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Sample records for asymmetric hydrovinylation ligands

  1. Tunable Phosphoramidite Ligands for Asymmetric Hydrovinylation: Ligands par excellence for Generation of All-Carbon Quaternary Centers

    Science.gov (United States)

    Smith, Craig R.; Lim, Hwan Jung; Zhang, Aibin; RajanBabu, T. V.

    2009-01-01

    1-Alkylstyrenes undergo efficient hydrovinylation (addition of ethylene) in the presence of a Ni-catalyst prepared from [(allyl)NiBr]2, Na+ [BAr4]− (Ar = 3,5-bis-trifluromethylphenyl), and a phosphoramidite ligand giving products in excellent yields and enantioselectivities. In many cases phosphoramidites derived from achiral 2,2′-biphenol are almost as good as ligands derived from the more expensive enantiopure 2,2′-binaphthols. The hydrovinylation products, which carry two versatile latent functionalities, an aryl and a vinyl group, are potentially useful for the synthesis of several important natural products containing benzylic all-carbon quaternary centers. PMID:19763244

  2. Asymmetric hydrogenation using monodentate phosphoramidite ligands

    NARCIS (Netherlands)

    Minnaard, Adriaan J.; Feringa, Ben L.; Lefort, Laurent; De Vries, Johannes G.

    2007-01-01

    Monodentate phosphoramidites are excellent ligands for Rh-catalyzed asymmetric hydrogenations of substituted olefins. Enantioselectivities between 95 and 99% were obtained in the asymmetric hydrogenation of protected alpha- and beta-dehydroamino acids and esters, itaconic acid and esters, aromatic

  3. (TIQ) Thiazole and Oxazoline Ligands for Asymmetric Henry Reactions

    African Journals Online (AJOL)

    NICO

    TIQ) backbone were synthesized. Their application in the catalytic asymmetric Henry reaction was investigated with comparison to a corresponding TIQ oxazoline ligand. The Cu(II)-oxazoline complex was more reactive and furnished moderate ...

  4. New biphenol-based, fine-tunable monodentate phosphoramidite ligands for catalytic asymmetric transformations.

    Science.gov (United States)

    Hua, Zihao; Vassar, Victor C; Choi, Hojae; Ojima, Iwao

    2004-04-13

    Monodentate phosphoramidite ligands have been developed based on enantiopure 6,6'-dimethylbiphenols with axial chirality. These chiral ligands are easy to prepare and flexible for modifications. The fine-tuning capability of these ligands plays a significant role in achieving high enantioselectivity in the asymmetric hydroformylation of allyl cyanide and the conjugate addition of diethylzinc to cycloalkenones.

  5. New biphenol-based, fine-tunable monodentate phosphoramidite ligands for catalytic asymmetric transformations

    OpenAIRE

    Hua, Zihao; Vassar, Victor C.; Choi, Hojae; OJIMA, IWAO

    2004-01-01

    Monodentate phosphoramidite ligands have been developed based on enantiopure 6,6′-dimethylbiphenols with axial chirality. These chiral ligands are easy to prepare and flexible for modifications. The fine-tuning capability of these ligands plays a significant role in achieving high enantioselectivity in the asymmetric hydroformylation of allyl cyanide and the conjugate addition of diethylzinc to cycloalkenones.

  6. 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

    2015-03-04

    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.

  7. 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.

  8. as a Novel Chiral Ligand for Catalysis of the Asymmetric Diels-Al

    African Journals Online (AJOL)

    NJD

    2008-11-25

    Nov 25, 2008 ... the ligand in dichloromethane.22 The resultant catalyst complex was used to promote the described asymmetric Diels-Alder reaction (Scheme 1). From a range of metal salts evaluated, anhydrous Mg(ClO4)2 emerged as the best Lewis acid complex in terms of enantio- selectivity (Table 1, entry 6).

  9. Remote Cooperative Group Strategy Enables Ligands for Accelerative Asymmetric Gold Catalysis.

    Science.gov (United States)

    Wang, Zhixun; Nicolini, Corrado; Hervieu, Cedric; Wong, Yuk-Fai; Zanoni, Giuseppe; Zhang, Liming

    2017-11-15

    An accelerative asymmetric gold catalysis is achieved for the first time via chiral ligand metal cooperation. An asymmetrically positioned remote amide group in the designed chiral binaphthyl-based ligand plays the essential role of a general base catalyst and selectively accelerates the cyclizations of 4-allen-1-ols into one prochiral allene face. The reactions are mostly highly enantioselective with achiral substrates, and due to the accelerated nature of the catalysis catalyst loadings as low as 100 ppm are allowed. With a pre-existing chiral center at any of the backbone sp 3 -carbons, the reaction remained highly efficient and most importantly maintained excellent allene facial selectivities regardless of the substrate stereochemistry. By using different combinations of ligand and substrate enantiomers, it is now possible to access all four stereoisomers of versatile 2-vinyltetrahydrofurans with exceedingly high selectivity. The underpinning design of this chemistry reveals a novel and conceptually distinctive strategy to tackle challenging asymmetric gold catalysis, which to date has relied on decelerative asymmetric steric hindrance approaches.

  10. 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 ...

  11. The effect of particle size and ligand configuration on the asymmetric catalytic properties of proline-functionalized Pt-nanoparticles

    DEFF Research Database (Denmark)

    Schrader, Imke; Neumann, Sarah; Himstedt, Rieke

    2015-01-01

    The effect of particle size on the asymmetric catalytic properties of supported ligand-functionalized nanoparticles (NPs) was investigated for the first time and found to alter significantly the activity but surprisingly not the stereoselectivity. These results suggest that the stereoselectivity...... of these complex systems is primarily determined by the ligand-reactant interaction, whereas the activity is determined by the particle size....

  12. Synthesis of N-phenyl β-amino acids via iridium-catalyzed asymmetric hydrogenation using mixed monodentate ligands

    NARCIS (Netherlands)

    Mrsic, Natasa; Panella, Lavinia; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.

    2011-01-01

    The iridium-catalyzed asymmetric hydrogenation of N-phenyl-beta-dehydroamino acid derivatives was examined using monodentate phosphoramidite ligands. The highest yields and enantioselectivities were obtained using a mixed ligand approach with PipPhos L1 and achiral triphenylphosphine (full

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

    NARCIS (Netherlands)

    Rosati, F.; Roelfes, J.G.

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

  14. 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.

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

    Science.gov (United States)

    Mezzetti, Antonio

    2010-09-14

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

  16. 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.

  17. 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...

  18. 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%).

  19. 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.

  20. Palladium-catalyzed Asymmetric Hydrosilylation of Styrene and Its Derivatives with Chiral Phosphoramidite Ligands Containing Chiral Ferrocenyl Amine

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyun-Sub; Kim, Min Young; Ahn, Hyo Jin; Han, Jin Wook [Hanyang University, Seoul (Korea, Republic of)

    2016-06-15

    Asymmetric hydrosilylation was one of the most effective methods, which provided optically active organosilanes as a synthetically useful intermediate in organic synthesis. One useful transformation is the Tamao-Fleming oxidation, which is an oxidation reaction of carbon[BOND]silicone bond to afford optically active alcohols with retention of configuration. It is demonstrated that a palladium catalyst coordinating with phosphoramidite ligand (S {sub a},R {sub c},R {sub c,})-L3a from (S)-BINOL and chiral bis((R)-1-ferrocenylethyl) amine shows a high catalytic activity and enantioselectivity up to 97% ee in asymmetric hydrosilylation of styrene and its derivatives. The hydrosilylation of various olefin substrates using these ligands is in progress.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Yong Chul; Ahn, Dae Jun; Lee, Woo Sun; Lee, Seung Han; Ahn, Kwang Hyun [Chonnam National University, Gwangju (Korea, Republic of)

    2011-03-15

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

  2. 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......:9, with 92% ee for the major isomer, was obtained from the reaction of the p-methoxybenzoate derivative. The highest ee was 95%, for the trans isomer of a 80:20 diastereomer mixture (acetate derivative)....

  3. Asymmetric Iron-Catalyzed C-H Alkylation Enabled by Remote Ligand meta-Substitution.

    Science.gov (United States)

    Loup, Joachim; Zell, Daniel; Oliveira, João C A; Keil, Helena; Stalke, Dietmar; Ackermann, Lutz

    2017-11-06

    Highly enantioselective iron-catalyzed C-H alkylations by inner-sphere C-H activation were accomplished with ample scope. High levels of enantiocontrol proved viable through a novel ligand design that exploits a remote meta-substitution on N-heterocyclic carbenes within a facile ligand-to-ligand H-transfer C-H cleavage. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A Mixed Ligand Approach for the Asymmetric Hydrogenation of 2-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

    Herein we describe a new methodology for the asymmetric hydrogenation (AH) of 2-substituted pyridinium salts. An iridium catalyst based on a mixture of a chiral monodentate phosphoramidite and an achiral phosphine was shown to hydrogenate N-benzyl-2-arylpyiridinium bromides to the corresponding

  5. Iridium-Catalyzed Asymmetric Hydrogenation of Ketones with Accessible and Modular Ferrocene-Based Amino-phosphine Acid (f-Ampha) Ligands.

    Science.gov (United States)

    Yu, Jianfei; Long, Jiao; Yang, Yuhong; Wu, Weilong; Xue, Peng; Chung, Lung Wa; Dong, Xiu-Qin; Zhang, Xumu

    2017-02-03

    A series of tridentate ferrocene-based amino-phosphine acid (f-Ampha) ligands have been successfully developed. The f-Ampha ligands are extremely air stable and exhibited excellent performance in the Ir-catalyzed asymmetric hydrogenation of ketones (full conversions, up to >99% ee, and 500 000 TON). DFT calculations were performed to elucidate the reaction mechanism and the importance of the -COOH group. Control experiments also revealed that the -COOH group played a key role in this reaction.

  6. 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.

  7. Asymmetric ligand-exchange reaction of biphenol derivatives and chiral bis(oxazolinyl)phenyl-rhodium complex.

    Science.gov (United States)

    Inoue, Hiroko; Ito, Jun-ichi; Kikuchi, Makoto; Nishiyama, Hisao

    2008-09-01

    Chiral bis(oxazolinyl)phenyl-rhodium acetate complex can enantioselectively capture 1,1'-binaphthol derivatives by ligand-exchange reaction. The structure of the bis(oxazolinyl)phenyl-rhodium biphenol and binaphthol complexes were confirmed by X-ray analysis.

  8. Amino acid based phosphoramidite ligands for the rhodium-catalyzed asymmetric hydrogenation

    NARCIS (Netherlands)

    Breuil, P.A.R.; Reek, J.N.H.

    2009-01-01

    Two sets of amino acid based phosphoramidite ligands with either a BINOL backbone (S-b-1a-e and Rb-1a) or a flexible biphenol backbone (2a-c and 2f) were synthesized and evaluated in the rhodium-catalyzed hydrogenation of different functionalized alkenes: dimethyl itaconate (3), methyl

  9. 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.

  10. 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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Toolbox approach to the search for effective ligands for catalytic asymmetric Cr-mediated coupling reactions.

    Science.gov (United States)

    Guo, Haibing; Dong, Cheng-Guo; Kim, Dae-Shik; Urabe, Daisuke; Wang, Jiashi; Kim, Joseph T; Liu, Xiang; Sasaki, Takeo; Kishi, Yoshito

    2009-10-28

    Chromium catalysts derived from chiral sulfonamides represented by A effect the couplings of aldehydes with vinyl, allyl, or alkyl halides. With three distinct sites for structural modification, A affords access to a structurally diverse pool of chiral sulfonamides. The Cr catalysts derived from these sulfonamides exhibit a broad range of catalyst-substrate matching profiles. A strategy is presented to search for a satisfactory chiral sulfonamide for a given substrate. In order to demonstrate the generality and effectiveness of this approach, five diverse C-C bond-forming cases have been selected from the halichondrin synthesis. For each of the cases, two ligands have been deliberately searched for, to induce the formation of (R)- and (S)-alcohols, respectively, at the arbitrarily chosen efficiency level of ">or=80% yield with >or=20:1 stereoselectivity in the presence of

  12. Application of (S,S)-Pentacycloundecane bis(4-Phenyloxazoline) as a Novel Chiral Ligand for Catalysis of the Asymmetric Diels-Alder Reaction of Cyclopentadiene with 3-Acryloyl-2-oxazolidinone

    National Research Council Canada - National Science Library

    Arvidsson, Per I; Govender, Thavendran; Kruger, G; Maguire, M; Naicker, Tricia

    2009-01-01

    The synthesis of the novel C-1 symmetric (S,S)-pentacycloundecane bis(4-phenyloxazoline) ligand 5 and its evaluation as a chiral Lewis acid catalyst in the benchmark asymmetric Diels-Alder reaction between 3-acryloyloxazolidin-2-one...

  13. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, Lydia M.; Celeste, Lesa R.; Lovelace, Leslie L.; Lebioda, Lukasz (SC)

    2012-02-21

    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.

