multicatalytic methods are steadily gaining popularity in asymmetric catalysis. The use of chiral Brønsted acids such as phosphoric acids in conjunction with a range of transition metals has been proven to be effective in asymmetric synthesis. However, the lack of molecular-level understanding and the accompanying ambiguity on the role of the chiral species in stereoinduction continues to remain an unresolved puzzle. Herein, we intend to disclose some novel transition state models obtained through DFT(B3LYP and M06) computations for a quintessential reaction in this family, namely, palladium-catalyzed asymmetric Tsuji-Trost allylation of aldehydes. The aldehyde is activated as an enamine by the action of a secondary amine (organocatalysis), which then adds to an activated Pd-allylic species (transition metal catalysis) generated through the protonation of allyic alcohol by chiral BINOL-phosphoric acid (Brønsted acid catalysis). We aim to decipher the nature of chiral BINOL-phosphates and their role in creating a quaternary chiral carbon atom in this triple catalytic system. The study reports the first transition state model capable of rationalizing chiral counterion-induced enantioselectivity. It is found that the chiral phosphate acts as a counterion in the stereocontrolling event rather than the conventional ligand mode.

  4. Synthesis of Asymmetric Propanetriol Analogues

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    From natural tartaric acid, (R)-2-benzyloxy-3-(2-tetrahydropyranyloxy) propanol 3 was designed and synthesized, and (R)-2-benzyloxy-3-(4-methoxybenzyloxy) propanol 7 was prepared in a new method. They can be used as chiral synthons of lysophosphatidic acid and other compounds with asymmetric propanetriol backbone.

  5. Catalytic Asymmetric Bromocyclization of Polyenes.

    Science.gov (United States)

    Samanta, Ramesh C; Yamamoto, Hisashi

    2017-02-01

    The first catalytic asymmetric bromonium ion-induced polyene cyclization has been achieved by using a chiral BINOL-derived thiophosphoramide catalyst and 1,3-dibromo-5,5-dimethylhydantoin as an electrophilic bromine source. Bromocyclization products are obtained in high yields, with good enantiomeric ratios and high diastereoselectivity, and are abundantly found as scaffolds in natural products.

  6. Ligand modeling and design

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B. [Pacific Northwest Lab., Richland, WA (United States)

    1996-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used tin applications for the cost-effective removal of specific radionuclides from nuclear waste streams.

  7. Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters

    Directory of Open Access Journals (Sweden)

    Momoko Watanabe

    2011-06-01

    Full Text Available A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(arylmethanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM achieved excellent enantioselectivities.

  8. Ru/Me-BIPAM-catalyzed asymmetric addition of arylboronic acids to aliphatic aldehydes and α-ketoesters.

    Science.gov (United States)

    Yamamoto, Yasunori; Shirai, Tomohiko; Watanabe, Momoko; Kurihara, Kazunori; Miyaura, Norio

    2011-06-17

    A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(aryl)methanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM) achieved excellent enantioselectivities.

  9. Enantioselective Cu-II-Catalyzed Diels-Alder and Michael Addition Reactions in Water Using Bio-Inspired Triazacyclophane-Based Ligands

    NARCIS (Netherlands)

    Albada, H. Bauke; Rosati, Fiora; Coquiere, David; Roelfes, Gerard; Liskamp, Rob M. J.

    2011-01-01

    A triazacyclophane (TAC) scaffold decorated with three histidine amino acid residues was used as a tridentate ligand in asymmetric copper(II)-catalysed Diels-Alder and Michael addition reactions in water. Enantiomeric excesses up to 55% were obtained in Diels-Alder reactions using ligands in which t

  10. New Chiral Metal Cluster Systems for Catalytic Asymmetric Syntheses of Chiral Alcohols

    Institute of Scientific and Technical Information of China (English)

    LI Yan-yun; CHEN Jian-shan; YANG Chuan-bo; DONG Zhen-rong; LI Bao-zhu; ZHANG Hui; GAO Jing-xing; TAKAO Ikariya

    2004-01-01

    The efficient chiral Ru3(CO)12 systems were prepared in situ from Ru3(CO)12 and various chiral diiminoor diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu3(CO)11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru3 framework.

  11. Synthesis of Novel Chiral Dibenzo [ a, c ] cycloheptadiene Bis(oxazoline) and Catalytic Asymmetric Reactions

    Institute of Scientific and Technical Information of China (English)

    FU Bin; DU Da-Ming; WANG Jian-Bo

    2003-01-01

    @@ Over the last decade, C2-symmetric chiral oxazoline metal complexes have been recognized as an effective classof chiral catalyst in a variety of transition metal catalyzed asymmetric reactions. [1] High catalytic activities and enantiomeric excesses have been obtained using C2-symmetric chiral ligands in conjunction with suitable transition metal ion, for example, the hydrosilylation of ketone, allylic alkylation, Michael addition, Diels-Alder cycloaddition, and cyclopropanation. Thus, the design and synthesis of new chiral oxazoline ligands have inspired many scientists to work with great efforts.

  12. Asymmetric Multilevel Diversity Coding and Asymmetric Gaussian Multiple Descriptions

    CERN Document Server

    Mohajer, Soheil; Diggavi, Suhas N

    2009-01-01

    We consider the asymmetric multilevel diversity (A-MLD) coding problem, where a set of $2^K-1$ information sources, ordered in a decreasing level of importance, is encoded into $K$ messages (or descriptions). There are $2^K-1$ decoders, each of which has access to a non-empty subset of the encoded messages. Each decoder is required to reproduce the information sources up to a certain importance level depending on the combination of descriptions available to it. We obtain a single letter characterization of the achievable rate region for the 3-description problem. In contrast to symmetric multilevel diversity coding, source-separation coding is not sufficient in the asymmetric case, and ideas akin to network coding need to be used strategically. Based on the intuitions gained in treating the A-MLD problem, we derive inner and outer bounds for the rate region of the asymmetric Gaussian multiple description (MD) problem with three descriptions. Both the inner and outer bounds have a similar geometric structure t...

  13. New Chiral Ligands:From Fundamental Research to Potential Industrial Applications

    Institute of Scientific and Technical Information of China (English)

    Albert S. C. Chan

    2004-01-01

    Asymmetric catalysis is one of the most extensively studied areas in chemistry over the past three decades. In this presentation we will discuss the new advancements in the design,synthesis, and application of chiral ligands used for catalytic reactions in our laboratory. Particular emphasis will be placed on new, highly efficient synthetic methodologies and their potential industrial applications.

  14. Modelling asymmetric growth in crowded plant communities

    DEFF Research Database (Denmark)

    Damgaard, Christian

    2010-01-01

    A class of models that may be used to quantify the effect of size-asymmetric competition in crowded plant communities by estimating a community specific degree of size-asymmetric growth for each species in the community is suggested. The model consists of two parts: an individual size-asymmetric ......A class of models that may be used to quantify the effect of size-asymmetric competition in crowded plant communities by estimating a community specific degree of size-asymmetric growth for each species in the community is suggested. The model consists of two parts: an individual size...

  15. 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.

  16. Peptide Deravatives as New Chiral Ligands for Enantioselective Phenylacetylene Addition to Aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Yi-Feng; GAO,Yan-Feng; KANG,Yong-Feng; HAN,Zhi-Jian; YAN,Wen-Jin; NI,Ming; WANG,Rui

    2004-01-01

    @@ The asymmetric addition of alkynylzinc to aldehydes is an important method of synthesizing chiral propargyl alcohols, which are important precursors to many chiral organic compounds. Recently, many significant chiral ligands in this area have been disclosed.[1] Use of a short peptide as a catalyst would allow expansion beyond the (still uncharted) repertoire of single amino acids, while conserving the advantages of a small molecule catalyst. To the best of our knowledge,no results of peptide derivatives as chiral ligands in this reaction has been disclosed to date.[2] Herein, we report the initial results of peptide derivatives, which have been used directly as a chiral ligand in this reaction (Scheme 1).

  17. Terahertz metamaterial with asymmetric transmission

    CERN Document Server

    Singh, R; Menzel, C; Rockstuhl, C; Azad, A K; Cheville, R A; Lederer, F; Zhang, W; Zheludev, N I

    2009-01-01

    We show for the first time that a planar metamaterial, an array of coupled metal split-ring resonators with a unit cell lacking mirror symmetry, exhibits asymmetric transmission of terahertz radiation propagating through it in opposite directions. This intriguing effect, that is compatible with Lorentz reciprocity and time-reversal, depends on a directional difference in conversion efficiency of the incident circularly polarized wave into one of opposite handedness, that is only possible in lossy low-symmetry planar chiral metamaterials. We show that asymmetric transmission is linked to excitation of enantiomerically sensitive plasmons, these are induced charge-field excitations that depend on the mutual handedness of incident wave and metamaterial pattern. Various bands of positive, negative and zero phase and group velocities have been identified indicating the opportunity to develop polarization sensitive negative index and slow light media based on such metamaterials.

  18. 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.

  19. Asymmetrical Γ-Source Inverters

    DEFF Research Database (Denmark)

    Wei, Mo; Poh Chiang, Loh; Blaabjerg, Frede

    2014-01-01

    , inverters with coupled transformers have been introduced, but they usually lead to high turns ratio, and hence many winding turns, at high gain. An alternative would then be the asymmetrical Γ-source inverters proposed in this paper, whose gain is raised by lowering their turns ratio toward unity. The input...... current drawn by the proposed inverters is smoother and, hence, more adaptable by the source. Theories and experimental results have been presented in this paper for validating the concepts proposed....

  20. Dynamic kinetic cross-coupling strategy for the asymmetric synthesis of axially chiral heterobiaryls.

    Science.gov (United States)

    Ros, Abel; Estepa, Beatriz; Ramírez-López, Pedro; Álvarez, Eleuterio; Fernández, Rosario; Lassaletta, José M

    2013-10-23

    A dynamic kinetic asymmetric transformation (DYKAT) technique has been designed for the synthesis of 2'-substituted 2-aryl pyridines/isoquinolines and related heterobiaryls. In this way, the Pd(0)-catalyzed coupling of racemic 2-triflates with aryl boroxines using a TADDOL-derived phosphoramidite as the ligand provides the corresponding coupling products with good to excellent enantioselectivities. Structural studies support that the formation of configurationally labile oxidative addition palladacycles is the key for the success of the methodology.

  1. Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with secondary amine nucleophiles

    Directory of Open Access Journals (Sweden)

    Dingqiao Yang

    2009-10-01

    Full Text Available Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with various aliphatic and aromatic secondary amines are reported for the first time. The reaction gave the corresponding trans-1,2-dihydronaphthalenol derivatives in good yields with moderate enantioselectivities in the presence of 2.5 mol % [Ir(CODCl]2 and 5 mol % bisphosphine ligand (S-p-Tol-BINAP. The trans-configuration of 3f was confirmed by X-ray crystallography.

  2. Microwave-induced inactivation of DNA-based hybrid catalyst in asymmetric catalysis.

    Science.gov (United States)

    Zhao, Hua; Shen, Kai

    2016-03-01

    DNA-based hybrid catalysts have gained strong interests in asymmetric reactions. However, to maintain the high enantioselectivity, these reactions are usually conducted at relatively low temperatures (e.g. DNA-based hybrid catalyst even at low temperatures (such as 5 °C). Circular dichroism (CD) spectra and gel electrophoresis of DNA suggest that microwave exposure degrades DNA molecules and disrupts DNA double-stranded structures, causing changes of DNA-metal ligand binding properties and thus poor DNA catalytic performance.

  3. Up-down asymmetric tokamaks

    CERN Document Server

    Ball, Justin

    2016-01-01

    Bulk toroidal rotation has proven capable of stabilising both dangerous MHD modes and turbulence. In this thesis, we explore a method to drive rotation in large tokamaks: up-down asymmetry in the magnetic equilibrium. We seek to maximise this rotation by finding optimal up-down asymmetric flux surface shapes. First, we use the ideal MHD model to show that low order external shaping (e.g. elongation) is best for creating up-down asymmetric flux surfaces throughout the device. Then, we calculate realistic up-down asymmetric equilibria for input into nonlinear gyrokinetic turbulence analysis. Analytic gyrokinetics shows that, in the limit of fast shaping effects, a poloidal tilt of the flux surface shaping has little effect on turbulent transport. Since up-down symmetric surfaces do not transport momentum, this invariance to tilt implies that devices with mirror symmetry about any line in the poloidal plane will drive minimal rotation. Accordingly, further analytic investigation suggests that non-mirror symmetri...

  4. Asymmetric Schiff bases derived from diaminomaleonitrile and their metal complexes

    Science.gov (United States)

    Yang, Jianjie; Shi, Rufei; Zhou, Pei; Qiu, Qiming; Li, Hui

    2016-02-01

    Asymmetric Schiff bases, due to its asymmetric structure, can be used as asymmetric catalyst, antibacterial, and mimic molecules during simulate biological processes, etc. In recent years, research on synthesis and properties of asymmetric Schiff bases have become an increase interest of chemists. This review summarizes asymmetric Schiff bases derived from diaminomaleonitrile (DAMN) and DAMN-based asymmetric Schiff bases metal complexes. Applications of DAMN-based asymmetric Schiff bases are also discussed in this review.

  5. Ligand fitting with CCP4

    Science.gov (United States)

    2017-01-01

    Crystal structures of protein–ligand complexes are often used to infer biology and inform structure-based drug discovery. Hence, it is important to build accurate, reliable models of ligands that give confidence in the interpretation of the respective protein–ligand complex. This paper discusses key stages in the ligand-fitting process, including ligand binding-site identification, ligand description and conformer generation, ligand fitting, refinement and subsequent validation. The CCP4 suite contains a number of software tools that facilitate this task: AceDRG for the creation of ligand descriptions and conformers, Lidia and JLigand for two-dimensional and three-dimensional ligand editing and visual analysis, Coot for density interpretation, ligand fitting, analysis and validation, and REFMAC5 for macromolecular refinement. In addition to recent advancements in automatic carbohydrate building in Coot (LO/Carb) and ligand-validation tools (FLEV), the release of the CCP4i2 GUI provides an integrated solution that streamlines the ligand-fitting workflow, seamlessly passing results from one program to the next. The ligand-fitting process is illustrated using instructive practical examples, including problematic cases such as post-translational modifications, highlighting the need for careful analysis and rigorous validation. PMID:28177312

  6. Secondary interactions or ligand scrambling? Subtle steric effects govern the iridium(I) coordination chemistry of phosphoramidite ligands.

    Science.gov (United States)

    Osswald, Tina; Rüegger, Heinz; Mezzetti, Antonio

    2010-01-25

    The like and unlike isomers of phosphoramidite (P*) ligands are found to react differently with iridium(I), which is a key to explaining the apparently inconsistent results obtained by us and other research groups in a variety of catalytic reactions. Thus, the unlike diastereoisomer (aR,S,S)-[IrCl(cod)(1 a)] (2 a; cod=1,5-cyclooctadiene, 1 a=(aR,S,S)-(1,1'-binaphthalene)-2,2'-diyl bis(1-phenylethyl)phosphoramidite) forms, upon chloride abstraction, the monosubstituted complex (aR,S,S)-[Ir(cod)(1,2-eta-1 a,kappaP)](+) (3 a), which contains a chelating P* ligand that features an eta(2) interaction between a dangling phenyl group and iridium. Under analogous conditions, the like analogue (aR,R,R)-1 a' gives the disubstituted species (aR,R,R)-[Ir(cod)(1 a',kappaP)(2)](+) (4 a') with monodentate P* ligands. The structure of 3 a was assessed by a combination of X-ray and NMR spectroscopic studies, which indicate that it is the configuration of the binaphthol moiety (and not that of the dangling benzyl N groups) that determines the configuration of the complex. The effect of the relative configuration of the P* ligand on its iridium(I) coordination chemistry is discussed in the context of our preliminary catalytic results and of apparently random results obtained by other groups in the iridium(I)-catalyzed asymmetric allylic alkylation of allylic acetates and in rhodium(I)-catalyzed asymmetric cycloaddition reactions. Further studies with the unlike ligand (aS,R,R)-(1,1'-binaphthalene)-2,2'-diyl bis{[1-(1-naphthalene-1-yl)ethyl]phosphoramidite} (1 b) showed a yet different coordination mode, that is, the eta(4)-arene-metal interaction in (aS,R,R)-[Ir(cod)(1,2,3,4-eta-1 b,kappaP)](+) (3 b).

  7. Spontaneous baryogenesis from asymmetric inflaton

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Fuminobu [Tohoku Univ., Sendai (Japan). Dept. of Physics; Tokyo Univ., Chiba (Japan). Kavli IPMU (WPI), UTIAS; Yamada, Masaki [Tokyo Univ., Chiba (Japan). Kavli IPMU (WPI), UTIAS; Tokyo Univ., Chiba (Japan). Inst. for Cosmic Ray Research; DESY Hamburg (Germany)

    2015-10-15

    We propose a variant scenario of spontaneous baryogenesis from asymmetric inflaton based on current-current interactions between the inflaton and matter fields with a non-zero B-L charge. When the inflaton starts to oscillate around the minimum after inflation, it may lead to excitation of a CP-odd component, which induces an effective chemical potential for the B-L number through the current-current interactions. We study concrete inflation models and show that the spontaneous baryogenesis scenario can be naturally implemented in the chaotic inflation in supergravity.

  8. The asymmetric Goos-H\\"anchen effect

    OpenAIRE

    Araujo, Manoel P.; Carvalho, Silvânia A.; De Leo, Stefano

    2013-01-01

    We show in which conditions optical gaussian beams, propagating throughout an homogeneous dielectric right angle prism, present an asymmetric Goos-H\\"anchen (GH) effect. This asymmetric behavior is seen for incidence at critical angles and happens in the propagation direction of the outgoing beam. The asymmetric GH effect can be also seen as an amplification of the standard GH shift. Due to the fact that it only depends on the ratio between the wavelength and the minimal waist size of the inc...

  9. Review of Composite Asymmetric Spur Gear

    OpenAIRE

    Sandeep C. Dhaduti; Dr. S. G. Sarganachari

    2015-01-01

    Gears made from composite materials are widely used in many power and motion transmission applications. Due to lower weight to stiffness ratio, composite gears may be replaced by conventional material gears in power transmission systems. Design of gears with asymmetric teeth enables to increase load capacity, reduce weight, size and vibration level. This article includes a summary of asymmetric gear design parameters, new developments of asymmetric spur gear and their ...

  10. Asymmetric Tyrosine Kinase Arrangements in Activation or Autophosphorylation of Receptor Tyrosine Kinases

    Energy Technology Data Exchange (ETDEWEB)

    J Bae; J Schlessinger

    2011-12-31

    Receptor tyrosine kinases (RTKs) play important roles in the control of many cellular processes including cell proliferation, cell adhesion, angiogenesis, and apoptosis. Ligand-induced dimerization of RTKs leads to autophosphorylation and activation of RTKs. Structural studies have shown that while isolated ectodomains of several RTKs form symmetric dimers the isolated cytoplasmic kinase domains of epidermal growth factor receptor (EGFR) and fibroblast growth factor receptor (FGFR) form asymmetric dimers during their activation. Binding of one kinase molecule of EGFR to a second kinase molecule asymmetrically leads to stimulation of kinase activity and enhanced autophosphorylation. Furthermore, the structures of the kinase domain of FGFR1 and FGFR2 reveal the formation of asymmetric interfaces in the processes of autophosphorylation at their specific phosphotyrosine (pY) sites. Disruption of asymmetric dimer interface of EGFR leads to reduction in enzymatic activity and drastic reduction of autophosphorylation of FGFRs in ligandstimulated live cells. These studies demonstrate that asymmetric dimer formation is as a common phenomenon critical for activation and autophosphorylation of RTKs.

  11. The asymmetric Goos-H\\"anchen effect

    CERN Document Server

    Araujo, Manoel P; De Leo, Stefano

    2014-01-01

    We show in which conditions optical gaussian beams, propagating throughout an homogeneous dielectric right angle prism, present an asymmetric Goos-H\\"anchen (GH) effect. This asymmetric behavior is seen for incidence at critical angles and happens in the propagation direction of the outgoing beam. The asymmetric GH effect can be also seen as an amplification of the standard GH shift. Due to the fact that it only depends on the ratio between the wavelength and the minimal waist size of the incoming gaussian beam, it can be also used to determine one of these parameters. Multiple peaks interference is an additional phenomenon seen in the presence of such asymmetric effects.

  12. Progress of Chiral Schiff Bases with C1 Symmetry in Metal-Catalyzed Asymmetric Reactions.

    Science.gov (United States)

    Hayashi, Masahiko

    2016-12-01

    In this Personal Account, various chiral Schiff base-metal-catalyzed enantioselective organic reactions are reported; the Schiff bases used were O,N,O- as well as N,N,P-tridentate ligands and N,N-bidentate ligands having C1 symmetry. In particular, the enantioselective addition of trimethylsilyl cyanide, dialkylzinc, and organozinc halides to aldehydes, enantioselective 1,4-addition of dialkylzinc to cyclic and acyclic enones, and asymmetric allylic oxidation are reported. Typically, ketimine-type Schiff base-metal complexes exhibited higher reactivity and enantioselectivity compared with the corresponding aldimine-type Schiff base-metal complexes. Notably, remarkable ligand acceleration was observed for all reactions. The obtained products can be used as key intermediates for optically active natural products and pharmaceuticals.

  13. Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

    Directory of Open Access Journals (Sweden)

    Wei Jie Li

    2010-03-01

    Full Text Available Seven polyoxazoline ligands were synthesized in high yield in a one-pot reaction by heating polycarboxylic acids or their esters and chiral β-amino alcohols under reflux with concomitant removal of water or the alcohol produced in the reaction. The method is much simpler and more efficient in comparison to those methods reported in the literature.The compounds were used as chiral ligands in the rhodium-catalyzed asymmetric hydrosilylation of aromatic ketones, and the effects of the linkers and the substituents present on the oxazoline rings on the yield and enantioselectivity investigated. Compound 2 was identified as the best ligand of this family for the hydrosilylation of aromatic ketones.

  14. Thin lenses of asymmetric power

    Directory of Open Access Journals (Sweden)

    W. F. Harris

    2009-12-01

    Full Text Available It is generally supposed that thin systems, including refracting surfaces and thin lenses, have powers that are necessarily symmetric.  In other words they have powers which can be represented assymmetric dioptric power matrices and in the familar spherocylindrical form used in optometry and ophthalmology.  This paper shows that this is not correct and that it is indeed possible for a thin system to have a power that is not symmetric and which cannot be expressed in spherocylindrical form.  Thin systems of asymmetric power are illustratedby means of a thin lens that is modelled with small prisms and is chosen to have a dioptric power ma-trix that is antisymmetric.  Similar models can be devised for a thin system whose dioptric power matrix is any  2 2 ×  matrix.  Thus any power, symmetric, asymmetric or antisymmetric, is possible for a thin system.  In this sense our understanding of the power of thin systems is now complete.

  15. Excitons in asymmetric quantum wells

    Science.gov (United States)

    Grigoryev, P. S.; Kurdyubov, A. S.; Kuznetsova, M. S.; Ignatiev, I. V.; Efimov, Yu. P.; Eliseev, S. A.; Petrov, V. V.; Lovtcius, V. A.; Shapochkin, P. Yu.

    2016-09-01

    Resonance dielectric response of excitons is studied for the high-quality InGaAs/GaAs heterostructures with wide asymmetric quantum wells (QWs). To highlight effects of the QW asymmetry, we have grown and studied several heterostructures with nominally square QWs as well as with triangle-like QWs. Several quantum confined exciton states are experimentally observed as narrow exciton resonances. A standard approach for the phenomenological analysis of the profiles is generalized by introducing different phase shifts for the light waves reflected from the QWs at different exciton resonances. Good agreement of the phenomenological fit to the experimentally observed exciton spectra for high-quality structures allowed us to reliably obtain parameters of the exciton resonances: the exciton transition energies, the radiative broadenings, and the phase shifts. A direct numerical solution of the Schrödinger equation for the heavy-hole excitons in asymmetric QWs is used for microscopic modeling of the exciton resonances. Remarkable agreement with the experiment is achieved when the effect of indium segregation is taken into account. The segregation results in a modification of the potential profile, in particular, in an asymmetry of the nominally square QWs.

  16. Asymmetric Laguerre-Gaussian beams

    Science.gov (United States)

    Kovalev, A. A.; Kotlyar, V. V.; Porfirev, A. P.

    2016-06-01

    We introduce a family of asymmetric Laguerre-Gaussian (aLG) laser beams. The beams have been derived via a complex-valued shift of conventional LG beams in the Cartesian plane. While propagating in a uniform medium, the first bright ring of the aLG beam becomes less asymmetric and the energy is redistributed toward peripheral diffraction rings. The projection of the orbital angular momentum (OAM) onto the optical axis is calculated. The OAM is shown to grow quadratically with increasing asymmetry parameter of the aLG beam, which equals the ratio of the shift to the waist radius. Conditions for the OAM becoming equal to the topological charge have been derived. For aLG beams with zero radial index, we have deduced an expression to define the intensity maximum coordinates and shown the crescent-shaped intensity pattern to rotate during propagation. Results of the experimental generation and rotation of aLG beams agree well with theoretical predictions.

  17. Asymmetric monometallic nanorod nanoparticle dimer and related compositions and methods

    KAUST Repository

    Han, Yu

    2016-03-31

    The fabrication of asymmetric monometallic nanocrystals with novel properties for plasmonics, nanophotonics and nanoelectronics. Asymmetric monometallic plasmonic nanocrystals are of both fundamental synthetic challenge and practical significance. In an example, a thiol-ligand mediated growth strategy that enables the synthesis of unprecedented Au Nanorod-Au Nanoparticle (AuNR-AuNP) dimers from pre-synthesized AuNR seeds. Using high-resolution electron microscopy and tomography, crystal structure and three-dimensional morphology of the dimer, as well as the growth pathway of the AuNP on the AuNR seed, was investigated for this example. The dimer exhibits an extraordinary broadband optical extinction spectrum spanning the UV, visible, and near infrared regions (300 - 1300 nm). This unexpected property makes the AuNR-AuNP dimer example useful for many nanophotonic applications. In two experiments, the dimer example was tested as a surface- enhanced Raman scattering (SERS) substrate and a solar light harvester for photothermal conversion, in comparison with the mixture of AuNR and AuNP. In the SERS experiment, the dimer example showed an enhancement factor about 10 times higher than that of the mixture, when the excitation wavelength (660 nm) was off the two surface plasmon resonance (SPR) bands of the mixture. In the photothermal conversion experiment under simulated sunlight illumination, the dimer example exhibited an energy conversion efficiency about 1.4 times as high as that of the mixture.

  18. LigandRNA: computational predictor of RNA-ligand interactions.

    Science.gov (United States)

    Philips, Anna; Milanowska, Kaja; Lach, Grzegorz; Bujnicki, Janusz M

    2013-12-01

    RNA molecules have recently become attractive as potential drug targets due to the increased awareness of their importance in key biological processes. The increase of the number of experimentally determined RNA 3D structures enabled structure-based searches for small molecules that can specifically bind to defined sites in RNA molecules, thereby blocking or otherwise modulating their function. However, as of yet, computational methods for structure-based docking of small molecule ligands to RNA molecules are not as well established as analogous methods for protein-ligand docking. This motivated us to create LigandRNA, a scoring function for the prediction of RNA-small molecule interactions. Our method employs a grid-based algorithm and a knowledge-based potential derived from ligand-binding sites in the experimentally solved RNA-ligand complexes. As an input, LigandRNA takes an RNA receptor file and a file with ligand poses. As an output, it returns a ranking of the poses according to their score. The predictive power of LigandRNA favorably compares to five other publicly available methods. We found that the combination of LigandRNA and Dock6 into a "meta-predictor" leads to further improvement in the identification of near-native ligand poses. The LigandRNA program is available free of charge as a web server at http://ligandrna.genesilico.pl.

  19. Ligand-Receptor Interactions

    CERN Document Server

    Bongrand, Pierre

    2008-01-01

    The formation and dissociation of specific noncovalent interactions between a variety of macromolecules play a crucial role in the function of biological systems. During the last few years, three main lines of research led to a dramatic improvement of our understanding of these important phenomena. First, combination of genetic engineering and X ray cristallography made available a simultaneous knowledg of the precise structure and affinity of series or related ligand-receptor systems differing by a few well-defined atoms. Second, improvement of computer power and simulation techniques allowed extended exploration of the interaction of realistic macromolecules. Third, simultaneous development of a variety of techniques based on atomic force microscopy, hydrodynamic flow, biomembrane probes, optical tweezers, magnetic fields or flexible transducers yielded direct experimental information of the behavior of single ligand receptor bonds. At the same time, investigation of well defined cellular models raised the ...

  20. 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...

  1. 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. I...

  2. The Catalytic Asymmetric Intramolecular Stetter Reaction.

    Science.gov (United States)

    de Alaniz, Javier Read; Rovis, Tomislav

    2009-05-01

    This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows.

  3. Photomechanical actuation of ligand geometry in enantioselective catalysis.

    Science.gov (United States)

    Kean, Zachary S; Akbulatov, Sergey; Tian, Yancong; Widenhoefer, Ross A; Boulatov, Roman; Craig, Stephen L

    2014-12-22

    A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and selectivity upon switching can be attributed to intramolecular mechanical forces, thus laying the foundation for a new class of catalysts whose selectivity can be varied smoothly and in situ over a useful range by controlling molecular stress experienced by the catalyst during turnover. Forces on the order of 100 pN are generated, thus leading to measurable changes in the enantioselectivities of asymmetric Heck arylations and Trost allylic alkylations. The differential coupling between applied force and competing stereochemical pathways is quantified and found to be more efficient for the Heck arylations.

  4. Condensation on Slippery Asymmetric Bumps

    CERN Document Server

    Park, Kyoo-Chul; He, Neil; Aizenberg, Joanna

    2015-01-01

    Bumps are omnipresent from human skin to the geological structures on planets, which offer distinct advantages in numerous phenomena including structural color, drag reduction, and extreme wettability. Although the topographical parameters of bumps such as radius of curvature of convex regions significantly influence various phenomena including anti-reflective structures and contact time of impacting droplets, the effect of the detailed bump topography on growth and transport of condensates have not been clearly understood. Inspired by the millimetric bumps of the Namib Desert beetle, here we report the identified role of radius of curvature and width of bumps with homogeneous surface wettability in growth rate, coalescence and transport of water droplets. Further rational design of asymmetric convex topography and synergetic combination with slippery coating simultaneously enable self-transport, leading to unseen five-fold higher growth rate and an order of magnitude faster shedding time of droplets compared...

  5. New chiral N, S-ligands with Thiophenyl at Benzylic Position. Palladium(Ⅱ)-catalyzed Enantioselective Allylic Alkylation

    Institute of Scientific and Technical Information of China (English)

    WU,Hao(吴昊); WU,Xun-Wei(巫循伟); HOU,Xue-Long(侯雪龙); DAI,Li-Xin(戴立信); WANG,Quan-Rui(王全瑞)

    2002-01-01

    New chiral N, S-ligands with oxazoline and thiphenyl substituents at benzene ring and benzylic position have been prepared and applied in palladium-catalyzed asymmetric allylic alkylation reaction to provide the product with high yield and entantioselectivity (82%-93% ee).

  6. Bexarotene ligand pharmaceuticals.

    Science.gov (United States)

    Hurst, R E

    2000-12-01

    Bexarotene (LGD-1069), from Ligand, was the first retinoid X receptor (RXR)-selective, antitumor retinoid to enter clinical trials. The company launched the drug for the treatment of cutaneous T-cell lymphoma (CTCL), as Targretin capsules, in the US in January 2000 [359023]. The company filed an NDA for Targretin capsules in June 1999, and for topical gel in December 1999 [329011], [349982] specifically for once-daily oral administration for the treatment of patients with early-stage CTCL who have not tolerated other therapies, patients with refractory or persistent early stage CTCL and patients with refractory advanced stage CTCL. The FDA approved Targretin capsules at the end of December 1999 for once-daily oral treatment of all stages of CTCL in patients refractory to at least one prior systemic therapy, at an initial dose of 300 mg/m2/day. After an NDA was submitted in December 1999 for Targretin gel, the drug received Priority Review status for use as a treatment of cutaneous lesions in patients with stage IA, IB or IIA CTCL [354836]. The FDA issued an approvable letter in June 2000, and granted marketing clearance for CTCL in the same month [370687], [372768], [372769], [373279]. Ligand had received Orphan Drug designation for this indication [329011]. At the request of the FDA, Ligand agreed to carry out certain post-approval phase IV and pharmacokinetic studies [351604]. The company filed an MAA with the EMEA for Targretin Capsules to treat lymphoma in November 1999 [348944]. The NDA for Targretin gel is based on a multicenter phase III trial that was conducted in the US, Canada, Europe and Australia involving 50 patients and a multicenter phase I/II clinical program involving 67 patients. Targretin gel was evaluated for the treatment of patients with early stage CTCL (IA-IIA) who were refractory to, intolerant to, or reached a response plateau for at least 6 months on at least two prior therapies. Efficacy results exceeded the protocol-defined response

  7. Alternating Carrier Models of Asymmetric Glucose Transport Violate the Energy Conservation Laws

    Science.gov (United States)

    Naftalin, Richard J

    2008-01-01

    Alternating access transporters with high-affinity externally facing sites and low-affinity internal sites relate substrate transit directly to the unliganded asymmetric “carrier” (Ci) distribution. When both bathing solutions contain equimolar concentrations of ligand, zero net flow of the substrate-carrier complex requires a higher proportion of unliganded low-affinity inside sites (\\documentclass[10pt]{article} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{pmc} \\usepackage[Euler]{upgreek} \\pagestyle{empty} \\oddsidemargin -1.0in \\begin{document} \\begin{equation*}{\\propto}1/K_{{\\mathrm{D}}}^{{\\mathrm{in}}}\\end{equation*}\\end{document}) and slower unliganded “free” carrier transit from inside to outside than in the reverse direction. However, asymmetric rates of unliganded carrier movement, kij, imply that an energy source, ΔGcarrier = RT ln (koi/kio) = RT ln (Cin/Cout) = RT ln (\\documentclass[10pt]{article} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{pmc} \\usepackage[Euler]{upgreek} \\pagestyle{empty} \\oddsidemargin -1.0in \\begin{document} \\begin{equation*}K_{{\\mathrm{D}}}^{{\\mathrm{in}}}/K_{{\\mathrm{D}}}^{{\\mathrm{out}}}\\end{equation*}\\end{document}), where R is the universal gas constant (8.314 Joules/M/K°), and T is the temperature, assumed here to be 300 K°, sustains the asymmetry. Without this invalid assumption, the constraints of carrier path cyclicity, combined with asymmetric ligand affinities and equimolarity at equilibrium, are irreconcilable, and any passive asymmetric uniporter or cotransporter model system, e.g., Na-glucose cotransporters, espousing this fundamental error is untenable. With glucose transport via GLUT1, the higher maximal rate and Km of net ligand exit compared to net ligand entry is only properly

  8. Asymmetric stem cell division: lessons from Drosophila.

    Science.gov (United States)

    Wu, Pao-Shu; Egger, Boris; Brand, Andrea H

    2008-06-01

    Asymmetric cell division is an important and conserved strategy in the generation of cellular diversity during animal development. Many of our insights into the underlying mechanisms of asymmetric cell division have been gained from Drosophila, including the establishment of polarity, orientation of mitotic spindles and segregation of cell fate determinants. Recent studies are also beginning to reveal the connection between the misregulation of asymmetric cell division and cancer. What we are learning from Drosophila as a model system has implication both for stem cell biology and also cancer research.

  9. On-chip asymmetric microcavity optomechanics.

    Science.gov (United States)

    Soltani, Soheil; Hudnut, Alexa W; Armani, Andrea M

    2016-12-26

    High quality factor (Q) optical resonators have enabled rapid growth in the field of cavity-enhanced, radiation pressure-induced optomechanics. However, because research has focused on axisymmetric devices, the observed regenerative excited mechanical modes are similar. In the present work, a strategy for fabricating high-Q whispering gallery mode microcavities with varying degrees of asymmetry is developed and demonstrated. Due to the combination of high optical Q and asymmetric device design, two previously unobserved modes, the asymmetric cantilever and asymmetric crown mode, are demonstrated with sub-mW thresholds for onset of oscillations. The experimental results are in good agreement with computational modeling predictions.

  10. Regenerating a symmetry in asymmetric dark matter.

    Science.gov (United States)

    Buckley, Matthew R; Profumo, Stefano

    2012-01-06

    Asymmetric dark matter theories generically allow for mass terms that lead to particle-antiparticle mixing. Over the age of the Universe, dark matter can thus oscillate from a purely asymmetric configuration into a symmetric mix of particles and antiparticles, allowing for pair-annihilation processes. Additionally, requiring efficient depletion of the primordial thermal (symmetric) component generically entails large annihilation rates. We show that unless some symmetry completely forbids dark matter particle-antiparticle mixing, asymmetric dark matter is effectively ruled out for a large range of masses, for almost any oscillation time scale shorter than the age of the Universe.

  11. Absolute Asymmetric Synthesis Using A Cocrystal Approach

    Institute of Scientific and Technical Information of China (English)

    H.Koshima

    2007-01-01

    1 Results Absolute asymmetric synthesis by means of solid-state reaction of chiral crystals self-assembled from achiral molecules is an attractive and promising methodology for asymmetric synthesis because it is not necessary to employ any external chiral source like a chiral catalyst.In order to design reliably absolute asymmetric syntheses in the solid state,it is inevitable to prepare and predict the formation of chiral crystals from achiral compounds.We have prepared a number of chiral cocrystals co...

  12. Asymmetric dark matter in braneworld cosmology

    Energy Technology Data Exchange (ETDEWEB)

    Meehan, Michael T.; Whittingham, Ian B., E-mail: Michael.Meehan@my.jcu.edu.au, E-mail: Ian.Whittingham@jcu.edu.au [School of Engineering and Physical Sciences, James Cook University, Townsville, 4811 Australia (Australia)

    2014-06-01

    We investigate the effect of a braneworld expansion era on the relic density of asymmetric dark matter. We find that the enhanced expansion rate in the early universe predicted by the Randall-Sundrum II (RSII) model leads to earlier particle freeze-out and an enhanced relic density. This effect has been observed previously by Okada and Seto (2004) for symmetric dark matter models and here we extend their results to the case of asymmetric dark matter. We also discuss the enhanced asymmetric annihilation rate in the braneworld scenario and its implications for indirect detection experiments.

  13. Enantiopure sulfoxides: recent applications in asymmetric synthesis.

    Science.gov (United States)

    Carreño, M Carmen; Hernández-Torres, Gloria; Ribagorda, María; Urbano, Antonio

    2009-11-07

    Sulfoxides are nowadays recognised as powerful chiral auxiliaries that may participate in a wide range of asymmetric reactions. Their high configurational stability, the existence of several efficient methods allowing the access to both configurations as well as their synthetic versatility are characteristic features offering a tremendous potential to develop new applications. Significant recent advances leading to high asymmetric inductions in carbon-carbon and carbon-oxygen bond forming reactions, and applications of homochiral sulfoxides to atroposelective synthesis and asymmetric catalysis are discussed. New uses of sulfoxides in the design of chiroptical switches are also shown.

  14. Chlamydia trachomatis CT771 (nudH) is an asymmetric Ap4A hydrolase

    Science.gov (United States)

    Barta, Michael L.; Lovell, Scott; Sinclair, Amy N.; Battaile, Kevin P.; Hefty, P. Scott

    2014-01-01

    Asymmetric diadenosine 5′,5′″-P1,P4-tetraphosphate (Ap4A) hydrolases are members of the Nudix superfamily that asymmetrically cleave the metabolite Ap4A into ATP and AMP while facilitating homeostasis. The obligate intracellular mammalian pathogen Chlamydia trachomatis possesses a single Nudix family protein, CT771. As pathogens that rely on a host for replication and dissemination typically have one or zero Nudix family proteins, this suggests that CT771 could be critical for chlamydial biology and pathogenesis. We identified orthologs to CT771 within environmental Chlamydiales that share active site residues suggesting a common function. Crystal structures of both apo- and ligand-bound CT771 were determined to 2.6 Å and 1.9 Å resolution, respectively. The structure of CT771 shows a αβα-sandwich motif with many conserved elements lining the putative Nudix active site. Numerous aspects of the ligand-bound CT771 structure mirror those observed in the ligand-bound structure of the Ap4A hydrolase from Caenorhabditis elegans. These structures represent only the second Ap4A hydrolase enzyme member determined from eubacteria and suggest that mammalian and bacterial Ap4A hydrolases might be more similar than previously thought. The aforementioned structural similarities, in tandem with molecular docking, guided the enzymatic characterization of CT771. Together, these studies provide the molecular details for substrate binding and specificity, supporting the analysis that CT771 is an Ap4A hydrolase (nudH). PMID:24354275

  15. Direct and post-synthesis incorporation of chiral metallosalen catalysts into metal-organic frameworks for asymmetric organic transformations.

    Science.gov (United States)

    Xi, Weiqin; Liu, Yan; Xia, Qingchun; Li, Zijian; Cui, Yong

    2015-09-01

    Two chiral porous metal-organic frameworks (MOFs) were constructed from [VO(salen)]-derived dicarboxylate and dipyridine bridging ligands. After oxidation of V(IV) to V(V) , they were found to be highly effective, recyclable, and reusable heterogeneous catalysts for the asymmetric cyanosilylation of aldehydes with up to 95 % ee. Solvent-assisted linker exchange (SALE) treatment of the pillared-layer MOF with [Cr(salen)Cl]- or [Al(salen)Cl]-derived dipyridine ligands led to the formation of mixed-linker metallosalen-based frameworks and incorporation of [Cr(salen)] enabled its use as a heterogeneous catalyst in the asymmetric epoxide ring-opening reaction.

  16. Asymmetric dark matter bound state

    Science.gov (United States)

    Bi, Xiao-Jun; Kang, Zhaofeng; Ko, P.; Li, Jinmian; Li, Tianjun

    2017-02-01

    We propose an interesting framework for asymmetric scalar dark matter (ADM), which has novel collider phenomenology in terms of an unstable ADM bound state (ADMonium) produced via Higgs portals. ADMonium is a natural consequence of the basic features of ADM: the (complex scalar) ADM is charged under a dark local U (1 )d symmetry which is broken at a low scale and provides a light gauge boson X . The dark gauge coupling is strong and then ADM can annihilate away into X -pair effectively. Therefore, the ADM can form a bound state due to its large self-interaction via X mediation. To explore the collider signature of ADMonium, we propose that ADM has a two-Higgs doublet portal. The ADMonium can have a sizable mixing with the heavier Higgs boson, which admits a large cross section of ADMonium production associated with b b ¯. The resulting signature at the LHC depends on the decays of X . In this paper we consider a case of particular interest: p p →b b ¯ +ADMonium followed by ADMonium→2 X →2 e+e- where the electrons are identified as (un)converted photons. It may provide a competitive explanation to heavy di-photon resonance searches at the LHC.

  17. Twin Higgs Asymmetric Dark Matter.

    Science.gov (United States)

    García García, Isabel; Lasenby, Robert; March-Russell, John

    2015-09-18

    We study asymmetric dark matter (ADM) in the context of the minimal (fraternal) twin Higgs solution to the little hierarchy problem, with a twin sector with gauged SU(3)^{'}×SU(2)^{'}, a twin Higgs doublet, and only third-generation twin fermions. Naturalness requires the QCD^{'} scale Λ_{QCD}^{'}≃0.5-20  GeV, and that t^{'} is heavy. We focus on the light b^{'} quark regime, m_{b^{'}}≲Λ_{QCD}^{'}, where QCD^{'} is characterized by a single scale Λ_{QCD}^{'} with no light pions. A twin baryon number asymmetry leads to a successful dark matter (DM) candidate: the spin-3/2 twin baryon, Δ^{'}∼b^{'}b^{'}b^{'}, with a dynamically determined mass (∼5Λ_{QCD}^{'}) in the preferred range for the DM-to-baryon ratio Ω_{DM}/Ω_{baryon}≃5. Gauging the U(1)^{'} group leads to twin atoms (Δ^{'}-τ^{'}[over ¯] bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors.

  18. Force on an Asymmetric Capacitor

    CERN Document Server

    Bahder, T B; Bahder, Thomas B.; Fazi, Chris

    2002-01-01

    When a high voltage (~30 kV) is applied to a capacitor whose electrodes have different physical dimensions, the capacitor experiences a net force toward the smaller electrode (Biefeld-Brown effect). We have verified this effect by building four capacitors of different shapes. The effect may have applications to vehicle propulsion and dielectric pumps. We review the history of this effect briefly through the history of patents by Thomas Townsend Brown. At present, the physical basis for the Biefeld-Brown effect is not understood. The order of magnitude of the net force on the asymmetric capacitor is estimated assuming two different mechanisms of charge conduction between its electrodes: ballistic ionic wind and ionic drift. The calculations indicate that ionic wind is at least three orders of magnitude too small to explain the magnitude of the observed force on the capacitor. The ionic drift transport assumption leads to the correct order of magnitude for the force, however, it is difficult to see how ionic dr...

  19. Asymmetric total synthesis of vindoline.

    Science.gov (United States)

    Kato, Daisuke; Sasaki, Yoshikazu; Boger, Dale L

    2010-03-24

    A concise asymmetric total synthesis of (-)-vindoline (1) is detailed based on a tandem intramolecular [4+2]/[3+2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which the tether linking the initiating dienophile and oxadiazole bears a chiral substituent that controls the facial selectivity of the initiating Diels-Alder reaction and sets absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduces three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. Implementation of the approach also required the development of a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the Delta (6, 7)-double bond found in the core structure of vindoline and defined our use of a protected hydroxymethyl group as the substituent used to control the stereochemical course of the cycloaddition cascade.

  20. Polystyrene-supported cu(II)-R-Box as recyclable catalyst in asymmetric Friedel–Crafts reaction

    KAUST Repository

    Desyatkin, V. G.

    2017-02-12

    The complex of copper(II) trifluoromethanesulfonate with chiral isopropyl bis(oxazoline) ligand (i-Pr-Box) was immobilized on accessible and inexpensive Merrifield resin according to a “click” procedure. The resulting catalyst showed high efficiency and recyclability in the asymmetric Friedel–Crafts alkylation of indole and its derivatives. The catalyst can be recycled five times without appreciable loss in activity and enantioselectivity.

  1. 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.

  2. A novel asymmetric synthesis of cinacalcet hydrochloride

    OpenAIRE

    Arava, Veera R; Laxminarasimhulu Gorentla; Pramod K. Dubey

    2012-01-01

    A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R)-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described.

  3. A novel asymmetric synthesis of cinacalcet hydrochloride

    Directory of Open Access Journals (Sweden)

    Veera R. Arava

    2012-08-01

    Full Text Available A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described.

  4. A novel asymmetric synthesis of cinacalcet hydrochloride

    Science.gov (United States)

    Gorentla, Laxminarasimhulu; Dubey, Pramod K

    2012-01-01

    Summary A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R)-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described. PMID:23019473

  5. Catalytic Asymmetric Synthesis of Phosphine Boronates

    NARCIS (Netherlands)

    Hornillos, Valentin; Vila, Carlos; Otten, Edwin; Feringa, Ben L.

    2015-01-01

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of ,-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good y

  6. Asymmetric Swiss-cheese brane-worlds

    CERN Document Server

    Gergely, L A; K\\'{e}p\\'{\\i}r\\'{o}, Ibolya

    2006-01-01

    We consider Swiss-cheese brane universes embedded asymmetrically into the bulk. Neither the junction conditions between the Schwarzschild spheres and the sorrounding Friedmann brane regions with cosmological constant $\\Lambda $, nor the evolution of the scale factor are changed with respect to the symmetric case. The universe expands and decelerates forever. The asymmetry however has a drastic influence on the evolution of the cosmological fluid. Instead of the two branches of the symmetric case, in the asymmetric case four branches emerge. Moreover, the future pressure singularity arising in the symmetric case only for huge values of $\\Lambda $ becomes quite generic in the asymmetric case. Such pressure singularities emerge also when $\\Lambda=0$ is set. Then they are due entirely to the asymmetric embedding. For generic values of $\\Lambda $ we introduce a critical value of a suitably defined asymmetry parameter, which separates Swiss-cheese cosmologies with and without pressure singularities.

  7. 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.

  8. 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.

  9. DOES VOLATILITY RESPOND ASYMMETRIC TO PAST SHOCKS?

    OpenAIRE

    Claudiu Botoc

    2014-01-01

    The main aim of the paper is to examine if the stock market volatility exhibits asymmetric or an asymmetric response to past shocks, for certain CEE countries (Romania,Hungary, Bulgaria, Poland) over the period May 2004 - September 2014. For the stock marketsfrom East Europe the results are in line with the symmetric volatility, i.e. volatility is similaraffected by both positive and negative returns with the same magnitude. For the stock marketsfrom Central Europe the results are consistent ...

  10. High resolution crystal structures of unliganded and liganded human liver ACBP reveal a new mode of binding for the acyl-CoA ligand

    DEFF Research Database (Denmark)

    Taskinen, Jukka P; van Aalten, Daan M; Knudsen, Jens;

    2007-01-01

    The acyl-CoA binding protein (ACBP) is essential for the fatty acid metabolism, membrane structure, membrane fusion, and ceramide synthesis. Here high resolution crystal structures of human cytosolic liver ACBP, unliganded and liganded with a physiological ligand, myristoyl-CoA are described....... The binding of the acyl-CoA molecule induces only few structural differences near the binding pocket. The crystal form of the liganded ACBP, which has two ACBP molecules in the asymmetric unit, shows that in human ACBP the same acyl-CoA binding pocket is present as previously described for the bovine...... and Plasmodium falciparum ACBP and the mode of binding of the 3'-phosphate-AMP moiety is conserved. Unexpectedly, in one of the acyl-CoA binding pockets the acyl moiety is bound in a reversed mode as compared with the bovine and P. falciparum structures. In this binding mode, the myristoyl-CoA molecule is fully...

  11. Melatonin: functions and ligands.

    Science.gov (United States)

    Singh, Mahaveer; Jadhav, Hemant R

    2014-09-01

    Melatonin is a chronobiotic substance that acts as synchronizer by stabilizing bodily rhythms. Its synthesis occurs in various locations throughout the body, including the pineal gland, skin, lymphocytes and gastrointestinal tract (GIT). Its synthesis and secretion is controlled by light and dark conditions, whereby light decreases and darkness increases its production. Thus, melatonin is also known as the 'hormone of darkness'. Melatonin and analogs that bind to the melatonin receptors are important because of their role in the management of depression, insomnia, epilepsy, Alzheimer's disease (AD), diabetes, obesity, alopecia, migraine, cancer, and immune and cardiac disorders. In this review, we discuss the mechanism of action of melatonin in these disorders, which could aid in the design of novel melatonin receptor ligands.

  12. Macrocyclic G-quadruplex ligands

    DEFF Research Database (Denmark)

    Nielsen, M C; Ulven, Trond

    2010-01-01

    G-quadruplex stabilizing compounds have recently received increased interest due to their potential application as anticancer therapeutics. A significant number of structurally diverse G-quadruplex ligands have been developed. Some of the most potent and selective ligands currently known are macr...

  13. An Economical, Highly Efficient and Recyclable Catalyst System for Asymmetric Dihydroxylation of Olefins

    Institute of Scientific and Technical Information of China (English)

    金瑛; 孙晓莉; 姜茹; 张生勇

    2005-01-01

    A reusable cinchona alkaloid derivative ligand, which could be easily synthesized by two step transformation with cheap 3,6-dichloropyridazine and quinine as materials, was applied to homogeneous asymmetric dihydroxylation of olefins with NMO as co-oxidant in Me2CO-H20 system and the products could be extracted with Et2O from the recyclable catalyst system. 80%---93% yield and 51%-99% ee have been obtained. When trans-stilbene was chosen as the substrate for recycling experiment, 88%-92% yield and >99% ee have been obtained for ten recycles.

  14. Novel Chiral PNNP-Ru Complexes: Synthesis and Application in Asymmetric Transfer Hydrogenation of Ketones

    Institute of Scientific and Technical Information of China (English)

    CHENG Zhi-bo; YU Shen-luan; LI Yan-yun; DONG Zhen-rong; SUN Guo-song; HUANG Ke-lin; GAO Jing-xing

    2011-01-01

    The efficient catalytic systems generated in situ from RuCl2(PPh3)3 and chiral ligands N,N-bis[2-(di-otolylphosphino)-benzyl]cyclohexane-l,2-diamine(2) were employed for asymmetric transfer hydrogenation of aromatic ketones, giving the corresponding optically active alcohols with high activities(up to 99% conversion) and excellent enantioselectivities(up to 96% e.e.) under mild conditions. The chiral ruthenium(Ⅱ) complex (R,R)-3 has been prepared and characterized by NMR and X-ray crystallography.

  15. The first catalytic asymmetric addition of diethylzinc to aldehyde promoted by chiral thiourea

    Institute of Scientific and Technical Information of China (English)

    Zhi Guo Qiao; Tian Hua Shen; Zhen Fang Fu; Jun Qi Li; Hong Wang; Qing Bao Song

    2011-01-01

    A series of C2-symmetric and asymmetric chiral thiourea derivatives were synthesized from commercial L-phenylalanine. All of the new compounds have been fully characterized by IR, 1H NMR, 13C NMR, MS spectra and elemental analyses. The chiral thioureas were used as chiral ligands in the catalytic enantioselective ethylation of aldehydes with diethylzinc, the corresponding sec-alcohols were gained with excellent enantioselectivities (up to 87.1 % ee) and high yields (up to 76.7%) after the conditions were optimized.

  16. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

    KAUST Repository

    Stoltz, Brian

    2010-06-14

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  17. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates.

    Science.gov (United States)

    McDougal, Nolan T; Virgil, Scott C; Stoltz, Brian M

    2010-01-01

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  18. Asymmetric Hydroformylation of Olefins Catalyzed by a Chiral Diphosphite-Rhodium Complex

    Institute of Scientific and Technical Information of China (English)

    YAN, Ming(鄢明); LI, Xing-Shu(黎星术); CHAN, Albert Sun-Chi(陈新滋)

    2004-01-01

    A C2-symmetrical aryl diphosphite derived from chiral binaphthol was prepared and its rhodium complex was used as catalysts in the asymmetric hydroformylation of olefins. High catalytic activity and good regioselectivity were observed. Up to 31.2% ee and 38.1% ee were achieved for the hydroformylation of 4-fluoro-styrene and vinyl acetate respectively. The influences of ligand-to-metal ratio, reaction temperature and the pressure of syn-gas on the enantioselectivity and regioselectivity were also studied.

  19. Asymmetric tandem organic solar cells

    Science.gov (United States)

    Howells, Thomas J.

    where it is used to predict the short-circuit current (Jsc) generation of the sub-cells, which is not accessible experimentally. Current-matching is then used to predict the Jsc of the complete tandem device. . As a support to the optical modelling, ellipsometry measurements of thin films of ClAlPc are presented. These films of known thickness are analysed to extract the complex refractive index for use in optical modelling calculations. A dependence of the complex refractive index on film thickness and substrate is also noted. Finally, the external quantum efficiency (EQE) technique is considered as applied to solar cells, and an additional method is proposed to characterise current balancing in asymmetric tandem cells under illumination. This technique is verified experimentally by two separate sets of data..

  20. Phosphorylation of the Polarity Protein BASL Differentiates Asymmetric Cell Fate through MAPKs and SPCH.

    Science.gov (United States)

    Zhang, Ying; Guo, Xiaoyu; Dong, Juan

    2016-11-07

    Cell polarization is commonly used for the regulation of stem cell asymmetric division in both animals and plants. Stomatal development in Arabidopsis, a process that produces breathing pores in the epidermis, requires asymmetric cell division to differentiate highly specialized guard cells while maintaining a stem cell population [1, 2]. The BREAKING OF ASYMMETRY IN THE STOMATAL LINEAGE (BASL) protein exhibits a polarized localization pattern in the cell and is required for differential cell fates resulting from asymmetric cell division [3]. The polarization of BASL is made possible by a positive feedback loop with a canonical mitogen-activated protein kinase (MAPK) pathway that recruits the MAPKK kinase YODA (YDA) and MAPK 6 (MPK6) to the cortical polarity site [4]. Here, we study BASL intracellular dynamics and show that the membrane-associated BASL is slowly replenished at the cortical polarity site and that the mobility is tightly linked to its phosphorylation status. Because BASL polarity is only exhibited by one daughter cell after an asymmetric cell division, we study how BASL differentially functions in the two daughter cells. The YDA MAPK cascade transduces upstream ligand-receptor signaling [5-13] to the transcription factor SPEECHLESS (SPCH), which controls stomatal initiation and is directly suppressed by MPK3/6-mediated phosphorylation [14, 15]. We show that BASL polarization leads to elevated nuclear MPK6 signaling and lowered SPCH abundance in one of the two daughter cells. Therefore, two daughter cells are differentiated by BASL polarity-mediated differential suppression of SPCH, which may provide developmental plasticity in plant stem cell asymmetric cell division (ACD).

  1. Tunable Dendritic Ligands of Chiral 1,2-Diamine and Their Application in Asymmetric Transfer Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    LIU,Wei-Guo; CUI,Xin; CUN,Lin-Feng; WU,Jun; ZHU,Jin; DENG,Jin-Gen

    2004-01-01

    @@ Dendrimers are perfect monodisperse macromolecules with a regular and highly branched three-dimensional architecture, so their unique physical and chemical properties are noticed and utilized more and more.[1] The dendrimer architecture can offer a means of better controlling the disposition of the catalytic species in soluble polymer-based catalysts and such novel catalysts of nano-scale size may aid the recycling of catalysts simply by supra-filtration or solvent precipitation methods.

  2. Crystal Structure of a Nickel(Ⅱ) Complex with Asymmetric L-Histidine Ligand

    Institute of Scientific and Technical Information of China (English)

    JIN Yi; CHE Yun-Xia; ZHENG Ji-Min

    2006-01-01

    A novel nickel(Ⅱ) complex with L-histidine has been synthesized and solved by single-crystal X-ray diffraction analysis at physiological pH. The title complex (C7H16NiN4O6S, Mr= 343.01) crystallizes in monoclinic, space group P21 with a = 7.2194(7), b = 7.5968(7), c =12.2797(11) (A), β = 93.3110(10)°, V = 672.35(11) (A)3, Z = 2, Dc= 1.694 g/cm3, F(000) = 356,μ(MoKα) = 1.626 mm-1, T = 293(2) K, the final R = 0.0184 and wR = 0.0426 for 2207 observed reflections with I > 2σ(Ⅰ). The complex provides insights into a possible structural arrangement between nickel (Ⅱ) and L-histidine which may be physiologically important and abundantly present in biological systems.

  3. Glutamate receptor ligands

    DEFF Research Database (Denmark)

    Guldbrandt, Mette; Johansen, Tommy N; Frydenvang, Karla Andrea;

    2002-01-01

    Homologation and substitution on the carbon backbone of (S)-glutamic acid [(S)-Glu, 1], as well as absolute stereochemistry, are structural parameters of key importance for the pharmacological profile of (S)-Glu receptor ligands. We describe a series of methyl-substituted 2-aminoadipic acid (AA......-ray crystallographic analyses, chemical correlation, and CD spectral analyses. The effects of the individual stereoisomers at ionotropic and metabotropic (S)-Glu receptors (iGluRs and mGluRs) were characterized. Compounds with S-configuration at the alpha-carbon generally showed mGluR2 agonist activity of similar...... limited effect on pharmacology. Structure-activity relationships at iGluRs in the rat cortical wedge preparation showed a complex pattern, some compounds being NMDA receptor agonists [e.g., EC(50) =110 microM for (2S,5RS)-5-methyl-AA (6a,b)] and some compounds showing NMDA receptor antagonist effects [e...

  4. Control of apoptosis by asymmetric cell division.

    Directory of Open Access Journals (Sweden)

    Julia Hatzold

    2008-04-01

    Full Text Available Asymmetric cell division and apoptosis (programmed cell death are two fundamental processes that are important for the development and function of multicellular organisms. We have found that the processes of asymmetric cell division and apoptosis can be functionally linked. Specifically, we show that asymmetric cell division in the nematode Caenorhabditis elegans is mediated by a pathway involving three genes, dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail, that directly control the enzymatic machinery responsible for apoptosis. Interestingly, the MIDA1-like protein GlsA of the alga Volvox carteri, as well as the Snail-related proteins Snail, Escargot, and Worniu of Drosophila melanogaster, have previously been implicated in asymmetric cell division. Therefore, C. elegans dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail may be components of a pathway involved in asymmetric cell division that is conserved throughout the plant and animal kingdoms. Furthermore, based on our results, we propose that this pathway directly controls the apoptotic fate in C. elegans, and possibly other animals as well.

  5. [Development of new methods in asymmetric reactions and their applications].

    Science.gov (United States)

    Node, Manabu

    2002-01-01

    Several novel methods using chiral reagents and biocatalysts for asymmetric reactions are described. Among those reactions, asymmetric reduction via a novel tandem Michael addition/Meerwein-Ponndorf-Verley reduction of acyclic alpha,beta-unsaturated ketones using a chiral mercapto alcohol, asymmetric synthesis of allene-1,3-dicarboxylate via crystallization induced asymmetric transformation, and improved asymmetric nitroolefination of lactones and lactames at alpha-carbon using new chiral reagents were developed. In the reactions using biocatalysts, asymmetric dealkoxycarbonylation of bicyclic beta-keto diesters having sigma-symmetry with lipase or esterase to give optically active beta-keto esters, the asymmetric reduction of bicyclic 1,3-diketones having sigma-symmetry with Baker's yeast to give optically active keto alcohols, and the asymmetric aldol reaction of glycine with threonine aldolase were also developed. The above mentioned products were effectively utilized as chiral building blocks for the asymmetric synthesis of natural products and drugs.

  6. Dc SQUIDs with asymmetric shunt resistors

    Energy Technology Data Exchange (ETDEWEB)

    Rudolph, Matthias; Nagel, Joachim; Kemmler, Matthias; Koelle, Dieter; Kleiner, Reinhold [Physikalisches Institut - Experimentalphysik II and Center for Collective Quantum Phenomena in LISAplus, Universitaet Tuebingen (Germany); Meckbach, Johannes Maximilian; Ilin, Konstantin; Siegel, Michael [Institut fuer Mikro- und Nanoelektronische Systeme, Karlsruhe Institute of Technology, Karlsruhe (Germany)

    2013-07-01

    We have investigated asymmetrically shunted Nb/Al-AlO{sub x}/Nb dc SQUIDs. Simulations based on the coupled Langevin equations predict that the optimum energy resolution ε, and thus also the noise performance of such an asymmetric SQUID, can be 3-4 times better than that of its symmetric counterpart. While keeping the total resistance R identical to a comparable symmetric SQUID with R{sup -1} = R{sub 1}{sup -1} + R{sub 2}{sup -1}, we shunted only one of the two Josephson junctions with R = R{sub 1,2}/2. Both types of SQUIDs were characterized with respect to their transport and noise properties at temperature T = 4.2 K, and we compared the experimental results with numerical simulations. Experiments yielded ε ∼ 32 ℎ for an asymmetric SQUID with an inductance L = 22 pH, whereas a comparable symmetric device achieved ε = 110 ℎ.

  7. Asymmetric gear rectifies random robot motion

    Science.gov (United States)

    Li, He; Zhang, H. P.

    2013-06-01

    We experimentally study the dynamics of centimetric robots and their interactions with rotary gears through inelastic collisions. Under the impacts of self-propelled robots, a gear with symmetric teeth diffuses with no preferred direction of motion. An asymmetric gear, however, rectifies random motion of nearby robots which, in return, exert a torque on the gear and drive it into unidirectional motion. Rectification efficiency increases with the degree of gear asymmetry. Our work demonstrates that asymmetric environments can be used to rectify and extract energy from random motion of macroscopic self-propelled particles.

  8. 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.

  9. Asymmetric catalysis with short-chain peptides.

    Science.gov (United States)

    Lewandowski, Bartosz; Wennemers, Helma

    2014-10-01

    Within this review article we describe recent developments in asymmetric catalysis with peptides. Numerous peptides have been established in the past two decades that catalyze a wide variety of transformations with high stereoselectivities and yields, as well as broad substrate scope. We highlight here catalytically active peptides, which have addressed challenges that had thus far remained elusive in asymmetric catalysis: enantioselective synthesis of atropoisomers and quaternary stereogenic centers, regioselective transformations of polyfunctional substrates, chemoselective transformations, catalysis in-flow and reactions in aqueous environments.

  10. Asymmetric acoustic transmission in multiple frequency bands

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hong-xiang, E-mail: jsdxshx@ujs.edu.cn [Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013 (China); Laboratory of Modern Acoustics, Institute of Acoustics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China); State Key Laboratory of Acoustics, Institute of Acoustics, Chinese Academy of Sciences, Beijing 100190 (China); Yuan, Shou-qi, E-mail: Shouqiy@ujs.edu.cn [Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013 (China); Zhang, Shu-yi [Laboratory of Modern Acoustics, Institute of Acoustics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China)

    2015-11-23

    We report both experimentally and numerically that the multi-band device of the asymmetric acoustic transmission is realized by placing two periodic gratings with different periods on both sides of two brass plates immersed in water. The asymmetric acoustic transmission can exist in four frequency bands below 1500 kHz, which arises from the interaction between various diffractions from the two gratings and Lamb modes in the brass plates immersed in water. The results indicate that the device has the advantages of multiple band, broader bandwidth, and simpler structure. Our finding should have great potential applications in ultrasonic devices.

  11. Integrated asymmetric vertical coupler pressure sensors

    Science.gov (United States)

    Kiyat, Isa; Kocabas, Askin; Akcag, Imran; Aydinli, Atilla

    2004-08-01

    Design and analysis of a novel pressure sensor based on a silicon-on-insulator asymmetric integrated vertical coupler is presented. The coupler is composed of a single mode low index waveguide and a thin silicon slab. Wavelength selective optical modulation of asymmetric vertical coupler is examined in detail. Its potential for sensing applications is highlighted as an integrated optical pressure sensor which can be realized by standard silicon micro-fabrication. Sensitivity of transmission of such couplers on refractive index change of silicon slab ensures that they are good candidates for applications requiring high sensitivities.

  12. Asymmetric localization in disordered Landau bands

    Energy Technology Data Exchange (ETDEWEB)

    Nita, M [Institute of Physics and Technology of Materials, PO Box MG7, Bucharest-Magurele (Romania); Aldea, A [Institute of Physics and Technology of Materials, PO Box MG7, Bucharest-Magurele (Romania); Zittartz, J [Institute of Theoretical Physics, Cologne University, 50937 Cologne (Germany)

    2007-06-06

    We show that, due to band mixing, the eigenstate localization within the disordered Landau bands gets an asymmetric structure: the degree of localization increases in the lower part of the band and decreases in the upper one. The calculation is performed for a two-dimensional lattice with the Anderson disorder potential and we prove that this effect is related to the upper shift of the extended states within the band and is enhanced by the disorder strength. The asymmetric localization and the energy shift disappear when the interband coupling is switched off.

  13. Asymmetric multiscale behavior in PM2.5 time series: Based on asymmetric MS-DFA

    Science.gov (United States)

    Zhang, Chen; Ni, Zhiwei; Ni, Liping

    2016-11-01

    Particulate matter with an aerodynamic diameter of 2.5 mm or less (PM2.5) is one of the most serious air pollution, considered most harmful for people by World Health Organisation. In this paper, we utilized the asymmetric multiscale detrended fluctuation analysis (A-MSDFA) method to explore the existence of asymmetric correlation properties for PM2.5 daily average concentration in two USA cities (Fresno and Los Angeles) and two Chinese cities (Hong Kong and Shanghai), and to assess the properties of these asymmetric correlations. The results show the existences of asymmetric correlations, and the degree of asymmetric for two USA cities is stronger than that of two Chinese cities. Further, most of the local exponent β(n) are smaller than 0.5, which indicates the existence of anti-persistent long-range correlation for PM2.5 time series in four cities. In addition, we reanalyze the asymmetric correlation by the A-MSDFA method with secant rolling windows of different sizes, which can investigate dynamic changes in the multiscale correlation for PM2.5 time series with changing window size. Whatever window sizes, the correlations are asymmetric and display smaller asymmetries at small scales and larger asymmetries at large scales. Moreover, the asymmetries become increasingly weaker with the increase of window sizes.

  14. Dcc regulates asymmetric outgrowth of forebrain neurons in zebrafish.

    Directory of Open Access Journals (Sweden)

    Jingxia Gao

    Full Text Available The guidance receptor DCC (deleted in colorectal cancer ortholog UNC-40 regulates neuronal asymmetry development in Caenorhabditis elegans, but it is not known whether DCC plays a role in the specification of neuronal polarity in vertebrates. To examine the roles of DCC in neuronal asymmetry regulation in vertebrates, we studied zebrafish anterior dorsal telencephalon (ADt neuronal axons. We generated transgenic zebrafish animals expressing the photo-convertible fluorescent protein Kaede in ADt neurons and then photo-converted Kaede to label specifically the ADt neuron axons. We found that ADt axons normally project ventrally. Knock down of Dcc function by injecting antisense morpholino oligonucleotides caused the ADt neurons to project axons dorsally. To examine the axon projection pattern of individual ADt neurons, we labeled single ADt neurons using a forebrain-specific promoter to drive fluorescent protein expression. We found that individual ADt neurons projected axons dorsally or formed multiple processes after morpholino knock down of Dcc function. We further found that knock down of the Dcc ligand, Netrin1, also caused ADt neurons to project axons dorsally. Knockdown of Neogenin1, a guidance receptor closely related to Dcc, enhanced the formation of aberrant dorsal axons in embryos injected with Dcc morpholino. These experiments provide the first evidence that Dcc regulates polarized axon initiation and asymmetric outgrowth of forebrain neurons in vertebrates.

  15. Rh(I)–Bisphosphine-Catalyzed Asymmetric, Intermolecular Hydroheteroarylation of α-Substituted Acrylate Derivatives

    Science.gov (United States)

    2015-01-01

    Asymmetric hydroheteroarylation of alkenes represents a convenient entry to elaborated heterocyclic motifs. While chiral acids are known to mediate asymmetric addition of electron-rich heteroarenes to Michael acceptors, very few methods exploit transition metals to catalyze alkylation of heterocycles with olefins via a C–H activation, migratory insertion sequence. Herein, we describe the development of an asymmetric, intermolecular hydroheteroarylation reaction of α-substituted acrylates with benzoxazoles. The reaction provides 2-substitued benzoxazoles in moderate to excellent yields and good to excellent enantioselectivities. Notably, a series of mechanistic studies appears to contradict a pathway involving enantioselective protonation of a Rh(I)–enolate, despite the fact that such a mechanism is invoked almost unanimously in the related addition of aryl boronic acids to methacrylate derivatives. Evidence suggests instead that migratory insertion or beta-hydride elimination is enantiodetermining and that isomerization of a Rh(I)–enolate to a Rh(I)–heterobenzyl species insulates the resultant α-stereocenter from epimerization. A bulky ligand, CTH-(R)-Xylyl-P-Phos, is crucial for reactivity and enantioselectivity, as it likely discourages undesired ligation of benzoxazole substrates or intermediates to on- or off-cycle rhodium complexes and attenuates coordination-promoted product epimerization. PMID:25545834

  16. Structural tailoring effects on the magnetic behavior of symmetric and asymmetric cubane-type Ni complexes.

    Science.gov (United States)

    Ponomaryov, Alexey N; Kim, Namseok; Hwang, Jaewon; Nojiri, Hiroyuki; van Tol, Johan; Ozarowski, Andrew; Park, Jena; Jang, Zeehoon; Suh, Byoungjin; Yoon, Sungho; Choi, Kwang-Yong

    2013-06-01

    Using two kinds of carboxylate ligands with small but significant differences in steric size, symmetric and asymmetric Fe(II) and Ni(II) cubanes have been synthesized in a controlled fashion. Fast sweeping pulsed field measurements showed magnetization hysteresis loops for two cubane-type molecular complexes, [Ni4(μ-OMe)4(O2CAr(4F-Ph))4(HOMe)8] and [Ni4(μ-OMe)4(O2CAr(Tol))4(HOMe)6], thus suggesting single-molecule magnet behavior. To differentiate the magnetic properties between the symmetric and asymmetric cubanes, detailed electron paramagnetic resonance (EPR) measurements were performed. From the EPR data, taken at various frequencies and temperatures, zero-field splitting parameters D, E, and other higher-order parameters for both cubane samples were extracted. Compared to the symmetric Ni-cubane, the asymmetric one shows an increase in the D and E values by about 20%, thereby suggesting structural engineering effects on the magnetic properties. By using the magnetic parameters determined by EPR, a static magnetization curve at 2 K and a temperature dependence of the magnetic susceptibility were simulated. A good agreement between theoretical and experimental data confirms the validity of the values obtained from EPR measurements.

  17. Structure of a double-domain phosphagen kinase reveals an asymmetric arrangement of the tandem domains.

    Science.gov (United States)

    Wang, Zhiming; Qiao, Zhu; Ye, Sheng; Zhang, Rongguang

    2015-04-01

    Tandem duplications and fusions of single genes have led to magnificent expansions in the divergence of protein structures and functions over evolutionary timescales. One of the possible results is polydomain enzymes with interdomain cooperativities, few examples of which have been structurally characterized at the full-length level to explore their innate synergistic mechanisms. This work reports the crystal structures of a double-domain phosphagen kinase in both apo and ligand-bound states, revealing a novel asymmetric L-shaped arrangement of the two domains. Unexpectedly, the interdomain connections are not based on a flexible hinge linker but on a rigid secondary-structure element: a long α-helix that tethers the tandem domains in relatively fixed positions. Besides the connective helix, the two domains also contact each other directly and form an interdomain interface in which hydrogen bonds and hydrophobic interactions further stabilize the L-shaped domain arrangement. Molecular-dynamics simulations show that the interface is generally stable, suggesting that the asymmetric domain arrangement crystallographically observed in the present study is not a conformational state simply restrained by crystal-packing forces. It is possible that the asymmetrically arranged tandem domains could provide a structural basis for further studies of the interdomain synergy.