  15. Rh-Catalyzed Asymmetric Hydrogenation of Prochiral Olefins with a Dynamic Library of Chiral TROPOS Phosphorus Ligands

    NARCIS (Netherlands)

    Monti, Chiara; Gennari, Cesare; Piarulli, Umberto; Vries, Johannes G. de; Vries, André H.M. de; Lefort, Laurent

    2005-01-01

    A library of 19 chiral tropos phosphorus ligands, based on a flexible (tropos) biphenol unit and a chiral P-bound alcohol (11 phosphites) or secondary amine (8 phosphoramidites), was synthesized. These ligands were screened, individually and as a combination of two, in the rhodium-catalyzed

  16. Hydrophilic pyrazine-based phosphane ligands: synthesis and application in asymmetric hydride transfer and H2-hydrogenation of acetophenone

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, Jurriaan; Verboom, Willem

    2013-01-01

    Pyrazine-based hydrophilic phosphanes are useful ligands for the ruthenium- and rhodium-catalyzed hydrogenations of acetophenone under hydride transfer and dihydrogen conditions. The effect of alcohol additives on the catalytic, enantioselective aqueous hydrogenation of acetophenone is examined with

  17. Chiral ligands derived from monoterpenes: application in the synthesis of optically pure secondary alcohols via asymmetric catalysis.

    Science.gov (United States)

    El Alami, Mohammed Samir Ibn; El Amrani, Mohamed Amin; Agbossou-Niedercorn, Francine; Suisse, Isabelle; Mortreux, André

    2015-01-19

    The preparation of optically pure secondary alcohols in the presence of catalysts based on chiral ligands derived from monoterpenes, such as pinenes, limonenes and carenes, is reviewed. A wide variety of these ligands has been synthesized and used in several catalytic reactions, including hydrogen transfer, C-C bond formation via addition of organozinc compounds to aldehydes, hydrosilylation, and oxazaborolidine reduction, leading to high activities and enantioselectivities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis of chiral biphenol-based diphosphonite ligands and their application in palladium-catalyzed intermolecular asymmetric allylic amination reactions.

    Science.gov (United States)

    Shi, Ce; Chien, Chih-Wei; Ojima, Iwao

    2011-02-01

    A library of new 2,2'-bis(diphenylphosphinoyloxy)-1,1'-binaphthyl (binapo)-type chiral diphosphonite ligands was designed and synthesized based on chiral 3,3',5,5',6,6'-hexasubstituted biphenols. These bop ligands have exhibited excellent efficiency in a palladium-catalyzed intermolecular allylic amination reaction, which provides a key intermediate for the total synthesis of Strychnos indole alkaloids with enantiopurities of up to 96% ee. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Cu (II-Catalyzed Asymmetric Henry Reaction with a Novel C1-Symmetric Aminopinane-Derived Ligand

    Directory of Open Access Journals (Sweden)

    Liudmila Filippova

    2015-04-01

    Full Text Available A novel C1-symmetric dinitrogen ligand was synthesized in high yield from commercially available (1R,2R,3R,5S-(−-isopinocampheylamine and 1-methyl-2-imidazolecarboxaldehyde. In combination with Cu(OAc2H2O, this new ligand promote the reaction between nitromethane and aliphatic aldehydes with high yields (up to 97% and moderate enantioselectivities (up to 67% ee. The reactions with benzaldehyde required prolonged reaction time that resulted in diminished yields, but accompanied with ee-values in the 55%–76% range.

  20. Synthesis, crystal structures, and properties of two novel cadmium(II)-organic frameworks based on asymmetric dicarboxylate and N-donor ligands

    Science.gov (United States)

    Chen, Xiaoli; Gao, Loujun; Zhang, Xiaoge; Han, Xuhua; Wang, Yao; Sun, Rong

    2014-08-01

    Two novel cadmium(II)-organic frameworks with asymmetric dicarboxylate and N-donor ligands, namely [Cd(cpa)(phen)]n (1) and {[Cd2(cpa)2(bpy)1.5]·0.5H2O}n (2) (H2cpa = 3-(4-benzoic)propionic acid, phen = 1,10-phenanthroline, bpy = 4,4";-bipyridine) have been hydrothermally synthesized and characterized by elemental analyses, FT-IR spectra, single-crystal X-ray diffraction analyses, TGA, powder XRD and fluorescent measurements. 1 displays a double zigzag chain structure containing 8-number and 22-number circles. 2 Shows a 6-connected 3D polymer network based on tetranuclear cadmium cluster units. The most striking feature of 2 is that a pair of identical 3D networks are interlocked with each other to the form a 2-fold interpenetrated 3D α-Po structural topology. The diverse structures of two complexes indicate that the skeleton of N-donor ligands plays a great role in the assembly of such different frameworks. In addition, the thermal stabilities, XRD and photoluminescence properties of 1-2 were also studied.

  1. 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.

  2. 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. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Iron(III)- and copper(II) complexes of an asymmetric, pentadentate salen-like ligand bearing a pendant carboxylate group.

    Science.gov (United States)

    Jancsó, Attila; Paksi, Zoltán; Mikkola, Satu; Rockenbauer, Antal; Gajda, Tamás

    2005-07-01

    The equilibrium and solution structural properties of the iron(III) and copper(II) complexes of an asymmetric salen-like ligand (N,N'-bis(2-hydroxybenzyl)-2,3-diamino-propionic acid, H(3)bhbdpa) bearing a pendant carboxylate group were characterized in aqueous solution by potentiometric, pH-dependent electron paramagnetic resonance (EPR) and UV-Vis (UV-Visible) measurements. In the equimolar systems the pentadentate ligand forms very stable, differently protonated mononuclear complexes with both metal ions. In the presence of iron(III) {NH, PhO(-), COO(-)}, {2NH, 2PhO(-), COO(-)} and {2NH, 2PhO(-), COO(-), OH(-)} coordinated complexes are dominant. The EPR titrations reflected the presence of microscopic complex formation pathways, leading to the formation of binding isomers in case of Cu(H(2)bhbdpa)(+), Cu(Hbhbdpa) and Cu(bhbdpa)(-). The {2NH, 2PhO(-)+COO(-)/H(2)O} coordinated Cu(bhbdpa) is the only species between pH 6-11. At twofold excess of metal ion dinuclear complexes were detected with both iron(III) and copper(II). In presence of iron(III) a mu-carboxylato-mu-hydroxo-bridged dinuclear complex (Fe(2)(bhbdpa)(OH)(3)) is formed from Fe(H(2)bhbdpa)(2+) through overlapping proton release processes, providing one of the rare examples for the stabilization of an endogenous carboxylate bridged diiron core in aqueous solution. The complex Cu(2)(bhbdpa)(+) detected in the presence of copper(II) is a paramagnetic (S=1) species with relatively weakly coupled metal ions.

  4. One-pot synthesis of symmetric and asymmetric p-quinone ligands and unprecedented substituent induced reactivity in their dinuclear ruthenium complexes.

    Science.gov (United States)

    Schweinfurth, David; Das, Hari Sankar; Weisser, Fritz; Bubrin, Denis; Sarkar, Biprajit

    2011-02-07

    The compounds 2-[2-(trifluoromethyl)-anilino]-5-hydroxy-1,4-benzoquinone (L(1)), 2,5-di-[2-(trifluoromethyl)-anilino]-1,4-benzoquinone (L(2)), 2-[2-(methylthio)-anilino]-5-hydroxy-1,4-benzoquinone (L(3)), and 2,5-di-[2-(methylthio)-anilino]-1,4-benzoquinone (L(4)) were prepared in high yields by reacting 2,5-dihydroxy-1,4-benzoquinone with the corresponding amines in a one-pot synthesis in refluxing acetic acid. This straightforward and "green" synthesis delivers biologically relevant asymmetric p-quinones such as L(1) and L(3) in a rare, simple, one-step process. The proposed synthetic route is general and can be applied to generate a variety of such molecules with different substituents on the nitrogen atoms. Structural characterization of L(2) and L(4) shows electron delocalization across the "upper" and "lower" parts of the molecule, thus showing the importance of charge separated species in the proper description of such molecules. Reactions of these ligands with [Cl(η(6)-Cym)Ru(μ-Cl)(2)Ru(η(6)-Cym)Cl] (Cym = p-Cymene = 1-isopropyl-4-methyl-benzene) in the presence of a base result in the formation of complexes [{Cl(η(6)-Cym)Ru}(2)(μ-L(-2H)(1))] (1), [{Cl(η(6)-Cym)Ru}(2)(μ-L(-2H)(2))] (2), [{Cl(η(6)-Cym)Ru}(2)(μ-L(-2H)(3))] (3), and [{Cl(η(6)-Cym)Ru}(2)(μ-L(-2H)(4))] (4). Structural characterization of 2 and 4 shows a rare syn-coordination of the chloride atoms. The SMe groups in 3 and 4 are not coordinated to the ruthenium center, and the bridging ligands thus function in a bis-bidentate form. Abstraction of the chloride atoms in these complexes with AgClO(4) in CH(3)CN results in the expected formation of solvent substituted complexes [{(CH(3)CN)(η(6)-Cym)Ru}(2)(μ-L(-2H)(1))][ClO(4)](2) (5[ClO(4)](2)) and [{(CH(3)CN)(η(6)-Cym)Ru}(2)(μ-L(-2H)(2))][ClO(4)](2) (6[ClO(4)](2)) with the ligands where there are no additional donor atoms on the nitrogen substituents. The same chloride abstraction reaction in the cases of 3 and 4 leads to an

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

    Directory of Open Access Journals (Sweden)

    Norio Miyaura

    2012-12-01

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

  6. Pentamethylcyclopentadienyl-iridium(III) complexes with pyridylamino ligands: synthesis and applications as asymmetric catalysts for Diels-Alder reactions.

    Science.gov (United States)

    Carmona, Daniel; Pilar Lamata, M; Viguri, Fernando; Rodríguez, Ricardo; Lahoz, Fernando J; Dobrinovitch, Isabel T; Oro, Luis A

    2007-05-21

    Reaction of the dimer [(Cp*IrCl)2(P-Cl)2] with chiral pyridylamino ligands (pyam, L1-L5) in the presence of NaSbF6 gave complexes [Cp*IrCl(pyam)][SbF6] 1-5 as diastereomeric mixtures, which have been fully characterised, including the X-ray molecular structure determination of the complexes (S(Ir),R(N),R(C))-[Cp*IrClL1][SbF6] 1a and (R(Ir),S(N),S(C))-[Cp*IrClL5][SbF6] 5a. Treatment of these cations with AgSbF6 affords the corresponding aqua species [Cp*Ir(pyam)(H2O)][SbF6]2 6-10 which have been also fully characterised. The molecular structure of the complex (S(Ir),R(N),R(C))-[Cp*IrL,(H2O)][SbF6]2 6 has been determined by X-ray diffractometric methods. The aqua complexes [Cp*Ir(pyam)(H2O)][SbF6]2 (6, pyam = L2 (7), L3 (8)) evolve to the cyclometallated species [Cp*Ir{kappa3(N,N',C)-(R)-(C6H4)CH(CH3)NHCH2C5NH4}][SbF6] (11), [Cp*Ir{kappa3(N,N',C)-(R)-(C10H6)CH(CH3)-NHCH2C5NH4)}][SbF6] (12), and [Cp*Ir{kappa3(N,N',C)-(R)-(C10H6)CH(CH3)NHCH2C9NH6)}][SbF6] (13) respectively, via intramolecular activation of an ortho C-H aryl bond. Complexes 6-10 are enantioselective catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene. Reaction occurs rapidly at room temperature with good exo : endo selectivity (from 81 : 19 to 98 : 2) and moderate enantioselectivity (up to 72%). The involved intermediate Lewis acid-dienophile compounds [Cp*Ir(pyam)(methacrolein)][SbF]2 (pyam = L4 (14), L5 (15)) have been isolated and characterised.

  7. 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)

  8. Pd-catalyzed asymmetric allylic etherification using chiral biphenol-based diphosphinite ligands and its application for the formal total synthesis of (-)-galanthamine.

    Science.gov (United States)

    Zang, Yang; Ojima, Iwao

    2013-04-19

    A library of novel chiral biphenol-based diphosphinite (BOP) ligands was designed and created. These BOP ligands were applied to a Pd-catalyzed intermolecular allylic etherification reaction, which provided a key intermediate for the formal total synthesis of (-)-galanthamine with 97% ee in 97% yield.

  9. A Mixed-Ligand Approach Enables the Asymmetric Hydrogenation of an α-Isopropylcinnamic Acid en Route to the Renin Inhibitor Aliskiren

    NARCIS (Netherlands)

    Boogers, Jeroen A.F.; Felfer, Ulfried; Kotthaus, Martina; Lefort, Laurent; Steinbauer, Gerhard; Vries, André H.M. de; Vries, Johannes G. de

    2007-01-01

    An asymmetric hydrogenation process for an α-isopropyl dihydrocinnamic acid derivative, an intermediate for the renin inhibitor aliskiren, has been developed using a rhodium catalyst ligated with a chiral monodentate phosphoramidite and a nonchiral phosphine. Whereas catalysts based on two

  10. 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.