  18. Egf Signaling Directs Neoblast Repopulation by Regulating Asymmetric Cell Division in Planarians.

    Science.gov (United States)

    Lei, Kai; Thi-Kim Vu, Hanh; Mohan, Ryan D; McKinney, Sean A; Seidel, Chris W; Alexander, Richard; Gotting, Kirsten; Workman, Jerry L; Sánchez Alvarado, Alejandro

    2016-08-22

    A large population of proliferative stem cells (neoblasts) is required for physiological tissue homeostasis and post-injury regeneration in planarians. Recent studies indicate that survival of a few neoblasts after sublethal irradiation results in the clonal expansion of the surviving stem cells and the eventual restoration of tissue homeostasis and regenerative capacity. However, the precise mechanisms regulating the population dynamics of neoblasts remain largely unknown. Here, we uncovered a central role for epidermal growth factor (EGF) signaling during in vivo neoblast expansion mediated by Smed-egfr-3 (egfr-3) and its putative ligand Smed-neuregulin-7 (nrg-7). Furthermore, the EGF receptor-3 protein localizes asymmetrically on the cytoplasmic membrane of neoblasts, and the ratio of asymmetric to symmetric cell divisions decreases significantly in egfr-3(RNAi) worms. Our results not only provide the first molecular evidence of asymmetric stem cell divisions in planarians, but also demonstrate that EGF signaling likely functions as an essential regulator of neoblast clonal expansion.

  19. THz operation of asymmetric-nanochannel devices

    NARCIS (Netherlands)

    Balocco, C.; Halsall, M.; Vinh, N. Q.; Song, A. M.

    2008-01-01

    The THz spectrum lies between microwaves and the mid-infrared, a region that remains largely unexplored mainly due to the bottleneck issue of lacking compact, solid state, emitters and detectors. Here, we report on a novel asymmetric-nanochannel device, known as the self-switching device, which can

  20. Asymmetric conditional volatility in international stock markets

    Science.gov (United States)

    Ferreira, Nuno B.; Menezes, Rui; Mendes, Diana A.

    2007-08-01

    Recent studies show that a negative shock in stock prices will generate more volatility than a positive shock of similar magnitude. The aim of this paper is to appraise the hypothesis under which the conditional mean and the conditional variance of stock returns are asymmetric functions of past information. We compare the results for the Portuguese Stock Market Index PSI 20 with six other Stock Market Indices, namely the SP 500, FTSE 100, DAX 30, CAC 40, ASE 20, and IBEX 35. In order to assess asymmetric volatility we use autoregressive conditional heteroskedasticity specifications known as TARCH and EGARCH. We also test for asymmetry after controlling for the effect of macroeconomic factors on stock market returns using TAR and M-TAR specifications within a VAR framework. Our results show that the conditional variance is an asymmetric function of past innovations raising proportionately more during market declines, a phenomenon known as the leverage effect. However, when we control for the effect of changes in macroeconomic variables, we find no significant evidence of asymmetric behaviour of the stock market returns. There are some signs that the Portuguese Stock Market tends to show somewhat less market efficiency than other markets since the effect of the shocks appear to take a longer time to dissipate.

  1. Dynamic Conditional Correlations for Asymmetric Processes

    NARCIS (Netherlands)

    M. Asai (Manabu); M.J. McAleer (Michael)

    2010-01-01

    textabstractThe paper develops two Dynamic Conditional Correlation (DCC) models, namely the Wishart DCC (WDCC) model and the Matrix-Exponential Conditional Correlation (MECC) model. The paper applies the WDCC approach to the exponential GARCH (EGARCH) and GJR models to propose asymmetric DCC models.

  2. Weak chaos in the asymmetric heavy top

    CERN Document Server

    Barrientos, M; Ranada, A F

    1995-01-01

    We consider the dynamics of the slightly asymmetric heavy top, a non-integrable system obtained from the Lagrange top by breaking the symmetry of its inertia tensor. It shows signs of weak chaos, which we study numerically. We argue that it is a good example for introducing students to non-integrability and chaos. (author)

  3. Catalytic Asymmetric Synthesis of Phosphine Boronates.

    Science.gov (United States)

    Hornillos, Valentín; Vila, Carlos; Otten, Edwin; Feringa, Ben L

    2015-06-26

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of α,β-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good yields and high enantiomeric excess. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds.

  4. Beam-beam issues in asymmetric colliders

    Energy Technology Data Exchange (ETDEWEB)

    Furman, M.A.

    1992-07-01

    We discuss generic beam-beam issues for proposed asymmetric e{sup +}- e{sup -} colliders. We illustrate the issues by choosing, as examples, the proposals by Cornell University (CESR-B), KEK, and SLAC/LBL/LLNL (PEP-II).

  5. Three dimensional force balance of asymmetric droplets

    Science.gov (United States)

    Kim, Yeseul; Lim, Su Jin; Cho, Kun; Weon, Byung Mook

    2016-11-01

    An equilibrium contact angle of a droplet is determined by a horizontal force balance among vapor, liquid, and solid, which is known as Young's law. Conventional wetting law is valid only for axis-symmetric droplets, whereas real droplets are often asymmetric. Here we show that three-dimensional geometry must be considered for a force balance for asymmetric droplets. By visualizing asymmetric droplets placed on a free-standing membrane in air with X-ray microscopy, we are able to identify that force balances in one side and in other side control pinning behaviors during evaporation of droplets. We find that X-ray microscopy is powerful for realizing the three-dimensional force balance, which would be essential in interpretation and manipulation of wetting, spreading, and drying dynamics for asymmetric droplets. This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2016R1D1A1B01007133).

  6. 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

  7. Nucleation Process in Asymmetric Nuclear Matter

    CERN Document Server

    Peres-Menezes, D

    1998-01-01

    An extended version of the non linear Walecka model, with rho mesons and eletromagnetic field is used to investigate the possibility of phase transitions in hot (warm) nuclear matter, giving rise to droplet formation. Surface properties of asymmetric nuclear matter as the droplet surface energy and its thickness are also examined.

  8. Integrated Optical Asymmetric Coupler Pressure Sensor

    Science.gov (United States)

    Kiyat, Isa; Kocabas, Coskun; Aydinli, Atilla

    2004-05-01

    Analysis of a novel pressure sensor based on a silicon-on-insulator (SOI) asymmetric vertical coupler is presented. The integrated optical component is a coupler composed of a single mode (SM) low index waveguide and a thin silicon slab. High sensitivities of about 0.14 rad.kPa-1 should be achieved.

  9. Asymmetric relationships between proteins shape genome evolution.

    NARCIS (Netherlands)

    Notebaart, R.A.; Kensche, P.R.; Huynen, M.A.; Dutilh, B.E.

    2009-01-01

    BACKGROUND: The relationships between proteins are often asymmetric: one protein (A) depends for its function on another protein (B), but the second protein does not depend on the first. In metabolic networks there are multiple pathways that converge into one central pathway. The enzymes in the conv

  10. Standards vs. labels with imperfect competition and asymmetric information

    DEFF Research Database (Denmark)

    Baltzer, Kenneth Thomas

    2012-01-01

    I demonstrate that providing information about product quality is not necessarily the best way to address asymmetric information problems when markets are imperfectly competitive. In a vertical differentiation model I show that a Minimum Quality Standard, which retains asymmetric information...

  11. Standards vs. labels with imperfect competition and asymmetric information

    DEFF Research Database (Denmark)

    Baltzer, Kenneth Thomas

    I demonstrate that providing information about product quality is not necessarily the best way to address asymmetric information problems when markets are imperfectly competitive. In a vertical dierentiation model I show that a Minimum Quality Standard, which retains asymmetric information...

  12. Chiral ligand-protected gold nanoclusters:Considering the optical activity from a viewpoint of ligand dissymmetric field

    Institute of Scientific and Technical Information of China (English)

    Hiroshi Yao

    2016-01-01

    Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold) nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD) properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R)-/(S)-2-phenylpropane-1-thiol, (R)-/(S)-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD) derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of many related

  13. Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

    Directory of Open Access Journals (Sweden)

    Hiroshi Yao

    2016-10-01

    Full Text Available Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R-/(S-2-phenylpropane-1-thiol, (R-/(S-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of

  14. Charge Asymmetric Cosmic Rays as a probe of Flavor Violating Asymmetric Dark Matter

    DEFF Research Database (Denmark)

    Masina, Isabella; Sannino, Francesco

    2011-01-01

    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....

  15. Visualization of Metal-to-Ligand and Ligand-to-Ligand Charge Transfer in Metal-Ligand Complexes

    Institute of Scientific and Technical Information of China (English)

    Yong Ding; Jian-xiu Guo; Xiang-si Wang; Sha-sha Liu; Feng-cai Ma

    2009-01-01

    Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer (MLCT) in ruthenium(Ⅱ) ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os(bpy)(p0p)Cl ("Osp0p"; bpy=2,2'-bipyridyl; p0p=4,4'-bipyridyl) and the ligand-to-ligand charge transfer (LLCT) in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.

  16. Why mercury prefers soft ligands

    Energy Technology Data Exchange (ETDEWEB)

    Riccardi, Demian M [ORNL; Guo, Hao-Bo [ORNL; Gu, Baohua [ORNL; Parks, Jerry M [ORNL; Summers, Anne [University of Georgia, Athens, GA; Miller, S [University of California, San Francisco; Liang, Liyuan [ORNL; Smith, Jeremy C [ORNL

    2013-01-01

    Mercury (Hg) is a major global pollutant arising from both natural and anthropogenic sources. Defining the factors that determine the relative affinities of different ligands for the mercuric ion, Hg2+, is critical to understanding its speciation, transformation, and bioaccumulation in the environment. Here, we use quantum chemistry to dissect the relative binding free energies for a series of inorganic anion complexes of Hg2+. Comparison of Hg2+ ligand interactions in the gaseous and aqueous phases shows that differences in interactions with a few, local water molecules led to a clear periodic trend within the chalcogenide and halide groups and resulted in the well-known experimentally observed preference of Hg2+ for soft ligands such as thiols. Our approach establishes a basis for understanding Hg speciation in the biosphere.

  17. Molecular Recognition and Ligand Association

    Science.gov (United States)

    Baron, Riccardo; McCammon, J. Andrew

    2013-04-01

    We review recent developments in our understanding of molecular recognition and ligand association, focusing on two major viewpoints: (a) studies that highlight new physical insight into the molecular recognition process and the driving forces determining thermodynamic signatures of binding and (b) recent methodological advances in applications to protein-ligand binding. In particular, we highlight the challenges posed by compensating enthalpic and entropic terms, competing solute and solvent contributions, and the relevance of complex configurational ensembles comprising multiple protein, ligand, and solvent intermediate states. As more complete physics is taken into account, computational approaches increase their ability to complement experimental measurements, by providing a microscopic, dynamic view of ensemble-averaged experimental observables. Physics-based approaches are increasingly expanding their power in pharmacology applications.

  18. cis-2,5-Diaminobicyclo[2.2.2]octane, a New Chiral Scaffold for Asymmetric Catalysis.

    Science.gov (United States)

    Shaw, Subrata; White, James D

    2016-09-20

    Catalysis of widely used chemical transformations in which the goal is to obtain the product as a pure enantiomer has become a major preoccupation of synthetic organic chemistry over the past three decades. A large number of chiral entities has been deployed to this end, many with considerable success, but one of the simplest and most effective catalytic systems to have emerged from this effort is that based on a chiral diamine, specifically trans-1,2-diaminocyclohexane. While there have been attempts to improve upon this scaffold in asymmetric synthesis, few have gained the recognition needed to take their place alongside this classic diamine. The challenge is to design a scaffold that retains the assets of trans-1,2-diaminocyclohexane while enhancing its intrinsic chirality and maximizing the scope of its applications. It occurred to us that cis-2,5-diaminobicyclo[2.2.2]octane could be such a scaffold. Synthesis of this diamine in enantiopure form was completed from benzoic acid, and the (1R,2R,4R,5R) enantiomer was used in all subsequent experiments in this laboratory. Condensation of the diamine with various salicyl aldehydes generated imine derivatives which proved to be excellent "salen" ligands for encapsulation of transition and other metals. In total, 12 salen-metal complexes were prepared from this ligand, many of which were crystalline and three of which, along with the ligand itself, yielded to X-ray crystallography. An advantage of this ligand is that it can be tuned sterically or electronically to confer specific catalytic properties on the salen-metal complex, and this feature was used in several applications of our salen-metal complexes in asymmetric synthesis. Thus, replacement of one of the tert-butyl groups in each benzenoid ring of the salen ligand by a methoxy substituent enhanced the catalytic efficiency of a cobalt(II)-salen complex used in asymmetric cyclopropanation of 1,1-disubstituted alkenes; the catalyst was employed in an improved

  19. Enhancing molecule fluorescence with asymmetrical plasmonic antennas.

    Science.gov (United States)

    Lu, Guowei; Liu, Jie; Zhang, Tianyue; Shen, Hongming; Perriat, Pascal; Martini, Matteo; Tillement, Olivier; Gu, Ying; He, Yingbo; Wang, Yuwei; Gong, Qihuang

    2013-07-21

    We propose and justify by the finite-difference time-domain method an efficient strategy to enhance the spontaneous emission of a fluorophore with a multi-resonance plasmonic antenna. The custom-designed asymmetrical antenna consists of two plasmonic nanoparticles with different sizes and is able to couple efficiently to free space light through multiple localized surface plasmon resonances. This design simultaneously permits a large near-field excitation near the antenna as well as a high quantum efficiency, which results in an unusual and significant enhancement of the fluorescence of a single emitter. Such an asymmetrical antenna presents intrinsic advantages over single particle or dimer based antennas made using two identical nanostructures. This promising concept can be exploited in the large domain of light-matter interaction processes involving multiple frequencies.

  20. Design of Asymmetric Peptide Bilayer Membranes.

    Science.gov (United States)

    Li, Sha; Mehta, Anil K; Sidorov, Anton N; Orlando, Thomas M; Jiang, Zhigang; Anthony, Neil R; Lynn, David G

    2016-03-16

    Energetic insights emerging from the structural characterization of peptide cross-β assemblies have enabled the design and construction of robust asymmetric bilayer peptide membranes. Two peptides differing only in their N-terminal residue, phosphotyrosine vs lysine, coassemble as stacks of antiparallel β-sheets with precisely patterned charged lattices stabilizing the bilayer leaflet interface. Either homogeneous or mixed leaflet composition is possible, and both create nanotubes with dense negative external and positive internal solvent exposed surfaces. Cross-seeding peptide solutions with a preassembled peptide nanotube seed leads to domains of different leaflet architecture within single nanotubes. Architectural control over these cross-β assemblies, both across the bilayer membrane and along the nanotube length, provides access to highly ordered asymmetric membranes for the further construction of functional mesoscale assemblies.

  1. Asymmetric dark matter models in SO(10)

    Science.gov (United States)

    Nagata, Natsumi; Olive, Keith A.; Zheng, Jiaming

    2017-02-01

    We systematically study the possibilities for asymmetric dark matter in the context of non-supersymmetric SO(10) models of grand unification. Dark matter stability in SO(10) is guaranteed by a remnant Z2 symmetry which is preserved when the intermediate scale gauge subgroup of SO(10) is broken by a {126} dimensional representation. The asymmetry in the dark matter states is directly generated through the out-of-equilibrium decay of particles around the intermediate scale, or transferred from the baryon/lepton asymmetry generated in the Standard Model sector by leptogenesis. We systematically classify possible asymmetric dark matter candidates in terms of their quantum numbers, and derive the conditions for each case that the observed dark matter density is (mostly) explained by the asymmetry of dark matter particles.

  2. Asymmetric Dark Matter Models in SO(10)

    CERN Document Server

    Nagata, Natsumi; Zheng, Jiaming

    2016-01-01

    We systematically study the possibilities for asymmetric dark matter in the context of non-supersymmetric SO(10) models of grand unification. Dark matter stability in SO(10) is guaranteed by a remnant $\\mathbb{Z}_2$ symmetry which is preserved when the intermediate scale gauge subgroup of SO(10) is broken by a ${\\bf 126}$ dimensional representation. The asymmetry in the dark matter states is directly generated through the out-of-equilibrium decay of particles around the intermediate scale, or transferred from the baryon/lepton asymmetry generated in the Standard Model sector by leptogenesis. We systematically classify possible asymmetric dark matter candidates in terms of their quantum numbers, and derive the conditions for each case that the observed dark matter density is (mostly) explained by the asymmetry of dark matter particles.

  3. Cosmological signatures of time-asymmetric gravity

    CERN Document Server

    Cortês, Marina; Smolin, Lee

    2016-01-01

    We develop the model proposed by Cort\\^es, Gomes & Smolin, to predict cosmological signatures of time-asymmetric extensions of general relativity they proposed recently. Within this class of models the equation of motion of chiral fermions is modified by a torsion term. This term leads to a dispersion law for neutrinos that associates a new time-varying energy with each particle. We find a new neutrino contribution to the Friedmann equation resulting from the torsion term in the Ashtekar connection. In this note we explore the phenomenology of this term and observational consequences for cosmological evolution. We show that constraints on the critical energy density will ordinarily render this term unobservably small, a maximum of order $10^{-25}$ of the neutrino energy density today. However, if the time-asymmetric dark energy is tuned to cancel the cosmological constant, the torsion effect may be a dark matter candidate.

  4. Spectroscopic, Structural, and Computational Characterization of Three Bispidinone Derivatives, as Ligands for Enantioselective Metal Catalyzed Reactions.

    Science.gov (United States)

    Castellano, Carlo; Sacchetti, Alessandro; Meneghetti, Fiorella

    2016-04-01

    Three chiral derivatives of the alkaloid sparteine (bispidines), characterized by the 3,7-diazabicyclo[3.3.1]nonane moiety, were designed as efficient ligands in a number of enantioselective reactions due to their metal coordination properties. A full evaluation of the 3D properties of the compounds was carried out, as the geometrical features of the bicyclic framework are strictly related to the efficiency of the ligands in the asymmetric catalysis. The selected molecules have different molecular complexity for investigating the effects of different chiral groups on the bicycle conformation. We report here a thorough analysis of their molecular arrangement, by NMR spectroscopy, single crystal X-ray crystallography, and computational techniques, which put in evidence their conformational preferences and the parameters needed for the design of more efficient ligands in asymmetric synthetic routes. The results confirmed the high molecular flexibility of the compounds, and indicated how to achieve a control of the chair-chair/boat-chair conformational ratio, by adjusting the relative size of the substituents on the piperidine nitrogens.

  5. Towards a Dithiocarbamate Ligand for CdS Nanoparticle-based Photocatalysis

    Science.gov (United States)

    O'Hara, Andrew; Lacroix, Andrew D.; Pantelides, Sokrates T.; MacDonald, Janet E.

    Photocatalysis of water into H2 and O2 presents a clean, renewable route for energy storage and production. Traditionally, most semiconducting nanoparticle research on photocatalysis has focused on the ability to reduce chemical systems using the photoexcited electron. Here we employ a combination of theory and experiments to develop a possible route towards the oxidation of chemical systems via the hole from photoexcitation using an asymmetric bipyridine ligand with conjugated dithiocarbamate ligand bound to the surface of cadmium sulfide nanorods. In particular, we use density functional theory to calculate the electronic levels and optical absorption of the designer ligand, free from the cadmium sulfide surface as well as attached to the surface, with and without the copper center. These calculations are compared with experimental UV/VIS absorption and fluorescence spectroscopy measurements to understand the role of copper chelation. Furthermore, theoretical comparisons are made with a related ligand known to oxidize water under an applied potential bias. Finally, we discuss whether we expect photocatalysis from the ligand and possible improvements to its design.

  6. Tetradentate Schiff base ligands and their complexes: synthesis, structural characterization, thermal, electrochemical and alkane oxidation.

    Science.gov (United States)

    Ceyhan, Gökhan; Köse, Muhammet; McKee, Vickie; Uruş, Serhan; Gölcü, Ayşegül; Tümer, Mehmet

    2012-09-01

    Three Schiff base ligands (H(2)L(1)-H(2)L(3)) with N(2)O(2) donor sites were synthesized by condensation of 1,5-diaminonapthalene with benzaldehyde derivatives. A series of Cu(II), Co(II), Ni(II), Mn(II) and Cr(III) complexes were prepared and characterized by spectroscopic and analytical methods. Thermal, electrochemical and alkane oxidation reactions of the ligands and their metal complexes were investigated. Extensive application of 1D ((1)H, (13)C NMR) and 2D (COSY, HETCOR, HMBC and TOSCY) NMR techniques were used to characterize the structures of the ligands and establish the (1)H and (13)C resonance assignments of the three ligands. Ligands H(2)L(1) and H(2)L(3) were obtained as single crystals from THF solution and characterized by X-ray diffraction. Both molecules are centrosymmetric and asymmetric unit contains one half of the molecule. Catalytic alkane oxidation reactions with the transition metal complexes investigated using cyclohexane and cyclooctane as substrates. The Cu(II) and Cr(III) complexes showed good catalytic activity in the oxidation of cyclohexane and cyclooctane to desired oxidized products. Electrochemical and thermal properties of the compounds were also investigated.

  7. Venture Capital Contracting Under Asymmetric Information

    OpenAIRE

    Jeffrey Trester

    1993-01-01

    The author develops a model of venture capital contracting in which the entrepreneur and venture capitalist contract under symmetric information. A condition of asymmetric information may arise subsequent to the first contract. The author shows that this condition makes debt contracts infeasible and leads to the use of preferred equity contracts. The author notes that discussions of the relation between venture capital and capital structure are rare. This paper expands the literature by addre...

  8. Fluorous Mixture Synthesis of Asymmetric Dendrimers

    Science.gov (United States)

    Jiang, Zhong-Xing; Yu, Yihua Bruce

    2010-01-01

    A divergent fluorous mixture synthesis (FMS) of asymmetric fluorinated dendrimers has been developed. Four generations of fluorinated dendrimers with the same fluorinated moiety were prepared with high efficiency, yield and purity. Comparison of the physicochemical properties of these dendrimers provided valuable information for their application and future optimization. This strategy has not only provided a practical method for the synthesis and purification of dendrimers, but also established the possibility of utilizing the same fluorinated moiety for FMS. PMID:20170088

  9. 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....

  10. New electric field in asymmetric magnetic reconnection.

    Science.gov (United States)

    Malakit, K; Shay, M A; Cassak, P A; Ruffolo, D

    2013-09-27

    We present a theory and numerical evidence for the existence of a previously unexplored in-plane electric field in collisionless asymmetric magnetic reconnection. This electric field, dubbed the "Larmor electric field," is associated with finite Larmor radius effects and is distinct from the known Hall electric field. Potentially, it could be an important indicator for the upcoming Magnetospheric Multiscale mission to locate reconnection sites as we expect it to appear on the magnetospheric side, pointing earthward, at the dayside magnetopause reconnection site.

  11. Asymmetric Information – Adverse Selection Problem

    Directory of Open Access Journals (Sweden)

    Dumitru MARIN

    2007-01-01

    Full Text Available The present paper makes an introduction in the contract theory starting with the definitions of asymmetric information and some of the problems that generate: moral hazard and adverse selection. We provide an insight of the latest empirical studies in adverse selection in different markets. An adverse selection model, based on Rothchild and Stiglitz is also present to give a perspective of the theoretical framework.

  12. Zn-catalyzed Enantio- and Diastereoselective Formal [4+2] Cycloaddition Involving Two Electron-Deficient Partners: Asymmetric Synthesis of Piperidines from 1-Azadienes and Nitroalkenes

    OpenAIRE

    Chu, John C. K.; Dalton, Derek M.; Rovis, Tomislav

    2015-01-01

    We report a catalytic asymmetric synthesis of piperidines through [4+2] cycloaddition of 1-azadienes and nitroalkenes. The reaction uses earth abundant Zn as catalyst, and is highly diastereo- and regio-selective. A novel BOPA ligand (F-BOPA) confers high reactivity and enantioselectivity in the process. The presence of ortho substitution on the arenes adjacent to the bis(oxazolines) was found to be particularly impactful, due to limiting the undesired coordination of 1-azadiene to the Lewis ...

  13. A race for RAGE ligands.

    Science.gov (United States)

    Schleicher, Erwin D

    2010-08-01

    In experimental animals a causal involvement of the multiligand receptor for advanced glycation end products (RAGE) in the development of diabetic vascular complications has been demonstrated. However, the nature of RAGE ligands present in patients with diabetic nephropathy has not yet been defined; this leaves open the relevance of the RAGE system to the human disease.

  14. 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.

  15. Asymmetric Conditional Volatility in International Stock Markets

    CERN Document Server

    Ferreira, N B; Menezes, R; Ferreira, Nuno B.; Mendes, Diana A.; Menezes, Rui

    2006-01-01

    Recent studies show that a negative shock in stock prices will generate more volatility than a positive shock of similar magnitude. The aim of this paper is to appraise the hypothesis under which the conditional mean and the conditional variance of stock returns are asymmetric functions of past information. We compare the results for the Portuguese Stock Market Index PSI 20 with six other Stock Market Indices, namely the S&P 500, FTSE100, DAX 30, CAC 40, ASE 20, and IBEX 35. In order to assess asymmetric volatility we use autoregressive conditional heteroskedasticity specifications known as TARCH and EGARCH. We also test for asymmetry after controlling for the effect of macroeconomic factors on stock market returns using TAR and M-TAR specifications within a VAR framework. Our results show that the conditional variance is an asymmetric function of past innovations raising proportionately more during market declines, a phenomenon known as the leverage effect. However, when we control for the effect of chan...

  16. Multiple Traveling Salesmen in Asymmetric Metrics

    CERN Document Server

    Friggstad, Zachary

    2011-01-01

    We consider some generalizations of the Asymmetric Traveling Salesman Path problem. Suppose we have an asymmetric metric G = (V,A) with two distinguished nodes s,t. We are also given a positive integer k. The goal is to find k paths of minimum total cost from s to t whose union spans all nodes. We call this the k-Person Asymmetric Traveling Salesmen Path problem (k-ATSPP). Our main result for k-ATSPP is a bicriteria approximation that, for some parameter b >= 1 we may choose, finds between k and k + k/b paths of total length O(b log |V|) times the optimum value of an LP relaxation based on the Held-Karp relaxation for the Traveling Salesman problem. On one extreme this is an O(log |V|)-approximation that uses up to 2k paths and on the other it is an O(k log |V|)-approximation that uses exactly k paths. Next, we consider the case where we have k pairs of nodes (s_1,t_1), ..., (s_k,t_k). The goal is to find an s_i-t_i path for every pair such that each node of G lies on at least one of these paths. Simple appro...

  17. Traceless Synthesis of Asymmetrically Modified Bivalent Nucleosomes.

    Science.gov (United States)

    Lechner, Carolin C; Agashe, Ninad D; Fierz, Beat

    2016-02-18

    Nucleosomes carry extensive post-translational modifications (PTMs), which results in complex modification patterns that are involved in epigenetic signaling. Although two copies of each histone coexist in a nucleosome, they may not carry the same PTMs and are often differently modified (asymmetric). In bivalent domains, a chromatin signature prevalent in embryonic stem cells (ESCs), namely H3 methylated at lysine 4 (H3K4me3), coexists with H3K27me3 in asymmetric nucleosomes. We report a general, modular, and traceless method for producing asymmetrically modified nucleosomes. We further show that in bivalent nucleosomes, H3K4me3 inhibits the activity of the H3K27-specific lysine methyltransferase (KMT) polycomb repressive complex 2 (PRC2) solely on the same histone tail, whereas H3K27me3 stimulates PRC2 activity across tails, thereby partially overriding the H3K4me3-mediated repressive effect. To maintain bivalent domains in ESCs, PRC2 activity must thus be locally restricted or reversed.

  18. SPECT using asymmetric pinholes with truncated projections

    Energy Technology Data Exchange (ETDEWEB)

    Lin Jianyu; Meikle, Steven R, E-mail: jianyu.lin@curtin.edu.au [Ramaciotti Imaging Centre, Brain and Mind Research Institute, University of Sydney (Australia)

    2011-07-07

    Tomographic systems employing truncated projections have been developed for parallel and fan beam collimation and for cone beam CT but the idea has not been extensively explored in pinhole single photon emission computed tomography (SPECT). In this paper, we explore the sampling requirements and system performance of SPECT systems with asymmetric pinhole collimators and truncated projections. We demonstrate that complete 3D sampling can be achieved by using multiple detectors with truncated asymmetric pinholes, offset axially from each other, and a spiral orbit. The use of truncated projections can be exploited in the design of pinhole SPECT systems by moving the pinholes closer to the subject, resulting in increased sensitivity and improved spatial resolution. Truncated and untruncated pinhole systems were evaluated using the contrast-to-noise ratio (CNR) calculated from the linearized local impulse response as a figure of merit. The CNR for the truncated pinhole system was up to 60% greater than that for the untruncated system at matched resolution for a source voxel near the centre of a uniform phantom and 30% greater at the edge. We conclude that an object can be reconstructed from asymmetric pinholes with truncated projections, which leads to potentially important design considerations and applications in single- and multi-pinhole SPECT.

  19. A new loss-of-function allele 28y reveals a role of ARGONAUTE1 in limiting asymmetric division of stomatal lineage ground cell

    Institute of Scientific and Technical Information of China (English)

    Kezhen Yangy; Min Jiangy; Jie Le

    2014-01-01

    In Arabidopsis thaliana L., stomata are produced through a series of divisions including asymmetric and symmetric divisions. Asymmetric entry division of meristemoid mother cellproduces two daughter cells, the smal er meristemoid and the larger sister cell, a stomatal lineage ground cell(SLGC). Stomatal lineage ground cells can differentiate into epidermal pavement cells but have the potential to divide asymmetrical y, spacing divisions, to create satel ite meristemoids. Peptide ligands and TOO MANY MOUTHS (TMM) and ERECTA family receptors regulate the initiation of stomatal lineages, activity, and orientation of spacing divisions. Here, we reported that a natural mutant 28y displayed an increased stomatal density and index. Using map-based cloning, we identified mutation in ARGONAUTE1 (AGO1) as the cause of 28y phenotypes. Time-lapse tracing of stomatal lineage cells reveals that stomatal overproduction in 28y is caused by the excessive asymmetric spacing division of SLGCs.Further genetic results demonstrated that AGO1 acts down-stream of TMM and negatively regulates the SPCH transcripts, but in a brassinosteroid-independent manner. Upregulation of AGAMOUS-LIKE16 (AGL16) in 28y mutants suggests that AGO1 is required to restrict AGL16-mediated stomatal spacing divisions, an miRNA pathway in addition to ligand-receptor signaling modules.

  20. Some metal complexes of three new potentially heptadentate (N4O3) tripodal Schiff base ligands; synthesis, characterizatin and X-ray crystal structure of a novel eight coordinate Gd(III) complex

    Science.gov (United States)

    Golbedaghi, Reza; Moradi, Somaeyh; Salehzadeh, Sadegh; Blackman, Allan G.

    2016-03-01

    The symmetrical and asymmetrical potentially heptadentate (N4O3) tripodal Schiff base ligands (H3L1-H3L3) were synthesized from the condensation reaction of three tripodal tetraamine ligands tpt (trpn), tris (3-aminopropyl) amine; ppe (abap), (2-aminoethyl)bis(3-aminopropyl)amine, and tren, tris(2-aminoethyl)amine, with 5-methoxysalicylaldehyde. Then, the reaction of Ln(III) (Ln = Gd, La and Sm), Al(III), and Fe(III) metal ions with the above ligands was investigated. The resulting compounds were characterized by IR, mass spectrometry and elemental analysis in all cases and NMR spectroscopy in the case of the Schiff base ligands. The X-ray crystal structure of the Gd complex of H3L3 ligand showed that in addition to all donor atoms of the ligand one molecule of H2O is also coordinated to the metal ion and a neutral eight-coordinate complex is formed.

  1. Synthesis of Aminophosphine Ligands with Binaphthyl Backbones for Silver(I)-catalyzed Enantioselective Allylation of Benzaldehyde

    Institute of Scientific and Technical Information of China (English)

    WANG,Yi(王以); JI,Bao-Ming(吉保明); DING,Kui-Ling(丁奎岭)

    2002-01-01

    A series of aminophosphine ligands was synthesized from 2amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). Their asymmetric induction efficiency was examined for silver(I)catalyzed enantioselective allylation reaction of benzaldehyde with allyltributyltin.Under the optimized reaction conditions,quantitative yield as well as moderate ee value (54.5% ee)of product was achieved by the catalysis with silver(I)/3 complex. The effects of the binaphthyl backbone and the substituted situated at chelating N, Patoms on enantioselectivity of the reaction were also discussed.

  2. Controlled-deactivation cannabinergic ligands.

    Science.gov (United States)

    Sharma, Rishi; Nikas, Spyros P; Paronis, Carol A; Wood, Jodianne T; Halikhedkar, Aneetha; Guo, Jason Jianxin; Thakur, Ganesh A; Kulkarni, Shashank; Benchama, Othman; Raghav, Jimit Girish; Gifford, Roger S; Järbe, Torbjörn U C; Bergman, Jack; Makriyannis, Alexandros

    2013-12-27

    We report an approach for obtaining novel cannabinoid analogues with controllable deactivation and improved druggability. Our design involves the incorporation of a metabolically labile ester group at the 2'-position on a series of (-)-Δ(8)-THC analogues. We have sought to introduce benzylic substituents α to the ester group which affect the half-lives of deactivation through enzymatic activity while enhancing the affinities and efficacies of individual ligands for the CB1 and CB2 receptors. The 1'-(S)-methyl, 1'-gem-dimethyl, and 1'-cyclobutyl analogues exhibit remarkably high affinities for both CB receptors. The novel ligands are susceptible to enzymatic hydrolysis by plasma esterases in a controllable manner, while their metabolites are inactive at the CB receptors. In further in vitro and in vivo experiments key analogues were shown to be potent CB1 receptor agonists and to exhibit CB1-mediated hypothermic and analgesic effects.

  3. Self-Assembly of Nanoclusters into Mono-, Few-, and Multilayered Sheets via Dipole-Induced Asymmetric van der Waals Attraction.

    Science.gov (United States)

    Wu, Zhennan; Liu, Jiale; Li, Yanchun; Cheng, Ziyi; Li, Tingting; Zhang, Hao; Lu, Zhongyuan; Yang, Bai

    2015-06-23

    Two-dimensional (2D) nanomaterials possessing regular layered structures and versatile chemical composition are highly expected in many applications. Despite the importance of van der Waals (vdW) attraction in constructing and maintaining layered structures, the origin of 2D anisotropy is not fully understood, yet. Here, we report the 2D self-assembly of ligand-capped Au15 nanoclusters into mono-, few-, and multilayered sheets in colloidal solution. Both the experimental results and computer simulation reveal that the 2D self-assembly is initiated by 1D dipolar attraction common in nanometer-sized objects. The dense 1D attachment of Au15 leads to a redistribution of the surface ligands, thus generating asymmetric vdW attraction. The deliberate control of the coordination of dipolar and vdW attraction further allows to manipulate the thickness and morphologies of 2D self-assembly architectures.

  4. Asymmetric-Structure Analysis of Carbon and Energy Markets

    Science.gov (United States)

    Xu, Wei; Cao, Guangxi

    2016-02-01

    This study aimed to investigate the asymmetric structure between the carbon and energy markets from two aspects of different trends (up or down) and volatility-transmission direction using asymmetric detrended cross-correlation analysis (DCCA) cross-correlation coefficient test, multifractal asymmetric DCCA (MF-ADCCA) method, asymmetric volatility-constrained correlation metric and time rate of information-flow approach. We sampled 1283 observations from January 2008 to December 2012 among pairs of carbon and energy markets for analysis. Empirical results show that the (1) asymmetric characteristic from the cross-correlation between carbon and returns in the energy markets is significant, (2) asymmetric cross-correlation between carbon and energy market price returns is persistent and multifractral and (3) volatility of the base assets of energy market returns is more influential to the base asset of the carbon market than that of the energy market.

  5. Tumor targeting via integrin ligands

    Directory of Open Access Journals (Sweden)

    Udaya Kiran eMarelli

    2013-08-01

    Full Text Available Selective and targeted delivery of drugs to tumors is a major challenge for an effective cancer therapy and also to overcome the side effects associated with current treatments. Overexpression of various receptors on tumor cells is a characteristic structural and biochemical aspect of tumors and distinguishes them from physiologically normal cells. This abnormal feature is therefore suitable for selectively directing anticancer molecules to tumors by using ligands that can preferentially recognize such receptors. Several subtypes of integrin receptors that are crucial for cell adhesion, cell signaling, cell viability and motility have been shown to have an upregulated expression on cancer cells. Thus, ligands that recognize specific integrin subtypes represent excellent candidates to be conjugated to drugs or drug carrier systems and be targeted to tumors. In this regard, integrins recognizing the RGD cell adhesive sequence have been extensively targeted for tumor specific drug delivery. Here we review key recent examples on the presentation of RGD-based integrin ligands by means of distinct drug delivery systems, and discuss the prospects of such therapies to specifically target tumor cells.

  6. Quantum optics of lossy asymmetric beam splitters

    Science.gov (United States)

    Uppu, Ravitej; Wolterink, Tom A. W.; Tentrup, Tristan B. H.; Pinkse, Pepijn W. H.

    2016-07-01

    We theoretically investigate quantum interference of two single photons at a lossy asymmetric beam splitter, the most general passive 2$\\times$2 optical circuit. The losses in the circuit result in a non-unitary scattering matrix with a non-trivial set of constraints on the elements of the scattering matrix. Our analysis using the noise operator formalism shows that the loss allows tunability of quantum interference to an extent not possible with a lossless beam splitter. Our theoretical studies support the experimental demonstrations of programmable quantum interference in highly multimodal systems such as opaque scattering media and multimode fibers.

  7. Improved DFIG Capability during Asymmetrical Grid Faults

    DEFF Research Database (Denmark)

    Zhou, Dao; Blaabjerg, Frede

    2015-01-01

    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....

  8. Resonance phenomena for asymmetric weakly nonlinear oscillator

    Institute of Scientific and Technical Information of China (English)

    钱定边

    2002-01-01

    We establish the coexistence of periodic solution and unbounded solution, the infinity of largeamplitude subharmonics for asymmetric weakly nonlinear oscillator x" + a2x+ - b2x- + h(x) = p(t) with h(±∞) - 0 and xh(x) → +∞(x →∞), assuming that M(τ ) has zeros which are all simple and M(τ ) 0respectively, where M(τ ) is a function related to the piecewise linear equation x" + a2x+ - b2x- = p(t).``

  9. Dynamic Conditional Correlations for Asymmetric Processes

    OpenAIRE

    Asai, Manabu; McAleer, Michael

    2011-01-01

    The paper develops two Dynamic Conditional Correlation (DCC) models, namely the Wishart DCC (wDCC) model. The paper applies the wDCC approach to the exponential GARCH (EGARCH) and GJR models to propose asymmetric DCC models. We use the standardized multivariate t-distribution to accommodate heavy-tailed errors. The paper presents an empirical example using the trivariate data of the Nikkei 225, Hang Seng and Straits Times Indices for estimating and forecasting the wDCC-EGARCH and wDCC-GJR mod...

  10. On asymmetric causal relationships in Petropolitics

    Directory of Open Access Journals (Sweden)

    Balan Feyza

    2016-01-01

    Full Text Available The aim of this paper is to examine whether the First Law of Petropolitics denominated by Friedman in 2006 is valid for OPEC countries. To do this, this paper analyses the relationship between political risk and oil supply by applying the asymmetric panel causality test suggested by Hatemi-J (2011 to these countries for the period 1984-2014. The results show that the First Law of Petropolitics is valid for Angola, Iraq, Kuwait, Libya, Nigeria, Qatar, Saudi Arabia, and the UAE, given that positive oil supply shocks significantly lead to negative political stability shocks, and negative oil supply shocks significantly lead to positive shocks in political stability.

  11. Quantum optics of lossy asymmetric beam splitters

    CERN Document Server

    Uppu, Ravitej; Tentrup, Tristan B H; Pinkse, Pepijn W H

    2016-01-01

    We theoretically investigate quantum interference of two single photons at a lossy asymmetric beam splitter, the most general passive 2$\\times$2 optical circuit. The losses in the circuit result in a non-unitary scattering matrix with a non-trivial set of constraints on the elements of the scattering matrix. Our analysis using the noise operator formalism shows that the loss allows tunability of quantum interference to an extent not possible with a lossless beam splitter. Our theoretical studies support the experimental demonstrations of programmable quantum interference in highly multimodal systems such as opaque scattering media and multimode fibers.

  12. Asymmetric chemical reactions by polarized quantum beams

    Science.gov (United States)

    Takahashi, Jun-Ichi; Kobayashi, Kensei

    One of the most attractive hypothesis for the origin of homochirality in terrestrial bio-organic compounds (L-amino acid and D-sugar dominant) is nominated as "Cosmic Scenario"; a chiral impulse from asymmetric excitation sources in space triggered asymmetric reactions on the surfaces of such space materials as meteorites or interstellar dusts prior to the existence of terrestrial life. 1) Effective asymmetric excitation sources in space are proposed as polarized quantum beams, such as circularly polarized light and spin polarized electrons. Circularly polarized light is emitted as synchrotron radiation from tightly captured electrons by intense magnetic field around neutron stars. In this case, either left-or right-handed polarized light can be observed depending on the direction of observation. On the other hand, spin polarized electrons is emitted as beta-ray in beta decay from radioactive nuclei or neutron fireballs in supernova explosion. 2) The spin of beta-ray electrons is longitudinally polarized due to parity non-conservation in the weak interaction. The helicity (the the projection of the spin onto the direction of kinetic momentum) of beta-ray electrons is universally negative (left-handed). For the purpose of verifying the asymmetric structure emergence in bio-organic compounds by polarized quantum beams, we are now carrying out laboratory simulations using circularly polarized light from synchrotron radiation facility or spin polarized electron beam from beta-ray radiation source. 3,4) The target samples are solid film or aqueous solution of racemic amino acids. 1) K.Kobayashi, K.Kaneko, J.Takahashi, Y.Takano, in Astrobiology: from simple molecules to primitive life; Ed. V.Basiuk; American Scientific Publisher: Valencia, 2008. 2) G.A.Gusev, T.Saito, V.A.Tsarev, A.V.Uryson, Origins Life Evol. Biosphere. 37, 259 (2007). 3) J.Takahashi, H.Shinojima, M.Seyama, Y.Ueno, T.Kaneko, K.Kobayashi, H.Mita, M.Adachi, M.Hosaka, M.Katoh, Int. J. Mol. Sci. 10, 3044

  13. RHIC operation with asymmetric collisions in 2015

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Aschenauer, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Atoian, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Blaskiewicz, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Brown, K. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Bruno, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Connolly, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ottavio, T. D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Drees, K. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Fischer, W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gardner, C. J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gu, X. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hayes, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Huang, H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Laster, J. S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Luo, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Makdisi, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marr, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marusic, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Meot, F. [Brookhaven National Lab. (BNL), Upton, NY (United States); Mernick, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Michnoff, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Minty, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Montag, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Morris, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Narayan, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Nayak, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Nemesure, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Pile, P. [Brookhaven National Lab. (BNL), Upton, NY (United States); Poblaguev, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ranjbar, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Robert-Demolaize, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Roser, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Schmidke, B. [Brookhaven National Lab. (BNL), Upton, NY (United States); Schoefer, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Severino, F. [Brookhaven National Lab. (BNL), Upton, NY (United States); Shrey, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Smith, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Steski, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tepikian, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Trbojevic, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tsoupas, N. [Brookhaven National Lab. (BNL), Upton, NY (United States); Wang, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); White, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yip, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zaltsman, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zeno, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zhang, S. Y. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2015-08-07

    To study low-x shadowing/saturation physics as well as other nuclear effects [1], [2], proton-gold (p-Au, for 5 weeks) and proton-Aluminum (p-Al, for 2 weeks) collisions were provided for experiments in 2015 at the Relativistic Heavy Ion Collider (RHIC), with polarized proton beam in the Blue ring and Au/Al beam in the Yellow ring. The special features of the asymmetric run in 2015 will be introduced. The operation experience will be reviewed as well in the report.

  14. Photoresponse of silicon with asymmetric area contacts

    Science.gov (United States)

    Rabbani, M. Golam; Sundararajan, Jency P.; Verma, Amit; Nekovei, Reza; Khader, Mahmoud M.; Darling, R. B.; Patil, Sunil R.

    2017-01-01

    We report on high performance metal-semiconductor-metal (MSM) photosensors based on asymmetric metal pad areas. The reported devices require a single-step metal deposition, and exhibit large photo response even under zero-bias. Moreover the devices offer fast and stable light switching behavior. Device fabrication and electrical characterization results are presented that are further analyzed with TCAD modeling and simulation. Device simulations show that contact asymmetry along with surface recombination and barrier lowering plays an important role in the MSM I-V characteristics.

  15. Chiral Diamine-catalyzed Asymmetric Aldol Reaction

    Institute of Scientific and Technical Information of China (English)

    LI Hui; XU Da-zhen; WU Lu-lu; WANG Yong-mei

    2012-01-01

    A highly efficient catalytic system composed of a simple and commercially available chiral primary diamine (1R,2R)-cyclohexane-1,2-diamine(6) and trifluoroacetic acid(TFA) was employed for asymmetric Aldol reaction in i-PrOH at room temperature.A loading of 10%(molar fraction) catalyst 6 with TFA as a cocatalyst could catalyze the Aldol reactions of various ketones or aldehydes with a series of aromatic aldehydes,furnishing Aldol products in moderate to high yields(up to >99%) with enantioselectivities of up to >99% and diastereoselectivities of up to 99:1.

  16. Analysis of Asymmetric Piezoelectric Composite Beam

    CERN Document Server

    Chen, J -S; Wu, K -C

    2008-01-01

    This paper deals with the vibration analysis of an asymmetric composite beam composed of glass a piezoelectric material. The Bernoulli's beam theory is adopted for mechanical deformations, and the electric potential field of the piezoelectric material is assumed such that the divergence-free requirement of the electrical displacements is satisfied. The accuracy of the analytic model is assessed by comparing the resonance frequencies obtained by the analytic model with those obtained by the finite element method. The model developed can be used as a tool for designing piezoelectric actuators such as micro-pumps.

  17. Asymmetric Synthesis of Both Enantiomers of Disparlure

    Institute of Scientific and Technical Information of China (English)

    王志刚; 郑剑峰; 黄培强

    2012-01-01

    Starting from propargyl alcohol (12), and on the basis of Zhou's modified Sharpless asymmetric epoxidation, the sex pheromone of the Gypsy moth, disparlure (+)-8 and its enantiomer (-)-8 have been synthesized, each in six steps, with overall yields of 29% for (+)-8 and 27% for (-)-8 (ee〉98%). The use of the sequential coupling tactic renders the method flexible, which is applicable to the synthesis of other cis-epoxy pheromones.

  18. Nanotribology of Symmetric and Asymmetric Liquid Lubricants

    Directory of Open Access Journals (Sweden)

    Shinji Yamada

    2010-03-01

    Full Text Available When liquid molecules are confined in a narrow gap between smooth surfaces, their dynamic properties are completely different from those of the bulk. The molecular motions are highly restricted and the system exhibits solid-like responses when sheared slowly. This solidification behavior is very dependent on the molecular geometry (shape of liquids because the solidification is induced by the packing of molecules into ordered structures in confinement. This paper reviews the measurements of confined structures and friction of symmetric and asymmetric liquid lubricants using the surface forces apparatus. The results show subtle and complex friction mechanisms at the molecular scale.

  19. Neuronal Alignment On Asymmetric Textured Surfaces

    CERN Document Server

    Beighley, Ross; Sekeroglu, Koray; Atherton, Timothy; Demirel, Melik C; Staii, Cristian

    2013-01-01

    Axonal growth and the formation of synaptic connections are key steps in the development of the nervous system. Here we present experimental and theoretical results on axonal growth and interconnectivity in order to elucidate some of the basic rules that neuronal cells use for functional connections with one another. We demonstrate that a unidirectional nanotextured surface can bias axonal growth. We perform a systematic investigation of neuronal processes on asymmetric surfaces and quantify the role that biomechanical surface cues play in neuronal growth. These results represent an important step towards engineering directed axonal growth for neuro-regeneration studies.

  20. Asymmetric acoustic transmission in graded beam

    Science.gov (United States)

    Jing, Li; Wu, Jiu Hui; Guan, Dong; Lu, Kuan; Gao, Nansha; Songhua, Cao

    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.

  1. An Asymmetric Block Dynamic Conditional Correlation Multivariate GARCH Model

    OpenAIRE

    Vargas, Gregorio A.

    2006-01-01

    The Block DCC model for determining dynamic correlations within and between groups of financial asset returns is extended to account for asymmetric effects. Simulation results show that the Asymmetric Block DCC model is competitive in in-sample forecasting and performs better than alternative DCC models in out-of-sample forecasting of conditional correlation in the presence of asymmetric effect between blocks of asset returns. Empirical results demonstrate that the model is able to capture ...

  2. Asymmetric joint multifractal analysis in Chinese stock markets

    Science.gov (United States)

    Chen, Yuwen; Zheng, Tingting

    2017-04-01

    In this paper, the asymmetric joint multifractal analysis method based on statistical physics is proposed to explore the asymmetric correlation between daily returns and trading volumes in Chinese stock markets. The result shows asymmetric multifractal correlations exist between return and trading volume in Chinese stock markets. Moreover, when the stock indexes are upward, the fluctuations of returns are always weaker than when they are downward, whether the trading volumes are more or less.

  3. Asymmetric Campaigning as a Rational Choice: Planning Considerations

    Science.gov (United States)

    2006-06-01

    Maslow identified five levels: survival, safety, belonging, esteem, and self-actualization. He presented his theory as a pyramid with five layers...to be sustained by actions of the asymmetric opponent. For the media-fed frenzy over constraints and protraction to continue, the asymmetric...lot of people. The reason for this is twofold. First, the actor needs sufficient support to exist and to sustain an asymmetric campaign. Second, the

  4. Synthesis, Characterization and Properties of Asymmetric Methide Anion Based Ionic Liquids Containing Nitrile Groups

    Institute of Scientific and Technical Information of China (English)

    ZOU Ting; LU Liang; LIU Xiu-Li; ZHANG Zhan; WANG Li-Bing; FU Xian-Lei; GAO Guo-Hua; KOU Yuan; HE Ming-Yuan

    2008-01-01

    A series of asymmetric methide anion based ionic liquids containing nitrile groups have been synthesized for the first time using the method of ion-exchange between sodium/potassium methide and various quaternary bro-mide/chloride salts of trimethylamine, triethylamine, tributylamine, N-methylpyrrolidine, and N-methylimidazole. All of the functionalised ionic liquids were characterized by IR, 1H, 13C NMR, MS and elemental analysis. The de-composition temperature of the ionic liquids measured via TGA ranged from 219 to 339 ℃. The functionalised ionic liquid, [Bmim][C(CN)2COCH3], was used as a ligand for Suzuki coupling reaction. The yields of the coupling reaction increased 10%-15% by the addition of the functionalised ionic liquid, [Bmim] [C(CN)2COCH3].

  5. Asymmetric transmission: a generic property of lossy periodic interfaces

    CERN Document Server

    Plum, E; Zheludev, N I

    2010-01-01

    Asymmetric transmission of circularly polarized waves is a well-established property of lossy, anisotropic, two-dimensionally chiral patterns. Here we show that asymmetric transmission can be observed for oblique incidence onto any lossy periodically structured plane. Our results greatly expand the range of natural and artificial materials in which directionally asymmetric transmission can be expected making it a cornerstone electromagnetic effect rather than a curiosity of planar chiral metamaterials. Prime candidates for asymmetric transmission at oblique incidence are rectangular arrays of plasmonic spheres or semiconductor quantum dots, lossy double-periodic gratings and planar metamaterial structures.

  6. Quantity Discount Scheme in Supply Chain under Asymmetric Information

    Institute of Scientific and Technical Information of China (English)

    LI Ji-bin; PENG Zuo-he

    2007-01-01

    Quantity discount scheme plays an important role in supply chain management. The different quantity discount schemes under symmetric (full) information and asymmetric information, are analyzed by using principal-agent and optimal control theory. As a result, the research reveals that the optimal quantity discount solution under symmetric information is a special case of that under asymmetric information. At the same price, the critical value of quantity discount under asymmetric information is much lower than that under asymmetric information. Therefore, this leads to less cost for retailers and smaller profit for their supplier.

  7. Asymmetric disassembly and robustness in declining networks.

    Science.gov (United States)

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

    2008-10-28

    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.

  8. Algebraic Davis Decomposition and Asymmetric Doob Inequalities

    Science.gov (United States)

    Hong, Guixiang; Junge, Marius; Parcet, Javier

    2016-09-01

    In this paper we investigate asymmetric forms of Doob maximal inequality. The asymmetry is imposed by noncommutativity. Let {({M}, τ)} be a noncommutative probability space equipped with a filtration of von Neumann subalgebras {({M}_n)_{n ≥ 1}}, whose union {bigcup_{n≥1}{M}_n} is weak-* dense in {{M}}. Let {{E}_n} denote the corresponding family of conditional expectations. As an illustration for an asymmetric result, we prove that for {1 spaces {{H}_p^r({M})} and {{H}_p^c({M})} respectively. In particular, this solves a problem posed by the Defant and Junge in 2004. In the case p = 1, our results establish a noncommutative form of the Davis celebrated theorem on the relation betwe en martingale maximal and square functions in L 1, whose noncommutative form has remained open for quite some time. Given {1 ≤ p ≤ 2}, we also provide new weak type maximal estimates, which imply in turn left/right almost uniform convergence of {{E}_n(x)} in row/column Hardy spaces. This improves the bilateral convergence known so far. Our approach is based on new forms of Davis martingale decomposition which are of independent interest, and an algebraic atomic description for the involved Hardy spaces. The latter results are new even for commutative von Neumann algebras.

  9. 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.

  10. An asymmetric B factory based on PEP

    Energy Technology Data Exchange (ETDEWEB)

    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{sup +}e{sup {minus}} collider capable of achieving a luminosity of L = 3 {times} 10{sup 33} cm{sup {minus}2} s{sup {minus}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.

  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. At Low SNR Asymmetric Quantizers Are Better

    CERN Document Server

    Koch, Tobias

    2012-01-01

    We study the capacity of the discrete-time Gaussian channel when its output is quantized with a one-bit quantizer. We focus on the low signal-to-noise ratio (SNR) regime, where communication at very low spectral efficiencies takes place. In this regime a symmetric threshold quantizer is known to reduce channel capacity by 2/pi, i.e., to cause an asymptotic power loss of approximately two decibels. Here it is shown that this power loss can be entirely avoided by using asymmetric threshold quantizers and asymmetric signaling constellations. We prove that in order to avoid this power loss flash-signaling input-distributions are essential. Consequently, one-bit output quantization of the Gaussian channel reduces spectral efficiency. Threshold quantizers are not only asymptotically optimal: as we prove, at every fixed SNR, a threshold quantizer maximizes capacity among all one-bit output quantizers. The picture changes on the Rayleigh-fading channel. In the noncoherent case we show that a one-bit output quantizer ...

  13. Instability of asymmetric continuous shaft system

    Science.gov (United States)

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

    2016-11-01

    In this work, the governing equation of asymmetric continuous shaft in inertial frame of reference is studied. In particular, determination of the parameter ranges for the stability or instability of the shaft response is the focus of the present work. The governing equations are a fourth-order coupled partial differential equations containing time dependent coefficients. The equations are non-dimensionalized in terms of two parameters related to the average moment of inertia and the difference of moments of inertia about the principal axes. Using the latter as the asymptotic parameter and employing modal superposition, a formal methodology based on perturbation methods is developed to ascertain the stability and instability characteristics. The methodology is applicable to shafts subjected to some of the classical boundary conditions viz. simply supported, cantilever, and fixed-fixed. Similar stability curves are obtained for each mode for these different boundary conditions. The novel non-dimensionalization scheme chosen leads to the stability boundaries as well as the loci of varying speeds to be in the form of straight lines. The intersection of these lines determine the stable and unstable speed ranges of different asymmetric shafts. The results are generalized for different material and geometric properties of the shaft.

  14. Asymmetric transition disks: Vorticity or eccentricity?

    CERN Document Server

    Zsom, A; 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 act as dust traps, which would make them important laboratories for studying planet formation. It has been shown that an elongated giant vortex produced in a disk with a strong viscosity jump strikingly resembles the observed asymmetric rings. Aims. We aim to study a similar behavior for a disk in which a giant planet is embedded. However, a giant planet can induce two kinds of asymmetries: (1) a giant vortex, and (2) an eccentric disk. We studied under which conditions each of these can appear, and how one can observationally distinguish between them. This is important because only a vortex can trap particles both radially and azimuthally, while the eccentric ring can only trap particles in radial direction. Method...

  15. Properties of asymmetrically evolved community networks

    Institute of Scientific and Technical Information of China (English)

    Cui Di; Gao Zi-You; Zheng Jian-Feng

    2009-01-01

    This paper studies a simple asymmetrically evolved community network with a combination of preferential at-tachment and random properties. An important issue about community networks is to discover the different utility increments of two nodes, where the utility is introduced to investigate the asymmetrical effect of connecting two nodes. On the other hand, the connection of two nodes in community networks can be classified as two nodes belonging to the same or to different communities. The simulation results show that the model can reproduce a power-law utility distribution P(u)~ u-σ,σ=2+ 1/p, which can be obtained by using mean-field approximation methods. Furthermore, the model exhibits exponential behaviour with respect to small values of a parameter denoting the random effect in our model at the low-utility region and a power-law feature with respect to big values of this parameter at the high-utility region, which is in good agreement with theoretical analysis. This kind of community network can reproduce a unique utility distribution by theoretical and numerical analysis.

  16. Survey of Reflection-Asymmetric Nuclear Deformations

    Science.gov (United States)

    Olsen, Erik; Cao, Yuchen; Nazarewicz, Witold; Schunck, Nicolas

    2016-09-01

    Due to spontaneous symmetry breaking it is possible for a nucleus to have a deformed shape in its ground state. It is theorized that atoms whose nuclei have reflection-asymmetric or pear-like deformations could have non-zero electric dipole moments (EDMs). Such a trait would be evidence of CP-violation, a feature that goes beyond the Standard Model of Physics. It is the purpose of this project to predict which nuclei exhibit a reflection-asymmetric deformation and which of those would be the best candidates for an EDM measuring experiment. Using nuclear Density Functional Theory along with the new computer code AxialHFB and massively parallel computing we calculated ground state nuclear properties for thousands of even-even nuclei across the nuclear chart: from light to superheavy and from stable to short-lived systems. Six different Energy Density Functionals (EDFs) were used to assess systematic errors in our calculations. These results are to be added to the website Massexplorer (http://massexplorer.frib.msu.edu/) which contains results from earlier mass table calculations and information on single quasiparticle energies.

  17. Cooperativity of axial and centre chirality in the biaryl disulfoxide/Rh(i)-catalysed asymmetric 1,4-addition of arylboronic aids to 2-cyclohexenone: a DFT study.

    Science.gov (United States)

    Zha, Gao-Feng; Qin, Hua-Li; Kantchev, Eric Assen B

    2017-03-08

    Atropisomeric biaryl disulfoxides contain two independent chiral elements. Previously, the (M,S,S)-diastereomer showed very high catalytic activity and selectivity in the Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-enones whereas the (M,R,R) counterpart - none. Herein, DFT computations on the key transmetallation (turnover-determining) and carborhodation (enantioselectivity-determining) steps of the catalytic cycle show that the (M,S,S)-ligand gives rise to lower reaction barriers for these elementary steps. However, the barriers for the (M,R,R)-ligand are not sufficiently high to explain the lack of reactivity. Hence, this phenomenon is most likely due to the failure of catalyst formation from the ligand and the dimeric Rh precatalyst complex. The hitherto unknown (M,S,R)-ligand shows predicted enantioselectivity similar to the (M,S,S)-ligand as a consequence of lower reaction barriers associated with those isomers whose key features resemble the (M,S,S)-ligand.

  18. Rational design of catalysts for asymmetric diamination reaction using transition state modeling.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-05-07

    The stereoselective synthesis of 1,2-diamines has remained a formidable challenge. A recent palladium-catalyzed asymmetric diamination of conjugated double bonds using di-tert-butyldiaziridinone appears promising. The axially chiral binol phosphoramidite ligands are successful in offering high enantioselectivity. The density functional theory investigations revealed that the energies of the stereocontrolling transition states for the C-N bond formation depend on a number of weak non-covalent interactions such as C-H···π, C-H···O and anagostic interactions. We envisaged that the modulation in these interactions in the transition states, through subtle changes in chiral phosphoramidite substituents, could be exploited toward steering the stereoselectivity. The effect of systematic modifications on both 3,3' positions of the binol as well as on the amido nitrogen on the stereochemical outcome is predicted. It is identified that high enantioselectivity requires a balance between the nature of the substituents on binol and amido groups. The reduced size of the amido substituents demands increased bulk on the binol whereas lowering the size on the binol demands increased bulk on the amido for higher stereoselectivity. The substituent at the α-position of the amido group is found to be vital and appears to be a hot spot for modifications. These insights derived from studies on the stereocontrolling transition states could help improve the catalytic efficacies in palladium-catalyzed asymmetric diamination reactions.

  19. Ir-Catalyzed Enantioselective Hydrogenation of 2H-1,4-Benzoxazines with a Chiral 1,2,3,4- Tetrahydro-l-naphthylamine Derived Phosphine-aminophosphine Ligand

    Institute of Scientific and Technical Information of China (English)

    胡娟; 王道永; 郑卓; 胡向平

    2012-01-01

    Unsymmetrical hybrid chiral phosphine-aminophosphine ligand derived from 1,2,3,4-tetrahydro-l-naphthyl- amine has been found to be highly efficient in the Ir-catalyzed asymmetric hydrogenation of various 3-aryl-2H-1,4-benzoxazines, providing good enantioselectivities (up to 95% ee) and high catalytic activity (S/C up to 5000).

  20. Cu(Ⅰ) and Cu(Ⅱ) helical complexes formed with oligobipyridine ligand

    Institute of Scientific and Technical Information of China (English)

    舒谋海; 付有君; 孙为银; 唐雯霞; 张文剑; 段春迎

    1999-01-01

    A new asymmetric oligobipyridine ligand, 1-(5’-methyl-2, 2’-bipyridin-5-yl)-2-(6’-methyl-2, 2’-bipyridin-6-yl)ethane (L), in which the bipyridine units are bridged by CH2CH2 at 5, 6’-position has been synthesized. The ligand L reacts with Cu(Ⅰ) and Cu(Ⅱ) ions giving double-stranded helical complexes [Cu2ⅠL2] (ClO4)2·Et2O (1) and [Cu2ⅡL2 (OH) (H2O)][ClO4]3(2), respectively. Complexes 1 and 2 were characterized by X-ray diffraction analyses, ES-MS, ESR and cyclic voltammetry, etc. Differing from the oligobipyridine ligands bridged by CH2CH2 at 6,6’-or 5,5’-position, the ligand L not only forms a double-stranded helicate with Cu(Ⅰ) ion, but also gives a double-stranded helicate with Cu(Ⅱ) ion. The results show that the linkage mode of the spacer group to the bipyridine units exerts a great impact on the formation of helix.

  1. Axial coordination dichotomy in dirhodium carbenoid catalysis: a curious case of cooperative asymmetric dual-catalytic approach toward amino esters.

    Science.gov (United States)

    Kisan, Hemanta K; Sunoj, Raghavan B

    2015-02-20

    One of the most recent developments in asymmetric catalysis is to employ two or more catalysts under one-pot reaction conditions. This article presents some interesting mechanistic insights on a cooperative dual-catalytic protocol relying on the catalytic ability of dirhodium carbenoid (derived from rhodium(II) tetracarboxylate and a diazo compound) and a chiral spirophosphoric acid ((R)-SPA) in an asymmetric N-H insertion reaction. We have employed DFT(M06 and B3LYP) computational methods to identify the stereocontrolling transition states wherein a chiral (R)-SPA protonates a dirhodium-bound enol intermediate. A true cooperative action elicited by both catalysts has been noted in the enantioselective protonation. More importantly, whether the second axial ligand on the remote rhodium atom could influence the energetic features of the reaction has been probed for the first time. In all steps (such as nitrogen extrusion, addition of amine to the dirhodium carbenoid, and the enol formation), except that in the stereocontrolling event, no major effect of axial ligation has been noticed. However, the presence of the axial ligand helps in stabilizing the protonation transition state and reduces the activation barrier for protonation, suggesting a vital role in stereoselectivity. The predicted sense of stereoselectivities is in good agreement with the experimental results.

  2. Asymmetric Synthesis of (+)-(11 R,12S)-Mefloquine Hydrochloride

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The asymmetric synthesis of (+)-(11R,12S)-mefloquine hydrochloride, an antimalarial drug, was accomplished from commercially available 2-trifluoromethylaniline, ethyl 4,4,4-trifluoroacetoacetate and cyclopentanone in 7 steps with a 14% overall yield. The key steps were proline-catalyzed asymmetric direct aldol reaction and Beck-mann rearrangement. The absolute configuration was assigned by a Mosher's method.

  3. Extensive Taguchi's Quality Loss Function Based On Asymmetric tolerances

    Institute of Scientific and Technical Information of China (English)

    ZHU Wei; LI Yuan-sheng; LIU Feng

    2004-01-01

    If specification interval is asymmetric, basic specification is the target value of quality characteristics. In this paper Taguchi's quality loss function is applied to describe quality loss based on asymmetric tolerances. The measurement of quality loss which is caused by the deviation of quality characteristics from basic specification is further presented.

  4. A new convenient asymmetric approach to herbarumin Ⅲ

    Institute of Scientific and Technical Information of China (English)

    Xue Song Chen; Shi Jun Da; Li Hong Yang; Bo Yan Xu; Zhi Xiang Xie; Ying Li

    2007-01-01

    The asymmetric total synthesis of herbarumin Ⅲ 3, a naturally occurred phytotoxin, along with 8-epi-herbarumin Ⅲ 22, was succeeded in 12 steps from n-butyraldehyde based on Brown's asymmetric allylation, taking modified Julia olefination and Yamaguchi's macro-lactonization as key steps.

  5. Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B.

    Science.gov (United States)

    Trost, Barry M; Quintard, Adrien

    2012-09-01

    A concise catalytic asymmetric synthesis of the proposed structure of trocheliophorolide B is reported. The synthetic sequence notably features an asymmetric acetaldehyde alkynylation, a Ru-catalyzed alder-ene reaction, and a Zn-ProPhenol ynone aldol condensation. Comparison with the reported data suggests a misassignment of the natural product structure.

  6. Asymmetric group loans, non-assortative matching and adverse selection

    NARCIS (Netherlands)

    Gangopadhyay, Shubhashis; Lensink, Robert

    2014-01-01

    This paper shows that an asymmetric group debt contract, where one borrower co-signs for another, but not vice versa, leads to heterogeneous matching. The analysis suggests that micro finance organizations can achieve the first best by offering asymmetric group contracts. (C) 2014 Elsevier B.V. All

  7. Effect of asymmetric auxin application on Helianthus hypocotyl curvature

    Science.gov (United States)

    Migliaccio, F.; Rayle, D. L.

    1989-01-01

    Indole-3-acetic acid was applied asymmetrically to the hypocotyls of sunflower (Helianthus annuus L.) seedlings. After 5 hours on a clinostat, auxin gradients as small as 1 to 1.3 produced substantial (more than 60 degrees) hypocotyl curvature. This result suggests the asymmetric growth underlying hypocotyl gravitropism can be explained by lateral auxin redistribution.

  8. Crystal structure of a mixed-ligand terbium(III coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

    Directory of Open Access Journals (Sweden)

    Chainok Kittipong

    2016-01-01

    Full Text Available The title compound, poly[(μ3-formato(μ4-oxalatoterbium(III], [Tb(CHO2(C2O4]n, is a three-dimensional coordination polymer, and is isotypic with the LaIII, CeIII and SmIII analogues. The asymmetric unit contains one TbIII ion, one formate anion (CHO2− and half of an oxalate anion (C2O42−, the latter being completed by application of inversion symmetry. The TbIII ion is nine-coordinated in a distorted tricapped trigonal–prismatic manner by two chelating carboxylate groups from two C2O42− ligands, two carboxylate oxygen atoms from another two C2O42− ligands and three oxygen atoms from three CHO2− ligands, with the Tb—O bond lengths and the O—Tb—O bond angles ranging from 2.4165 (19 to 2.478 (3 Å and 64.53 (6 to 144.49 (4°, respectively. The CHO2− and C2O42− anions adopt μ3-bridging and μ4-chelating-bridging coordination modes, respectively, linking adjacent TbIII ions into a three-dimensional 12-connected fcu topology with point symbol (324.436.56. The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature.

  9. CB receptor ligands from plants.

    Science.gov (United States)

    Woelkart, Karin; Salo-Ahen, Outi M H; Bauer, Rudolf

    2008-01-01

    Advances in understanding the physiology and pharmacology of the endogenous cannabinoid system have potentiated the interest of cannabinoid receptors as potential therapeutic targets. Cannabinoids have been shown to modulate a variety of immune cell functions and have therapeutic implications on central nervous system (CNS) inflammation, chronic inflammatory conditions such as arthritis, and may be therapeutically useful in treating autoimmune conditions such as multiple sclerosis. Many of these drug effects occur through cannabinoid receptor signalling mechanisms and the modulation of cytokines and other gene products. Further, endocannabinoids have been found to have many physiological and patho-physiological functions, including mood alteration and analgesia, control of energy balance, gut motility, motor and co-ordination activities, as well as alleviation of neurological, psychiatric and eating disorders. Plants offer a wide range of chemical diversity and have been a growing domain in the search for effective cannabinoid ligands. Cannabis sativa L. with the known plant cannabinoid, Delta(9-)tetrahydrocannabinol (THC) and Echinacea species with the cannabinoid (CB) receptor-binding lipophilic alkamides are the best known herbal cannabimimetics. This review focuses on the state of the art in CB ligands from plants, as well their possible therapeutic and immunomodulatory effects.

  10. Ligand photo-isomerization triggers conformational changes in iGluR2 ligand binding domain.

    Directory of Open Access Journals (Sweden)

    Tino Wolter

    Full Text Available Neurological glutamate receptors bind a variety of artificial ligands, both agonistic and antagonistic, in addition to glutamate. Studying their small molecule binding properties increases our understanding of the central nervous system and a variety of associated pathologies. The large, oligomeric multidomain membrane protein contains a large and flexible ligand binding domains which undergoes large conformational changes upon binding different ligands. A recent application of glutamate receptors is their activation or inhibition via photo-switchable ligands, making them key systems in the emerging field of optochemical genetics. In this work, we present a theoretical study on the binding mode and complex stability of a novel photo-switchable ligand, ATA-3, which reversibly binds to glutamate receptors ligand binding domains (LBDs. We propose two possible binding modes for this ligand based on flexible ligand docking calculations and show one of them to be analogues to the binding mode of a similar ligand, 2-BnTetAMPA. In long MD simulations, it was observed that transitions between both binding poses involve breaking and reforming the T686-E402 protein hydrogen bond. Simulating the ligand photo-isomerization process shows that the two possible configurations of the ligand azo-group have markedly different complex stabilities and equilibrium binding modes. A strong but slow protein response is observed after ligand configuration changes. This provides a microscopic foundation for the observed difference in ligand activity upon light-switching.

  11. Polyimides Derived from Novel Asymmetric Benzophenone Dianhydrides

    Science.gov (United States)

    Chuang, Chun-Hua (Inventor)

    2015-01-01

    This invention relates to the composition and processes for preparing thermoset polyimides derived from an asymmetric dianhydride, namely 2,3,3',4'-benzophenone dianhydride (a-BTDA) with at least one diamine, and a monofunctional terminal endcaps. The monofunctional terminating groups include 4-phenylethynylphthalic anhydride ester-acid derivatives, phenylethyl trimellitic anhydride (PETA) and its ester derivatives as well as 3-phenylethynylaniline. The process of polyimide composite comprises impregnating monomer reactants of dianhydride or its ester-acid derivatives, diamine and with monofunctional reactive endcaps into glass, carbon, quartz or synthetic fibers and fabrics, and then stack up into laminates and subsequently heated to between 150-375.degree. C. either at atmosphere or under pressure to promote the curing and crosslinking of the reactive endcaps to form a network of thermoset polyimides.

  12. Asymmetric quantum dialogue in noisy environment

    Science.gov (United States)

    Banerjee, Anindita; Shukla, Chitra; Thapliyal, Kishore; Pathak, Anirban; Panigrahi, Prasanta K.

    2017-02-01

    A notion of asymmetric quantum dialogue (AQD) is introduced. Conventional protocols of quantum dialogue are essentially symmetric as the users (Alice and Bob) can encode the same amount of classical information. In contrast, the proposed scheme for AQD provides different amount of communication powers to Alice and Bob. The proposed scheme offers an architecture, where the entangled state to be used and the encoding scheme to be shared between Alice and Bob depend on the amount of classical information they want to exchange with each other. The general structure for the AQD scheme has been obtained using a group theoretic structure of the operators introduced in Shukla et al. (Phys Lett A 377:518, 2013). The effect of different types of noises (e.g., amplitude damping and phase damping noise) on the proposed scheme is investigated, and it is shown that the proposed scheme for AQD is robust and it uses an optimized amount of quantum resources.

  13. Asymmetric Ferromagnet-Superconductor-Ferromagnet Switch

    Energy Technology Data Exchange (ETDEWEB)

    Cadden-Zimansky, P.; Bazaliy, Ya.B.; Litvak, L.M.; Jiang, J.S.; Pearson, J.; Gu, J.Y.; You, Chun-Yeol; Beasley, M.R.; Bader, S.D.