  11. Hydroxamic acids in asymmetric synthesis.

    Science.gov (United States)

    Li, Zhi; Yamamoto, Hisashi

    2013-02-19

    Metal-catalyzed stereoselective reactions are a central theme in organic chemistry research. In these reactions, the stereoselection is achieved predominantly by introducing chiral ligands at the metal catalyst's center. For decades, researchers have sought better chiral ligands for asymmetric catalysis and have made great progress. Nevertheless, to achieve optimal stereoselectivity and to catalyze new reactions, new chiral ligands are needed. Because of their high metal affinity, hydroxamic acids play major roles across a broad spectrum of fields from biochemistry to metal extraction. Dr. K. Barry Sharpless first revealed their potential as chiral ligands for asymmetric synthesis in 1977: He published the chiral vanadium-hydroxamic-acid-catalyzed, enantioselective epoxidation of allylic alcohols before his discovery of Sharpless asymmetric epoxidation, which uses the titanium-tartrate complex as the chiral reagent. However, researchers have reported few highly enantioselective reactions using metal-hydroxamic acid as catalysts since then. This Account summarizes our research on metal-catalyzed asymmetric epoxidation using hydroxamic acids as chiral ligands. We designed and synthesized a series of new hydroxamic acids, most notably the C2-symmetric bis-hydroxamic acid (BHA) family. V-BHA-catalyzed epoxidation of allylic and homoallylic alcohols achieved higher activity and stereoselectivity than Sharpless asymmetric epoxidation in many cases. Changing the metal species led to a series of unprecedented asymmetric epoxidation reactions, such as (i) single olefins and sulfides with Mo-BHA, (ii) homoallylic and bishomoallylic alcohols with Zr- and Hf-BHA, and (iii) N-alkenyl sulfonamides and N-sulfonyl imines with Hf-BHA. These reactions produce uniquely functionalized chiral epoxides with good yields and enantioselectivities.

  12. 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...

  13. DNA and HSA interaction of Vanadium (IV), Copper (II), and Zinc (II) complexes derived from an asymmetric bidentate Schiff-base ligand: multi spectroscopic, viscosity measurements, molecular docking, and ONIOM studies.

    Science.gov (United States)

    Dehkhodaei, Monireh; Sahihi, Mehdi; Amiri Rudbari, Hadi; Momenbeik, Fariborz

    2018-03-01

    The interaction of three complexes [Zn(II), Cu(II), and V(IV)] derived from an asymmetric bidentate Schiff-base ligand with DNA and HSA was studied using fluorescence quenching, UV-Vis spectroscopy, viscosity measurements, and computational methods [molecular docking and our Own N-layered Integrated molecular Orbital and molecular Mechanics (ONIOM)]. The obtained results revealed that the DNA and HSA affinities for binding of the synthesized compounds follow as V(IV) > Zn(II) > Cu(II) and Zn(II) > V(IV) > Cu(II), respectively. The distance between these compounds and HSA was obtained based on the Förster's theory of non-radiative energy transfer. Furthermore, computational molecular docking was carried out to investigate the DNA- and HSA-binding pose of the compounds. Molecular docking calculations showed that H-bond, hydrophobic, and π-cation interactions have dominant role in stability of the compound-HSA complexes. ONIOM method was utilized to investigate the HSA binding of the compounds more precisely in which molecular-mechanics method (UFF) and semi-empirical method (PM6) were selected for the low layer and the high layer, respectively. The results show that the structural parameters of the compounds changed along with binding, indicating the strong interaction between the compounds with HSA and DNA. Viscosity measurements as well as computational docking data suggest that all metal complexes interact with DNA, presumably by groove-binding mechanism.

  14. 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

  15. 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)

  16. Metal-complexes as ligands to generate asymmetric homo- and heterodinuclear M(A)(III)M(B)(II) species: a magneto-structural and spectroscopic comparison of imidazole-N versus pyridine-N.

    Science.gov (United States)

    Biswas, Biplab; Salunke-Gawali, Sunita; Weyhermüller, Thomas; Bachler, Vinzenz; Bill, Eckhard; Chaudhuri, Phalguni

    2010-01-18

    Ten hetero- and homodinuclear M(A)(III)M(B)(III) complexes, 1-10, containing the metal centers Fe(III)Zn(II) (1), Fe(III)Cu(II) (2), Fe(III)Ni(II) (3), Fe(III)Fe(II) (4), Fe(III)Mn(II) (5), Cr(III)Ni(II) (6), Cr(III)Zn(II) (7), Ga(III)Ni(II) (8), Co(III)Fe(II) (9), and Mn(III)Mn(II) (10) are described. The tridentate ligation property of the divalent metal complexes tris(1-methylimidazole-2-aldoximato)metal(II) with three facially disposed pendent oxime O-atoms has been utilized to generate the said complexes. Complexes were characterized by various physical methods including MS, IR, UV-vis, Mossbauer and EPR spectroscopy, cyclic voltammetry (CV), variable-temperature (2-290 K) magnetic susceptibility, and X-ray diffraction techniques. Binuclear complexes 1-10 contain three oximato anions as bridging ligands and are isostructural in the sense that they all contain a metal(III) ion, LM(A)(III) (L = 1,4,7-trimethyl-1,4,7-triazacyclononane), in a distorted octahedral environment M(A)(III)N(3)O(3) and a second six-coordinated divalent metal ion, M(B)(II), in a trigonally distorted M(B)(II)N(6) geometry. A comparison of the cyclic voltammograms of the complexes with those of similar systems reveal both ligand-centered and metal-centered redox processes. Complexes 2, 3, 5, and 6 display antiferromagnetic exchange coupling of the neighboring metal centers in the order Fe(III)Mn(II) (5) III)Ni(II) (3) III)Cu(II) (2) whereas Fe(III)Ni(II) (3) > Cr(III)Ni(II) (6). On the contrary, complex 10, containing high-spin Mn(III) and Mn(II) centers, exhibits ferromagnetic coupling yielding a "high-spin" molecule with an S(t) = (9)/(2) ground state. X-band electron paramagnetic resonance (EPR) spectroscopy for 6, Cr(III)Ni(II) and 3, Fe(III)Ni(II) has been used to establish the electronic ground state in great detail and to complement the magnetic susceptibility measurements. Moreover, computational results have been included to compare the sigma-bonding character of the nitrogen lone

  17. Total Synthesis of Enantiopure (+)-γ -Lycorane Using Highly Efficient Pd-Catalyzed Asymmetric Allylic Alkylation

    Science.gov (United States)

    Chapsal, Bruno D.; Ojima, Iwao

    2008-01-01

    Highly efficient short total synthesis of γ -lycorane (>99% ee, 41% overall yield) was achieved by using the asymmetric allylic alkylation in the key step catalyzed by palladium complexes with novel chiral biphenol-based monodentate phosphoramidite ligands. PMID:16562900

  18. Total Synthesis of Enantiopure (+)-γ -Lycorane Using Highly Efficient Pd-Catalyzed Asymmetric Allylic Alkylation

    OpenAIRE

    Chapsal, Bruno D.; OJIMA, IWAO

    2006-01-01

    Highly efficient short total synthesis of γ -lycorane (>99% ee, 41% overall yield) was achieved by using the asymmetric allylic alkylation in the key step catalyzed by palladium complexes with novel chiral biphenol-based monodentate phosphoramidite ligands.

  19. The Evaluation of Novel Camphor-derived Pyridyl Ligands as ...

    African Journals Online (AJOL)

    NJD

    2009-03-03

    Mar 3, 2009 ... catalysts in the asymmetric Diels-Alder reaction.19–21 These ligands have proven to be reasonably successful in terms of selectivity with enantiomeric excesses in the 80 and low 90 % range. Herein we report the evaluation of a series of recently reported2,3 camphor-derived pyridyl ligands 4-9 (Fig.

  20. Two novel mixed-ligand complexes containing organosulfonate ligands.

    Science.gov (United States)

    Li, Mingtian; Huang, Jun; Zhou, Xuan; Fang, Hua; Ding, Liyun

    2008-07-01

    The structures reported herein, viz. bis(4-aminonaphthalene-1-sulfonato-kappaO)bis(4,5-diazafluoren-9-one-kappa(2)N,N')copper(II), [Cu(C(10)H(8)NO(3)S)(2)(C(11)H(6)N(2)O)(2)], (I), and poly[[[diaquacadmium(II)]-bis(mu-4-aminonaphthalene-1-sulfonato)-kappa(2)O:N;kappa(2)N:O] dihydrate], {[Cd(C(10)H(8)NO(3)S)(2)(H(2)O)(2)].2H(2)O}(n), (II), are rare examples of sulfonate-containing complexes where the anion does not fulfill a passive charge-balancing role, but takes an active part in coordination as a monodentate and/or bridging ligand. Monomeric complex (I) possesses a crystallographic inversion center at the Cu(II) atom, and the asymmetric unit contains one-half of a Cu atom, one complete 4-aminonaphthalene-1-sulfonate (ans) ligand and one 4,5-diazafluoren-9-one (DAFO) ligand. The Cu(II) atom has an elongated distorted octahedral coordination geometry formed by two O atoms from two monodentate ans ligands and by four N atoms from two DAFO molecules. Complex (II) is polymeric and its crystal structure is built up by one-dimensional chains and solvent water molecules. Here also the cation (a Cd(II) atom) lies on a crystallographic inversion center and adopts a slightly distorted octahedral geometry. Each ans anion serves as a bridging ligand linking two Cd(II) atoms into one-dimensional infinite chains along the [010] direction, with each Cd(II) center coordinated by four ans ligands via O and N atoms and by two aqua ligands. In both structures, there are significant pi-pi stacking interactions between adjacent ligands and hydrogen bonds contribute to the formation of two- and three-dimensional networks.

  1. Asymmetric Divisions in Oogenesis.

    Science.gov (United States)

    Bilinski, Szczepan M; Kubiak, Jacek Z; Kloc, Malgorzata

    In the majority of animals, the oocyte/egg is structurally, molecularly, and functionally asymmetric. Such asymmetry is a prerequisite for a flawless fertilization and faithful segregation of maternal determinants during subsequent embryonic development. The oocyte asymmetry develops during oogenesis and must be maintained during consecutive and obligatorily asymmetric oogonial divisions, which depending on the species lead to the formation of either oocyte alone or oocyte and nurse cell complex. In the following chapter, we summarize current knowledge on the asymmetric oogonial divisions in invertebrate (insects) and vertebrate (Xenopus) species.

  2. Allenes in Asymmetric Catalysis. Asymmetric Ring-Opening of Meso-Epoxides Catalyzed by Allene-Containing Phosphine Oxides

    Science.gov (United States)

    Pu, Xiaotao; Qi, Xiangbing; Ready, Joseph M.

    2009-01-01

    Unsymmetrically substituted allenes (1,2 dienes) are inherently chiral and can be prepared in optically pure form. Nonetheless, to date the allene framework has not been incorporated into ligands for asymmetric catalysis. Since allenes project functionality differently than either tetrahedral carbon or chiral biaryls, they may create complementary chiral environments. This study demonstrates that optically active C2 symmetric allene-containing bisphosphine oxides can catalyze the addition of SiCl4 to meso epoxides with high enantioselectivity. The epoxide-opening likely involves generation of a Lewis acidic, cationic (bisphosphine oxide)SiCl3 complex. The fact that high asymmetric induction is observed suggests that allenes may represent a new platform for the development of ligands and catalysts for asymmetric synthesis. PMID:19722613

  3. Copper-catalyzed asymmetric oxidation of sulfides.

    Science.gov (United States)

    O'Mahony, Graham E; Ford, Alan; Maguire, Anita R

    2012-04-06

    Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee).

  4. 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.

  5. 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

  6. How Is Nature Asymmetric?

    Indian Academy of Sciences (India)

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

  7. Highly asymmetric rice genomes

    Directory of Open Access Journals (Sweden)

    Chen Jian-Qun

    2007-06-01

    Full Text Available Abstract Background Individuals in the same species are assumed to share the same genomic set. However, it is not unusual to find an orthologous gene only in small subset of the species, and recent genomic studies suggest that structural rearrangements are very frequent between genomes in the same species. Two recently sequenced rice genomes Oryza sativa L. var. Nipponbare and O. sativa L. var. 93-11 provide an opportunity to systematically investigate the extent of the gene repertoire polymorphism, even though the genomic data of 93-11 derived from whole-short-gun sequencing is not yet as complete as that of Nipponbare. Results We compared gene contents and the genomic locations between two rice genomes. Our conservative estimates suggest that at least 10% of the genes in the genomes were either under presence/absence polymorphism (5.2% or asymmetrically located between genomes (4.7%. The proportion of these "asymmetric genes" varied largely among gene groups, in which disease resistance (R genes and the RLK kinase gene group had 11.6 and 7.8 times higher proportion of asymmetric genes than housekeeping genes (Myb and MADS. The significant difference in the proportion of asymmetric genes among gene groups suggests that natural selection is responsible for maintaining genomic asymmetry. On the other hand, the nucleotide diversity in 17 R genes under presence/absence polymorphism was generally low (average nucleotide diversity = 0.0051. Conclusion The genomic symmetry was disrupted by 10% of asymmetric genes, which could cause genetic variation through more unequal crossing over, because these genes had no allelic counterparts to pair and then they were free to pair with homologues at non-allelic loci, during meiosis in heterozygotes. It might be a consequence of diversifying selection that increased the structural divergence among genomes, and of purifying selection that decreased nucleotide divergence in each R gene locus.

  8. 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.

  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 Evolutionary Games.