    2011-11-04

    In layered ferromagnet-superconductor-ferromagnet F{sub 1} /S/F{sub 2} structures, the critical temperature T{sub c} of the superconductors depends on the magnetic orientation of the ferromagnetic layers F{sub 1} and F{sub 2} relative to each other. So far, the experimentally observed magnitude of change in T{sub c} for structures utilizing weak ferromagnets has been 2 orders of magnitude smaller than is expected from calculations. We theoretically show that such a discrepancy can result from the asymmetry of F/S boundaries, and we test this possibility by performing experiments on structures where F{sub 1} and F{sub 2} are independently varied. Our experimental results indicate that asymmetric boundaries are not the source of the discrepancy. If boundary asymmetry is causing the suppressed magnitude of T{sub c} changes, it may only be possible to detect in structures with thinner ferromagnetic layers.

  14. Distributed Function Computation in Asymmetric Communication Scenarios

    CERN Document Server

    Agnihotri, Samar

    2009-01-01

    We consider the distributed function computation problem in asymmetric communication scenarios, where the sink computes some deterministic function of the data split among N correlated informants. The distributed function computation problem is addressed as a generalization of distributed source coding (DSC) problem. We are mainly interested in minimizing the number of informant bits required, in the worst-case, to allow the sink to exactly compute the function. We provide a constructive solution for this in terms of an interactive communication protocol and prove its optimality. The proposed protocol also allows us to compute the worst-case achievable rate-region for the computation of any function. We define two classes of functions: lossy and lossless. We show that, in general, the lossy functions can be computed at the sink with fewer number of informant bits than the DSC problem, while computation of the lossless functions requires as many informant bits as the DSC problem.

  15. Universality in freezing of an asymmetric drop

    Science.gov (United States)

    Ismail, Md Farhad; Waghmare, Prashant R.

    2016-12-01

    We present the evidence of universality in conical tip formation during the freezing of arbitrary-shaped sessile droplets. The focus is to demonstrate the relationship between this universality and the liquid drop shape. We observe that, in the case of asymmetric drops, this universal shape is achieved when the tip reconfigures by changing its location, which subsequently alters the frozen drop shape. The proposed "two-triangle" model quantifies the change in the tip configuration as a function of the asymmetry of the drop that shows a good agreement with the experimental evidence. Finally, based on the experimental and theoretical exercise, we propose the scaling dependence between the variations in the tip configuration and the asymmetry of the drop.

  16. Activation of carboxylic acids in asymmetric organocatalysis.

    Science.gov (United States)

    Monaco, Mattia Riccardo; Poladura, Belén; Diaz de Los Bernardos, Miriam; Leutzsch, Markus; Goddard, Richard; List, Benjamin

    2014-07-01

    Organocatalysis, catalysis using small organic molecules, has recently evolved into a general approach for asymmetric synthesis, complementing both metal catalysis and biocatalysis. Its success relies to a large extent upon the introduction of novel and generic activation modes. Remarkably though, while carboxylic acids have been used as catalyst directing groups in supramolecular transition-metal catalysis, a general and well-defined activation mode for this useful and abundant substance class is still lacking. Herein we propose the heterodimeric association of carboxylic acids with chiral phosphoric acid catalysts as a new activation principle for organocatalysis. This self-assembly increases both the acidity of the phosphoric acid catalyst and the reactivity of the carboxylic acid. To illustrate this principle, we apply our concept in a general and highly enantioselective catalytic aziridine-opening reaction with carboxylic acids as nucleophiles.

  17. THz operation of asymmetric-nanochannel devices

    Science.gov (United States)

    Balocco, C.; Halsall, M.; Vinh, N. Q.; Song, A. M.

    2008-09-01

    The THz spectrum lies between microwaves and the mid-infrared, a region that remains largely unexplored mainly due to the bottleneck issue of lacking compact, solid state, emitters and detectors. Here, we report on a novel asymmetric-nanochannel device, known as the self-switching device, which can operate at frequencies up to 2.5 THz for temperature up to 150 K. This is, to our knowledge, not only the simplest diode but also the quickest acting electronic nanodevice reported to date. The radiation was generated by the free electron laser FELIX (Netherlands). The dependences of the device efficiency as a function of the electric bias, radiation intensity, radiation frequency and temperature are reported.

  18. Isospin dependent properties of asymmetric nuclear matter

    CERN Document Server

    Chowdhury, P Roy; 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 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.

  19. Chilly Dark Sectors and Asymmetric Reheating

    CERN Document Server

    Adshead, Peter; Shelton, Jessie

    2016-01-01

    In a broad class of theories, the relic abundance of dark matter is determined by interactions internal to a thermalized dark sector, with no direct involvement of the Standard Model (SM). We point out that these theories raise an immediate cosmological question: how was the dark sector initially populated in the early universe? Motivated in part by the difficulty of accommodating large amounts of entropy carried in dark radiation with cosmic microwave background measurements of the effective number of relativistic species at recombination, $N_{\\mathrm{eff}}$, we aim to establish which admissible cosmological histories can populate a thermal dark sector that never reaches thermal equilibrium with the SM. The minimal cosmological origin for such a dark sector is asymmetric reheating, when the same mechanism that populates the SM in the early universe also populates the dark sector at a lower temperature. Here we demonstrate that the resulting inevitable inflaton-mediated scattering between the dark sector and ...

  20. Spectral measurements of asymmetrically irradiated capsule backlighters

    Science.gov (United States)

    Keiter, P. A.; Drake, R. P.

    2016-11-01

    Capsule backlighters provide a quasi-continuum x-ray spectrum over a wide range of photon energies [J. F. Hansen et al., Rev. Sci. Instrum. 79, 013504 (2008)]. Ideally one irradiates the capsule backlighter symmetrically, however, in complex experimental geometries, this is not always possible. In recent experiments we irradiated capsule backlighters asymmetrically and measured the x-ray spectrum from multiple directions. We will present time-integrated spectra over the photon energy range of 2-13 keV and time-resolved spectra over the photon energy range of 2-3 keV. We will compare the spectra from different lines of sight to determine if the laser asymmetry results in an angular dependence in the x-ray emission.

  1. Magnetoresistive system with concentric ferromagnetic asymmetric nanorings

    Energy Technology Data Exchange (ETDEWEB)

    Avila, J. I., E-mail: javila@ulg.ac.be; Tumelero, M. A.; Pasa, A. A.; Viegas, A. D. C. [Laboratório de Filmes Finos e Superfícies (LFFS), Departamento de Física, Universidade Federal de Santa Catarina, CP 476 Florianópolis (Brazil)

    2015-03-14

    A structure consisting of two concentric asymmetric nanorings, each displaying vortex remanent states, is studied with micromagnetic calculations. By orienting in suitable directions, both the asymmetry of the rings and a uniform magnetic field, the vortices chiralities can be switched from parallel to antiparallel, obtaining in this way the analogue of the ferromagnetic and antiferromagnetic configurations found in bar magnets pairs. Conditions on the thickness of single rings to obtain vortex states, as well as formulas for their remanent magnetization are given. The concentric ring structure enables the creation of magnetoresistive systems comprising the qualities of magnetic nanorings, such as low stray fields and high stability. A possible application is as contacts in spin injection in semiconductors, and estimations obtained here of magnetoresistance change for a cylindrical spin injection based device show significant variations comparable to linear geometries.

  2. Asymmetric Beam Combination for Optical Interferometry

    CERN Document Server

    Monnier, J D

    2001-01-01

    Optical interferometers increasingly use single-mode fibers as spatial filters to convert varying wavefront distortion into intensity fluctuations which can be monitored for accurate calibration of fringe amplitudes. Here I propose using an asymmetric coupler to allow the photometric intensities of each telescope beam to be measured at the same time as the fringe visibility, but without the need for dedicated photometric outputs, which reduce the light throughput in the interferometric channels. In the read-noise limited case often encountered in the infrared, I show that a 53% improvement in signal-to-noise ratio for the visibility amplitude measurement is achievable, when compared to a balanced coupler setup with 50% photometric taps (e.g., the FLUOR experiment). In the Poisson-noise limit appropriate for visible light, the improvement is reduced to only ~8%. This scheme also reduces the cost and complexity of the beam combination since fewer components and detectors are required, and can be extended to mor...

  3. Asymmetric EPR entanglement in continuous variable systems

    CERN Document Server

    Wagner, Katherine; Armstrong, Seiji; Morizur, Jean-Francois; Lam, Ping Koy; Bachor, Hans-Albert

    2012-01-01

    Continuous variable entanglement can be produced in nonlinear systems or via interference of squeezed states. In many of optical systems, such as parametric down conversion or interference of optical squeezed states, production of two perfectly symmetric subsystems is usually used for demonstrating the existence of entanglement. This symmetry simplifies the description of the concept of entanglement. However, asymmetry in entanglement may arise naturally in a real experiment, or be intentionally introduced in a given quantum information protocol. These asymmetries can emerge from having the output beams experience different losses and environmental contamination, or from the availability of non-identical input quantum states in quantum communication protocols. In this paper, we present a visualisation of entanglement using quadrature amplitude plots of the twin beams. We quantitatively discuss the strength of asymmetric entanglement using EPR and inseparability criteria and theoretically show that the optimal...

  4. Measurement of protein-ligand complex formation.

    Science.gov (United States)

    Lowe, Peter N; Vaughan, Cara K; Daviter, Tina

    2013-01-01

    Experimental approaches to detect, measure, and quantify protein-ligand binding, along with their theoretical bases, are described. A range of methods for detection of protein-ligand interactions is summarized. Specific protocols are provided for a nonequilibrium procedure pull-down assay, for an equilibrium direct binding method and its modification into a competition-based measurement and for steady-state measurements based on the effects of ligands on enzyme catalysis.

  5. Scaffold of Asymmetric Organic Compounds - Magnetite Plaquettes

    Science.gov (United States)

    Chan, Q. H. S.; Zolensky, M. E.; Martinez, J.

    2015-01-01

    Life on Earth shows preference towards the set of organics with particular spatial configurations, this 'selectivity' is a crucial criterion for life. With only rare exceptions, life prefers the left- (L-) form over the right- (D-) form of amino acids, resulting in an L-enantiomeric excess (L-ee). Recent studies have shown Lee for alpha-methyl amino acids in some chondrites. Since these amino acids have limited terrestrial occurrence, the origin of their stereoselectivity is nonbiological, and it seems appropriate to conclude that chiral asymmetry, the molecular characteristic that is common to all terrestrial life form, has an abiotic origin. A possible abiotic mechanism that can produce chiral asymmetry in meteoritic amino acids is their formation with the presence of asymmetric catalysts, as mineral crystallization can produce spatially asymmetric structures. Magnetite is shown to be an effective catalyst for the formation of amino acids that are commonly found in chondrites. Magnetite 'plaquettes' (or 'platelets'), first described by Jedwab, show an interesting morphology of barrel-shaped stacks of magnetite disks with an apparent dislocation-induced spiral growth that seem to be connected at the center. A recent study by Singh et al. has shown that magnetites can self-assemble into helical superstructures. Such molecular asymmetry could be inherited by adsorbed organic molecules. In order to understand the distribution of 'spiral' magnetites in different meteorite classes, as well as to investigate their apparent spiral configurations and possible correlation to molecular asymmetry, we observed polished sections of carbonaceous chondrites (CC) using scanning electron microscope (SEM) imaging. The sections were also studied by electron backscattered diffraction (EBSD) in order to reconstruct the crystal orientation along the stack of magnetite disks.

  6. The evolution of cooperation in asymmetric systems

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Explaining the "Tragedy of the Commons" of the evolution of cooperation remains one of the greatest problems for both biology and social science.Asymmetrical interaction,which is one of the most important characteristics of cooperative systems,has not been sufficiently considered in the existing models of the evolution of cooperation.Considering the inequality in the number and payoff between the cooperative actors and recipients in cooperation systems,discriminative density-dependent interference competition will occur in limited dispersal systems.Our model and simulation show that the local but not the global stability of a cooperative interaction can be maintained if the utilization of common resource remains unsaturated,which can be achieved by density-dependent restraint or competition among the cooperative actors.More intense density dependent interference competition among the cooperative actors and the ready availability of the common resource,with a higher intrinsic contribution ratio of a cooperative actor to the recipient,will increase the probability of cooperation.The cooperation between the recipient and the cooperative actors can be transformed into conflict and,it oscillates chaotically with variations of the affecting factors under different environmental or ecological conditions.The higher initial relatedness(i.e.similar to kin or reciprocity relatedness),which is equivalent to intrinsic contribution ratio of a cooperative actor to the recipient,can be selected for by penalizing less cooperative or cheating actors but rewarding cooperative individuals in asymmetric systems.The initial relatedness is a pivot but not the aim of evolution of cooperation.This explains well the direct conflict observed in almost all cooperative systems.

  7. Synthesis, characterization and theoretical study of a new asymmetrical tripodal amine containing morpholine moiety

    Directory of Open Access Journals (Sweden)

    Majid Rezaeivala

    2016-11-01

    Full Text Available A new asymmetrical tripodal amine, [H3L2]Br3 containing morpholine moiety was prepared from reacting of one equivalent of N-(3-aminopropylmorpholine and two equivalents of tosylaziridine, followed by detosylation with HBr/CH3COOH. The products were characterized by various spectroscopic methods such as FAB-MS, elemental analysis, 1H and 13C NMR spectroscopy. The crystal structure of the hydrobromide salt of the latter amine, [H3L2]Br3, was also determined. For triprotonated form of the ligand L2 we can consider several microspecies and/or conformers. A theoretical study at B3LYP/6-31G∗∗ level of theory showed that the characterized microspecies is the most stable microspecies for the triprotonated form of the ligand. It was shown that the experimental NMR data for [H3L2]Br3 in solution have good correlation with the corresponding calculated data for the most stable microspecies of [H3L2]3+ in the gas phase.

  8. Special Issue of "Asymmetric Synthesis"%Special Issue of "Asymmetric Synthesis"

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Organic chemistry exploring the world at a molecu- lar level remains essential for our society in the 21st century. Asymmetric synthesis, particularly those em- ploying catalytic approach, is one of the most important research fields in organic synthesis providing chiral compounds in an enantiopure form. The latter is critical since the two enantiomers of one chiral compound, in many cases, have a different response in biological sys- tems. The huge markets of non-racemic chiral com- pounds as synthetic intermediates, pharmaceuticals,

  9. Axially chiral imidodiphosphoric Acid catalyst for asymmetric sulfoxidation reaction: insights on asymmetric induction.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-04-22

    Insights into chiral induction for an asymmetric sulfoxidation reaction involving a single oxygen atom transfer are gained through analyzing the stereocontrolling transition states. The fitting of the substrate into the chiral cavity of a new class of imidodiphosphoric Brønsted acids, as well as weak CH⋅⋅⋅π and CH⋅⋅⋅O noncovalent interactions, are identified as responsible for the observed chiral induction.

  10. Enantiopure C1-symmetric N-Heterocyclic Carbene Ligands from Desymmetrized meso-1,2-Diphenylethylenediamine: Application in Ruthenium-Catalyzed Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Veronica Paradiso

    2016-11-01

    Full Text Available In order to design improved chiral ruthenium catalysts for asymmetric olefin metathesis, enantiomeric catalysts incorporating C1-symmetric N-Heterocyclic carbenes (NHC ligands with syn-related substituents on the backbone were synthesized starting from meso-1,2-diphenylethylenediamine. The absolute configuration of the enantiomers of the desymmetrized meso diamine was assigned by optical rotation analysis and in silico calculations, and was found to be maintained in their respective ruthenium catalysts by comparison of the relative electronic circular dichroism (ECD spectra. The catalytic behaviour of the enantiomeric ruthenium complexes was investigated in model asymmetric metathesis transformations and compared to that of analogous complexes bearing C1-symmetric NHC ligands with an anti backbone. Modest enantioselectivities were registered and different catalyst properties depending on the nature of stereochemical relationship of substituents on the backbone were observed.

  11. The mechanism of asymmetric reduction catalyzed by a C2 symmetric bis-amino alcohol catalyst——In situ NMR study of the structure of new type of dual-centered catalyst

    Institute of Scientific and Technical Information of China (English)

    赵金铠; 韩秀文; 刘秀梅; 包信和; 杭剑峰; 姜标

    2000-01-01

    By means of 1H, 13C, 11B NMR, polar transfer DEPT135, DEPT90 and 2D NMR experiments, IR, etc, the structure of the diaminodihydroxyl ligand and its derivatives used in the asymmetric reduction of prochiral ketones were detected. The catalysts derived from the ligand and bo-rane formed in situ were also studied and the structure transformations in solution were monitored.The structure of the catalyst was proved to be a new type of dual-centered catalyst——bis-oxazaborolidine.

  12. Rhodium olefin complexes of diiminate type ligands

    NARCIS (Netherlands)

    Willems, Sander Theodorus Hermanus

    2003-01-01

    The mono-anionic beta-diiminate ligand (ArNC(CH3)CHC(CH3)NAr) on several previous occasions proved useful in stabilising low coordination numbers for both early and late transition metals. In this thesis the reactivity of the rhodium olefin complexes of one of these beta-diiminate ligands (Ar = 2,6-

  13. Ligand sphere conversions in terminal carbide complexes

    DEFF Research Database (Denmark)

    Morsing, Thorbjørn Juul; Reinholdt, Anders; Sauer, Stephan P. A.

    2016-01-01

    Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first exam...

  14. Flexible Ligand Docking Using Evolutionary Algorithms

    DEFF Research Database (Denmark)

    Thomsen, Rene

    2003-01-01

    The docking of ligands to proteins can be formulated as a computational problem where the task is to find the most favorable energetic conformation among the large space of possible protein–ligand complexes. Stochastic search methods such as evolutionary algorithms (EAs) can be used to sample large...

  15. Simulation of Chaos in Asymmetric Nonlinear Chua's Circuit

    Institute of Scientific and Technical Information of China (English)

    WANG Yu-fei; QIAO Shu-tong; JIANG Jian-guo

    2008-01-01

    In order to describe practical chaotic systems exactly, we presented a simple modified Chua's circuit,which contains an asymmetric nonlinear resistive element. Mathematical analysis was made, and simulation study was performed by MATLAB. By varying the value of linear resistor in the circuit, rich variety dynamical behaviors were observed, such as DC equilibrium point, Hopf bifurcation, period-doubling bifurcation,single-scroll strange attractor, periodic windows, and asymmetric double-scroll strange attractor. The extreme sensitivity in the state trajectory with respect to the initial conditions was exhibited; the special characteristic of asymmetric nonlinear Chua's circuit was found also.

  16. The Dualism of Asymmetric Information in Agricultural Insurance

    Directory of Open Access Journals (Sweden)

    Xuemei Yang

    2013-07-01

    Full Text Available Asymmetric information objectively exists in the insurance market, especially in agricultural insurance, which has a great impact on the insurance contract and market operation. This paper designs two game models to analyse the dualism of asymmetric information in agricultural insurance and its reasons of forming. We find that, the particularity of agricultural production, the agricultural risk diversification and the benefits’ spillover of the agricultural insurance are the main causes of asymmetric information. Therefore, this paper puts forward that establishment of appropriate agricultural insurance mode, optimization of insurance policy design and increasing investment in science and technology, increasing farmers’ insurance consciousness and establishing supervision system

  17. Asymmetric Orbifolds, Noncommutative Geometry and Type I String Vacua

    CERN Document Server

    Blumenhagen, R; Körs, B; Lüst, Dieter; Blumenhagen, Ralph; Goerlich, Lars; Kors, Boris; Lust, Dieter

    2000-01-01

    We investigate the D-brane contents of asymmetric orbifolds. Using T-dualitywe find that the consistent description of open strings in asymmetric orbifoldsrequires to turn on background gauge fields on the D-branes. Hence open stringsand D-branes in generic asymmetric orbifolds necessarily lead to noncommutativegeometry. We derive the corresponding noncommutative geometry arising on suchD-branes with mixed Neumann-Dirichlet boundary conditions by applying anasymmetric rotation to ordinary D-branes with pure Dirichlet boundaryconditions. As a concrete application of our results we construct asymmetrictype I vacua requiring open strings with mixed boundary conditions for tadpolecancellation.

  18. Mechanisms of asymmetric cell divisions in Drosophila melanogaster neuroblasts

    Directory of Open Access Journals (Sweden)

    X Jiang

    2014-04-01

    Full Text Available Stem cells possess the properties of self-renewal and differentiation, and mainly rely on two strategies for division, including symmetric and asymmetric cell divisions. In this review, we summarize the latest progress on asymmetric cell divisions in Drosophila melanogaster neuroblasts (NBs, which focus on the establishment of cell polarity, mitotic spindle orientation, the asymmetric segregation of cell fate determinants as well as cell-cycle control. Here we also introduce five major cell fate determinants, including Numb, Prospero, Brat, Miranda, and Pon, which are thought to be unequally segregated to the ganglion mother cells (GMCs and play an important role in the formation of stem cell-derived tumors

  19. Generic approach for synthesizing asymmetric nanoparticles and nanoassemblies

    Science.gov (United States)

    Sun, Yugang; Hu, Yongxing

    2015-05-26

    A generic route for synthesis of asymmetric nanostructures. This approach utilizes submicron magnetic particles (Fe.sub.3O.sub.4--SiO.sub.2) as recyclable solid substrates for the assembly of asymmetric nanostructures and purification of the final product. Importantly, an additional SiO.sub.2 layer is employed as a mediation layer to allow for selective modification of target nanoparticles. The partially patched nanoparticles are used as building blocks for different kinds of complex asymmetric nanostructures that cannot be fabricated by conventional approaches. The potential applications such as ultra-sensitive substrates for surface enhanced Raman scattering (SERS) have been included.

  20. The experimental study of acoustic field in an asymmetric borehole

    Institute of Scientific and Technical Information of China (English)

    LINWeijun; ZHANGChengyu; ZHANGHailan; WANGXiuming

    2003-01-01

    The acoustic field in an asymmetric borehole was investigated by recording and comparing the waveforms with different offset in both axial symmetric borehole and axial asymmetric borehole. The two-dimensional spectrum in wave-number and frequency domain was also calculated and compared with the result of numeric simulation with 2.5-D finite difference method, and a consistent result was obtained. This work provides an accurate verification of our investigation of asymmetric borehole with 2.5-D finite difference method.

  1. 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

  2. Mono- and Dinuclear Manganese Carbonyls Supported by 1,8-Disubstituted (L = Py, SMe, SH) Anthracene Ligand Scaffolds.

    Science.gov (United States)

    Manes, Taylor A; Rose, Michael J

    2016-06-06

    Presented herein is a synthetic scheme to generate symmetric and asymmetric ligands based on a 1,8-disubstituted anthracene scaffold. The metal-binding scaffolds were prepared by aryl chloride activation of 1,8-dichloroanthracene using Suzuki-type couplings facilitated by [Pd(dba)2] as a Pd source; the choice of cocatalyst (XPhos or SPhos) yielded symmetrically or asymmetrically substituted scaffolds (respectively): namely, Anth-SMe2 (3), Anth-N2 (4), and Anth-NSMe (6). The ligands exhibit a nonplanar geometry in the solid state (X-ray), owing to steric hindrance between the anthracene scaffold and the coupled aryl units. To determine the flexibility and binding characteristics of the anthracene-based ligands, the symmetric scaffolds were complexed with [Mn(CO)5Br] to afford the mononuclear species [(Anth-SMe2)Mn(CO)3Br] (8) and [(Anth-N2)Mn(CO)3Br] (9), in which the donor moieties chelate the Mn center in a cis fashion. The asymmetric ligand Anth-NSMe (6) binds preferentially through the py moieties, affording the bis-ligated complex [(Anth-NSMe)2Mn(CO)3Br] (10), wherein the thioether-S donors remain unbound. Alternatively, deprotection of the thioether in 6 affords the free thiol ligand Anth-NSH (7), which more readily binds the Mn center. Complexation of 7 ultimately affords the mixed-valence Mn(I)/Mn(II) dimer of formula [(Anth-NS)3Mn2(CO)3] (11), which exhibits a fac-{Mn(CO)3} unit supported by a triad of bridging thiolates, which are in turn ligated to a supporting Mn(II) center (EPR: |D| = 0.053 cm(-1), E/|D| = 0.3, Aiso = -150 MHz). All of the metal complexes have been characterized by single-crystal X-ray diffraction, IR spectroscopy and NMR/EPR measurements-all of which demonstrate that the meta-linked, anthracene-based ligand scaffold is a viable approach for the coordination of metal carbonyls.

  3. Ligand binding mechanics of maltose binding protein.

    Science.gov (United States)

    Bertz, Morten; Rief, Matthias

    2009-11-13

    In the past decade, single-molecule force spectroscopy has provided new insights into the key interactions stabilizing folded proteins. A few recent studies probing the effects of ligand binding on mechanical protein stability have come to quite different conclusions. While some proteins seem to be stabilized considerably by a bound ligand, others appear to be unaffected. Since force acts as a vector in space, it is conceivable that mechanical stabilization by ligand binding is dependent on the direction of force application. In this study, we vary the direction of the force to investigate the effect of ligand binding on the stability of maltose binding protein (MBP). MBP consists of two lobes connected by a hinge region that move from an open to a closed conformation when the ligand maltose binds. Previous mechanical experiments, where load was applied to the N and C termini, have demonstrated that MBP is built up of four building blocks (unfoldons) that sequentially detach from the folded structure. In this study, we design the pulling direction so that force application moves the two MBP lobes apart along the hinge axis. Mechanical unfolding in this geometry proceeds via an intermediate state whose boundaries coincide with previously reported MBP unfoldons. We find that in contrast to N-C-terminal pulling experiments, the mechanical stability of MBP is increased by ligand binding when load is applied to the two lobes and force breaks the protein-ligand interactions directly. Contour length measurements indicate that MBP is forced into an open conformation before unfolding even if ligand is bound. Using mutagenesis experiments, we demonstrate that the mechanical stabilization effect is due to only a few key interactions of the protein with its ligand. This work illustrates how varying the direction of the applied force allows revealing important details about the ligand binding mechanics of a large protein.

  4. Evacuation dynamics of asymmetrically coupled pedestrian pairs

    CERN Document Server

    Müller, Frank

    2016-01-01

    We propose and analyze extended floor field cellular automaton models for evacuation dynamics of inhomogeneous pedestrian pairs which are coupled by asymmetric group interactions. Such pairs consist of a leader, who mainly determines the couple's motion and a follower, who has a defined tendency to follow the leader. Examples for such pairs are mother and child or two siblings of different age. We examine the system properties and compare them to the case of a homogeneous crowd. We find a strong impact on evacuation times for the regime of strong pair coupling due to the occurrence of a clogging phenomenon. In addition we obtain a non-trivial dependence of evacuation times on the followers' coupling to the static floor field, which carries the information of the shortest way to the exit location. In particular we find that systems with fully passive followers, who are solely coupled to their leaders, show lower evacuation times than homogeneous systems where all pedestrians have an equal tendency to move towa...

  5. Asymmetric vector mesons produced in nuclear collisions

    CERN Document Server

    Dremin, I M

    2016-01-01

    It is argued that the experimentally observed phenomenon of asymmetric shapes of vector mesons produced in nuclear media during high energy nucleus-nucleus collisions can be explained as Fano-Feshbach resonances. It has been observed that the mass distributions of lepton pairs created at meson decays decline from the traditional Breit-Wigner shape with some excess in the low-mass wing of the resonance. It is clear that the whole phenomenon is related to some interaction with the nuclear medium. Moreover, it can be further detalized in quantum mechanics as the interference of direct and continuum states in Fano-Feshbach effect. To reveal the nature of the interaction it is proposed to use a phenomenological model of the additional contribution due to Cherenkov gluons. They can be created because of the excess of the refractivity index over 1 just in the low-mass wing as required by the classical Cherenkov treatment. In quantum mechanics, this requirement is related to the positive real part of the interaction ...

  6. ADMonium: Asymmetric Dark Matter Bound State

    CERN Document Server

    Bi, Xiao-Jun; Ko, P; Li, Jinmian; Li, Tianjun

    2016-01-01

    We propose a novel framework for asymmetric scalar dark matter (ADM), which has interesting collider phenomenology in terms of an unstable ADM bound state (ADMonium) produced via Higgs portals. ADMonium is a natural consequence of the basic features of ADM: the (complex scalar) ADM is charged under a dark local $U(1)_d$ symmetry which is broken at a low scale and provides a light gauge boson $X$. The dark gauge coupling is strong and then ADM can annihilate away into $X$-pair effectively. Therefore, the ADM can form bound state due to its large self-interaction via $X$ mediation. To explore the collider signature of ADMonium, we propose that ADM has a two-Higgs doublet portal. The ADMonium can have a sizable mixing with the heavier Higgs boson, which admits a large cross section of ADMonium production associated with $b\\bar b$. Of particular interest, our setup nicely explains the recent di-photon anomaly at 750 GeV via the events from ${\\rm ADMonium}\\ra 2X(\\ra e^+e^-)$, where the electrons are identified as ...

  7. Asymmetric vector mesons produced in nuclear collisions

    Science.gov (United States)

    Dremin, I. M.; Nechitailo, V. A.

    2016-09-01

    It is argued that the experimentally observed phenomenon of asymmetric shapes of vector mesons produced in nuclear media during high-energy nucleus-nucleus collisions can be explained as Fano-Feshbach resonances. It has been observed that the mass distributions of lepton pairs created at meson decays decline from the traditional Breit-Wigner shape with some excess in the low-mass wing of the resonance. It is clear that the whole phenomenon is related to some interaction with the nuclear medium. Moreover, it can be further described in quantum mechanics as the interference of direct and continuum states in the Fano-Feshbach effect. To reveal the nature of the interaction it is proposed to use a phenomenological model of the additional contribution due to Cherenkov gluons. They can be created because of the excess of the refractivity index over 1 just in the low-mass wing as required by the classical Cherenkov treatment. In quantum mechanics, this requirement is related to the positive real part of the interaction amplitude in this wing. The corresponding parameters are found from the comparison with ρ-meson data and admit reasonable explanation.

  8. Barbed congruence of the asymmetric chi calculus

    Institute of Scientific and Technical Information of China (English)

    DONG Xiao-ju; FU Yu-xi

    2006-01-01

    The chi calculus is a model of mobile processes. It has evolved from the pi-calculus with motivations from simplification and communication-as-cut-elimination. This paper studies the chi calculus in the framework incorporating asymmetric communication. The major feature of the calculus is the identification of two actions:x/x and τ. The investigation on the barbed bisimilarity shows how the property affects the observational theory.Based on the definition of the barbed bisimilarity, the simulation properties of the barbed bisimilarity are studied. It shows that the algebraic properties of the barbed bisimilarity have changed greatly compared with the chi calculus. Although the definition of the barbed bisimilarity is very simple, the property of closeness under contexts makes it difficult to understand the barbed bisimilarity directly. Therefore an open style definition of the barbed bisimilarity is given, which is a context free description of barbed bisimilarity. Its definition is complex,but it is a well-behaved relation for it coincides with the barbed bisimilarity. It also helps to build an axiomatization system for the barbed congruence. Besides the axioms for the strong barbed bisimilarity, the paper proposes a new tau law and four new update laws for the barbed congruence. Both the operational and algebraic properties of the enriched calculus improve the understanding of the bisimulation behaviors of the model.

  9. Magnetohydrodynamic Waves in an Asymmetric Magnetic Slab

    Science.gov (United States)

    Allcock, Matthew; Erdélyi, Robert

    2017-02-01

    Analytical models of solar atmospheric magnetic structures have been crucial for our understanding of magnetohydrodynamic (MHD) wave behaviour and in the development of the field of solar magneto-seismology. Here, an analytical approach is used to derive the dispersion relation for MHD waves in a magnetic slab of homogeneous plasma enclosed on its two sides by non-magnetic, semi-infinite plasma with different densities and temperatures. This generalises the classic magnetic slab model, which is symmetric about the slab. The dispersion relation, unlike that governing a symmetric slab, cannot be decoupled into the well-known sausage and kink modes, i.e. the modes have mixed properties. The eigenmodes of an asymmetric magnetic slab are better labelled as quasi-sausage and quasi-kink modes. Given that the solar atmosphere is highly inhomogeneous, this has implications for MHD mode identification in a range of solar structures. A parametric analysis of how the mode properties (in particular the phase speed, eigenfrequencies, and amplitudes) vary in terms of the introduced asymmetry is conducted. In particular, avoided crossings occur between quasi-sausage and quasi-kink surface modes, allowing modes to adopt different properties for different parameters in the external region.

  10. Asymmetric vector mesons produced in nuclear collisions

    Energy Technology Data Exchange (ETDEWEB)

    Dremin, I.M.; Nechitailo, V.A. [Lebedev Physical Institute, Moscow (Russian Federation); National Research Nuclear University ' ' MEPhI' ' , Moscow (Russian Federation)

    2016-09-15

    It is argued that the experimentally observed phenomenon of asymmetric shapes of vector mesons produced in nuclear media during high-energy nucleus-nucleus collisions can be explained as Fano-Feshbach resonances. It has been observed that the mass distributions of lepton pairs created at meson decays decline from the traditional Breit-Wigner shape with some excess in the low-mass wing of the resonance. It is clear that the whole phenomenon is related to some interaction with the nuclear medium. Moreover, it can be further described in quantum mechanics as the interference of direct and continuum states in the Fano-Feshbach effect. To reveal the nature of the interaction it is proposed to use a phenomenological model of the additional contribution due to Cherenkov gluons. They can be created because of the excess of the refractivity index over 1 just in the low-mass wing as required by the classical Cherenkov treatment. In quantum mechanics, this requirement is related to the positive real part of the interaction amplitude in this wing. The corresponding parameters are found from the comparison with ρ-meson data and admit reasonable explanation. (orig.)

  11. Asymmetric Swiss-cheese brane-worlds

    Science.gov (United States)

    Gergely, László Á.; Képíró, Ibolya

    2007-07-01

    We study a brane-world cosmological scenario with local inhomogeneities represented by black holes. The brane is asymmetrically embedded into the bulk. The black strings/cigars penetrating the Friedmann brane generate a Swiss-cheese-type structure. This universe forever expands and decelerates, as its general relativistic analogue. The evolution of the cosmological fluid, however, can proceed along four branches, two allowed to have positive energy density, and one of them having the symmetric embedding limit. On this branch a future pressure singularity can arise for either (a) a difference in the cosmological constants of the cosmological and black hole brane regions or (b) a difference in the left and right bulk cosmological constants. While behaviour (a) can be avoided by a redefinition of the fluid variables, (b) establishes a critical value of the asymmetry over which the pressure singularity occurs. We introduce the pressure singularity censorship which bounds the degree of asymmetry in the bulk cosmological constant. We also show as a model-independent generic feature that the asymmetry source term due to the bulk cosmological constant increases in the early universe. In order to obey the nucleosynthesis constraints, the brane tension should be constrained therefore both from below and from above. With the maximal degree of asymmetry obeying the pressure singularity censorship, the higher limit is ten times the lower limit. The degree of asymmetry allowed by present cosmological observations is, however, much less, pushing the upper limit to infinity.

  12. The Asymmetric Pupil Fourier Wavefront Sensor

    CERN Document Server

    Martinache, Frantz

    2013-01-01

    This paper introduces a novel wavefront sensing approach that relies on the Fourier analysis of a single conventional direct image. In the high Strehl ratio regime, the relation between the phase measured in the Fourier plane and the wavefront errors in the pupil can be linearized, as was shown in a previous work that introduced the notion of generalized closure-phase, or kernel-phase. The technique, to be usable as presented requires two conditions to be met: (1) the wavefront errors must be kept small (of the order of one radian or less) and (2) the pupil must include some asymmetry, that can be introduced with a mask, for the problem to become solvable. Simulations show that this asymmetric pupil Fourier wavefront sensing or APF-WFS technique can improve the Strehl ratio from 50 to over 90 % in just a few iterations, with excellent photon noise sensitivity properties, suggesting that on-sky close loop APF-WFS is possible with an extreme adaptive optics system.

  13. Asymmetric Electrostatic Radiation Shielding for Spacecraft

    Science.gov (United States)

    Metzger, Philip T.; Youngquist, Robert C.; Lane, John E.

    2005-01-01

    A paper describes the types, sources, and adverse effects of energetic-particle radiation in interplanetary space, and explores a concept of using asymmetric electrostatic shielding to reduce the amount of such radiation impinging on spacecraft. Typically, such shielding would include a system of multiple inflatable, electrically conductive spheres deployed in clusters in the vicinity of a spacecraft on lightweight structures that would maintain the spheres in a predetermined multipole geometry. High-voltage generators would maintain the spheres at potential differences chosen in conjunction with the multipole geometry so that the resulting multipole field would gradually divert approaching energetic atomic nuclei from a central region occupied by the spacecraft. The spheres nearest the center would be the most positive, so as to repel the positively charged impinging nuclei from the center. At the same time, the monopole potential of the overall spacecraft-and-shielding system would be made negative so as to repel thermal electrons. The paper presents results of computational simulations of energetic-particle trajectories and shield efficiency for a trial system of 21 spheres arranged in three clusters in an overall linear quadrupole configuration. Further development would be necessary to make this shielding concept practical.

  14. 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.

  15. Polyimides Derived from Novel Asymmetric Dianhydrides

    Science.gov (United States)

    Chuang, Chun-Hua (Inventor)

    2012-01-01

    This invention relates to the compositions and processes for preparing thermoset and thermoplastic polyimides derived from novel asymmetrical dianhydrides: specifically 2,3,3',4' benzophenone dianhydride (a-BTDA), and 3,4'-(hexafluoroisopropylidene)diphthalic anhydride (a-6FDA). The a-BTDA anhydride is prepared by Suzuki coupling with catalysts from a mixed anhydride of 3,4-dimethylbenzoic acid or 2,3-dimethylbenzoic acid with 2,3-dimethylphenylboronic acid or 3,4-dimethylphenylboronic acid respectively, to form 2,3,3',4'-tetramethylbenzophenone which is oxidized to form 2,3,3',4'-benzophenonetetracarboxylic acid followed by cyclodehydration to obtain a-BTDA. The a-6FDA is prepared by nucleophilic triflouoromethylation of 2,3,3',4'-tetramethylbenzophenone with trifluoromethyltrimethylsilane to form 3,4'-(trifluoromethylmethanol)-bis(o-xylene) which is converted to 3,4'-(hexafluoroisopropylidene-bis(o-xylene). The 3,4'-(hexafluoroisopropylidene)-bis(o-xylene) is oxidized to the corresponding tetraacid followed by cyclodehydration to yield a-6FDA.

  16. Correcting ligands, metabolites, and pathways

    Directory of Open Access Journals (Sweden)

    Vriend Gert

    2006-11-01

    Full Text Available Abstract Background A wide range of research areas in bioinformatics, molecular biology and medicinal chemistry require precise chemical structure information about molecules and reactions, e.g. drug design, ligand docking, metabolic network reconstruction, and systems biology. Most available databases, however, treat chemical structures more as illustrations than as a datafield in its own right. Lack of chemical accuracy impedes progress in the areas mentioned above. We present a database of metabolites called BioMeta that augments the existing pathway databases by explicitly assessing the validity, correctness, and completeness of chemical structure and reaction information. Description The main bulk of the data in BioMeta were obtained from the KEGG Ligand database. We developed a tool for chemical structure validation which assesses the chemical validity and stereochemical completeness of a molecule description. The validation tool was used to examine the compounds in BioMeta, showing that a relatively small number of compounds had an incorrect constitution (connectivity only, not considering stereochemistry and that a considerable number (about one third had incomplete or even incorrect stereochemistry. We made a large effort to correct the errors and to complete the structural descriptions. A total of 1468 structures were corrected and/or completed. We also established the reaction balance of the reactions in BioMeta and corrected 55% of the unbalanced (stoichiometrically incorrect reactions in an automatic procedure. The BioMeta database was implemented in PostgreSQL and provided with a web-based interface. Conclusion We demonstrate that the validation of metabolite structures and reactions is a feasible and worthwhile undertaking, and that the validation results can be used to trigger corrections and improvements to BioMeta, our metabolite database. BioMeta provides some tools for rational drug design, reaction searches, and

  17. Design and synthesis of chiral Ti-1,1'-bi-2-naphthol coordination polymers for heterogeneous catalytic asymmetric oxidation of sulfides

    Institute of Scientific and Technical Information of China (English)

    YUAN Xiao-ya; WANG Xiao-tian

    2008-01-01

    Polymer-immobilized catalysis has many advantages such as easy recovery and reuse of catalyst. We prepared three novel chiral 1,1'-bi-2-naphthol-Ti coordination polymers with properly designed ligands and Ti(OiPr)4 under mild conditions. The prepared polymers exhibited good activity and excellent enantioselectivity (over 99%ee) in catalyzing the asymmetric oxidation of sulfides. The bridge linker in the polymer and the reaction solvent noticeably affected the enantioselectivity. The chiral coordination polymer was very stable and easy to separate from catalyzed reaction systems, with no significant loss of activity or enantioselectivity after reuse for at least ten times. These findings suggest a promising type of catalysts for synthesizing the widely used sulfoxides by asymmetrically oxidizing sulfides.

  18. Loss Aversion and the Asymmetric Transmission of Monetary Policy

    DEFF Research Database (Denmark)

    Santoro, Emiliano; Petrella, Ivan; Pfajfar, Damjan

    2014-01-01

    There is widespread evidence that monetary policy exerts asymmetric effects on output over contractions and expansions in economic activity, while price responses display no sizeable asymmetry. To rationalize these facts we develop a dynamic general equilibrium model where households’ utility...

  19. Magnetic Field and Force Calculations for ATLAS Asymmetrical Structure

    CERN Document Server

    Nessi, Marzio

    2001-01-01

    Magnetic field distortion in the assymetrical ATLAS structure are calculated. Magnetic forces in the system are estimated. 3D magnetic field simulation by the Opera3D code for symmetrical and asymmetrical systems is used.

  20. Asymmetric H-D exchange reactions of fluorinated aromatic ketones

    KAUST Repository

    Zhao, Yujun

    2012-01-01

    Chiral bicyclic guanidine catalyzes the asymmetric H-D exchange reactions. Up to 30% ee was achieved. DFT calculations were employed to elucidate and explain the origin of the reaction\\'s stereoselectivity. © 2012 The Royal Society of Chemistry.

  1. Asymmetric Intramolecular Cyclopropanation Induced by (β-Diketone)-copper Complex

    Institute of Scientific and Technical Information of China (English)

    Qing Fang CHENG; Xing You XU; Wei Xing MA; Tian Pa YOU

    2005-01-01

    Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influencing enantioselectivity were discussed.

  2. Salt supply to and significance of asymmetric salt diapirs

    DEFF Research Database (Denmark)

    Koyi, H.; Burliga, S.; Chemia, Zurab

    2012-01-01

    Salt diapirs can be asymmetric both internally and externally reflecting their evolution history. As such, this asymmetry bear a significant amount of information about the differential loading (± lateral forces) and in turn the salt supply that have shaped the diapir. In two dimensions......, In this study we compare results of analogue and numerical models of diapirs with two natural salt diapris (Klodawa and Gorleben diapirs) to explain their salt supply and asymmetric evolution. In a NW-SE section, the Gorleben salt diapir possesses an asymmetric external geometry represented by a large...... southeastern overhang due to salt extrusion during Middle Cretaceous followed by its burial in Tertiary. This external asymmetry is also reflected in the internal configuration of the diapir which shows different rates of salt flow on the two halves of the structure. The asymmetric external and internal...

  3. Asymmetric Dark Matter in the shear-dominated universe

    Science.gov (United States)

    Iminniyaz, Hoernisa

    2017-02-01

    We explore the relic abundance of asymmetric Dark Matter in shear-dominated universe in which it is assumed the universe is expanded anisotropically. The modified expansion rate leaves its imprint on the relic density of asymmetric Dark Matter particles if the asymmetric Dark Matter particles are decoupled in shear dominated era. We found the relic abundances for particle and anti-particle are increased. The particle and anti-particle abundances are almost in the same amount for the larger value of the shear factor xe which makes the indirect detection possible for asymmetric Dark Matter. We use the present day Dark Matter density from the observation to find the constraints on the parameter space in this model.

  4. Asymmetric periflexural exanthema: A report in an adult patient

    Directory of Open Access Journals (Sweden)

    Zawar V

    2003-11-01

    Full Text Available Asymmetric periflexural exanthem (APE is a distinctive exanthem, probably viral in origin. It is largely a disease of childhood and is uncommon in adults. We report an adult man presenting with the typical clinical findings of APE.

  5. 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.

  6. Abundance of Asymmetric Dark Matter in Brane World Cosmology

    Science.gov (United States)

    Abdusattar, Haximjan; Iminniyaz, Hoernisa

    2016-09-01

    Relic abundance of asymmetric Dark Matter particles in brane world cosmological scenario is investigated in this article. Hubble expansion rate is enhanced in brane world cosmology and it affects the relic abundance of asymmetric Dark Matter particles. We analyze how the relic abundance of asymmetric Dark Matter is changed in this model. We show that in such kind of nonstandard cosmological scenario, indirect detection of asymmetric Dark Matter is possible if the cross section is small enough which let the anti-particle abundance kept in the same amount with the particle. We show the indirect detection signal constraints can be used to such model only when the cross section and the 5-dimensional Planck mass scale are in appropriate values. Supported by the National Natural Science Foundation of China under Grant No. 11365022

  7. Asymptotic Theory for Extended Asymmetric Multivariate GARCH Processes

    NARCIS (Netherlands)

    M. Asai (Manabu); M.J. McAleer (Michael)

    2016-01-01

    textabstractThe paper considers various extended asymmetric multivariate conditional volatility models, and derives appropriate regularity conditions and associated asymptotic theory. This enables checking of internal consistency and allows valid statistical inferences to be drawn based on empirical

  8. 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.

  9. Asymmetric dynamic phase holographic grating in nematic liquid crystal

    Science.gov (United States)

    Ren, Chang-Yu; Shi, Hong-Xin; Ai, Yan-Bao; Yin, Xiang-Bao; Wang, Feng; Ding, Hong-Wei

    2016-09-01

    A new scheme for recording a dynamic phase grating with an asymmetric profile in C60-doped homeotropically aligned nematic liquid crystal (NLC) was presented. An oblique incidence beam was used to record the thin asymmetric dynamic phase holographic grating. The diffraction efficiency we achieved is more than 40%, exceeding the theoretical limit for symmetric profile gratings. Both facts can be explained by assuming that a grating with an asymmetric saw-tooth profile is formed in the NLC. Finally, physical mechanism and mathematical model for characterizing the asymmetric phase holographic grating were presented, based on the photo-refractive-like (PR-like) effect. Project supported by the Science and Technology Programs of the Educational Committee of Heilongjiang Province, China (Grant No. 12541730) and the National Natural Science Foundation of China (Grant No. 61405057).

  10. Results of investigations into coal cutting by asymmetric disks

    Energy Technology Data Exchange (ETDEWEB)

    Krauze, K.

    1985-02-01

    Effects are analyzed of design and specifications of asymmetric disk cutters on coal cutting by a shearer loader with disk cutters on helical cutting drums. Effects of disk diameter, wedge angle, cutting depth and chip thickness on cutting resistance were analyzed under operational conditions (a coal seam was cut by asymmetric disk cutters). On the basis of analysis of coal resistance to cutting by asymmetric cutting disks, regression equations were derived which describe coal cutting. Effects of disk parameters and cutting conditions on cutting resistance were determined. Analyses show that replacing radial cutting tools with asymmetric disk cutters would cause an increase in energy consumption of cutting and increase coal resistance to cutting. 1 reference.

  11. Research on the Design and Modification of Asymmetric Spur Gear

    OpenAIRE

    Xiaohe Deng; Lin Hua; Xinghui Han

    2015-01-01

    A design method for the geometric shape and modification of asymmetric spur gear was proposed, in which the geometric shape and modification of the gear can be obtained directly according to the rack-cutter profile. In the geometric design process of the gear, a rack-cutter with different pressure angles and fillet radius in the driving side and coast side was selected, and the generated asymmetric spur gear profiles also had different pressure angles and fillets accordingly. In the modificat...

  12. Catalytic Methods in Asymmetric Synthesis Advanced Materials, Techniques, and Applications

    CERN Document Server

    Gruttadauria, Michelangelo

    2011-01-01

    This book covers advances in the methods of catalytic asymmetric synthesis and their applications. Coverage moves from new materials and technologies to homogeneous metal-free catalysts and homogeneous metal catalysts. The applications of several methodologies for the synthesis of biologically active molecules are discussed. Part I addresses recent advances in new materials and technologies such as supported catalysts, supports, self-supported catalysts, chiral ionic liquids, supercritical fluids, flow reactors and microwaves related to asymmetric catalysis. Part II covers advances and milesto

  13. Cooperative Mechanism of Supply Chain Under Asymmetric Information

    Institute of Scientific and Technical Information of China (English)

    郭敏; 王红卫; 瞿坦

    2003-01-01

    The cooperative mechanism is one main issue in the decentralized supply chain system, especially in an asymmetric information structure. We analyze the non-cooperative game behavior of a 2-echelon distribution supply chain, compare the results with the system optimal solution, and give the supplier dominated cooperative mechanisms. We also analyze the validity of our contract under the asymmetric retailers' holding cost information and give some useful conclusions.

  14. Asymmetric zygote division: A mystery starting point of embryogenesis.

    Science.gov (United States)

    Zhao, Jing; Sun, Meng-Xiang

    2016-10-02

    In angiosperm, asymmetric zygote division is critical for embryogenesis. The molecular mechanism underlying this process has gained a great attention recently. Some players involve in the control of both accurate position and correct orientation of zygote division plane have been found, which provide useful clues for the extensive investigations. It is getting clear that both internal and external factors are involved in this complex regulatory mechanism and the asymmetric zygote division seems with great impact in cell fate determination and embryo pattern formation.

  15. Reduction of contact stresses using involute gears with asymmetric teeth

    OpenAIRE

    2015-01-01

    Asymmetrical involute gears have a different value of the operating pressure angle for right and left side of the gear. These teeth are suitable for one direction of rotation. Such teeth enable to change the length of the generating line. They enable to improve the value of reduced radii of curvature. Asymmetrical teeth allow reducing the values of Hertz's pressures, especially on the root of the teeth. Hertz pressures are directly related to the asymmetry.

  16. The Asymmetric Impact of Growth Fluctuation on Human Development

    OpenAIRE

    Serap Bedir

    2015-01-01

    In this paper, we re-examine the impact of economic growth fluctuation on human development indicators. Using the per capita growth rate and human development indicators for 131 countries between 1974 and 2007, we find that growth acceleration and deceleration have significant impact on the human development indicators. We also find that the effects are asymmetric. This asymmetric effect is valid both in terms of acceleration and deceleration periods and countries which are classified accordi...

  17. A tetrasilver(Iditungsten(VI cluster with sulfide and bis(diphenylphosphinomethane ligands

    Directory of Open Access Journals (Sweden)

    Cun-Lin Zhang

    2010-10-01

    Full Text Available The asymmetric unit of the title complex, [Ag4W2S8(C25H22P23]·2C3H7NO, tris[μ2-bis(diphenylphosphinomethane]-3:6κ2P:P′;4:5κ2P:P′;5:6κ2P:P′-μ5-sulfido-2:3:4:5:6κ5S-μ3-sulfido-1:3:4κ3S-tetra-μ2-sulfido-1:3κ2S;1:4κ2S;2:5κ2S;2:6κ2S-disulfido-1κS,2κS-tetrasilver(Iditungsten(VI N,N-dimethylformamide disolvate, contains two [WS4]2− anions, four silver cations, three bidentate–bridging bis(diphenylphosphinomethane (dppm ligands and two N,N-dimethylformamide (DMF solvent molecules. The coordination geometry of each Ag atom is distorted tetrahedral. Two Ag ions are coordinated by μ2-S and μ5-S atoms, and by two P atoms from two dppm ligands, while the other two Ag atoms are coordinated by μ2-S, μ3-S and μ5-S atoms, and by one P atom from a dppm ligand.

  18. Multicomponent mixtures for cryoprotection and ligand solubilization

    Directory of Open Access Journals (Sweden)

    Lidia Ciccone

    2015-09-01

    Full Text Available Mixed cryoprotectants have been developed for the solubilization of ligands for crystallization of protein–ligand complexes and for crystal soaking. Low affinity lead compounds with poor solubility are problematic for structural studies. Complete ligand solubilization is required for co-crystallization and crystal soaking experiments to obtain interpretable electron density maps for the ligand. Mixed cryo-preserving compounds are needed prior to X-ray data collection to reduce radiation damage at synchrotron sources. Here we present dual-use mixes that act as cryoprotectants and also promote the aqueous solubility of hydrophobic ligands. Unlike glycerol that increases protein solubility and can cause crystal melting the mixed solutions of cryo-preserving compounds that include precipitants and solubilizers, allow for worry-free crystal preservation while simultaneously solubilizing relatively hydrophobic ligands, typical of ligands obtained in high-throughput screening. The effectiveness of these mixture has been confirmed on a human transthyretin crystals both during crystallization and in flash freezing of crystals.

  19. Coordinate unsaturation with fluorinated ligands

    Energy Technology Data Exchange (ETDEWEB)

    Rack, J.L.; Hurlburt, P.K.; Anderson, O.P.; Strauss, S.H. [Colorado State Univ., Ft. Collins, CO (United States)

    1993-12-31

    The preparation and characterization of Zn(OTeF{sub 5}){sub 2} has resulted in a model compound with which to explore the concept of coordinative unsaturation. The coordination of solvents of varying donicity and dielectric constant to the Zn(II) ions in Zn(OTeF{sub 5}){sub 2} was studied by vapor phase monometry, NMR and IR spectroscopy, conductimetry, and X-Ray crystallography. The structures of [Zn(C{sub 6}H{sub 5}NO{sub 2}){sub 2}(OTeF{sub 5})2]2 and Zn(C{sub 6}H{sub 5}NO{sub 2}){sub 3}(OTEF{sub 5}){sub 2} demonstrate the electronic flexibility of some weakly coordinating solvents in that nitrobenzene can function as either an {eta}{sup 1}O or {eta}{sup 2}O,O`-ligand. The dependence of the number of bound solvent molecules and the degree of OTeF{sub 5}{minus} dissociation on solvent donor number and dielectric constant will be presented.

  20. Asymmetric neuroimaging in Creutzfeldt-Jakob disease: a ruse.

    Science.gov (United States)

    Bavis, James; Reynolds, Patrick; Tegeler, Charles; Clark, Paige

    2003-10-01

    Creutzfeldt-Jakob disease (CJD) causes diffuse neurological symptoms, but asymmetric lesions have been found on conventional magnetic resonance imaging (MRI) and diffusion-weighted imaging (DWI). Less often, position emission tomography (PET) scanning can also reveal asymmetric lesions in patients with CJD. Such imaging may mislead clinicians. The authors present a case of a woman with CJD who was diagnosed as having suffered a stroke because she had asymmetric T2-weighted imaging (T2WI) MRI abnormalities that were interpreted as a stroke. It was noted that the patient had clinical features consistent with CJD, including rapidly progressive dementia, myoclonus, cerebellar dysfunction, and pyramidal and extrapyramidal signs. This diagnosis was supported by periodic epileptiform discharges on the electroencephalogram (EEG) and by elevated 14-3-3 protein in the cerebrospinal fluid. MRI T2WI and DWI showed dramatically asymmetric abnormalities involving the left cortex. A PET study found decreased metabolism in the left cerebral and right cerebellar hemispheres. The patient's clinical, EEG, and laboratory data were all consistent with CJD, not other diseases, but the MRI and PET had atypical, asymmetric findings. This case demonstrates that CJD should be considered in the differential diagnosis of patients with rapidly progressive neurological decline, even if they have asymmetric imaging findings.

  1. Asymmetric nucleosomes flank promoters in the budding yeast genome.

    Science.gov (United States)

    Ramachandran, Srinivas; Zentner, Gabriel E; Henikoff, Steven

    2015-03-01

    Nucleosomes in active chromatin are dynamic, but whether they have distinct structural conformations is unknown. To identify nucleosomes with alternative structures genome-wide, we used H4S47C-anchored cleavage mapping, which revealed that 5% of budding yeast (Saccharomyces cerevisiae) nucleosome positions have asymmetric histone-DNA interactions. These asymmetric interactions are enriched at nucleosome positions that flank promoters. Micrococcal nuclease (MNase) sequence-based profiles of asymmetric nucleosome positions revealed a corresponding asymmetry in MNase protection near the dyad axis, suggesting that the loss of DNA contacts around H4S47 is accompanied by protection of the DNA from MNase. Chromatin immunoprecipitation mapping of selected nucleosome remodelers indicated that asymmetric nucleosomes are bound by the RSC chromatin remodeling complex, which is required for maintaining nucleosomes at asymmetric positions. These results imply that the asymmetric nucleosome-RSC complex is a metastable intermediate representing partial unwrapping and protection of nucleosomal DNA on one side of the dyad axis during chromatin remodeling.

  2. Ordered arrays of semi-crown ligands on an Au(111) electrode surface:in situ STM study

    Institute of Scientific and Technical Information of China (English)

    PAN Gebo; LI Huijing; YUAN Qunhui; CHEN Yongjun; WAN Lijun; BAI Chunli

    2004-01-01

    In situ scanning tunneling microscopy (STM) and cyclic voltammetry were employed to investigate the adsorption structures of three semi-crown ligands on an Au(111) surface under the potential control. It is found that all the molecules formed ordered arrays in 0.1 mol/L HCIO4solution, although their geometric structures are complex and asymmetric. The driving force was supposed to come from the balance between intermolecular and molecule-substrate interactions.High resolution STM images revealed internal molecular structures, orientations and packing arrangements in the ordered adlayers. The results are useful for preparing ordered arrays of transition metal-mediated nanostructures.

  3. Asymmetric Facial Bone Fragmentation Mirrors Asymmetric Distribution of Cranial Neuromasts in Blind Mexican Cavefish.

    Science.gov (United States)

    Gross, Joshua B; Gangidine, Andrew; Powers, Amanda K

    2016-11-01

    Craniofacial asymmetry is a convergent trait widely distributed across animals that colonize the extreme cave environment. Although craniofacial asymmetry can be discerned easily, other complex phenotypes (such as sensory organ position and numerical variation) are challenging to score and compare. Certain bones of the craniofacial complex demonstrate substantial asymmetry, and co-localize to regions harboring dramatically expanded numbers of mechanosensory neuromasts. To determine if a relationship exists between this expansion and bone fragmentation in cavefish, we developed a quantitative measure of positional symmetry across the left-right axis. We found that three different cave-dwelling populations were significantly more asymmetric compared to surface-dwelling fish. Moreover, cave populations did not differ in the degree of neuromast asymmetry. This work establishes a method for quantifying symmetry of a complex phenotype, and demonstrates that facial bone fragmentation mirrors the asymmetric distribution of neuromasts in different cavefish populations. Further developmental studies will provide a clearer picture of the developmental and cellular changes that accompany this extreme phenotype, and help illuminate the genetic basis for facial asymmetry in vertebrates.

  4. Orientation- and position-controlled alignment of asymmetric silicon microrod on a substrate with asymmetric electrodes

    Science.gov (United States)

    Shibata, Akihide; Watanabe, Keiji; Sato, Takuya; Kotaki, Hiroshi; Schuele, Paul J.; Crowder, Mark A.; Zhan, Changqing; Hartzell, John W.; Nakatani, Ryoichi

    2014-03-01

    In this paper, we demonstrate the orientation-controlled alignment of asymmetric Si microrods on a glass substrate with an asymmetric pair of electrodes. The Si microrods have the shape of a paddle with a blade and a shaft part, and the pair of electrodes consists of a narrow electrode and a wide electrode. By applying AC bias to the electrodes, the Si microrods suspended in a fluid align in such a way to settle across the electrode pair, and over 80% of the aligned Si microrods have an orientation with the blade and the shaft of the paddle on the wide and the narrow electrodes, respectively. When Si microrods have a shell of dielectric film and its thickness on the top face is thicker than that on the bottom face, 97.8% of the Si microrods are aligned with the top face facing upwards. This technique is useful for orientation-controlled alignment of nano- and microsized devices that have polarity or a distinction between the top and bottom faces.

  5. Hemispherical anomaly from asymmetric initial states

    Science.gov (United States)

    Ashoorioon, Amjad; Koivisto, Tomi

    2016-08-01

    We investigate if the hemispherical asymmetry in the CMB is produced from "asymmetric" excited initial conditions. We show that in the limit where the deviations from the Bunch-Davies vacuum are large and the scale of new physics is maximally separated from the inflationary Hubble parameter, the primordial power spectrum is modulated only by position-dependent dipole and quadrupole terms. Requiring the dipole contribution in the power spectrum to account for the observed power asymmetry, A =0.07 ±0.022 , we show that the amount of quadrupole terms is roughly equal to A2. The mean local bispectrum, which gets enhanced for the excited initial state, is within the 1 σ bound of Planck 2015 results for a large field model, fNL≃4.17 , but is reachable by future CMB experiments. The amplitude of the local non-Gaussianity modulates around this mean value, depending on the angle that the correlated patches on the 2d CMB surface make with the preferred direction. The amount of variation is minimized for the configuration in which the short and long wavelength modes are around the preferred pole and |k→3|≈|k→l ≈10|≪|k→1|≈|k→2|≈|k→l ≈2500| with fNLmin≈3.64 . The maximum occurs when these modes are at the antipode of the preferred pole, fNLmax≈4.81 . The difference of non-Gaussianity between these two configurations is as large as ≃1.17 , which can be used to distinguish this scenario from other scenarios that try to explain the observed hemispherical asymmetry.

  6. Asymmetric transfer of auditory perceptual learning

    Directory of Open Access Journals (Sweden)

    Sygal eAmitay

    2012-11-01

    Full Text Available Perceptual skills can improve dramatically even with minimal practice. A major and practical benefit of learning, however, is in transferring the improvement on the trained task to untrained tasks or stimuli, yet the mechanisms underlying this process are still poorly understood. Reduction of internal noise has been proposed as a mechanism of perceptual learning, and while we have evidence that frequency discrimination (FD learning is due to a reduction of internal noise, the source of that noise was not determined. In this study, we examined whether reducing the noise associated with neural phase locking to tones can explain the observed improvement in behavioural thresholds. We compared FD training between two tone durations (15 and 100 ms that straddled the temporal integration window of auditory nerve fibers upon which computational modeling of phase locking noise was based. Training on short tones resulted in improved FD on probe tests of both the long and short tones. Training on long tones resulted in improvement only on the long tones. Simulations of FD learning, based on the computational model and on signal detection theory, were compared with the behavioral FD data. We found that improved fidelity of phase locking accurately predicted transfer of learning from short to long tones, but also predicted transfer from long to short tones. The observed lack of transfer from long to short tones suggests the involvement of a second mechanism. Training may have increased the temporal integration window which could not transfer because integration time for the short tone is limited by its duration. Current learning models assume complex relationships between neural populations that represent the trained stimuli. In contrast, we propose that training-induced enhancement of the signal-to-noise ratio offers a parsimonious explanation of learning and transfer that easily accounts for asymmetric transfer of learning.

  7. Asymmetric inhibitory treatment effects in multilingual aphasia.

    Science.gov (United States)

    Goral, Mira; Naghibolhosseini, Maryam; Conner, Peggy S

    2013-01-01

    Findings from recent psycholinguistic studies of bilingual processing support the hypothesis that both languages of a bilingual are always active and that bilinguals continually engage in processes of language selection. This view aligns with the convergence hypothesis of bilingual language representation. Furthermore, it is hypothesized that when bilinguals perform a task in one language they need to inhibit their other, nontarget language(s) and that stronger inhibition is required when the task is performed in the weaker language than in the stronger one. The study of multilingual individuals who acquire aphasia resulting from a focal brain lesion offers a unique opportunity to test the convergence hypothesis and the inhibition asymmetry. We report on a trilingual person with chronic nonfluent aphasia who at the time of testing demonstrated greater impairment in her first acquired language (Persian) than in her third, later learned language (English). She received treatment in English followed by treatment in Persian. An examination of her connected language production revealed improvement in her grammatical skills in each language following intervention in that language, but decreased grammatical accuracy in English following treatment in Persian. The increased error rate was evident in structures that are used differently in the two languages (e.g., auxiliary verbs). The results support the prediction that greater inhibition is applied to the stronger language than to the weaker language, regardless of their age of acquisition. We interpret the findings as consistent with convergence theories that posit overlapping neuronal representation and simultaneous activation of multiple languages and with proficiency-dependent asymmetric inhibition in multilinguals.

  8. Chilly dark sectors and asymmetric reheating

    Science.gov (United States)

    Adshead, Peter; Cui, Yanou; Shelton, Jessie

    2016-06-01

    In a broad class of theories, the relic abundance of dark matter is determined by interactions internal to a thermalized dark sector, with no direct involvement of the Standard Model (SM). We point out that these theories raise an immediate cosmological question: how was the dark sector initially populated in the early universe? Motivated in part by the difficulty of accommodating large amounts of entropy carried in dark radiation with cosmic microwave background measurements of the effective number of relativistic species at recombination, N eff , we aim to establish which admissible cosmological histories can populate a thermal dark sector that never reaches thermal equilibrium with the SM. The minimal cosmological origin for such a dark sector is asymmetric reheating, when the same mechanism that populates the SM in the early universe also populates the dark sector at a lower temperature. Here we demonstrate that the resulting inevitable inflaton-mediated scattering between the dark sector and the SM can wash out a would-be temperature asymmetry, and establish the regions of parameter space where temperature asymmetries can be generated in minimal reheating scenarios. Thus obtaining a temperature asymmetry of a given size either restricts possible inflaton masses and couplings or necessitates a non-minimal cosmology for one or both sectors. As a side benefit, we develop techniques for evaluating collision terms in the relativistic Boltzmann equation when the full dependence on Bose-Einstein or Fermi-Dirac phase space distributions must be retained, and present several new results on relativistic thermal averages in an appendix.

  9. Impact and Use of the Asymmetric Property in Bi-directional Cooperative Relaying under Asymmetric Traffic Conditions

    Science.gov (United States)

    Saeki, Takaaki; Yamamoto, Koji; Murata, Hidekazu; Yoshida, Susumu

    Cooperative relaying (CR) is a promising technique to provide spatial diversity by combining multiple signals from source and relay stations. In the present paper, the impact and use of the asymmetric property in bi-directional CR under asymmetric traffic conditions are discussed assuming that CR involves one communication pair and one relay station in a time division duplex (TDD) system. The asymmetric property means that the average communication quality differs for each transmission direction because of the difference in signal power between the combined signals for each direction. First, numerical results show the asymmetric property of bi-directional CR. Next, in order to evaluate the impact of the asymmetric property, the optimal relay position and resource allocation are compared to those in simple multi-hop relaying, which does not have the asymmetric property. Numerical results show that, in order to maximize the overall quality of bi-directional communication, the optimal relay position in CR depends on the offered traffic ratio, which is defined as the traffic ratio of each transmission direction, while the offered traffic ratio does not affect the optimal relay position in multi-hop relaying. Finally, the asymmetric property is used to enhance the overall quality. Specifically, a high overall quality can be achieved by, for example, opportunistically switching to the transmission direction with higher quality. Under asymmetric traffic conditions, weighted proportionally fair scheduling (WPFS), which is proposed in the context of downlink scheduling in a cellular network, is applied to transmission direction switching. Numerical results reveal that WPFS provides a high overall quality and that the quality ratio is similar to the offered traffic ratio.

  10. Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

    Directory of Open Access Journals (Sweden)

    Aparecida M. Kawamoto

    2002-11-01

    Full Text Available A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R-N-(para-toluenesulfonyl-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

  11. Ligand-enabled multiple absolute stereocontrol in metal-catalysed cycloaddition for construction of contiguous all-carbon quaternary stereocentres.

    Science.gov (United States)

    Ohmatsu, Kohsuke; Imagawa, Naomichi; Ooi, Takashi

    2014-01-01

    The development of a general catalytic method for the direct and stereoselective construction of contiguous all-carbon quaternary stereocentres remains a formidable challenge in chemical synthesis. Here, we report a highly enantio- and diastereoselective [3+2] annulation reaction of 5-vinyloxazolidinones and activated trisubstituted alkenes catalysed by a palladium complex bearing a newly devised phosphine ligand with a chiral ammonium salt component, which enables the single-step construction of three contiguous stereocentres, including vicinal all-carbon quaternary stereocentres, in a five-membered heterocyclic framework. This stereoselective cycloaddition protocol relies on the remarkable ability of the chiral ligand to rigorously control the absolute stereochemistry of each chiral centre associated with the multiple bond-forming events, and provides a reliable catalytic process for the asymmetric synthesis of densely functionalized pyrrolidines.

  12. Ligand inducible assembly of a DNA tetrahedron.

    Science.gov (United States)

    Dohno, Chikara; Atsumi, Hiroshi; Nakatani, Kazuhiko

    2011-03-28

    Here we show that a small synthetic ligand can be used as a key building component for DNA nanofabrication. Using naphthyridinecarbamate dimer (NCD) as a molecular glue for DNA hybridization, we demonstrate NCD-triggered formation of a DNA tetrahedron.

  13. Two lanthanum(III) complexes containing η2-pyrazolate and η2-1,2,4-triazolate ligands: intramolecular C-H...N/O interactions and coordination geometries.

    Science.gov (United States)

    Wang, Yu-Long; Feng, Meng; Tao, Xian; Tang, Qing-Yun; Shen, Ying-Zhong

    2013-01-01

    The lanthanum(III) complexes tris(3,5-diphenylpyrazolato-κ(2)N,N')tris(tetrahydrofuran-κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C(15)H(11)N(2))(3)(C(4)H(8)O)(3)]·C(4)H(8)O, (I), and tris(3,5-diphenyl-1,2,4-triazolato-κ(2)N(1),N(2))tris(tetrahydrofuran-κO)lanthanum(III), [La(C(14)H(10)N(3))(3)(C(4)H(8)O)(3)], (II), both contain La(III) atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer-distorted octahedral geometry, while complex (II) has a fac-distorted configuration. The difference in the coordination geometries and the existence of asymmetric La-N bonding in the two complexes is associated with intramolecular C-H...N/O interactions between the ligands.

  14. Structural ordering of disordered ligand-binding loops of biotin protein ligase into active conformations as a consequence of dehydration.

    Directory of Open Access Journals (Sweden)

    Vibha Gupta

    Full Text Available Mycobacterium tuberculosis (Mtb, a dreaded pathogen, has a unique cell envelope composed of high fatty acid content that plays a crucial role in its pathogenesis. Acetyl Coenzyme A Carboxylase (ACC, an important enzyme that catalyzes the first reaction of fatty acid biosynthesis, is biotinylated by biotin acetyl-CoA carboxylase ligase (BirA. The ligand-binding loops in all known apo BirAs to date are disordered and attain an ordered structure only after undergoing a conformational change upon ligand-binding. Here, we report that dehydration of Mtb-BirA crystals traps both the apo and active conformations in its asymmetric unit, and for the first time provides structural evidence of such transformation. Recombinant Mtb-BirA was crystallized at room temperature, and diffraction data was collected at 295 K as well as at 120 K. Transfer of crystals to paraffin and paratone-N oil (cryoprotectants prior to flash-freezing induced lattice shrinkage and enhancement in the resolution of the X-ray diffraction data. Intriguingly, the crystal lattice rearrangement due to shrinkage in the dehydrated Mtb-BirA crystals ensued structural order of otherwise flexible ligand-binding loops L4 and L8 in apo BirA. In addition, crystal dehydration resulted in a shift of approximately 3.5 A in the flexible loop L6, a proline-rich loop unique to Mtb complex as well as around the L11 region. The shift in loop L11 in the C-terminal domain on dehydration emulates the action responsible for the complex formation with its protein ligand biotin carboxyl carrier protein (BCCP domain of ACCA3. This is contrary to the involvement of loop L14 observed in Pyrococcus horikoshii BirA-BCCP complex. Another interesting feature that emerges from this dehydrated structure is that the two subunits A and B, though related by a noncrystallographic twofold symmetry, assemble into an asymmetric dimer representing the ligand-bound and ligand-free states of the protein, respectively. In

  15. Nye ligander for Pt-MOF strukturer

    OpenAIRE

    Jakobsen, Søren

    2006-01-01

    Metalorganic frameworks (MOFs) are a new type of compounds which have been intensely investigated during the last few years. They have been synthesized using a wide variety of metals and ligands constructing a vast number of 1, 2 and 3 dimensional structures, some of which possess zeolite-type physics and chemistry. Our approach is to incorporate platinum metal sites into the structures making them bimetallic and potentially catalytically active. Therefore a number of N-N-type ligands (dii...

  16. Examining the lateral displacement of HL60 cells rolling on asymmetric P-selectin patterns.

    Science.gov (United States)

    Lee, Chia-Hua; Bose, Suman; Van Vliet, Krystyn J; Karp, Jeffrey M; Karnik, Rohit

    2011-01-01

    The lateral displacement of cells orthogonal to a flow stream by rolling on asymmetrical receptor patterns presents a new opportunity for the label-free separation and analysis of cells. Understanding the nature of cell rolling trajectories on such substrates is necessary to the engineering of substrates and the design of devices for cell separation and analysis. Here, we investigate the statistical nature of cell rolling and the effect of pattern geometry and flow shear stress on cell rolling trajectories using micrometer-scale patterns of biomolecular receptors with well-defined edges. Leukemic myeloid HL60 cells expressing the PSGL-1 ligand were allowed to flow across a field of patterned lines fabricated using microcontact printing and functionalized with the P-selectin receptor, leveraging both the specific adhesion of this ligand-receptor pair and the asymmetry of the receptor pattern inclination angle with respect to the fluid shear flow direction (α = 5, 10, 15, and 20°). The effects of the fluid shear stress magnitude (τ = 0.5, 1, 1.5, and 2.0 dyn/cm(2)), α, and P-selectin incubation concentration were quantified in terms of the rolling velocity and edge tracking length. Rolling cells tracked along the inclined edges of the patterned lines before detaching and reattaching on another line. The detachment of rolling cells after tracking along the edge was consistent with a Poisson process of history-independent interactions. Increasing the edge inclination angle decreased the edge tracking length in an exponential manner, contrary to the shear stress magnitude and P-selectin incubation concentration, which did not have a significant effect. On the basis of these experimental data, we constructed an empirical model that predicted the occurrence of the maximum lateral displacement at an edge angle of 7.5°. We also used these findings to construct a Monte Carlo simulation for the prediction of rolling trajectories of HL60 cells on P

  17. 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.