    Science.gov (United States)

    McAvoy, Alex; Hauert, Christoph

    2015-08-01

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

  11. New mechanistic aspects of the asymmetric homogeneous hydrogenation of alkenes.

    Science.gov (United States)

    Brown, J M; Giernoth, R

    2000-11-01

    Progress in homogeneous catalysis depends upon an understanding of the reaction mechanism; in asymmetric catalysis this entails an insight into the origins of enantioselectivity. Significant advances have been made in the area of alkene reduction catalyzed by rhodium or ruthenium complexes, which has been in tandem with the development of new, more effective ligands for the reaction. The combination of quantum chemical calculations and direct spectroscopic observation of catalytic intermediates has proved powerful in this regard.

  12. Asymmetric fluorocyclizations of alkenes.

    Science.gov (United States)

    Wolstenhulme, Jamie R; Gouverneur, Véronique

    2014-12-16

    CONSPECTUS: The vicinal fluorofunctionalization of alkenes is an attractive transformation that converts feedstock olefins into valuable cyclic fluorinated molecules for application in the pharmaceutical, agrochemical, medical, and material sectors. The challenges associated with asymmetric fluorocyclizations induced by F(+) reagents are distinct from other types of halocyclizations. Processes initiated by the addition of an F(+) reagent onto an alkene do not involve the reversible formation of bridged fluoronium ions but generate acyclic β-fluorocationic intermediates. This mechanistic feature implies that fluorocyclizations are not stereospecific. A discontinuity exists between the importance of this class of fluorocyclization and the activation modes currently available to implement successful catalysis. Progress toward fluorocyclization has been achieved by investing in neutral and cationic [NF] reagent development. The body of work on asymmetric fluorination using chiral cationic [NF](+) reagents prepared by fluorine transfer from the dicationic [NF](2+) reagent Selectfluor to quinuclidines, inspired the development of asymmetric F(+)-induced fluorocyclizations catalyzed by cinchona alkaloids; for catalysis, the use of N-fluorobenzenesulfonimide, which is less reactive than Selectfluor, ensures that the achiral F(+) source remains unreactive toward the alkene. These organocatalyzed enantioselective fluorocyclizations can be applied to indoles to install the fluorine on a quaternary benzylic stereogenic carbon center and to afford fluorinated analogues of natural products featuring the hexahydropyrrolo[2,3-b]indole or the tetrahydro-2H-furo[2,3-b]indole skeleton. In an alternative approach, the poor solubility of dicationic Selectfluor bis(tetrafluoroborate) in nonpolar solvent was exploited with anionic phase transfer catalysis as the operating activation mode. Exchange of the tetrafluoroborate ions of Selectfluor with bulky lipophilic chiral anions (e

  13. 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.

  14. Catalytic asymmetric fluorinations.

    Science.gov (United States)

    Bobbio, Carla; Gouverneur, Véronique

    2006-06-07

    The appearance of structurally diverse fluorinating reagents displaying a large spectrum of reactivity has been critical to the development of the catalytic asymmetric fluorination processes known to date. In this article, we discuss how this area of research emerged and which strategies have allowed for the successful development of both nucleophilic and electrophilic catalytic enantioselective fluorinations. We also present the fundamental understanding of catalytic activity and enantioselectivity for the most efficient processes and highlight the first synthetic application with the preparation of a complex fluorinated target.

  15. 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

  16. Asymmetric Organocatalytic Cycloadditions

    DEFF Research Database (Denmark)

    Mose, Rasmus

    2016-01-01

    were pioneered by Otto Paul Hermann Diels and Kurt Alder who discovered what later became known as the Diels Alder reaction. The Diels Alder reaction is a [4+2] cycloaddition in which a π4 component reacts with a π2 component via a cyclic transition state to generate a 6 membered ring. This reaction...... undergo cascade reactions with different electron deficient dienophiles in Diels Alder – nucleophilic ring closing reactions. This methodology opens up for the direct asymmetric formation of hydroisochromenes and hydroisoquinolines which may possess interesting biological activities. It is also...

  17. Asymmetric inclusion process.

    Science.gov (United States)

    Reuveni, Shlomi; Eliazar, Iddo; Yechiali, Uri

    2011-10-01

    We introduce and explore the asymmetric inclusion process (ASIP), an exactly solvable bosonic counterpart of the fermionic asymmetric exclusion process (ASEP). In both processes, random events cause particles to propagate unidirectionally along a one-dimensional lattice of n sites. In the ASEP, particles are subject to exclusion interactions, whereas in the ASIP, particles are subject to inclusion interactions that coalesce them into inseparable clusters. We study the dynamics of the ASIP, derive evolution equations for the mean and probability generating function (PGF) of the sites' occupancy vector, obtain explicit results for the above mean at steady state, and describe an iterative scheme for the computation of the PGF at steady state. We further obtain explicit results for the load distribution in steady state, with the load being the total number of particles present in all lattice sites. Finally, we address the problem of load optimization, and solve it under various criteria. The ASIP model establishes bridges between statistical physics and queueing theory as it represents a tandem array of queueing systems with (unlimited) batch service, and a tandem array of growth-collapse processes.

  18. 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.

  19. Rhodium-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Carbonyl Compounds via Thiourea Hydrogen Bonding.

    Science.gov (United States)

    Wen, Jialin; Jiang, Jun; Zhang, Xumu

    2016-09-16

    The strategy of secondary interaction enables enantioselectivity for homogeneous hydrogenation. By introducing hydrogen bonding of substrates with thiourea from the ligand, α,β-unsaturated carbonyl compounds, such as amides and esters, are hydrogenated with high enantiomeric excess. The substrate scope for this chemical transformation is broad with various substituents at the β-position. Control experiments revealed that each unit of the ligand ZhaoPhos is irreplaceable. No nonlinear effect was observed for this Rh/ZhaoPhos-catalyzed asymmetric hydrogenation.

  20. Symmetric Decomposition of Asymmetric Games.

    Science.gov (United States)

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

    2018-01-17

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

  1. Minimal asymmetric dark matter

    Directory of Open Access Journals (Sweden)

    Sofiane M. Boucenna

    2015-09-01

    Full Text Available In the early Universe, any particle carrying a conserved quantum number and in chemical equilibrium with the thermal bath will unavoidably inherit a particle–antiparticle asymmetry. A new particle of this type, if stable, would represent a candidate for asymmetric dark matter (DM with an asymmetry directly related to the baryon asymmetry. We study this possibility for a minimal DM sector constituted by just one (generic SU(2L multiplet χ carrying hypercharge, assuming that at temperatures above the electroweak phase transition an effective operator enforces chemical equilibrium between χ and the Higgs boson. We argue that limits from DM direct detection searches severely constrain this scenario, leaving as the only possibilities scalar or fermion multiplets with hypercharge y=1, preferentially quintuplets or larger SU(2 representations, and with a mass in the few TeV range.

  2. 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.

  3. Asymmetric Realized Volatility Risk

    Directory of Open Access Journals (Sweden)

    David E. Allen

    2014-06-01

    Full Text Available In this paper, we document that realized variation measures constructed from high-frequency returns reveal a large degree of volatility risk in stock and index returns, where we characterize volatility risk by the extent to which forecasting errors in realized volatility are substantive. Even though returns standardized by ex post quadratic variation measures are nearly Gaussian, this unpredictability brings considerably more uncertainty to the empirically relevant ex ante distribution of returns. Explicitly modeling this volatility risk is fundamental. We propose a dually asymmetric realized volatility model, which incorporates the fact that realized volatility series are systematically more volatile in high volatility periods. Returns in this framework display time varying volatility, skewness and kurtosis. We provide a detailed account of the empirical advantages of the model using data on the S&P 500 index and eight other indexes and stocks.

  4. Dynamic control of chirality in phosphine ligands for enantioselective catalysis.

    Science.gov (United States)

    Zhao, Depeng; Neubauer, Thomas M; Feringa, Ben L

    2015-03-25

    Chirality plays a fundamental role in biology and chemistry and the precise control of chirality in a catalytic conversion is a key to modern synthesis most prominently seen in the production of pharmaceuticals. In enantioselective metal-based catalysis, access to each product enantiomer is commonly achieved through ligand design with chiral bisphosphines being widely applied as privileged ligands. Switchable phosphine ligands, in which chirality is modulated through an external trigger signal, might offer attractive possibilities to change enantioselectivity in a catalytic process in a non-invasive manner avoiding renewed ligand synthesis. Here we demonstrate that a photoswitchable chiral bisphosphine based on a unidirectional light-driven molecular motor, can be used to invert the stereoselectivity of a palladium-catalysed asymmetric transformation. It is shown that light-induced changes in geometry and helicity of the switchable ligand enable excellent selectivity towards the racemic or individual enantiomers of the product in a Pd-catalysed desymmetrization reaction.

  5. Concise enantioselective synthesis of duloxetine via direct catalytic asymmetric aldol reaction of thioamide.

    Science.gov (United States)

    Suzuki, Yuta; Iwata, Mitsutaka; Yazaki, Ryo; Kumagai, Naoya; Shibasaki, Masakatsu

    2012-05-04

    Direct catalytic asymmetric aldol reaction of thioamide offers a new entry to the concise enantioselective synthesis of duloxetine. The direct aldol protocol was scalable (>20 g) to afford the aldol product in 92% ee after LiAlH(4) reduction, and 84% of the chiral ligand was recovered after recrystallization. The following four steps of transformation delivered duloxetine.

  6. The Combinatorial Approach to Asymmetric Hydrogenation : Phosphoramidite Libraries, Ruthenacycles, and Artificial Enzymes

    NARCIS (Netherlands)

    Vries, Johannes G. de; Lefort, Laurent

    2006-01-01

    For a more general implementation of asymmetric catalysis in the production of fine chemicals, the screening for new catalysts and ligands must be dramatically accelerated. This is possible with a high-throughput experimentation (HTE) approach. However, implementation of this technology requires the

  7. Asymmetric bifurcated halogen bonds.

    Science.gov (United States)

    Novák, Martin; Foroutan-Nejad, Cina; Marek, Radek

    2015-03-07

    Halogen bonding (XB) is being extensively explored for its potential use in advanced materials and drug design. Despite significant progress in describing this interaction by theoretical and experimental methods, the chemical nature remains somewhat elusive, and it seems to vary with the selected system. In this work we present a detailed DFT analysis of three-center asymmetric halogen bond (XB) formed between dihalogen molecules and variously 4-substituted 1,2-dimethoxybenzene. The energy decomposition, orbital, and electron density analyses suggest that the contribution of electrostatic stabilization is comparable with that of non-electrostatic factors. Both terms increase parallel with increasing negative charge of the electron donor molecule in our model systems. Depending on the orientation of the dihalogen molecules, this bifurcated interaction may be classified as 'σ-hole - lone pair' or 'σ-hole - π' halogen bonds. Arrangement of the XB investigated here deviates significantly from a recent IUPAC definition of XB and, in analogy to the hydrogen bonding, the term bifurcated halogen bond (BXB) seems to be appropriate for this type of interaction.

  8. 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....

  9. 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

  10. Asymmetric Ion-Pairing Catalysis

    Science.gov (United States)

    Brak, Katrien

    2014-01-01

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

  11. Asymmetric Gepner models (revisited)

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-12-11

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

  12. Catalytic Asymmetric Transfer Hydrogenation of Imines: Recent Advances.

    Science.gov (United States)

    Foubelo, Francisco; Yus, Miguel

    2015-10-01

    In this review article recent developments in the asymmetric transfer hydrogenation of imines from 2008 up to today are presented. The main methodology involves either metal-catalyzed procedures in the presence of a chiral ligand or organocatalyzed technologies using a Hantzsch ester and a chiral BINOL-derived phosphoric acid. The most important procedures are collected, paying special attention to the application of this methodology in synthetic organic chemistry. Copyright © 2015 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Ligand-free palladium catalysed Heck reaction of methyl 2-acetamido acrylate and aryl bromides as key step in the synthesis of enantiopure substituted phenylalanines

    NARCIS (Netherlands)

    Willans, Charlotte E.; Mulders, Jan M.C.A.; Vries, Johannes G. de; Vries, André H.M. de

    2003-01-01

    A range of substituted aryl bromides were coupled with methyl 2-acetamido acrylate using ligand-free palladium catalysis. Subsequently asymmetric hydrogenation with Rh/MonoPhos yielded substituted phenylalanines in high enantioselectivities (e.e. 92-99%).

  14. 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.

  15. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...

  16. Does asymmetric correlation affect portfolio optimization?

    Science.gov (United States)

    Fryd, Lukas

    2017-07-01

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

  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. Structure of asymmetrical peptide dendrimers

    NARCIS (Netherlands)

    Okrugin, B.M.; Neelov, I.M.; Leermakers, F.A.M.; Borisov, Oleg V.

    2017-01-01

    Structural properties of asymmetric peptide dendrimers up to the 11th generation are studied on the basis of the self-consistent field Scheutjens-Fleer numerical approach. It is demonstrated that large scale properties such as, e.g., the gyration radius, are relatively weakly affected by the

  19. Construction of dinuclear complexes using multidentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Sampson, C.L

    2000-04-01

    This work details the synthesis of novel copper(I), copper(II), nickel(II) and zinc(II) dinuclear complexes. Attempts have been made to control the co-ordination architectures of the metal centres by using bis-bidentate and tridentate chelating N,S- and N-donor ligands to generate dinuclear systems. The ligands were both symmetrically and asymmetrically disubstituted pyridazine-based and pyridine-based ligands consisting of a mixture of N-only and mixed N,S-donors. The study using the pyridazine-based ligands continues previous research in our group using 3,6-bis disubstituted pyridazine-based ligands to form complexes with copper(l) and copper(II). The pyridazine-based ligands have been seen to be bis-bidentate upon co-ordination of copper. The pyridazine-based ligands could be envisaged to generate dinuclear complexes by directly bridging between two metal ions. This study involved the formation of copper(l), nickel(II) and zinc(II) complexes with these ligands. The structural properties of two particular complexes have been explored using X-ray crystallography and spectroscopic techniques. Pyridine-based ligands have also been used previously in our group as tridentate chelating ligands. They have been seen to form dinuclear complexes with copper(I) and copper(II) when reacted with an additional bridging ligand e.g. 4,4'-bipyridine. This provides an alternative method for generating dinuclear complexes. Chapter 1 presents an introduction to the area of supramolecular chemistry from which we can learn the principles of polymer formation and them 'in reverse' to generate discrete dinuclear systems. Chapter 2 details the synthesis of the pyridazine and pyridine-based ligands including a detailed nmr study of the ligands. Since the ligands were synthesised using cyclic thioamides as terminal groups it has been found that thiol-thione tautomerisation occurred during synthesis giving rise to two possible ligand conformations. The nmr study has been used

  20. 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.

  1. Asymmetric Transfer Hydrogenation of Ketones with Modified Grubbs Metathesis Catalysts : On the Way to a Tandem Process

    NARCIS (Netherlands)

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

    2016-01-01

    Herein, we report the successful transformation of a 1(st) generation Grubbs metathesis catalyst into an asymmetric transfer hydrogenation (ATH) catalyst. Upon addition of a chiral amine ligand, an alcohol and a base, the 1(st) generation Hoveyda-Grubbs catalyst (HG-I) was found to promote the

  2. 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.

  3. A Note on Asymmetric Thick Branes

    Directory of Open Access Journals (Sweden)

    D. Bazeia

    2014-01-01

    Full Text Available We study asymmetric thick braneworld scenarios, generated after adding a constant to the superpotential associated with the scalar field. We study in particular models with odd and even polynomial superpotentials, and we show that asymmetric brane can be generated irrespective of the potential being symmetric or asymmetric. We study in addition the nonpolynomial sine-Gordon like model, also constructed with the inclusion of a constant in the standard superpotential, and we investigate gravitational stability of the asymmetric brane. The results suggest robustness of the new braneworld scenarios and add further possibilities of the construction of asymmetric branes.

  4. Asymmetric rhenium tricarbonyl complexes show superior luminescence properties in live cell imaging.

    Science.gov (United States)

    Raszeja, Lukasz J; Siegmund, Daniel; Cordes, Anna L; Güldenhaupt, Jörn; Gerwert, Klaus; Hahn, Stephan; Metzler-Nolte, Nils

    2017-01-16

    The synthesis and photophysical properties of a novel series of rhenium tricarbonyl complexes based on tridentate phenanthridinyl-containing ligands are described. Photophysical data reveal beneficial luminescence behaviour especially for compounds with an asymmetric ligand set. These advantageous properties are not limited to organic solvents, but indeed also improved in aqueous solutions. The suitability of our new rhenium complexes as potent imaging agents has been confirmed by fluorescence microscopy on living cancer cells, which also confirms superior long-time stability under fluorescence microscopy conditions. Colocalisation studies with commercial organelle stains reveal an accumulation of the complexes in the endoplasmic reticulum for all tested cell lines.

  5. 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.

  6. Geodesics in Asymmetric Metric Spaces

    Directory of Open Access Journals (Sweden)

    Mennucci Andrea C. G.

    2014-01-01

    Full Text Available In a recent paper [17] we studied asymmetric metric spaces; in this context we studied the length of paths, introduced the class of run-continuous paths; and noted that there are different definitions of “length spaces” (also known as “path-metric spaces” or “intrinsic spaces”. In this paper we continue the analysis of asymmetric metric spaces.We propose possible definitions of completeness and (local compactness.We define the geodesics using as admissible paths the class of run-continuous paths.We define midpoints, convexity, and quasi-midpoints, but without assuming the space be intrinsic.We distinguish all along those results that need a stronger separation hypothesis. Eventually we discuss how the newly developed theory impacts the most important results, such as the existence of geodesics, and the renowned Hopf-Rinow (or Cohn-Vossen theorem.

  7. Electron Jet of Asymmetric Reconnection

    Science.gov (United States)

    Khotyaintsev, Yu. V.; Graham, D. B.; Norgren, C.; Eriksson, E.; Li, W.; Johlander, A.; Vaivads, A.; Andre, M.; Pritchett, P. L.; Retino, A.; hide

    2016-01-01

    We present Magnetospheric Multiscale observations of an electron-scale current sheet and electron outflow jet for asymmetric reconnection with guide field at the subsolar magnetopause. The electron jet observed within the reconnection region has an electron Mach number of 0.35 and is associated with electron agyrotropy. The jet is unstable to an electrostatic instability which generates intense waves with E(sub parallel lines) amplitudes reaching up to 300 mV/m and potentials up to 20% of the electron thermal energy. We see evidence of interaction between the waves and the electron beam, leading to quick thermalization of the beam and stabilization of the instability. The wave phase speed is comparable to the ion thermal speed, suggesting that the instability is of Buneman type, and therefore introduces electron-ion drag and leads to braking of the electron flow. Our observations demonstrate that electrostatic turbulence plays an important role in the electron-scale physics of asymmetric reconnection.

  8. 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.

  9. Comprehensive asymmetric dark matter model

    OpenAIRE

    Lonsdale, Stephen J.; Volkas, Raymond R.

    2018-01-01

    Asymmetric dark matter (ADM) is motivated by the similar cosmological mass densities measured for ordinary and dark matter. We present a comprehensive theory for ADM that addresses the mass density similarity, going beyond the usual ADM explanations of similar number densities. It features an explicit matter-antimatter asymmetry generation mechanism, has one fully worked out thermal history and suggestions for other possibilities, and meets all phenomenological, cosmological and astrophysical...

  10. 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...

  11. 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.

    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

  12. 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.

  13. Lie Group Analysis of the Photo-Induced Fluorescence of Drosophila Oogenesis with the Asymmetrically Localized Gurken Protein.

    Directory of Open Access Journals (Sweden)

    Jen-Cheng Wang

    Full Text Available Lie group analysis of the photo-induced fluorescence of Drosophila oogenesis with the asymmetrically localized Gurken protein has been performed systematically to assess the roles of ligand-receptor complexes in follicle cells. The (2×2 matrix representations resulting from the polarized tissue spectra were employed to characterize the asymmetrical Gurken distributions. It was found that the fluorescence of the wild-type egg shows the Lie point symmetry X 23 at early stages of oogenesis. However, due to the morphogen regulation by intracellular proteins and extracellular proteins, the fluorescence of the embryogenesis with asymmetrically localized Gurken expansions exhibits specific symmetry features: Lie point symmetry Z 1 and Lie point symmetry X 1. The novel approach developed herein was successfully used to validate that the invariant-theoretical characterizations are consonant with the observed asymmetric fluctuations during early embryological development.

  14. Tris(pyridinealdoximato)metal complexes as ligands for the synthesis of asymmetric heterodinuclear Cr(III)M species [M = Zn(II), Cu(II), Ni(II), Fe(II), Mn(II), Cr(II), Co(III)]: a magneto-structural study.

    Science.gov (United States)

    Ross, S; Weyhermüller, T; Bill, E; Wieghardt, K; Chaudhuri, P

    2001-12-17

    Reactions of the LCr(III) unit with an in situ prepared M(PyA)(3)(n-) ion, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane and PyA(-) is the monoanion of pyridine-2-aldoxime, yield heterodinuclear complexes of general formula [LCr(III)(PyA)(3)M](2+/3+) as perchlorate salts, where M = Cr(II) (1), Mn(II) (2), low-spin Fe(II) (3), Ni(II) (4), Cu(II) (5), Zn(II) (6), and low-spin Co(III) (7). These compounds contain three oximato anions as bridging ligands. The hexadentate ligand with the identical donor atoms, tris(2-aldoximato-6-pyridyl)phosphine, P(PyA)(3), has been employed to prepare a second Cr(III)Ni(II) species 8, whose magnetic properties differ significantly from those of 4. Complexes 1-8 have been characterized on the basis of elemental analysis, mass spectrometry, IR, UV-vis, Mössbauer, and EPR spectroscopies, and variable-temperature (2-295 K) magnetic susceptibility measurements. They are isostructural in the sense that they all contain a terminal Cr(III) ion in a distorted octahedral environment, CrN(3)O(3), and a second six-coordinated metal ion M in a mostly trigonal prismatic MN(6) geometry. The crystal structures of the perchlorate salts of 2-5, 7, and 8 have been determined by X-ray crystallography at 100 K. The structures consist of mixed-metal Cr(III)M(II) and Cr(III)Co(III) complexes with a geometry in which two pseudooctahedral polyhedra are joined by three oximato (=N-O(-)) groups, with an intramolecular Cr.M(Co) distance in the range of 3.4-3.7 A. The cyclic voltammograms of the complexes reveal ligand oxidation and reduction processes, and in addition, metal-centered oxidation processes have been observed. X-band EPR spectroscopy has been used to establish the electronic ground state of the heterodinuclear complexes. Analysis of the susceptibility data indicates the presence of weak exchange interactions, both ferro- and antiferromagnetic, between the paramagnetic centers. A qualitative rationale on the basis of the Goodenough

  15. Copper(II)-mediated transformation of a tridentate non-innocent ligand into a tetradentate salen-type innocent ligand.

    Science.gov (United States)

    Ghorai, Samir; Mukherjee, Chandan

    2014-12-01

    A non-innocent ligand, H4L(CH2NH2), was synthesized by introducing a -CH2NH2 group at the ortho carbon atom to the aniline moiety of 2-anilino-4,6-di-tert-butylphenol. The new ligand was characterized by IR and NMR spectroscopy and mass spectrometry techniques. Upon treatment with CuCl2⋅2H2O, this non-innocent ligand provided a mononuclear four-coordinate salen-type Cu(II) complex by complete modification of the ligand backbone. The complex was characterized by IR spectroscopy, mass spectrometry, X-ray single-crystal diffraction, electron paramagnetic resonance (EPR) spectroscopy, and UV/Vis/near-IR spectroscopy techniques. X-ray crystallographic analysis showed an asymmetric environment around the Cu(II) center with a small (≈12°) twist between the two biting planes. Analysis of the X-band EPR spectrum also supported the asymmetric environment and also indicated the presence of an unpaired electron on the dx2-y2 orbital. The UV/Vis/near-IR spectrum showed strong absorption bands for metal-to-ligand charge transfer and ligand-to-metal charge transfer along with a Cu(II) -centered d-d transition. Mechanistic investigation of the formation of complex 1 indicated that modification of the ligand backbone proceeded through ligand-centered amine to imine oxidation as well as through C-N bond-breaking processes. During these processes, 3,5-di-tert-butyl-1,2-benzoquinone and 2-aminobenzylidene were produced. Ammonia, generated in situ through hydrolysis of the imine to the aldehyde, reacted with 3,5-di-tert-butyl-1,2-benzoquinone to form the corresponding 3,5-di-tert-butyl-1,2-iminobenzoquinone moiety, which upon two-electron reduction in the reaction medium formed 3,5-di-tert-butyl-1,2-aminophenol. This aminophenol underwent condensation with the H2L5 ligand that was formed by self-condensation of two molecules of 2-aminobenzaldehyde and provided the modified ligand backbone. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. LG tools for asymmetric wargaming

    Science.gov (United States)

    Stilman, Boris; Yakhnis, Alex; Yakhnis, Vladimir

    2002-07-01

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

  17. Loan sales under asymmetric information

    OpenAIRE

    Vargas Martínez, Mónica

    2010-01-01

    Loans are illiquid assets that can be sold in a secondary market even that buyers have no certainty about their quality. I study a model in which a lender has access to new investment opportunities when all her assets are illiquid. To raise funds, the lender may either borrow using her assets as collateral, or she can sell them in a secondary market. Given asymmetric information about assets quality, the lender cannot recover the total value of her assets. There is then a role for the governm...

  18. Asymmetric liberations in exterior resonances

    Science.gov (United States)

    Beauge, C.

    1994-10-01

    The purpose of this paper is to present a general analysis of the planar circular restricted problem of three bodies in the case of exterior mean-motion resonances. Particularly, our aim is to map the phase space of various commensurabilities and determine the singular solutions of the averaged system, comparing them to the well-known case of interior resonances. In some commensurabilities (e.g. 1/2, 1/3) we show the existence of asymmetric librations; that is, librations in which the stationary value of the critical angle theta = (p+q) lambda1-p lambda-q pi is not equal to either zero or pi. The origin, stability and morphogenesis of these solutions are discussed and compared to symmetric librations. However, in some other resonances (e.g. 2/3, 3/4), these fixed points of the mean system seem to be absent. Librations in such cases are restricted to theta = O mod(pi). Asymmetric singular solutions of the plane circular problem are unknown in the case of interior resonances and cannot be reproduced by the reduced Andoyer Hamiltonian known as the Second Fundamental Model for Resonance. However, we show that the extended version of this Hamiltonian function, in which harmonics up to order two are considered, can reproduce fairly well the principal topological characteristics of the phase space and thereby constitutes a simple and useful analytical approximation for these resonances.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Asymmetric Warfare and the Will to Win

    National Research Council Canada - National Science Library

    Herrera, Cary

    2001-01-01

    This thesis explores the will to win in asymmetric war. Asymmetric war, in which one side has an overwhelming advantage over its opponent, will likely be the war of the future for the United States in the post-Cold War uni-polar world...