  18. Zn-catalyzed enantio- and diastereoselective formal [4 + 2] cycloaddition involving two electron-deficient partners: asymmetric synthesis of piperidines from 1-azadienes and nitro-alkenes.

    Science.gov (United States)

    Chu, John C K; Dalton, Derek M; Rovis, Tomislav

    2015-04-08

    We report a catalytic asymmetric synthesis of piperidines through [4 + 2] cycloaddition of 1-azadienes and nitro-alkenes. The reaction uses earth abundant Zn as catalyst and is highly diastereo- and regioselective. A novel BOPA ligand (F-BOPA) confers high reactivity and enantioselectivity in the process. The presence of ortho substitution on the arenes adjacent to the bis(oxazolines) was found to be particularly impactful, due to limiting the undesired coordination of 1-azadiene to the Lewis acid and thus allowing the reaction to be carried out at lower temperature. A series of secondary kinetic isotope effect studies using a range of ligands implicates a stepwise mechanism for the transformation, involving an initial Michael-type addition of the imine to the nitro-alkene followed by a cyclization event. The stepwise mechanism obviates the electronic requirement inherent to a concerted mechanism, explaining the successful cycloaddition between two electron-deficient partners.

  19. Designer TGFβ superfamily ligands with diversified functionality.

    Directory of Open Access Journals (Sweden)

    George P Allendorph

    Full Text Available Transforming Growth Factor--beta (TGFβ superfamily ligands, including Activins, Growth and Differentiation Factors (GDFs, and Bone Morphogenetic Proteins (BMPs, are excellent targets for protein-based therapeutics because of their pervasiveness in numerous developmental and cellular processes. We developed a strategy termed RASCH (Random Assembly of Segmental Chimera and Heteromer, to engineer chemically-refoldable TGFβ superfamily ligands with unique signaling properties. One of these engineered ligands, AB208, created from Activin-βA and BMP-2 sequences, exhibits the refolding characteristics of BMP-2 while possessing Activin-like signaling attributes. Further, we find several additional ligands, AB204, AB211, and AB215, which initiate the intracellular Smad1-mediated signaling pathways more strongly than BMP-2 but show no sensitivity to the natural BMP antagonist Noggin unlike natural BMP-2. In another design, incorporation of a short N-terminal segment from BMP-2 was sufficient to enable chemical refolding of BMP-9, without which was never produced nor refolded. Our studies show that the RASCH strategy enables us to expand the functional repertoire of TGFβ superfamily ligands through development of novel chimeric TGFβ ligands with diverse biological and clinical values.

  20. Fully Flexible Docking of Medium Sized Ligand Libraries with RosettaLigand.

    Directory of Open Access Journals (Sweden)

    Samuel DeLuca

    Full Text Available RosettaLigand has been successfully used to predict binding poses in protein-small molecule complexes. However, the RosettaLigand docking protocol is comparatively slow in identifying an initial starting pose for the small molecule (ligand making it unfeasible for use in virtual High Throughput Screening (vHTS. To overcome this limitation, we developed a new sampling approach for placing the ligand in the protein binding site during the initial 'low-resolution' docking step. It combines the translational and rotational adjustments to the ligand pose in a single transformation step. The new algorithm is both more accurate and more time-efficient. The docking success rate is improved by 10-15% in a benchmark set of 43 protein/ligand complexes, reducing the number of models that typically need to be generated from 1000 to 150. The average time to generate a model is reduced from 50 seconds to 10 seconds. As a result we observe an effective 30-fold speed increase, making RosettaLigand appropriate for docking medium sized ligand libraries. We demonstrate that this improved initial placement of the ligand is critical for successful prediction of an accurate binding position in the 'high-resolution' full atom refinement step.

  1. LigandRFs: random forest ensemble to identify ligand-binding residues from sequence information alone

    KAUST Repository

    Chen, Peng

    2014-12-03

    Background Protein-ligand binding is important for some proteins to perform their functions. Protein-ligand binding sites are the residues of proteins that physically bind to ligands. Despite of the recent advances in computational prediction for protein-ligand binding sites, the state-of-the-art methods search for similar, known structures of the query and predict the binding sites based on the solved structures. However, such structural information is not commonly available. Results In this paper, we propose a sequence-based approach to identify protein-ligand binding residues. We propose a combination technique to reduce the effects of different sliding residue windows in the process of encoding input feature vectors. Moreover, due to the highly imbalanced samples between the ligand-binding sites and non ligand-binding sites, we construct several balanced data sets, for each of which a random forest (RF)-based classifier is trained. The ensemble of these RF classifiers forms a sequence-based protein-ligand binding site predictor. Conclusions Experimental results on CASP9 and CASP8 data sets demonstrate that our method compares favorably with the state-of-the-art protein-ligand binding site prediction methods.

  2. Asymmetrical reinforcement and Wolbachia infection in Drosophila.

    Directory of Open Access Journals (Sweden)

    John Jaenike

    2006-10-01

    Full Text Available Reinforcement refers to the evolution of increased mating discrimination against heterospecific individuals in zones of geographic overlap and can be considered a final stage in the speciation process. One the factors that may affect reinforcement is the degree to which hybrid matings result in the permanent loss of genes from a species' gene pool. Matings between females of Drosophila subquinaria and males of D. recens result in high levels of offspring mortality, due to interspecific cytoplasmic incompatibility caused by Wolbachia infection of D. recens. Such hybrid inviability is not manifested in matings between D. recens females and D. subquinaria males. Here we ask whether the asymmetrical hybrid inviability is associated with a corresponding asymmetry in the level of reinforcement. The geographic ranges of D. recens and D. subquinaria were found to overlap across a broad belt of boreal forest in central Canada. Females of D. subquinaria from the zone of sympatry exhibit much stronger levels of discrimination against males of D. recens than do females from allopatric populations. In contrast, such reproductive character displacement is not evident in D. recens, consistent with the expected effects of unidirectional cytoplasmic incompatibility. Furthermore, there is substantial behavioral isolation within D. subquinaria, because females from populations sympatric with D. recens discriminate against allopatric conspecific males, whereas females from populations allopatric with D. recens show no discrimination against any conspecific males. Patterns of general genetic differentiation among populations are not consistent with patterns of behavioral discrimination, which suggests that the behavioral isolation within D. subquinaria results from selection against mating with Wolbachia-infected D. recens. Interspecific cytoplasmic incompatibility may contribute not only to post-mating isolation, an effect already widely recognized, but also to

  3. Synthesis, Spectroscopy and Crystal Structure of a New Copper Complex Builtup by Cationic (Dimethylphosphorylmethanaminium Ligands

    Directory of Open Access Journals (Sweden)

    Manuela E. Richert

    2014-05-01

    Full Text Available A new transition metal complex of the mono-protonated ligand (dimethylphosphorylmethanamine (dpmaH+ was obtained by equimolar reaction of copper(II chloride dihydrate and dpma in concentrated hydrochloric acid. The asymmetric unit of the title structure, [CuCl2(C3H11NOP4][CuCl4]2, consists of one half of a fourfold charged trans-dichloridotetrakis[(dimethylphosphorylmethanaminium]copper(II complex with the copper atom located on an inversion centre and one tetrachloridocuprate(II dianion found in a general position. The copper centre in the cationic complex shows a tetragonally distorted octahedral environment composed of four oxygen atoms in a square plane and two trans-coordinated chlorido ligands. This 4+2-coordination causes elongated Cu-Cl distances because of the Jahn-Teller effect. The geometry of the tetrachloridocuprate(II dianion is best described as a seriously distorted tetrahedron. Analysis of the hydrogen bonding scheme by graph-set theory shows three patterns of rings in the title compound. The cationic copper complex reveals intramolecular hydrogen bonds between two aminium groups and the two axial chlorido ligands. Further hydrogen bonding among the cations and anions, more precisely between four aminium groups and the chlorido ligands of four adjacent tetrachloridocuprate(II anions, lead to a chain-type structure. Comparing the coordination chemistry of the title structure with an analogue cobalt(II compound only disclose differences in hydrogen bonding pattern resulting in an unusual chain propagation. Besides the crystal structure received spectroscopic data are in accordance with appropriate literature.

  4. Synthesis and characterization of mixed ligand chiral nanoclusters

    KAUST Repository

    Guven, Zekiye P.

    2016-06-22

    Chiral mixed ligand silver nanoclusters were synthesized in the presence of a chiral and an achiral ligand. While the chiral ligand led mostly to the formation of nanoparticles, the presence of the achiral ligand drastically increased the yield of nanoclusters with enhanced chiral properties. © 2016 The Royal Society of Chemistry.

  5. Asymmetric bias in user guided segmentations of brain structures.

    Science.gov (United States)

    Maltbie, Eric; Bhatt, Kshamta; Paniagua, Beatriz; Smith, Rachel G; Graves, Michael M; Mosconi, Matthew W; Peterson, Sarah; White, Scott; Blocher, Joseph; El-Sayed, Mohammed; Hazlett, Heather C; Styner, Martin A

    2012-01-16

    Brain morphometric studies often incorporate comparative hemispheric asymmetry analyses of segmented brain structures. In this work, we present evidence that common user guided structural segmentation techniques exhibit strong left-right asymmetric biases and thus fundamentally influence any left-right asymmetry analyses. In this study, MRI scans from ten pediatric subjects were employed for studying segmentations of amygdala, globus pallidus, putamen, caudate, and lateral ventricle. Additionally, two pediatric and three adult scans were used for studying hippocampus segmentation. Segmentations of the sub-cortical structures were performed by skilled raters using standard manual and semi-automated methods. The left-right mirrored versions of each image were included in the data and segmented in a random order to assess potential left-right asymmetric bias. Using shape analysis we further assessed whether the asymmetric bias is consistent across subjects and raters with the focus on the hippocampus. The user guided segmentation techniques on the sub-cortical structures exhibited left-right asymmetric volume bias with the hippocampus displaying the most significant asymmetry values (pstudy is to raise awareness in the neuroimaging community regarding the presence of the asymmetric bias and its influence on any left-right hemispheric analyses. We also recommend reexamining previous research results in the light of this new finding.

  6. Performance of JPEG Image Transmission Using Proposed Asymmetric Turbo Code

    Directory of Open Access Journals (Sweden)

    Siddiqi Mohammad Umar

    2007-01-01

    Full Text Available This paper gives the results of a simulation study on the performance of JPEG image transmission over AWGN and Rayleigh fading channels using typical and proposed asymmetric turbo codes for error control coding. The baseline JPEG algorithm is used to compress a QCIF ( "Suzie" image. The recursive systematic convolutional (RSC encoder with generator polynomials , that is, (13/11 in decimal, and 3G interleaver are used for the typical WCDMA and CDMA2000 turbo codes. The proposed asymmetric turbo code uses generator polynomials , that is, (13/11; 13/9 in decimal, and a code-matched interleaver. The effect of interleaver in the proposed asymmetric turbo code is studied using weight distribution and simulation. The simulation results and performance bound for proposed asymmetric turbo code for the frame length , code rate with Log-MAP decoder over AWGN channel are compared with the typical system. From the simulation results, it is observed that the image transmission using proposed asymmetric turbo code performs better than that with the typical system.

  7. Performance of JPEG Image Transmission Using Proposed Asymmetric Turbo Code

    Directory of Open Access Journals (Sweden)

    Mohamad Yusoff Alias

    2007-01-01

    Full Text Available This paper gives the results of a simulation study on the performance of JPEG image transmission over AWGN and Rayleigh fading channels using typical and proposed asymmetric turbo codes for error control coding. The baseline JPEG algorithm is used to compress a QCIF (176×144 “Suzie” image. The recursive systematic convolutional (RSC encoder with generator polynomials (1,D3+D2+1/D3+D+1, that is, (13/11 in decimal, and 3G interleaver are used for the typical WCDMA and CDMA2000 turbo codes. The proposed asymmetric turbo code uses generator polynomials (1,D3+D2+1/D3+D+1;D3+D2+1/D3+1, that is, (13/11; 13/9 in decimal, and a code-matched interleaver. The effect of interleaver in the proposed asymmetric turbo code is studied using weight distribution and simulation. The simulation results and performance bound for proposed asymmetric turbo code for the frame length N=400, code rate r=1/3 with Log-MAP decoder over AWGN channel are compared with the typical system. From the simulation results, it is observed that the image transmission using proposed asymmetric turbo code performs better than that with the typical system.

  8. Thermal transport across symmetric and asymmetric solid-solid interfaces

    Science.gov (United States)

    Bi, Kedong; Liu, Yadong; Zhang, Chunwei; Li, Jiapeng; Chen, Minhua; Chen, Yunfei

    2016-10-01

    Thermal transport across symmetric and asymmetric solid-solid interfaces is investigated by non-equilibrium molecular dynamics simulations. For symmetric interfaces, simulation results demonstrate that the thermal interface resistance is reduced greatly with the temperature increasing from 20 to 70 K. Besides, the introduction of an interlayer in the region of a highly mismatched interface is predicted to effectively decrease the thermal interface resistance due to the vibrational bridge role of the interlayer in connecting two vibrationally mismatched materials. As for the case of asymmetric interfaces, it is found that the capacity of thermal transport across an asymmetric interface is related to the effective interfacial area, namely the smaller cross-section area of component materials. In addition, effects of the transition angle at asymmetric interfaces on the thermal interface resistance are further studied when heat flows through interfaces from the side with larger cross-section area to the other. It is shown that a smoother transition is preferred for thermal transport through an asymmetric interface.

  9. Success Factors of Asymmetric Connections - Example of Large Slovenian Enterprises

    Directory of Open Access Journals (Sweden)

    Viktor Vračar

    2014-11-01

    Full Text Available More and more companies realize the fact that networking or partner collaborations, which are based on partner relations between companies, are essential for their long-term existence. In today’s global competitive environment each company is included at least in some different connections. Very common connections occur between large and smaller enterprises, where the so called asymmetric connections occur, which may be understood as the ability of one organisation to establish power, influence and control over the other organisation and its resources. According to numerous statements, the connections between enterprises are very frequently uneffectivenessful, with opinions on the optimal nature of asymmetric connections being quite common as well, whereby it is, as a rule, a synergic complementing of missing content for both partners. To verify the thesis, that companies achieve more competitiveness and effectiveness through connections, whereby the so called asymmetric connections are common, a structural model of the evolution of asymmetric connection has been developed, which connects the theoretically identified factors and all dependent concepts of competitiveness, efficiency and effectiveness. The empirical research also attempts to further expose the factors of asymmetric connections, which affect efficiency and effectiveness of the connected enterprises.

  10. Stereoselective coordination: a six-membered P,N-chelate tailored for asymmetric allylic alkylation.

    Science.gov (United States)

    Császár, Z; Farkas, G; Bényei, A; Lendvay, G; Tóth, I; Bakos, J

    2015-10-01

    Six-membered chelate complexes [Pd(1a-b)Cl2], (2a-b) and [Pd(1a-b)(η(3)-PhCHCHCHPh)]BF4, (3a-b) of P,N-type ligands 1a, ((2S,4S)-2-diphenyl-phosphino-4-isopropylamino-pentane) and 1b, ((2S,4S)-2-diphenyl-phosphino-4-methylamino-pentane) have been prepared. The Pd-complexes have been characterized in solution by 1D and 2D NMR spectroscopy. The observed structures were confirmed by DFT calculations and in the case of 2a also by X-ray crystallography. Unexpectedly, the coordination of the all-carbon-backbone aminophosphine 1a resulted in not only a stereospecific locking of the donor nitrogen atom into one of the two possible configurations but also the conformation of the six-membered chelate rings containing three alkyl substituents was forced into the same single chair structure showing the axially placed isopropyl group on the coordinated N-atom. The stereodiscriminative complexation of 1a led to the formation of a palladium catalyst with a conformationally rigid chelate having a configurationally fixed nitrogen and electronically different coordination sites due to the presence of P and N donors. The stereochemically fixed catalyst provided excellent ee's (up to 96%) and activities in asymmetric allylic alkylation reactions. In contrast, the chelate rings formed by 1b exist in two different chair conformations, both containing axial methyl groups, but with the opposite configurations of the coordinated N-atom. Pd-complexes of 1b provided low enantioselectivities in similar alkylations, therefore emphasizing the importance of the stereoselective coordination of N-atoms in analogous P-N chelates. The factors determining the coordination of the ligands were also studied with respect to the chelate ring conformation and the nitrogen configuration.

  11. Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso-ene mechanism.

    Science.gov (United States)

    Porter, David; Poon, Belinda M-L; Rutledge, Peter J

    2015-01-01

    Iron(II) complexes of the tetradentate amines tris(2-pyridylmethyl)amine (TPA) and N,N'-bis(2-pyridylmethyl)-N,N'-dimethylethane-1,2-diamine (BPMEN) are established catalysts of C-O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein we report the capacity of these catalysts to promote C-N bond formation, via allylic amination of alkenes. The combination of N-Boc-hydroxylamine with either FeTPA (1 mol %) or FeBPMEN (10 mol %) converts cyclohexene to the allylic hydroxylamine (tert-butyl cyclohex-2-en-1-yl(hydroxy)carbamate) in moderate yields. Spectroscopic studies and trapping experiments suggest the reaction proceeds via a nitroso-ene mechanism, with involvement of a free N-Boc-nitroso intermediate. Asymmetric induction is not observed using the chiral tetramine ligand (+)-(2R,2'R)-1,1'-bis(2-pyridylmethyl)-2,2'-bipyrrolidine ((R,R')-PDP).

  12. Spacial Structure of Cationic Phosphorus Ligand-Ru (Ⅱ) Halide Complexes-by DFT Study

    Institute of Scientific and Technical Information of China (English)

    Yi Xin ZHAO; Shu Guang WANG

    2005-01-01

    The full-parameter geometry optimization of cationic (S)-BINAP-Ru (Ⅱ) halide complex was performed by DFT method using B3LYP, PW91 and PBE potentials with several basis sets. PW91 with 3-21G / SDD basis sets is found to be the most suitable method with consideration of both precision and efficiency. The dihedral angles (θ) of the binaphthyl or biphenyl with different phosphorus ligand-Ru (Ⅱ) halide complexes were found changing from 59.9 to 79.3 degree, while the natural bite angle (βn) of those complexes only changes from 87.4to 90.3 degree. It is different from the common view of asymmetric organic chemists' that θ directly influences βn.

  13. Plasmon coupling of magnetic resonances in an asymmetric gold semishell

    Science.gov (United States)

    Ye, Jian; Kong, Yan; Liu, Cheng

    2016-05-01

    The generation of magnetic dipole resonances in metallic nanostructures is of great importance for constructing near-zero or even negative refractive index metamaterials. Commonly, planar two-dimensional (2D) split-ring resonators or relevant structures are basic elements of metamaterials. In this work, we introduce a three-dimensional (3D) asymmetric Au semishell composed of two nanocups with a face-to-face geometry and demonstrate two distinct magnetic resonances spontaneously in the visible-near infrared optical wavelength regime. These two magnetic resonances are from constructive and destructive hybridization of magnetic dipoles of individual nanocups in the asymmetric semishell. In contrast, complete cancellation of magnetic dipoles in the symmetric semishell leads to only a pronounced electric mode with near-zero magnetic dipole moment. These 3D asymmetric resonators provide new ways for engineering hybrid resonant modes and ultra-high near-field enhancement for the design of 3D metamaterials.

  14. Experimental Quantification of Asymmetric Einstein-Podolsky-Rosen Steering.

    Science.gov (United States)

    Sun, Kai; Ye, Xiang-Jun; Xu, Jin-Shi; Xu, Xiao-Ye; Tang, Jian-Shun; Wu, Yu-Chun; Chen, Jing-Ling; Li, Chuan-Feng; Guo, Guang-Can

    2016-04-22

    Einstein-Podolsky-Rosen (EPR) steering describes the ability of one observer to nonlocally "steer" the other observer's state through local measurements. EPR steering exhibits a unique asymmetric property; i.e., the steerability can differ between observers, which can lead to one-way EPR steering in which only one observer obtains steerability in the steering process. This property is inherently different from the symmetric concepts of entanglement and Bell nonlocality, and it has attracted increasing interest. Here, we experimentally demonstrate asymmetric EPR steering for a class of two-qubit states in the case of two measurement settings. We propose a practical method to quantify the steerability. We then provide a necessary and sufficient condition for EPR steering and clearly demonstrate one-way EPR steering. Our work provides new insight into the fundamental asymmetry of quantum nonlocality and has potential applications in asymmetric quantum information processing.

  15. Multiband Asymmetric Transmission of Airborne Sound by Coded Metasurfaces

    Science.gov (United States)

    Xie, Boyang; Cheng, Hua; Tang, Kun; Liu, Zhengyou; Chen, Shuqi; Tian, Jianguo

    2017-02-01

    We present the design, characterization, and theoretical and experimental demonstration of multiband asymmetric transmission of airborne sound using an ultrathin coded metasurface formed by an alternating arrangement of the coding elements 0 and 1. The asymmetric transmission effect can be easily controlled to selectively achieve off and on by coding different patterns. Both frequency- and angle-selective transmission is discussed. The proposed multiband asymmetric transmission stems from the constructive and destructive interferences of acoustic-wave coupling between the coded elements. The experimental results are in relative agreement with numerical simulations. This work opens an alternative path for ultrathin acoustic-device design and shows promise for application in acoustic rectification and noise control.

  16. Gravity-induced asymmetric distribution of a plant growth hormone

    Science.gov (United States)

    Bandurski, R. S.; Schulze, A.; Momonoki, Y.

    1984-01-01

    Dolk (1936) demonstrated that gravistimulation induced an asymmetric distribution of auxin in a horizontally-placed shoot. An attempt is made to determine where and how that asymmetry arises, and to demonstrate that the endogenous auxin, indole-3-acetic acid, becomes asymmetrically distributed in the cortical cells of the Zea mays mesocotyl during 3 min of geostimulation. Further, indole-3-acetic acid derived by hydrolysis of an applied transport form of the hormone, indole-3-acetyl-myo-inositol, becomes asymmetrically distributed within 15 min of geostimulus time. From these and prior data is developed a working theory that the gravitational stimulus induces a selective leakage, or secretion, of the hormone from the vascular tissue to the cortical cells of the mesocotyl.

  17. New Asymmetric Fuzzy PID Control for Pneumatic Position Control System

    Institute of Scientific and Technical Information of China (English)

    薛阳; 彭光正; 范萌; 伍清河

    2004-01-01

    A fuzzy control algorithm of asymmetric fuzzy strategy is introduced for a servo-pneumatic position system. It can effectively solve the difficult problems of single rod low friction cylinders, which are mainly caused by asymmetric structures and different friction characteristics in two directions. On the basis of this algorithm, a traditional PID control is used to improve dynamic performance. Furthermore, a new asymmetric fuzzy PID control with α factor is advanced to improve the self-adaptability and robustness of the system. Both the theoretical analyses and experimental results prove that, with this control strategy, the dynamic performance of the system can be greatly improved. The system using this control algorithm has strong robustness and it obtains desired overshoot and repeatability in both transient and steady-state responses.

  18. Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes

    Science.gov (United States)

    Hashimoto, Takuya; Sakata, Kazuki; Tamakuni, Fumiko; Dutton, Mark J.; Maruoka, Keiji

    2013-03-01

    Allenes are molecules based on three carbons connected by two cumulated carbon-carbon double bonds. Given their axially chiral nature and unique reactivity, substituted allenes have a variety of applications in organic chemistry as key synthetic intermediates and directly as part of biologically active compounds. Although the demands for these motivated many endeavours to make axially chiral, substituted allenes by exercising asymmetric catalysis, the catalytic asymmetric synthesis of fully substituted ones (tetrasubstituted allenes) remained largely an unsolved issue. The fundamental obstacle to solving this conundrum is the lack of a simple synthetic transformation that provides tetrasubstituted allenes in the action of catalysis. We report herein a strategy to overcome this issue by the use of a phase-transfer-catalysed asymmetric functionalization of 1-alkylallene-1,3-dicarboxylates with N-arylsulfonyl imines and benzylic and allylic bromides.

  19. Asymmetric spindle pole formation in CPAP-depleted mitotic cells.

    Science.gov (United States)

    Lee, Miseon; Chang, Jaerak; Chang, Sunghoe; Lee, Kyung S; Rhee, Kunsoo

    2014-02-21

    CPAP is an essential component for centriole formation. Here, we report that CPAP is also critical for symmetric spindle pole formation during mitosis. We observed that pericentriolar material between the mitotic spindle poles were asymmetrically distributed in CPAP-depleted cells even with intact numbers of centrioles. The length of procentrioles was slightly reduced by CPAP depletion, but the length of mother centrioles was not affected. Surprisingly, the young mother centrioles of the CPAP-depleted cells are not fully matured, as evidenced by the absence of distal and subdistal appendage proteins. We propose that the selective absence of centriolar appendages at the young mother centrioles may be responsible for asymmetric spindle pole formation in CPAP-depleted cells. Our results suggest that the neural stem cells with CPAP mutations might form asymmetric spindle poles, which results in premature initiation of differentiation.

  20. Characteristic of involute slope modification of asymmetric spur gear

    Institute of Scientific and Technical Information of China (English)

    DENG Xiao-he; HUA Lin; HAN Xing-hui

    2015-01-01

    The meshing characteristic of asymmetric involute spur gear was studied, the equations of the geometric shape of the asymmetric gear for both sides were deduced, and the equations of contact ratio and the key points of contact were also obtained. Meanwhile, an involute slope modification method considering the effects of static transmission errors was proposed based on the meshing properties. The characteristic of the involute slope modification was analyzed by changing different modification parameters. The mesh stiffness and synthetic mesh stiffness of unmodified and modified asymmetric spur gears were investigated. Furthermore, the spectrums of synthetic mesh stiffness under different modification parameters were compared. Research results showed that the modification parameters influence the meshing performance of gear pairs, and the proposed modification method was feasible to improve the transmission performance of gear pairs with appropriate modification parameters.

  1. Continuous Flavor Symmetries and the Stability of Asymmetric Dark Matter

    CERN Document Server

    Bishara, Fady

    2014-01-01

    Generically, the asymmetric interactions in asymmetric dark matter (ADM) models lead to decaying DM. We show that, for ADM that carries nonzero baryon number, the continuous flavor symmetries that generate the flavor structure in the quark sector also imply a looser lower bound on the mass scale of the asymmetric mediators between the dark and visible sectors. The mediators for $B=2$ ADM that can produce a signal in the future indirect dark matter searches can thus also be searched for at the LHC. For two examples of the mediator models, with either the MFV or Froggatt-Nielsen flavor breaking pattern, we derive the FCNC constraints and discuss the search strategies at the LHC.

  2. Asymmetric nanoparticle may go "active" at room temperature

    Science.gov (United States)

    Sheng, Nan; Tu, YuSong; Guo, Pan; Wan, RongZheng; Wang, ZuoWei; Fang, HaiPing

    2017-04-01

    Using molecular dynamics simulations, we show that an asymmetrically shaped nanoparticle in dilute solution possesses a spontaneously curved trajectory within a finite time interval, instead of the generally expected random walk. This unexpected dynamic behavior has a similarity to that of active matters, such as swimming bacteria, cells, or even fish, but is of a different physical origin. The key to the curved trajectory lies in the non-zero resultant force originated from the imbalance of the collision forces acted by surrounding solvent molecules on the asymmetrically shaped nanoparticle during its orientation regulation. Theoretical formulae based on microscopic observations have been derived to describe this non-zero force and the resulting motion of the asymmetrically shaped nanoparticle.

  3. Role of Asymmetric Clusters in Desynchronization of Coherent Motion

    DEFF Research Database (Denmark)

    Popovych, O.; Maistrenko, Y.; Mosekilde, Erik

    2002-01-01

    The transition from full synchronization (coherent motion) to two-cluster dynamics is studied for a system of N globally coupled logistic maps. When increasing the nonlinearity parameter of the individual map, new periodic and strongly asymmetric two-cluster states are found to emerge in the same...... order as the periodic windows arise in the logistic map. These strongly asymmetric two-cluster states are generally first to stabilize when reducing the coupling strength. Similar phenomena are also observed for a system of globally coupled Henon maps.......The transition from full synchronization (coherent motion) to two-cluster dynamics is studied for a system of N globally coupled logistic maps. When increasing the nonlinearity parameter of the individual map, new periodic and strongly asymmetric two-cluster states are found to emerge in the same...

  4. Sara endosomes and the asymmetric division of intestinal stem cells.

    Science.gov (United States)

    Montagne, Chrystelle; Gonzalez-Gaitan, Marcos

    2014-05-01

    Tissue homeostasis is maintained by adult stem cells, which self-renew and give rise to differentiating cells. The generation of daughter cells with different fates is mediated by signalling molecules coming from an external niche or being asymmetrically dispatched between the two daughters upon stem cell mitosis. In the adult Drosophila midgut, the intestinal stem cell (ISC) divides to generate a new ISC and an enteroblast (EB) differentiating daughter. Notch signalling activity restricted to the EB regulates intestinal cell fate decision. Here, we show that ISCs divide asymmetrically, and Sara endosomes in ISCs are specifically dispatched to the presumptive EB. During ISC mitosis, Notch and Delta traffic through Sara endosomes, thereby contributing to Notch signalling bias, as revealed in Sara mutants: Sara itself contributes to the control of the ISC asymmetric division. Our data uncover an intrinsic endosomal mechanism during ISC mitosis, which participates in the maintenance of the adult intestinal lineage.

  5. Verifying a theoretical model of loads on an asymmetric disk

    Energy Technology Data Exchange (ETDEWEB)

    Krauze, K.

    1985-02-01

    The results are evaluated of testing a single asymmetric disk cutter used for coal cutting under operational conditions in an underground mine. The tests were aimed at verifying a mathematical model of coal cutting. The mean conventional pressure, a term used by the author, was determined. Forces acting on an asymmetric cutting disk calculated by mathematical modeling were compared to those determined in the tests. Comparisons showed that the model accurately describes coal cutting: in the case of tangential force error was not higher than 18%, in the case of lateral force it was not higher than 46% and in the case of compression force it was not higher than 15%. The method for calculating loads on an asymmetric disk cutter was characterized by reduced labor consumption and low number of tests. 1 reference.

  6. Complete polarimetry on the asymmetric transmission through subwavelength hole arrays.

    Science.gov (United States)

    Arteaga, Oriol; Maoz, Ben M; Nichols, Shane; Markovich, Gil; Kahr, Bart

    2014-06-02

    Dissymmetric, periodically nanostructured metal films can show non-reciprocal transmission of polarized light, in apparent violation of the Lorentz reciprocity theorem. The wave vector dependence of the extraordinary optical transmission in gold films with square and oblique subwavelength hole arrays was examined for the full range of polarized light input states. In normal incidence, the oblique lattice, in contrast to square lattice, showed strong asymmetric, non-reciprocal transmission of circularly polarized light. By analyzing the polarization of the input and the output with a complete Mueller matrix polarimeter the mechanisms that permits asymmetric transmission while preserving the requirement of electromagnetic reciprocity is revealed: the coupling of the linear anisotropies induced by misaligned surface plasmons in the film. The square lattice also shows asymmetric transmission at non-normal incidence, whenever the plane of incidence does not coincide with a mirror line.

  7. Inferring asymmetric limb cloudiness on exoplanets from transit light curves

    CERN Document Server

    von Paris, P; Bordé, P; Leconte, J; Selsis, F

    2016-01-01

    Clouds have been shown to be present in many exoplanetary atmospheres. Cloud formation modeling predicts considerable inhomogeneities of cloud cover, consistent with optical phase curve observations. However, optical phase curves cannot resolve some existing degeneracies between cloud location and cloud optical properties. We present a conceptually simple technique to detect inhomogeneous cloud cover on exoplanets. Such an inhomogeneous cloud cover produces an asymmetric primary transit of the planet in front of the host star. Asymmetric transits produce characteristic residuals compared to a standard symmetric model. Furthermore, bisector spans can be used to determine asymmetries in the transit light curve. We apply a model of asymmetric transits to the light curves of HAT-P-7b, Kepler-7b and HD209458b and search for possible cloud signatures. The nearly uninterrupted Kepler photometry is particularly well-suited for this method since it allows for a very high time resolution. We do not find any statistical...

  8. Asymmetric and axisymmetric dynamics of tropical cyclones

    Directory of Open Access Journals (Sweden)

    J. Persing

    2013-05-01

    into annular rings, the azimuthally-averaged heating rate and radial gradient thereof is considerably less than that in the AX model. This lack of organization results broadly in a slower intensification rate in the 3-D model and leads ultimately to a weaker mature vortex after 12 days of model integration. While axisymmetric heating rates in the 3-D model are weaker than those in the AX model, local heating rates in the 3-D model exceed those in the AX model and at times the vortex in the 3-D model intensifies more rapidly than AX. Analyses of the 3-D model output do not support a recent hypothesis concerning the key role of small-scale vertical mixing processes in the upper-tropospheric outflow in controlling the intensification process. In the 3-D model, surface drag plays a particularly important role in the intensification process for the prototype intensification problem on meteorologically relevant time scales by helping foster the organization of convection in azimuth. There is a radical difference in the behaviour of the 3-D and AX simulations when the surface drag is reduced or increased from realistic values. Borrowing from ideas developed in a recent paper, we give a partial explanation for this difference in behaviour. Our results provide new qualitative and quantitative insight into the differences between the asymmetric and symmetric dynamics of tropical cyclones and would appear to have important consequences for the formulation of a fluid dynamical theory of tropical cyclone intensification and mature intensity. In particular, the results point to some fundamental limitations of strict axisymmetric theory and modelling for representing the azimuthally-averaged behaviour of tropical cyclones in three dimensions.

  9. Dynamic JUNQ inclusion bodies are asymmetrically inherited in mammalian cell lines through the asymmetric partitioning of vimentin.

    Science.gov (United States)

    Ogrodnik, Mikołaj; Salmonowicz, Hanna; Brown, Rachel; Turkowska, Joanna; Średniawa, Władysław; Pattabiraman, Sundararaghavan; Amen, Triana; Abraham, Ayelet-chen; Eichler, Noam; Lyakhovetsky, Roman; Kaganovich, Daniel

    2014-06-01

    Aging is associated with the accumulation of several types of damage: in particular, damage to the proteome. Recent work points to a conserved replicative rejuvenation mechanism that works by preventing the inheritance of damaged and misfolded proteins by specific cells during division. Asymmetric inheritance of misfolded and aggregated proteins has been shown in bacteria and yeast, but relatively little evidence exists for a similar mechanism in mammalian cells. Here, we demonstrate, using long-term 4D imaging, that the vimentin intermediate filament establishes mitotic polarity in mammalian cell lines and mediates the asymmetric partitioning of damaged proteins. We show that mammalian JUNQ inclusion bodies containing soluble misfolded proteins are inherited asymmetrically, similarly to JUNQ quality-control inclusions observed in yeast. Mammalian IPOD-like inclusion bodies, meanwhile, are not always inherited by the same cell as the JUNQ. Our study suggests that the mammalian cytoskeleton and intermediate filaments provide the physical scaffold for asymmetric inheritance of dynamic quality-control JUNQ inclusions. Mammalian IPOD inclusions containing amyloidogenic proteins are not partitioned as effectively during mitosis as their counterparts in yeast. These findings provide a valuable mechanistic basis for studying the process of asymmetric inheritance in mammalian cells, including cells potentially undergoing polar divisions, such as differentiating stem cells and cancer cells.

  10. Immobilisation of ligands by radio-derivatized polymers; Immobilisering av ligander med radioderiverte polymerer

    Energy Technology Data Exchange (ETDEWEB)

    Varga, J.M.; Fritsch, P.

    1995-01-30

    The invention relates to radio-derivatized polymers and a method of producing them by contacting non-polymerizable conjugands with radiolysable polymers in the presence of irradiation. The resulting radio-derivatized polymers can be further linked with ligand of organic or inorganic nature to immobilize such ligands. 2 figs., 5 tabs.