  4. 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...

  5. Asymmetric Quantum Codes on Toric Surfaces

    DEFF Research Database (Denmark)

    Hansen, Johan P.

    2017-01-01

    Asymmetric quantum error-correcting codes are quantum codes defined over biased quantum channels: qubit-flip and phase-shift errors may have equal or different probabilities. The code construction is the Calderbank-Shor-Steane construction based on two linear codes. We present families of toric...... surfaces, toric codes and associated asymmetric quantum error-correcting codes....

  6. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    OpenAIRE

    Chauhan, Pankaj; Chimni, Swapandeep Singh

    2012-01-01

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

  7. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    Science.gov (United States)

    Chauhan, Pankaj

    2012-01-01

    Summary Ball-milling and pestle and mortar grinding have emerged as powerful methods for the development of environmentally benign chemical transformations. Recently, the use of these mechanochemical techniques in asymmetric organocatalysis has increased. This review highlights the progress in asymmetric organocatalytic reactions assisted by mechanochemical techniques. PMID:23243475

  8. Worst Asymmetrical Short-Circuit Current

    DEFF Research Database (Denmark)

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

    2010-01-01

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

  9. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    Directory of Open Access Journals (Sweden)

    Pankaj Chauhan

    2012-12-01

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

  10. Sterically demanding iminopyridine ligands

    NARCIS (Netherlands)

    Irrgang, Torsten; Keller, Sandra; Maisel, Heidi; Kretschmer, Winfried; Kempe, Rhett

    Two sterically demanding iminopyridine ligands, (2,6-diisopropylphenyl)[6-(2,4,6-triisopropylphenyl)pyridin-2-ylmeth- ylene]amine and (2,6-diisopropylphenyl)]6-(2,6-dimethylphenyl)pyridin-2-ylmethylene]amine, were prepared by a two-step process: first, condensation of 6-bromopyridine-2-carbaldehyde

  11. Asymmetric Digital Subscriber Line (ADSL

    Directory of Open Access Journals (Sweden)

    Slavko Šarić

    2012-10-01

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

  12. Research on asymmetric searchable encryption

    Science.gov (United States)

    Yu, Zonghua; Wu, Yudong

    2017-05-01

    Cloud server side to ease the user's local storage pressure at the same time, there are hidden data on the hidden dangers, the user often choose to upload the data in the form of cipher text to the cloud server. However, the classic data encryption and decryption algorithms are not provided search function, affecting the user's efficiency. To this end, an asymmetric searchable encryption scheme is proposed. The scheme can be used for any person can generate a trapdoor, cipher text can be free modified, the key pair generated by the user themselves, encrypt the identity, S-shaped virtual and other five loopholes to improve. The analysis results show that the scheme solves the above five vulnerabilities in the original scheme, so that the information semantics of both parties of communication can be guaranteed.

  13. Metal-ligand cooperation at tethered pi-ligands

    NARCIS (Netherlands)

    Verhoeven, Dide G. A.; Moret, Marc-Etienne

    2016-01-01

    Metal–ligand cooperativity in homogeneous catalysis is emerging as a powerful tool for the design of efficient transition-metal catalysts. This perspective highlights recent advances in the use of neutral π-coordinating ligands, tethered to a transition-metal center by other donor ligands, as

  14. Asymmetric construction of binaphthyl by the chiral diether-mediated conjugate addition of naphthyllithium to naphthalenecarboxylic acid 2,6-di-t-butyl-4-methoxyphenyl ester.

    Science.gov (United States)

    Shindo, Mitsuru; Yamamoto, Yasutomo; Yamada, Ken-Ichi; Tomioka, Kiyoshi

    2009-07-01

    Two ways for the synthesis of binaphthyl were examined based on a chiral ligand-mediated asymmetric conjugate addition of 1-naphthyllithium to naththalene-2-carboxylic acid 2,6-di-t-butyl-4-methoxyphenyl esters. The one pot method by conjugate addition-elimination gave a relatively higher enantioselectivity than the two step synthesis based on addition and subsequent oxidative aromatization.

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

  16. Nondeterministic self-assembly with asymmetric interactions

    Science.gov (United States)

    Tesoro, S.; Göpfrich, K.; Kartanas, T.; Keyser, U. F.; Ahnert, S. E.

    2016-08-01

    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation.

  17. Chiral fullerenes from asymmetric catalysis.

    Science.gov (United States)

    Maroto, Enrique E; Izquierdo, Marta; Reboredo, Silvia; Marco-Martínez, Juan; Filippone, Salvatore; Martín, Nazario

    2014-08-19

    Fullerenes are among the most studied molecules during the last three decades, and therefore, a huge number of chemical reactions have been tested on these new carbon allotropes. However, the aim of most of the reactions carried out on fullerenes has been to afford chemically modified fullerenes that are soluble in organic solvents or even water in the search for different mechanical, optical, or electronic properties. Therefore, although a lot of effort has been devoted to the chemical functionalization of these molecular allotropes of carbon, important aspects in the chemistry of fullerenes have not been properly addressed. In particular, the synthesis of chiral fullerenes at will in an efficient manner using asymmetric catalysis has not been previously addressed in fullerene science. Thus, despite the fact that the chirality of fullerenes has always been considered a fundamental issue, the lack of a general stereoselective synthetic methodology has restricted the use of enantiopure fullerene derivatives, which have usually been obtained only after highly expensive HPLC isolation on specific chiral columns or prepared from a pool of chiral starting materials. In this Account, we describe the first stereodivergent catalytic enantioselective syntheses in fullerene science, which have allowed the highly efficient synthesis of enantiomerically pure derivatives with total control of the stereochemical result using metallic catalysts and/or organocatalysts under very mild conditions. Density functional theory calculations strongly support the experimental findings for the assignment of the absolute configuration of the new stereocenters, which has also been ascertained by application of the sector rule and single-crystal X-ray diffraction. The use of the curved double bond of fullerene cages as a two-π-electron component in a variety of stereoselective cycloaddition reactions represents a challenging goal considering that, in contrast to most of the substituted

  18. Modeling of asymmetrical boost converters

    Directory of Open Access Journals (Sweden)

    Eliana Isabel Arango Zuluaga

    2014-01-01

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

  19. Modeling of asymmetrical boost converters

    Directory of Open Access Journals (Sweden)

    Eliana Isabel Arango Zuluaga

    2014-03-01

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

  20. Asymmetrical Warfare, Transformation, and Foreign Language Capability

    National Research Council Canada - National Science Library

    Porter, Clifford F

    2006-01-01

    .... There is no doubt that the current global war on terrorism is an asymmetrical war against an unpredictable enemy rather than the predictable or symmetrical threats against self-important dictators or the Soviet Union...

  1. 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.

  2. 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.

  3. Modeling Asymmetric Volatility In Oil Prices

    National Research Council Canada - National Science Library

    Syed Aun Hassan

    2011-01-01

    .... The paper uses daily crude oil price data for the past 10 years to test and model the oil price volatility by fitting different variations of GARCH including a univariate asymmetric GARCH model to the series...

  4. Asymmetric dense matter in holographic QCD

    Directory of Open Access Journals (Sweden)

    Shin Ik Jae

    2012-02-01

    Full Text Available We study asymmetric dense matter in holographic QCD.We construct asymmetric dense matter by considering two quark flavor branes with dierent quark masses in a D4/D6/D6 model. To calculate the symmetry energy in nuclear matter, we consider two quarks with equal masses and observe that the symmetry energy increases with the total charge showing the stiff dependence. This behavior is universal in the sense that the result is independent of parameters in the model. We also study strange (or hyperon matter with one light and one intermediate mass quarks. In addition to the vacuum properties of asymmetric matter, we calculate meson masses in asymmetric dense matter and discuss our results in the light of in-medium kaon masses.

  5. 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.

  6. A DFT investigation on interactions between asymmetric derivatives of cisplatin and nucleobase guanine

    Science.gov (United States)

    Tai, Truong Ba; Nhat, Pham Vu

    2017-07-01

    The interactions of hydrolysis products of cisplatin and its asymmetric derivatives cis- and trans-[PtCl2(iPram)(Mepz)] with guanine were studied using DFT methods. These interactions are dominated by electrostatic effects, namely hydrogen bond contributions and there exists a charge flow from H-atoms of ligands to the O-atoms of guanine. The replacement of NH3 moieties by larger functional groups accompanies with a moderate reaction between PtII and guanine molecule, diminishing the cytotoxicity of the drug. The asymmetric and symmetric NH2 stretching modes of complexes having strong hydrogen bond interactions are red shifted importantly as compared to complexes without presence of hydrogen bond interactions.

  7. Designing Asymmetric Multiferroics with Strong Magnetoelectric Coupling

    OpenAIRE

    Lu, X. Z.; Xiang, H. J.

    2014-01-01

    Multiferroics offer exciting opportunities for electric-field control of magnetism. Unfortunately, single-phase multiferroics suitable for such applications at room temperature has not been discovered. Here, we propose the concept of a new type of multiferroics, namely, "asymmetric multiferroic". In asymmetric multiferroics, two locally stable ferroelectric states are not symmetrically equivalent, leading to different magnetic properties between these two states. Furthermore, we predict from ...

  8. Stable Bound States of Asymmetric Dark Matter

    OpenAIRE

    Wise, Mark B.; Zhang, Yue

    2014-01-01

    The simplest renormalizable effective field theories with asymmetric dark matter bound states contain two additional gauge singlet fields one being the dark matter and the other a mediator particle that the dark matter annihilates into. We examine the physics of one such model with a Dirac fermion as the dark matter and a real scalar mediator. For a range of parameters the Yukawa coupling of the dark matter to the mediator gives rise to stable asymmetric dark matter bound states. We derive pr...

  9. Characteristics of Braced Excavation under Asymmetrical Loads

    Directory of Open Access Journals (Sweden)

    Changjie Xu

    2013-01-01

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

  10. Asymmetric Bessel-Gauss beams.

    Science.gov (United States)

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

    2014-09-01

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

  11. The complex interplay between ligand binding and conformational structure of the folate binding protein (folate receptor)

    DEFF Research Database (Denmark)

    Holm, Jan; Bruun, Susanne Wrang; Hansen, Steen I.

    2015-01-01

    , and the binding induces a conformational change with formation of hydrophilic and stable holo-FBP. Holo-FBP exhibits a ligand-mediated concentration-dependent self-association into multimers of great thermal and chemical stability due to strong intermolecular forces. Both ligand and FBP are thus protected against...... biological/physicochemical decomposition. In biological fluids with low FBP concentrations, e.g., saliva, semen and plasma, hydrophobic apo-monomers and hydrophilic holo-monomers associate into stable asymmetrical complexes with aberrant binding kinetics unless detergents, e.g., cholesterol or phospholipids...

  12. 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.......g., IC(50) = 300 microM for (2R,4S)-4-methyl-AA (5d)]. The two unsaturated analogs (S)- (7a) and (R)-(E)-Delta(4)-5-methyl-AA (7b) turned out to be a weak AMPA receptor agonist and a weak mixed NMDA/AMPA receptor antagonist, respectively....

  13. AMPA receptor ligands

    DEFF Research Database (Denmark)

    Strømgaard, Kristian; Mellor, Ian

    2004-01-01

    Alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptors (AMPAR), subtype of the ionotropic glutamate receptors (IGRs), mediate fast synaptic transmission in the central nervous system (CNS), and are involved in many neurological disorders, as well as being a key player...... polyamines are known to modulate the function of these receptors in vivo. In this study, recent developments in the medicinal chemistry of polyamine-based ligands are given, particularly focusing on the use of solid-phase synthesis (SPS) as a tool for the facile generation of libraries of polyamine toxin...

  14. 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.

  15. Ligand effect in enantioselective hydrogenation on skeletal copper-palladium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Vedenyapin, A.A.; Kuznetsova, T.I.; Klabunovskii, E.I.

    1987-08-10

    In the continuation of the study of the capacity of skeletal Cu-Pd catalysts modified with RR-tartaric acid and containing no more than 5 at.% Pd, to conduct enantioselective hydrogenation of ethylacetoacetate (EAA) into R-ethyl-..beta..-hydroxybutyrate (R-EHB), they studied this phenomenon in more detail and made the previously obtained data more precise. Pronounced synergism of the asymmetric effect of chiral copper-palladium catalysts related to manifestation of a ligand effect was found.

  16. Design, synthesis, and applications of potential substitutes of t-Bu-phosphinooxazoline in Pd-catalyzed asymmetric transformations and their use for the improvement of the enantioselectivity in the Pd-catalyzed allylation reaction of fluorinated allyl enol carbonates.

    Science.gov (United States)

    Bélanger, Étienne; Pouliot, Marie-France; Courtemanche, Marc-André; Paquin, Jean-François

    2012-01-06

    The design, synthesis, and applications of potential substitutes of t-Bu-PHOX in asymmetric catalysis is reported. The design relies on the incorporation of geminal substituents at C5 in combination with a substituent at C4 other than t-butyl (i-Pr, i-Bu, or s-Bu). Most of these new members of the PHOX ligand family behave similarly in terms of stereoinduction to t-Bu-PHOX in three palladium-catalyzed asymmetric transformations. Electronically modified ligands were also prepared and used to improve the enantioselectivity in the Pd-catalyzed allylation reaction of fluorinated allyl enol carbonates.

  17. Asymmetrical soft palate cleft repair: preliminary results.

    Science.gov (United States)

    Bütow, K-W; Engelbrecht, H; Naidoo, S

    2014-06-01

    The reconstructions of the asymmetrical soft palate cleft is a surgical challenge when it comes to achieving symmetry and optimal soft palate muscular function. Three different versions of the intravelar veloplasty have been used: the intravelar veloplasty (1969) (type I), the modification according to anatomical defects (1991) (type II), and the modification using part of Sommerlad's technique and part of Ivanov's technique (2008) (type III). The perioperative outcomes of the type II and type III intravelar veloplasty were assessed and compared in asymmetrical cleft cases. Two hundred and seventy-seven soft palate clefts were reconstructed: 153 type II and 124 type III. Of these, 49 were asymmetrical (17.7%); 23 underwent the type II procedure and 26 the type III procedure. Of the type II procedure cases, 30.4% remained asymmetrical postoperatively compared to 3.8% of the type III cases. The uvula appeared subjectively atrophic in 47.8% of the type II cases and in 7.7% of type III cases. Oro-nasal fistula occurred in 13.0% of the type II cases and 3.8% of the type III cases. Speech results will only be assessed after 4 years of age. The type III modified intravelar veloplasty has had a major beneficial impact on patients who had an asymmetrical soft palate cleft. Copyright © 2014. Published by Elsevier Ltd.

  18. Control of apoptosis by asymmetric cell division.

    Science.gov (United States)

    Hatzold, Julia; Conradt, Barbara

    2008-04-08

    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.

  19. 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.

  20. A sampling theory for asymmetric communities.

    Science.gov (United States)

    Noble, Andrew E; Temme, Nico M; Fagan, William F; Keitt, Timothy H

    2011-03-21

    We introduce the first analytical model of asymmetric community dynamics to yield Hubbell's neutral theory in the limit of functional equivalence among all species. Our focus centers on an asymmetric extension of Hubbell's local community dynamics, while an analogous extension of Hubbell's metacommunity dynamics is deferred to an appendix. We find that mass-effects may facilitate coexistence in asymmetric local communities and generate unimodal species abundance distributions indistinguishable from those of symmetric communities. Multiple modes, however, only arise from asymmetric processes and provide a strong indication of non-neutral dynamics. Although the exact stationary distributions of fully asymmetric communities must be calculated numerically, we derive approximate sampling distributions for the general case and for nearly neutral communities where symmetry is broken by a single species distinct from all others in ecological fitness and dispersal ability. In the latter case, our approximate distributions are fully normalized, and novel asymptotic expansions of the required hypergeometric functions are provided to make evaluations tractable for large communities. Employing these results in a bayesian analysis may provide a novel statistical test to assess the consistency of species abundance data with the neutral hypothesis. Copyright © 2010 Elsevier Ltd. All rights reserved.

  1. Metal-ligand cooperation at tethered π-ligands.

    Science.gov (United States)

    Verhoeven, Dide G A; Moret, Marc-Etienne

    2016-10-12

    Metal-ligand cooperativity in homogeneous catalysis is emerging as a powerful tool for the design of efficient transition-metal catalysts. This perspective highlights recent advances in the use of neutral π-coordinating ligands, tethered to a transition-metal center by other donor ligands, as cooperative reaction centers. The state-of-the-art organometallic complexes, including π-coordinating ligands originating from C[double bond, length as m-dash]C, C[double bond, length as m-dash]E (E = O, N) and boron containing moieties, are described here, with special attention on their specific reactivity. Geometric and electronic aspects of ligand design and their influence on the coordination mode and reactivity of the π-system are discussed.

  2. Asymmetric microscope. Fusho no kenbisho [exclamation point

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Tadashi. (Tokyo Institute of Technology, Tokyo (Japan))

    1999-07-01

    It is difficult for a conventional optical analysis means to determine the configuration of a substance with an ultra low optical purity. Recently, an asymmetric microscope has been reported as a new concept for solving the above-mentioned problem. Specifically, a product with slight asymmetry is obtained by using the substance with an ultra low optical purity as the chiral initiation, and then the asymmetry of the product is amplified dramatically due to the asymmetric autocatalysis, thus obtaining a product having a high optical purity. A new means is to determine the configuration of the original substance having the low optical purity from the configuration of the substance having the high optical purity. According to this method, the chirality of the substance having the low optical purity is transcribed to alkanol, and the chirality is amplified due to the asymmetric autocatalysis, thus the absolute configuration of the original compound can be determined from the absolute configuration of the final product. (NEDO)

  3. Multi-agent Bargaining under Asymmetric Information

    DEFF Research Database (Denmark)

    Asplund, Marcus; Genesove, David

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

  4. Asymmetric synthesis II more methods and applications

    CERN Document Server

    Christmann, Mathias

    2012-01-01

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

  5. Macrocyclic G-quadruplex ligands

    DEFF Research Database (Denmark)

    Nielsen, M C; Ulven, Trond

    2010-01-01

    are macrocyclic structures which have been modeled after the natural product telomestatin or from porphyrin-based ligands discovered in the late 1990s. These two structural classes of G-quadruplex ligands are reviewed here with special attention to selectivity and structure-activity relationships, and with focus...

  6. Algebraic Davis decomposition and asymmetric Doob inequalities

    OpenAIRE

    Hong, Guixiang; Junge, Marius; Parcet, Javier

    2015-01-01

    In this paper we investigate asymmetric forms of Doob maximal inequality. The asymmetry is imposed by noncommutativity. Let $(\\M,\\tau)$ be a noncommutative probability space equipped with a weak-$*$ dense filtration of von Neumann subalgebras $(\\M_n)_{n \\ge 1}$. Let $\\E_n$ denote the corresponding family of conditional expectations. As an illustration for an asymmetric result, we prove that for $1 < p < 2$ and $x \\in L_p(\\M,\\tau)$ one can find $a, b \\in L_p(\\M,\\tau)$ and contractions $u_n, v_...

  7. 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.

  8. Cell-sized asymmetric lipid vesicles facilitate the investigation of asymmetric membranes

    Science.gov (United States)

    Kamiya, Koki; Kawano, Ryuji; Osaki, Toshihisa; Akiyoshi, Kazunari; Takeuchi, Shoji

    2016-09-01

    Asymmetric lipid giant vesicles have been used to model the biochemical reactions in cell membranes. However, methods for producing asymmetric giant vesicles lead to the inclusion of an organic solvent layer that affects the mechanical and physical characteristics of the membrane. Here we describe the formation of asymmetric giant vesicles that include little organic solvent, and use them to investigate the dynamic responses of lipid molecules in the vesicle membrane. We formed the giant vesicles via the inhomogeneous break-up of a lipid microtube generated by applying a jet flow to an asymmetric planar lipid bilayer. The asymmetric giant vesicles showed a lipid flip-flop behaviour in the membrane, superficially similar to the lipid flip-flop activity observed in apoptotic cells. In vitro synthesis of membrane proteins into the asymmetric giant vesicles revealed that the lipid asymmetry in bilayer membranes improves the reconstitution ratio of membrane proteins. Our asymmetric giant vesicles will be useful in elucidating lipid-lipid and lipid-membrane protein interactions involved in the regulation of cellular functions.

  9. Ligand Self-Sorting and Nonlinear Effects in Dinuclear Asymmetric Hydrogenation: Complexity in Catalysis

    NARCIS (Netherlands)

    Terrade, F.G.; Lutz, M.|info:eu-repo/dai/nl/304828971; Reek, J.N.H.

    2013-01-01

    Nature has been a source of inspiration for scientists as billion years of evolution have resulted in magnificent examples of how processes can be controlled efficiently. In the field of supramolecular catalysis, enzymes have been the major source of inspiration. As such, many synthetic systems have

  10. Synthesis and Application of New Chiral Ligands for the Asymmetric Borane Reduction of Prochiral Ketones

    NARCIS (Netherlands)

    Hulst, Ron; Heres, Hero; Peper, Nathalie C.M.W.; Kellogg, Richard M.

    Two chiral nonracemic γ-amino alcohols, ephedrine thiol and the corresponding (thio)-phosphoramidates and (thio)-phosphinamides have been examined as catalysts for the reduction of propiophenone by various boranes. Up to 95% e.e. can be obtained with the phosphorus derivatives.

  11. 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.

  12. RSA Asymmetric Cryptosystem beyond Homogeneous Transformation

    African Journals Online (AJOL)

    PROF. O. E. OSUAGWU

    2013-12-01

    Dec 1, 2013 ... The Internet is an insecure open network and its use and connectivity have witnessed a significant growth, and this has made it vulnerable to all forms of attacks. A threat to a network can cause harm or interrupt the network. In this paper, we looked at the security of data and message, using asymmetric.

  13. Settling dynamics of asymmetric rigid fibers

    Science.gov (United States)

    E.J. Tozzi; C Tim Scott; David Vahey; D.J. Klingenberg

    2011-01-01

    The three-dimensional motion of asymmetric rigid fibers settling under gravity in a quiescent fluid was experimentally measured using a pair of cameras located on a movable platform. The particle motion typically consisted of an initial transient after which the particle approached a steady rate of rotation about an axis parallel to the acceleration of gravity, with...

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

    African Journals Online (AJOL)

    determine how the modal characteristics change as circular Bragg fiber is changed to asymmetric Bragg fiber. The key to this transfer matrix method (TMM) is the accurate calculation of the propagation constants of modes. And validity of this method is verified by FDTD method. We compare these results with obtained from ...

  15. Organocatalytic asymmetric transfer hydrogenation of imines

    NARCIS (Netherlands)

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

    2011-01-01

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

  16. Spatially inhomogeneous condensate in asymmetric nuclear matter

    NARCIS (Netherlands)

    Sedrakian, A

    We study the isospin singlet pairing in asymmetric nuclear matter with nonzero total momentum of the condensate Cooper pairs. The quasiparticle excitation spectrum is fourfold split compared to the usual BCS spectrum of the symmetric, homogeneous matter. A twofold splitting of the spectrum into

  17. Asymmetric volatility connectedness on the forex market

    Czech Academy of Sciences Publication Activity Database

    Baruník, Jozef; Kočenda, Evžen; Vácha, Lukáš

    2017-01-01

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

  18. Asymmetric Drift and the Stellar Velocity Ellipsoid

    NARCIS (Netherlands)

    Westfall, Kyle B.; Bershady, Matthew A.; Verheijen, Marc A. W.; Andersen, David R.; Swaters, Rob A.

    2007-01-01

    We present the decomposition of the stellar velocity ellipsoid using stellar velocity dispersions within a 40° wedge about the major-axis (smaj), the epicycle approximation, and the asymmetric drift equation. Thus, we employ no fitted forms for smaj and escape interpolation errors resulting from

  19. 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.

  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. Spectral inequalities for the quantum asymmetric top

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-03-06

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

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

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 4. Palladium catalysed asymmetric alkylation of benzophenone Schiff base glycine esters in ionic liquids. Dae Hyun Kim Jin Kyu Im Dae Won Kim Minserk Cheong Hoon Sik Kim Deb Kumar Mukherjee. Volume 123 Issue 4 July 2011 pp 467-476 ...

  3. RSA Asymmetric Cryptosystem beyond Homogeneous Transformation

    African Journals Online (AJOL)

    The Internet is an insecure open network and its use and connectivity have witnessed a significant growth, and this has made it vulnerable to all forms of attacks. A threat to a network can cause harm or interrupt the network. In this paper, we looked at the security of data and message, using asymmetric cryptography, with ...

  4. Mixed gas plasticization phenomena in asymmetric membranes

    NARCIS (Netherlands)

    Visser, Tymen

    2006-01-01

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

  5. 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....

  6. Determinant of asymmetric risks in Nigerian loan market: any ...

    African Journals Online (AJOL)

    Bank lending in Nigeria was dominated by the presence of asymmetric information, a wedge to financial intermediation. Using probit and correlation test methodology, evidence of low level asymmetric risk was found and the determinants of asymmetric risks in the market were not significantly different. The size of default ...

  7. Deprotonation induced ligand-to-metal electron transfer: Synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen

    NARCIS (Netherlands)

    Tejel, C.; Ciriano, M.A.; del Río, M.P.; van den Bruele, F.J.; Hetterscheid, D.G.H.; Tsichlis i Spithas, N.; de Bruin, B.

    2008-01-01

    Treatment of bis(2-picolyl)amine (bpa) with [{Rh(nbd)(mu-OMe))(2)] leads to unexpected and unique redox asymmetric dinuclear Rh-I, Rh+I complex [{Rh(ndb)}(2)(bpa-2H)] (2) with a pi-coordinating imine bound to a tetrahedral low valent rhodate(-I). Mono-oxygenation of the deprotonated bpa ligand in 2

  8. Correcting ligands, metabolites, and pathways

    NARCIS (Netherlands)

    Ott, M.A.; Vriend, G.