  11. Multiple ligand simultaneous docking: orchestrated dancing of ligands in binding sites of protein.

    Science.gov (United States)

    Li, Huameng; Li, Chenglong

    2010-07-30

    Present docking methodologies simulate only one single ligand at a time during docking process. In reality, the molecular recognition process always involves multiple molecular species. Typical protein-ligand interactions are, for example, substrate and cofactor in catalytic cycle; metal ion coordination together with ligand(s); and ligand binding with water molecules. To simulate the real molecular binding processes, we propose a novel multiple ligand simultaneous docking (MLSD) strategy, which can deal with all the above processes, vastly improving docking sampling and binding free energy scoring. The work also compares two search strategies: Lamarckian genetic algorithm and particle swarm optimization, which have respective advantages depending on the specific systems. The methodology proves robust through systematic testing against several diverse model systems: E. coli purine nucleoside phosphorylase (PNP) complex with two substrates, SHP2NSH2 complex with two peptides and Bcl-xL complex with ABT-737 fragments. In all cases, the final correct docking poses and relative binding free energies were obtained. In PNP case, the simulations also capture the binding intermediates and reveal the binding dynamics during the recognition processes, which are consistent with the proposed enzymatic mechanism. In the other two cases, conventional single-ligand docking fails due to energetic and dynamic coupling among ligands, whereas MLSD results in the correct binding modes. These three cases also represent potential applications in the areas of exploring enzymatic mechanism, interpreting noisy X-ray crystallographic maps, and aiding fragment-based drug design, respectively.

  12. Organotellurium ligands - designing and complexation reactions

    Indian Academy of Sciences (India)

    Ajai K Singh

    2002-08-01

    A variety of tellurium ligands has been designed and studied for their complexation reactions in the last decade. Of these hybrid telluroethers, halotellurium ligands and polytellurides are the most notable ones. RTe- and polytelluride ions have also been used to design clusters. Ligation of ditelluroethers and several hybrid telluroethers is extensively studied in our laboratories. The ditelluroether ligand RTeCH2TeR (where R = 4-MeOC6H4) (1), similar to dppm [1,2-bis(diphenylphosphino) methane], has been synthesized in good yield (∼80 %) by reacting CHCl3 with RTe- (generated in situ by borohydride reduction of R2Te2). Iodine reacts with 1 to give tetra-iodo derivative, which has intermolecular Te$\\cdots$I interactions resulting in a macro structure containing rectangular Te-I$\\cdots$Te bridges. 1 readily forms four membered rings with Pd(II) and Ru(II). On the formation of this chelate ring, the signal in 125Te NMR spectra shifts significantly upfield (50-60 ppm). The bridging mode of 1 has been shown in [Ru(-cymene)Cl2](-1)[Ru(-cymene)Cl2]. The hybrid telluroether ligands explored are of the types (Te, S), (Te, N) and (Te, O). The tellurium donor site has strong trans influence, which is manifested more strongly in square planar complexes of palladium(II). The morpholine N-donor site has been found to have weaker donor characteristics in (Te, N) ligands than pyridine and alkylamine donor sites of analogous ligands. The singlet oxygen readily oxidises the coordinated Te. This oxidation follows first order kinetics. The complexation reaction of RuCl3.H2O with N-[2-(4-methoxyphenyltelluro)ethyl]phthalimide (2) results in a novel (Te, N, O)-heterocycle, Te-chloro,Te-anisyl-1a-aza-4-oxa-3-tellura-1H, 2H, 4aH-9 fluorenone. The (Te, O) ligands can be used as hemilabile ligands, the oxygen atom temporarily protects the vacant coordination site before the arrival of the substrate. The chelate shifts observed in 125Te NMR spectra of metal complexes of Te-ligands have

  13. Control Strategies of Asymmetric Strip Shape in Six-High Cold Rolling Mill%Control Strategies of Asymmetric Strip Shape in Six-High Cold Rolling Mill

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yun; YANG Quan; WANG Xiao-chen

    2011-01-01

    It is a complicated problem for cold-rolled strip to improve asymmetric strip shape in strip production. A roll system and strip coupled model of six-high cold rolling mill was established with finite element method to estimate the effect of intermediate roll shifting, tilting, symmetric and asymmetric bending technologies on strip profile. To reduce asymmetric defects of strip shape as much as possible, some control strategies were proposed, including tilting and asymmetric bending of intermediate roll and work roll. The combinations of these three control strategies can effectively eliminate asymmetric strip shape defects. Finally, the closed-loop control model of asymmetric flat- ness at the last stand was given, and the flatness control system with the function of asymmetric strip shape control was also designed for cold tandem mill.

  14. Dockomatic - automated ligand creation and docking

    Directory of Open Access Journals (Sweden)

    Hampikian Greg

    2010-11-01

    Full Text Available Abstract Background The application of computational modeling to rationally design drugs and characterize macro biomolecular receptors has proven increasingly useful due to the accessibility of computing clusters and clouds. AutoDock is a well-known and powerful software program used to model ligand to receptor binding interactions. In its current version, AutoDock requires significant amounts of user time to setup and run jobs, and collect results. This paper presents DockoMatic, a user friendly Graphical User Interface (GUI application that eases and automates the creation and management of AutoDock jobs for high throughput screening of ligand to receptor interactions. Results DockoMatic allows the user to invoke and manage AutoDock jobs on a single computer or cluster, including jobs for evaluating secondary ligand interactions. It also automates the process of collecting, summarizing, and viewing results. In addition, DockoMatic automates creation of peptide ligand .pdb files from strings of single-letter amino acid abbreviations. Conclusions DockoMatic significantly reduces the complexity of managing multiple AutoDock jobs by facilitating ligand and AutoDock job creation and management.

  15. A new class of PN3-pincer ligands for metal–ligand cooperative catalysis

    KAUST Repository

    Li, Huaifeng

    2014-12-01

    Work on a new class of PN3-pincer ligands for metal-ligand cooperative catalysis is reviewed. While the field of the pyridine-based PN3-transition metal pincer complexes is still relatively young, many important applications of these complexes have already emerged. In several cases, the PN3-pincer complexes for metal-ligand cooperative catalysis result in significantly improved or unprecedented activities. The synthesis and coordination chemistry of PN3-pincer ligands are briefly summarized first to cover the synthetic routes for their preparation, followed by a focus review on their applications in catalysis. A specific emphasis is placed on the later section about the role of PN3-pincer ligands\\' dearomatization-rearomatization steps during the catalytic cycles. The mechanistic insights from density functional theory (DFT) calculations are also discussed.

  16. Sliding tethered ligands add topological interactions to the toolbox of ligand-receptor design

    Science.gov (United States)

    Bauer, Martin; Kékicheff, Patrick; Iss, Jean; Fajolles, Christophe; Charitat, Thierry; Daillant, Jean; Marques, Carlos M.

    2015-09-01

    Adhesion in the biological realm is mediated by specific lock-and-key interactions between ligand-receptor pairs. These complementary moieties are ubiquitously anchored to substrates by tethers that control the interaction range and the mobility of the ligands and receptors, thus tuning the kinetics and strength of the binding events. Here we add sliding anchoring to the toolbox of ligand-receptor design by developing a family of tethered ligands for which the spacer can slide at the anchoring point. Our results show that this additional sliding degree of freedom changes the nature of the adhesive contact by extending the spatial range over which binding may sustain a significant force. By introducing sliding tethered ligands with self-regulating length, this work paves the way for the development of versatile and reusable bio-adhesive substrates with potential applications for drug delivery and tissue engineering.

  17. Smurfs have "fused" into the asymmetric division of stem cells

    Institute of Scientific and Technical Information of China (English)

    Steven Y. Cheng; Ying E. Zhang

    2011-01-01

    @@ The asymmetric cell division is the way in which a stem cell divides into one daughter stem cell and one differentiated daughter cell.This process is one of the key principles of developmental biology that ensures the perpetual supply of stem cells while allowing a particular cell lineage to be populated.During Drosophila oogenesis, the fate of the daughter stem cell produced from the asymmetric division of germline stem cells (GSCs) is specified by Decapentaplegic (Dpp), but the other daughter cell has almost equal access to the Dpp signal.

  18. Six transformer based asymmetrical embedded Z-source inverters

    DEFF Research Database (Denmark)

    Wei, Mo; Poh Chiang, Loh; Chi, Jin

    2013-01-01

    Embedded/Asymmetrical embedded Z-source inverters were proposed to maintain smooth input current/voltage across the dc source and within the impedance network, remain the shoot-through feature used to boost up the dc-link voltage without adding bulky filter at input side. This paper introduces...... a class of transformer based asymmetrical embedded Z-source inverters which keep the smooth input current and voltage while achieving enhanced voltage boost capability. The presented inverters are verified by laboratory prototypes experimentally....

  19. Spectroscopic calculation of asymmetric top free radicals: method and program

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    This paper sketches out the effective Hamiltonian and basis set adopted in the spectroscopic calcula tion of asymmetric top free radicals, and details the machine implementation of the spectral analysis of asymmetric top free radicals, the design and usage of the program package. To demonstrate the application of this program, analyses have been performed on the far infrared laser magnetic resonance spectrum of 14N16O2( I = 1) and the infrared diode laser spectrum of the v3 band of PO2( I = 1/2) using the program.

  20. Climate agreements under limited participation, asymmetric information and market imperfections

    Energy Technology Data Exchange (ETDEWEB)

    Hagem, Cathrine

    1996-12-31

    This thesis relates to climate agreements and cost efficiency by analysing the formation of a system of quota leading to distributed discharge of emissions between countries. Main fields concerned are the greenhouse effect, the political process, efficient and cost-effective climate agreements, and climate agreements under limited participation, asymmetric information and market imperfections covering fields like limited participation in climate agreements, limited participation and indirect impact on non-participating countries` emissions, limited participation and direct impact on non-participating countries` emissions under asymmetric information, and non-competitive market for tradeable quotas. 166 refs., 7 tabs.

  1. DYNAMICS OF THE ZONAL ASYMMETRIC STRUCTURE OF ARCTIC OSCILLATION

    Institute of Scientific and Technical Information of China (English)

    WANG Xiu-hong; YU Wei-dong; LUO Ti-qian

    2004-01-01

    The Arctic Oscillation(AO),though basically is a zonal symmetric phenomenon,also shows zonal asymmetric variation.The dynamics of this zonal variation is considered here from the point of view of the planetary propagation on the earth sphere.Based on the linear barotropic vorticity equation,the planetary wave ray path is calculated in the winter January.It shows that NAO(North Atlantic Oscillation),AO and North Pacific could be linked through the planetary wave propagation,which acts as the atmospheric bridge.The zonal symmetric and asymmetric structures both have association with these Rossby wave activities.

  2. Generation of isolated asymmetric umbilics in light's polarization

    CERN Document Server

    Galvez, Enrique J; Kumar, Vijay; Viswanathan, Nirmal K

    2014-01-01

    Polarization-singularity C-points, a form of line singularities, are the vectorial counterparts of the optical vortices of spatial modes and fundamental optical features of polarization-spatial modes. Their generation in tailored beams has been limited to lemon and star C-points that contain symmetric dislocations in state-of-polarization patterns. In this article we present the theory and laboratory measurements of two complementary methods to generate isolated asymmetric C-points in tailored beams, of which symmetric lemons and stars are limiting cases; and we report on the generation of monstars, an asymmetric C-point with characteristics of both lemons and stars.

  3. Imperfect pitchfork bifurcation in asymmetric two-compartment granular gas

    Institute of Scientific and Technical Information of China (English)

    Zhang Yin; Li Yin-Chang; Liu Rui; Cui Fei-Fei; Pierre Evesque; Hou Mei-Ying

    2013-01-01

    The clustering behavior of a mono-disperse granular gas is experimentally studied in an asymmetric two-compartment setup.Unlike the random clustering in either compartment in the case of symmetric configuration when lowering the shaking strength to below a critical value,the directed clustering is observed,which corresponds to an imperfect pitchfork bifurcation.Numerical solutions of the flux equation using a modified simple flux function show qualitative agreements with the experimental results.The potential application of this asymmetric structure is discussed.

  4. Decoding Pure Rotational Molecular Spectra for Asymmetric Molecules

    CERN Document Server

    Cooke, S A

    2012-01-01

    In this paper we demonstrate how asymmetric molecular rotational spectra may be introduced to students both "pictorially" and with simple formulae. It is shown that the interpretation of such spectra relies heavily upon pattern recognition. The presentation of some common spectral patterns in near-prolate asymmetric rotational spectra provides a means by which spectral assignment, and approximate rotational constant determination, may be usefully explored in the physics and chemistry classrooms. To aid in this endeavor we have created a supporting, free, web page and mobile web page.

  5. Ideal MHD beta-limits of poloidally asymmetric equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Todd, A.M.M.; Miller, A.E.; Grimm, R.C.; Okabayashi, M.; Dalhed, H.E. Jr.

    1981-05-01

    The ideal MHD stability of poloidally asymmetric equilibria, which are typical of a tokamak reactor design with a single-null poloidal divertor is examined. As with symmetric equilibria, stability to non-axisymmetric modes improves with increasing triangularity and ellipticity, and with lower edge safety factor. Pressure profiles optimized with respect to ballooning stability are obtained for an asymmetric shape, resulting in ..beta../sub critical/ approx. = 5.7%. The corresponding value for an equivalent symmetric shape is ..beta../sub critical/ approx. = 6.5%.

  6. Nonreciprocal Coupling in Asymmetric Dual-Core Photonic Crystal Fibres

    Institute of Scientific and Technical Information of China (English)

    ZHANG Lin; YANG Chang-Xi

    2004-01-01

    @@ The photonic crystal fibre with asymmetric dual cores is shown to attain strongly nonreciprocal coupling of the lightwave propagating along the fibre, for the first time to our knowledge. It is found that the coupling properties can be quite different when the incident position is changed. This kind of fibre could have potential for unidirectional coupler applications in fibre-optic local and metropolitan area networks. We also examine the polarization and wavelength dependence of the coupling nonreciprocity in the asymmetric dual-core photonic crystal fibres.

  7. THE PROBLEM OF AN EXTERNAL CIRCULAR CRACK UNDER ASYMMETRIC LOADINGS

    Institute of Scientific and Technical Information of China (English)

    王银邦

    2001-01-01

    Using the boundary integral equation method, the problem of an external circular crack in a three-dimensional infinite elastic body under asymmetric loadings is investigated. The two- dimensional singular boundary integral equations of the problem were reduced to a system of Abel integral equations by means of Fourier series and hypergeometric functions. The exact solutions of stress intensity factors are obtained for the problem of an external circular crack under asymmetric loadings, which are even more universal than the results obtained by the use of Hankel transform method. The results demonstrate that the boundary integral equation method has great potential as a new analytic method.

  8. Asymmetric Mutualism in Two- and Three-Dimensional Range Expansions

    Science.gov (United States)

    Lavrentovich, Maxim O.; Nelson, David R.

    2014-04-01

    Genetic drift at the frontiers of two-dimensional range expansions of microorganisms can frustrate local cooperation between different genetic variants, demixing the population into distinct sectors. In a biological context, mutualistic or antagonistic interactions will typically be asymmetric between variants. By taking into account both the asymmetry and the interaction strength, we show that the much weaker demixing in three dimensions allows for a mutualistic phase over a much wider range of asymmetric cooperative benefits, with mutualism prevailing for any positive, symmetric benefit. We also demonstrate that expansions with undulating fronts roughen dramatically at the boundaries of the mutualistic phase, with severe consequences for the population genetics along the transition lines.

  9. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou

    2015-12-01

    Full Text Available Copper-catalyzed (or -mediated asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds.

  10. Data analysis of asymmetric structures advanced approaches in computational statistics

    CERN Document Server

    Saito, Takayuki

    2004-01-01

    Data Analysis of Asymmetric Structures provides a comprehensive presentation of a variety of models and theories for the analysis of asymmetry and its applications and provides a wealth of new approaches in every section. It meets both the practical and theoretical needs of research professionals across a wide range of disciplines and  considers data analysis in fields such as psychology, sociology, social science, ecology, and marketing. In seven comprehensive chapters this guide details theories, methods, and models for the analysis of asymmetric structures in a variety of disciplines and presents future opportunities and challenges affecting research developments and business applications.

  11. Asymmetrical dynamic propagation problems on mode Ⅲ interface crack

    Institute of Scientific and Technical Information of China (English)

    L(U) Nian-chun; YANG Ding-ning; CHENG Yun-hong; CHENG Jin

    2007-01-01

    By the application of the theory of complex functions, asymmetrical dynamic propagation problems on mode Ⅲ interface crack are studied. The universal representations of analytical solutions are obtained by the approaches of serf-similar function. The problems researched can be facilely transformed into Riemann-Hilbert problems and analytical solution to an asymmetrical propagation crack under the condition of point loads and unit-step loads, respectively, is acquired. After those solutions were used by superposition theorem, the solutions of arbitrarily complex problems could be attained.

  12. Finite stage asymmetric repeated games: Both players' viewpoints

    KAUST Repository

    Li, Lichun

    2017-01-05

    In asymmetric zero-sum games, one player has superior information about the game over the other. It is known that the informed players (maximizer) face the tradeoff of exploiting its superior information at the cost of revealing its superior information, but the basic point of the uninformed player (minimizer)\\'s decision making remains unknown. This paper studies the finite stage asymmetric repeated games from both players\\' viewpoints, and derives that not only security strategies but also the opponents\\' corresponding best responses depends only on the informed player\\'s history action sequences. Moreover, efficient LP formulations to compute both player\\'s security strategies are provided.

  13. Preview-based Asymmetric Load Reduction of Wind Turbines

    DEFF Research Database (Denmark)

    Madsen, Mathias; Filsø, Jakob; Soltani, Mohsen

    2012-01-01

    Fatigue loads on wind turbines caused by an asymmetric wind field become an increasing concern when the scale of wind turbines increases. This paper presents a model based predictive approach to reduce asymmetric loads by using Light Detection And Ranging (LIDAR) measurements. The Model Predictive...... Controller (MPC) developed is based on a model with individual blade pitching to utilize the LIDAR measurements. The MPC must also maintain a given power reference while satisfying a set of actuator constraints. The designed controller was tested on a 5 MW wind turbine in the FAST simulator and compared...

  14. Strongly asymmetric discrete Painlevé equations: The multiplicative case

    Science.gov (United States)

    Grammaticos, B.; Ramani, A.; Tamizhmani, K. M.; Tamizhmani, T.; Satsuma, J.

    2016-04-01

    We examine a class of multiplicative discrete Painlevé equations which may possess a strongly asymmetric form. When the latter occurs, the equation is written as a system of two equations the right hand sides of which have different functional forms. The present investigation focuses upon two canonical families of the Quispel-Roberts-Thompson classification which contain equations associated with the affine Weyl groups D5 ( 1 ) and E6 ( 1 ) (or groups appearing lower in the degeneration cascade of these two). Many new discrete Painlevé equations with strongly asymmetric forms are obtained.

  15. Asymmetric transportation induced by thermal noise at the nanoscale

    Institute of Scientific and Technical Information of China (English)

    WAN RongZheng; HU Jun; FANG HaiPing

    2012-01-01

    Based on a simple model,we theoretically show that asymmetric transportation is possible in nanoscale systems experiencing thermal noise without the presence of external fluctuations.The key to this theoretical advance is that the correlation lengths of the thermal fluctuations become significantly long for nanoscale systems.This differs from macroscopic systems in which the thermal noises are usually treated as white noise.Our observation does not violate the second law of thermodynamics,since at the nanoscale,extra energy is required to keep the asymmetric structure against thermal fluctuations.

  16. NMR screening of new carbocyanine dyes as ligands for affinity chromatography.

    Science.gov (United States)

    Cruz, Carla; Boto, Renato E F; Drzazga, Anna K; Almeida, Paulo; Queiroz, João A

    2014-04-01

    Four new carbocyanines containing symmetric and asymmetric heterocyclic moieties and N-carboxyalkyl groups have been synthesized and characterized. The binding mechanism established between these cyanines and several proteins was evaluated using saturation transfer difference (STD) NMR. The results obtained for the different dyes revealed a specific interaction to the standard proteins lysozyme, α-chymotrypsin, ribonuclease (RNase), bovine serum albumin (BSA), and gamma globulin. For instance, the two un-substituted symmetrical dyes (cyanines 1 and 3) interacted preferentially through its benzopyrrole and dibenzopyrrole units with lysozyme, α-chymotrypsin, and RNase, whereas the symmetric disulfocyanine dye (cyanine 2) bound BSA and gamma globulin through its carboxyalkyl chains. On the other hand, the asymmetric dye (cyanine 4) interacts with lysozyme and α-chymotrypsin through benzothiazole moiety and with RNase through dibenzopyrrole unit. Thus, STD-NMR technique was successfully used to screen cyanine-protein interactions and determine potential binding sites of the cyanines for posterior use as ligands in affinity chromatography.

  17. Crystal structures and ligand binding of PurM proteins from Thermus thermophilus and Geobacillus kaustophilus.

    Science.gov (United States)

    Kanagawa, Mayumi; Baba, Seiki; Watanabe, Yuzo; Nakagawa, Noriko; Ebihara, Akio; Kuramitsu, Seiki; Yokoyama, Shigeyuki; Sampei, Gen-Ichi; Kawai, Gota

    2016-03-01

    Crystal structures of 5-aminoimidazole ribonucleotide (AIR) synthetase, also known as PurM, from Thermus thermophilus (Tt) and Geobacillus kaustophilus (Gk) were determined. For TtPurM, the maximum resolution was 2.2 Å and the space group was P21212 with four dimers in an asymmetric unit. For GkPurM, the maximum resolution was 2.2 Å and the space group was P21212 with one monomer in asymmetric unit. The biological unit is dimer for both TtPurM and GkPurM and the dimer structures were similar to previously determined structures of PurM in general. For TtPurM, ∼50 residues at the amino terminal were disordered in the crystal structure whereas, for GkPurM, the corresponding region covered the ATP-binding site forming an α helix in part, suggesting that the N-terminal region of PurM changes its conformation upon binding of ligands. FGAM binding site was predicted by the docking simulation followed by the MD simulation based on the SO4 (2-) binding site found in the crystal structure of TtPurM.

  18. Symmetric signaling by an asymmetric 1 erythropoietin: 2 erythropoietin receptor complex.

    Science.gov (United States)

    Zhang, Yingxin L; Radhakrishnan, Mala L; Lu, Xiaohui; Gross, Alec W; Tidor, Bruce; Lodish, Harvey F

    2009-01-30

    Via sites 1 and 2, erythropoietin binds asymmetrically to two identical receptor monomers, although it is unclear how asymmetry affects receptor activation and signaling. Here we report the design and validation of two mutant erythropoietin receptors that probe the role of individual members of the receptor dimer by selectively binding either site 1 or site 2 on erythropoietin. Ba/F3 cells expressing either mutant receptor do not respond to erythropoietin, but cells co-expressing both receptors respond to erythropoietin by proliferation and activation of the JAK2-Stat5 pathway. A truncated receptor with only one cytosolic tyrosine (Y343) is sufficient for signaling in response to erythropoietin, regardless of the monomer on which it is located. Similarly, only one receptor in the dimer needs a juxtamembrane hydrophobic L253 or W258 residue, essential for JAK2 activation. We conclude that despite asymmetry in the ligand-receptor interaction, both sides are competent for signaling, and appear to signal equally.

  19. A series of isoreticular chiral metal-organic frameworks as a tunable platform for asymmetric catalysis.

    Science.gov (United States)

    Ma, Liqing; Falkowski, Joseph M; Abney, Carter; Lin, Wenbin

    2010-10-01

    Metal-organic frameworks, built by bridging metal ions with organic linkers, represent a new class of porous hybrid materials with attractive tunability in compositions, structures and functions. In particular, the mild conditions typically employed for their synthesis allow for the functionalization of their building blocks, and thus the rational design of novel materials. Here we demonstrate the systematic design of eight mesoporous chiral metal-organic frameworks, with the framework formula [LCu2(solvent)2] (where L is a chiral tetracarboxylate ligand derived from 1,1'-bi-2-naphthol), that have the same structures but channels of different sizes. Chiral Lewis acid catalysts were generated by postsynthesis functionalization with Ti(OiPr)4, and the resulting materials proved to be highly active asymmetric catalysts for diethylzinc and alkynylzinc additions, which converted aromatic aldehydes into chiral secondary alcohols. The enantioselectivities of these reactions can be modified by tuning the size of the channels, which alters the diffusion rates of the organic substrates.

  20. Development of the titanium–TADDOLate-catalyzed asymmetric fluorination of β-ketoesters

    Directory of Open Access Journals (Sweden)

    Lukas Hintermann

    2011-10-01

    Full Text Available Titanium-based Lewis acids catalyze the α-fluorination of β-ketoesters by electrophilic N–F-fluorinating reagents. Asymmetric catalysis with TADDOLato–titanium(IV dichloride (TADDOL = α,α,α',α'-tetraaryl-(1,3-dioxolane-4,5-diyl-dimethanol Lewis acids produces enantiomerically enriched α-fluorinated β-ketoesters in up to 91% enantiomeric excess, with either F–TEDA (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate in acetonitrile solution or NFSI (N-fluorobenzenesulfonimide in dichloromethane solution as fluorinating reagents. The effects of various reaction parameters and of the TADDOL ligand structure on the catalytic activity and enantioselectivity were investigated. The absolute configuration of several fluorination products was assigned through correlation. Evidence for ionization of the catalyst complex by chloride dissociation, followed by generation of titanium β-ketoenolates as key reaction intermediates, was obtained. Based on the experimental findings, a general mechanistic sketch and a steric model of induction are proposed.

  1. Cationic ruthenium alkylidene catalysts bearing phosphine ligands.

    Science.gov (United States)

    Endo, Koji; Grubbs, Robert H

    2016-02-28

    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  2. Synthesis of 3,3-Disubstituted Oxindoles by Palladium-Catalyzed Asymmetric Intramolecular α-Arylation of Amides: Reaction Development and Mechanistic Studies.

    Science.gov (United States)

    Katayev, Dmitry; Jia, Yi-Xia; Sharma, Akhilesh K; Banerjee, Dipshikha; Besnard, Céline; Sunoj, Raghavan B; Kündig, E Peter

    2013-09-02

    Palladium complexes incorporating chiral N-heterocyclic carbene (NHC) ligands catalyze the asymmetric intramolecular α-arylation of amides producing 3,3-disubstituted oxindoles. Comprehensive DFT studies have been performed to gain insight into the mechanism of this transformation. Oxidative addition is shown to be rate-determining and reductive elimination to be enantioselectivity-determining. The synthesis of seven new NHC ligands is detailed and their performance is compared. One of them, L8, containing a tBu and a 1-naphthyl group at the stereogenic centre, proved superior and was very efficient in the asymmetric synthesis of fifteen new spiro-oxindoles and three azaspiro-oxindoles often in high yields (up to 99 %) and enantioselectivities (up to 97 % ee; ee=enantiomeric excess). Three palladacycle intermediates resulting from the oxidative addition of [Pd(NHC)] into the aryl halide bond were isolated and structurally characterized (X-ray). Using these intermediates as catalysts showed alkene additives to play an important role in increasing turnover number and frequency.

  3. Efficient chemoenzymatic synthesis of chiral pincer ligands.

    Science.gov (United States)

    Felluga, Fulvia; Baratta, Walter; Fanfoni, Lidia; Pitacco, Giuliana; Rigo, Pierluigi; Benedetti, Fabio

    2009-05-01

    Chiral, nonracemic pincer ligands based on the 6-phenyl-2-aminomethylpyridine and 2-aminomethylbenzo[h]quinoline scaffolds were obtained by a chemoenzymatic approach starting from 2-pyridyl and 2-benzoquinolyl ethanone. In the enantiodifferentiating step, secondary alcohols of opposite absolute configuration were obtained by a baker's yeast reduction of the ketones and by lipase-mediated dynamic kinetic resolution of the racemic alcohols. Their transformation into homochiral 1-methyl-1-heteroarylethanamines occurred without loss of optical purity, giving access to pincer ligands used in enantioselective catalysis.

  4. CLiBE: a database of computed ligand binding energy for ligand-receptor complexes.

    Science.gov (United States)

    Chen, X; Ji, Z L; Zhi, D G; Chen, Y Z

    2002-11-01

    Consideration of binding competitiveness of a drug candidate against natural ligands and other drugs that bind to the same receptor site may facilitate the rational development of a candidate into a potent drug. A strategy that can be applied to computer-aided drug design is to evaluate ligand-receptor interaction energy or other scoring functions of a designed drug with that of the relevant ligands known to bind to the same binding site. As a tool to facilitate such a strategy, a database of ligand-receptor interaction energy is developed from known ligand-receptor 3D structural entries in the Protein Databank (PDB). The Energy is computed based on a molecular mechanics force field that has been used in the prediction of therapeutic and toxicity targets of drugs. This database also contains information about ligand function and other properties and it can be accessed at http://xin.cz3.nus.edu.sg/group/CLiBE.asp. The computed energy components may facilitate the probing of the mode of action and other profiles of binding. A number of computed energies of some PDB ligand-receptor complexes in this database are studied and compared to experimental binding affinity. A certain degree of correlation between the computed energy and experimental binding affinity is found, which suggests that the computed energy may be useful in facilitating a qualitative analysis of drug binding competitiveness.

  5. Rh-Catalyzed Asymmetric Hydrogenation of 1,2-Dicyanoalkenes.

    Science.gov (United States)

    Li, Meina; Kong, Duanyang; Zi, Guofu; Hou, Guohua

    2017-01-06

    A highly efficient enantioselective hydrogenation of 1,2-dicyanoalkenes catalyzed by the complex of rhodium and f-spiroPhos has been developed. A series of 1,2-dicyanoalkenes were successfully hydrogenated to the corresponding chiral 1,2-dicyanoalkanes under mild conditions with excellent enantioselectivities (up to 98% ee). This methodology provides efficient access to the asymmetric synthesis of chiral diamines.

  6. Asymmetrical transformer-based embedded Z-source inverters

    DEFF Research Database (Denmark)

    Wei, Mo; Loh, Poh Chiang; Blaabjerg, Frede

    2013-01-01

    their performances, a number of asymmetrical transformer-based embedded Z-source inverters are proposed. Through theoretical derivation and experiments, the proposed inverters have been shown to draw a smooth input current and produce a high gain by varying the transformer turns ratio n. The range of variation for n...

  7. Asymmetrical and symmetrical embedded Z-source inverters

    DEFF Research Database (Denmark)

    Gao, F.; Loh, P.C.; Li, D.

    2011-01-01

    This study presents two types of embedded Z-source inverters with each type further divided into asymmetrical and symmetrical realisations. Being different from their traditional counterparts, the presented inverters have their dc sources inserted within their X-shaped impedance networks so...

  8. Adoption subsidy versus technology standards under asymmetric information

    NARCIS (Netherlands)

    I.V. Ossokina (Ioulia); O.H. Swank (Otto)

    2008-01-01

    textabstractMarket-based instruments are believed to create more efficient incentives for firms to adopt new technologies than command-and-control policies. We compare the effects of a direct technology regulation and of an adoption subsidy under asymmetric information about the costs of technologic

  9. Unexpected phase behavior of an asymmetric diblock copolymer

    DEFF Research Database (Denmark)

    Papadakis, Christine Maria; Almdal, Kristoffer; Mortensen, Kell;

    1999-01-01

    We report on measurements of the transmitted depolarized light intensity and on small-angle neutron scattering (SANS) measurements on a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) diblock copolymer studied in the bulk. SANS measurements were made both on isotropic a...

  10. Novel FinFET Device Using Asymmetric Doping

    DEFF Research Database (Denmark)

    Moradi, Farshad

    2012-01-01

    In this paper, a new technique is proposed to improve the device characteristics by introducing asymmetric doping at the source and the drain of the conventional FinFET. Specifically, the proposed device exhibits 9X increase of the Ion/Ioff ratio and 3X improved DIBL compared to conventional...

  11. Recent advances in rhodium-catalyzed asymmetric synthesis of heterocycles.

    Science.gov (United States)

    Chen, Wen-Wen; Xu, Ming-Hua

    2017-02-01

    Heterocycles are crucial structural motifs that are ubiquitously present in biologically active natural products and pharmaceutically important compounds. Over the past few decades, great attention has been paid to develop efficient methodologies for the construction of diverse enantioenriched heterocyclic frameworks. This review focuses on the recent impressive progress and advances in the asymmetric synthesis of heterocycles under rhodium catalysis.

  12. Research on the Design and Modification of Asymmetric Spur Gear

    Directory of Open Access Journals (Sweden)

    Xiaohe Deng

    2015-01-01

    Full Text Available A design method for the geometric shape and modification of asymmetric spur gear was proposed, in which the geometric shape and modification of the gear can be obtained directly according to the rack-cutter profile. In the geometric design process of the gear, a rack-cutter with different pressure angles and fillet radius in the driving side and coast side was selected, and the generated asymmetric spur gear profiles also had different pressure angles and fillets accordingly. In the modification design of the gear, the pressure angle modification of rack-cutter was conducted firstly and then the corresponding modified involute gear profile was obtained. The geometric model of spur gears was developed using computer-aided design, and the meshing process was analyzed using finite element simulation method. Furthermore, the transmission error and load sharing ratio of unmodified and modified asymmetric spur gears were investigated. Research results showed that the proposed gear design method was feasible and desired spur gear can be obtained through one time rapid machining by the method. Asymmetric spur gear with better transmission characteristic can be obtained via involute modification.

  13. Bisimulation Lattice of Asymmetric Chi Calculus with Mismatch

    Institute of Scientific and Technical Information of China (English)

    Dong Xiaoju(董笑菊); Zhong Farong; Fu Yuxi

    2003-01-01

    This paper carries out a systematic investigation into the bisimulation lattice of asymmetric chi calculus with a mismatch combinator. It is shown that all the sixty three L-bisimilarities collapse to twelve distinct relations and they form a bisimulation lattice with respect to set inclusion. The top of the lattice coincides with the barbed bisimilarity.

  14. On te generic stability of mixed strategies in asymmetric contests

    NARCIS (Netherlands)

    Bhaskar, V.

    1995-01-01

    Although a mixed strategy can never be evolutionarily stable in a truly asymmetric contest, examples show that mixed strategies can satisfy the weaker criterion on neutral stability. This paper shows that such examples are rare, and, generically, a mixed strategy is unstable. We apply the result to

  15. Short-range correlations in asymmetric nuclear matter

    OpenAIRE

    2003-01-01

    The spectral function of protons in the asymmetric nuclear matter is calculated in the self-consistent T-matrix approach. The spectral function per proton increases with increasing asymmetry. This effect and the density dependence of the spectral function partially explain the observed increase of the spectral function with the mass number of the target nuclei in electron scattering experiments.

  16. On the topology defined by Thurston's asymmetric metric

    DEFF Research Database (Denmark)

    Papadopoulos, Athanase; Theret, Guillaume

    2007-01-01

    We establish some properties of Thurston's asymmetric metric L on the Teichmüller space of a surface of genus with punctures and with negative Euler characteristic. We study convergence of sequences of elements in in the sense of L, as well as sequences that tend to infinity in . We show that the...

  17. The Analysis on Translation System Based on Asymmetric Cyclic Polling

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    By the imbedded Markov chain theory and the probability generating function method, this paper discusses the queuing model of the switch node at the router and analyzes the derivative characters of first and second order of discrete asymmetric tri-queuing gate polling system. The average waiting time and the average queuing length are explicitly obtained and these results are verified by simulation.

  18. Sensory feedback and coordinating asymmetrical landing in toads.

    Science.gov (United States)

    Cox, S M; Gillis, Gary B

    2016-06-01

    Coordinated landing requires anticipating the timing and magnitude of impact, which in turn requires sensory input. To better understand how cane toads, well known for coordinated landing, prioritize visual versus vestibular feedback during hopping, we recorded forelimb joint angle patterns and electromyographic data from five animals hopping under two conditions that were designed to force animals to land with one forelimb well before the other. In one condition, landing asymmetry was due to mid-air rolling, created by an unstable takeoff surface. In this condition, visual, vestibular and proprioceptive information could be used to predict asymmetric landing. In the other, animals took off normally, but landed asymmetrically because of a sloped landing surface. In this condition, sensory feedback provided conflicting information, and only visual feedback could appropriately predict the asymmetrical landing. During the roll treatment, when all sensory feedback could be used to predict an asymmetrical landing, pre-landing forelimb muscle activity and movement began earlier in the limb that landed first. However, no such asymmetries in forelimb preparation were apparent during hops onto sloped landings when only visual information could be used to predict landing asymmetry. These data suggest that toads prioritize vestibular or proprioceptive information over visual feedback to coordinate landing.

  19. Symmetric/asymmetric bifurcation behaviours of a bogie system

    DEFF Research Database (Denmark)

    Xue-jun, Gao; Ying-hui, Li; Yuan, Yue;

    2013-01-01

    Based on the bifurcation and stability theory of dynamical systems, the symmetric/asymmetric bifurcation behaviours and chaotic motions of a railway bogie system under a complex nonlinear wheel–rail contact relation are investigated in detail by the ‘resultant bifurcation diagram’ method with slo...

  20. Attempt to accelerate asymmetric species with unequal frequencies in RHIC

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Luo, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marusic, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Minty, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Robert-Demolaize, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Smith, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Mernick, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hayes, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Severino, F. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2015-07-09

    This report summarizes the beam studies on accelerating asymmetric beams with unequal frequencies, during the proton-Gold/Aluminum run in 2015. The experiment failed due to modulated beam-beam effects even though the beams were separated by at least 15 mm.