    2006-01-01

    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,

  9. FAS Ligand Triggers Pulmonary Silicosis

    Science.gov (United States)

    Borges, Valéria M.; Falcão, Haroldo; Leite-Júnior, José H.; Alvim, Luciana; Teixeira, Gerlinde P.; Russo, Momtchilo; Nóbrega, Alberto F.; Lopes, Marcela F.; Rocco, Patricia M.; Davidson, Wendy F.; Linden, Rafael; Yagita, Hideo; Zin, Walter A.; DosReis, George A.

    2001-01-01

    We investigated the role of Fas ligand in murine silicosis. Wild-type mice instilled with silica developed severe pulmonary inflammation, with local production of tumor necrosis factor (TNF)-α, and interstitial neutrophil and macrophage infiltration in the lungs. Strikingly, Fas ligand–deficient generalized lymphoproliferative disease mutant (gld) mice did not develop silicosis. The gld mice had markedly reduced neutrophil extravasation into bronchoalveolar space, and did not show increased TNF-α production, nor pulmonary inflammation. Bone marrow chimeras and local adoptive transfer demonstrated that wild-type, but not Fas ligand–deficient lung macrophages recruit neutrophils and initiate silicosis. Silica induced Fas ligand expression in lung macrophages in vitro and in vivo, and promoted Fas ligand–dependent macrophage apoptosis. Administration of neutralizing anti-Fas ligand antibody in vivo blocked induction of silicosis. Thus, Fas ligand plays a central role in induction of pulmonary silicosis. PMID:11457890

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

    Science.gov (United States)

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

    2015-04-01

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

  11. 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

  12. 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

  13. Settling dynamics of asymmetric rigid fibers

    Science.gov (United States)

    Tozzi, E. J.; Scott, C. T.; Vahey, D.; Klingenberg, D. J.

    2011-03-01

    The three-dimensional motion of asymmetric rigid fibers settling under gravity in a quiescent fluid was experimentally measured using a pair of cameras located on a movable platform. The particle motion typically consisted of an initial transient after which the particle approached a steady rate of rotation about an axis parallel to the acceleration of gravity, with its center of mass following a helical trajectory. Numerical and analytical methods were used to predict translational and angular velocities as well as the evolution of the fiber orientation as a function of time. A comparison of calculated and measured values shows that it is possible to quantitatively predict complex motions of particles that have highly asymmetric shape. The relations between particle shape and settling trajectory have potential applications for hydrodynamic characterization of fiber shapes and fiber separation.

  14. 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.

  15. Defect induced asymmetric pit formation on hydroxyapatite.

    Science.gov (United States)

    Kwon, Ki-Young; Wang, Eddie; Chung, Alice; Chang, Neil; Saiz, Eduardo; Choe, Uh-Joo; Koobatian, Maxwell; Lee, Seung-Wuk

    2008-10-07

    Defect sites on bone minerals play a critical role in bone remodeling processes. We investigated single crystal hydroxyapatite (100) surfaces bearing crystal defects under acidic dissolution conditions using real-time in situ atomic force microscopy. At defect sites, surface structure-dependent asymmetric hexagonal etch pits were formed, which dominated the overall dissolution rate. Meanwhile, dissolution from the flat terraces proceeded by stochastic formation of flat bottom etch pits. The resulting pit shapes were intrinsically dictated by the HAP crystal structure. Computational modeling also predicted different step energies associated with different facets of the asymmetric etch pits. Our microscopic observations of HAP dissolution are significant for understanding the effects of local surface structure on the bone mineral remodeling process and provide useful insights for the design of novel therapies for treating osteoporosis and dental caries.

  16. Asymmetric synthesis and sensory evaluation of sedanenolide.

    Science.gov (United States)

    Oguro, Daichi; Watanabe, Hidenori

    2011-01-01

    The synthesis and sensory evaluation of enantiomeric sets of sedanenolide (1) and 3-butylphthalide (3) are described. The asymmetric synthesis was achieved via the intramolecular Diels-Alder reaction of chiral propargylester (5) which was prepared from optically active propargyl alcohol (4) and 2,4-pentadienoic acid. The sensory evaluation of these enantiomers revealed that there were distinct differences between their aroma character and odor threshold.

  17. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. 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....

  19. Asymmetric monetary policy effects in EMU

    OpenAIRE

    Clausen, Volker; Hayo, Bernd

    2002-01-01

    This paper uses a semi-structural dynamic modelling approach to investigate asymmetric monetary transmission in Europe. A system of equations containing reaction functions for monetary policy, output and inflation equations is simultaneously estimated for France, Germany, and Italy. Extensive cross equation tests show that relatively large differences in simulated impulse responses are still consistent with the notion that the transmission mechanism is homogeneous across the three major EMU c...

  20. Predicting tensorial electrophoretic effects in asymmetric colloids

    Science.gov (United States)

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

    2017-12-01

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

  1. 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.

  2. Flow Asymmetric Propargylation: Development of Continuous Processes for the Preparation of a Chiral β-Amino Alcohol.

    Science.gov (United States)

    Li, Hui; Sheeran, Jillian W; Clausen, Andrew M; Fang, Yuan-Qing; Bio, Matthew M; Bader, Scott

    2017-08-01

    The development of a flow chemistry process for asymmetric propargylation using allene gas as a reagent is reported. The connected continuous process of allene dissolution, lithiation, Li-Zn transmetallation, and asymmetric propargylation provides homopropargyl β-amino alcohol 1 with high regio- and diastereoselectivity in high yield. This flow process enables practical use of an unstable allenyllithium intermediate. The process uses the commercially available and recyclable (1S,2R)-N-pyrrolidinyl norephedrine as a ligand to promote the highly diastereoselective (32:1) propargylation. Judicious selection of mixers based on the chemistry requirement and real-time monitoring of the process using process analytical technology (PAT) enabled stable and scalable flow chemistry runs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Sixteen isostructural phosphonate metal-organic frameworks with controlled Lewis acidity and chemical stability for asymmetric catalysis.

    Science.gov (United States)

    Chen, Xu; Peng, Yongwu; Han, Xing; Liu, Yan; Lin, Xiaochao; Cui, Yong

    2017-12-19

    Heterogeneous catalysts typically lack the specific steric control and rational electronic tuning required for precise asymmetric catalysis. Here we demonstrate that a phosphonate metal-organic framework (MOF) platform that is robust enough to accommodate up to 16 different metal clusters, allowing for systematic tuning of Lewis acidity, catalytic activity and enantioselectivity. A total of 16 chiral porous MOFs, with the framework formula [M3 L 2(solvent)2] that have the same channel structures but different surface-isolated Lewis acid metal sites, are prepared from a single phosphono-carboxylate ligand of 1,1'-biphenol and 16 different metal ions. The phosphonate MOFs possessing tert-butyl-coated channels exhibited high thermal stability and good tolerances to boiling water, weak acid and base. The MOFs provide a versatile family of heterogeneous catalysts for asymmetric allylboration, propargylation, Friedel-Crafts alkylation and sulfoxidation with good to high enantioselectivity. In contrast, the homogeneous catalyst systems cannot catalyze the test reactions enantioselectively.

  4. Development of atom-economical catalytic asymmetric reactions under proton transfer conditions: construction of tetrasubstituted stereogenic centers and their application to therapeutics.

    Science.gov (United States)

    Kumagai, Naoya

    2011-01-01

    The development of atom-economical catalytic asymmetric reactions based on two distinct sets of catalyst, a rare earth metal/amide-based ligand catalyst and a soft Lewis acid/hard Brønsted base catalyst, is reviewed. These catalytic systems exhibit high catalytic activity and stereoselectivity by harnessing a cooperative catalysis through hydrogen bond/metal coordination and soft-soft interactions/hard-hard interactions, respectively. The effectiveness of these cooperative catalysts is clearly delineated by the high stereoselectivity in reactions with highly coordinative substrates, and the specific activation of otherwise low-reactive pronucleophiles under proton transfer conditions. The rare earth metal/amide-based ligand catalyst was successfully applied to catalytic asymmetric aminations, nitroaldol (Henry) reactions, Mannich-type reactions, and conjugate addition reactions, generating stereogenic tetrasubstituted centers. Catalytic asymmetric amination and anti-selective catalytic asymmetric nitroaldol reactions were successfully applied to the efficient enantioselective synthesis of therapeutic candidates, such as AS-3201 and the β(3)-adrenoreceptor agonist, showcasing the practical utility of the present protocols. The soft Lewis acid/hard Brønsted base cooperative catalyst was specifically developed for the chemoselective activation of soft Lewis basic allylic cyanides and thioamides, which are otherwise low-reactive pronucleophiles. The cooperative action of the catalyst allowed for efficient catalytic generation of active carbon nucleophiles in situ, which were integrated into subsequent enantioselective additions to carbonyl-type electrophiles.

  5. Asymmetrical lumbosacral transitional vertebrae in dogs may promote asymmetrical hip joint development.

    Science.gov (United States)

    Flückiger, Mark A; Steffen, Frank; Hässig, Michael; Morgan, Joseph P

    2017-03-20

    This study examines the relationship between the morphology of the lumbosacral transitional vertebra (LTV) and asymmetrical development of the hip joints in dogs. A total of 4000 dogs which had been consecutively scored for canine hip dysplasia were checked for the presence of a LTV. A LTV was noted in 138 dogs and classified depending on the morphology of the transverse processes and the degree of contact with the ilium. In dogs with an asymmetrical LTV, the hip joint was significantly more predisposed to subluxation and malformation on the side of the intermediate or sacral-like transverse process (p hip joint conformation was less affected on the side featuring a free transverse process (p hip joint, and secondary osteoarthritis. Asymmetrical hip conformation may therefore be the sequela of a LTV and mask or aggravate genetically induced canine hip dysplasia.

  6. 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.

  7. Recent approaches for asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes.

    Science.gov (United States)

    Wang, Yibing; Song, Xiaohan; Wang, Jiang; Moriwaki, Hiroki; Soloshonok, Vadim A; Liu, Hong

    2017-07-03

    This review article critically discusses examples of asymmetric synthesis of tailor-made α-amino acids via homologation of Ni(II) complexes of glycine and alanine Schiff bases, reported in the literature from 2013 through the end of 2016. Where it is possible, reaction mechanism and origin of the stereochemical outcome is discussed in detail. Special attention is given to various aspects of practicality and scalability of the reported methods. Among the most noticeable developments in this area are novel designs of axially chiral ligands, application of electro- and mechano-chemical (ball-milling) conditions, and development of dynamic kinetic resolution procedures.

  8. Rosetta Ligand docking with flexible XML protocols.

    Science.gov (United States)

    Lemmon, Gordon; Meiler, Jens

    2012-01-01

    RosettaLigand is premiere software for predicting how a protein and a small molecule interact. Benchmark studies demonstrate that 70% of the top scoring RosettaLigand predicted interfaces are within 2Å RMSD from the crystal structure [1]. The latest release of Rosetta ligand software includes many new features, such as (1) docking of multiple ligands simultaneously, (2) representing ligands as fragments for greater flexibility, (3) redesign of the interface during docking, and (4) an XML script based interface that gives the user full control of the ligand docking protocol.

  9. 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...... to the same controller without LIDAR data. The results showed that the MPC with LIDAR was able to reduce the asymmetric loads compared to the MPC without LIDAR while still maintaining the power reference....

  10. 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.

  11. Combined shear/compression structural testing of asymmetric sandwich structures

    OpenAIRE

    Castanié, Bruno; Barrau, Jean-Jacques; Jaouen, Jean-Pierre; Rivallant, Samuel

    2004-01-01

    Asymmetric sandwich technology can be applied in the design of lightweight, non-pressurized aeronautical structures such as those of helicopters. A test rig of asymmetric sandwich structures subjected to compression/shear loads was designed, validated, and set up. It conforms to the standard certification procedure for composite aeronautical structures set out in the “test pyramid”, a multiscale approach. The static tests until failure showed asymmetric sandwich structures to be extremely res...

  12. Asymmetric acoustic transmission in graded beam

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-01

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

  13. 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.

  14. 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.

  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. 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.

  17. THERMODYNAMIC ASSESSMENT OF ANIONIC LIGANDS ...

    African Journals Online (AJOL)

    DJFLEX

    2010-06-30

    Jun 30, 2010 ... ion. This brings about repulsion between the adsorbent and positively charged ion and consequently a reduction in the amount of heavy metal adsorbed at lower pH. (Lee, 1999). The effectiveness of the anionic ligands in the removal of heavy metal ions from aqueous solution seems to be low for the EDTA.

  18. Asymmetric Cycloaddition and Cyclization Reactions Catalyzed by Chiral N,N'-Dioxide-Metal Complexes.

    Science.gov (United States)

    Liu, Xiaohua; Zheng, Haifeng; Xia, Yong; Lin, Lili; Feng, Xiaoming

    2017-10-17

    Catalytic asymmetric cycloadditions and cascade cyclizations are a major focus for the enantioselective construction of chiral carbo- and heterocycles. A number of chiral Lewis acids and organocatalysts have been designed for such reactions. The development of broadly applicable catalysts bearing novel chiral backbones to meet the demands of various applications is an ongoing challenge. Approximately 10 years ago, we introduced a group of conformationally flexible C2-symmetric N,N'-dioxide amide compounds, which represent a new class of privileged ligands. The coordination of the four oxygens of a chiral N,N'-dioxide around a central metal generates an octahedral tricyclometalated Lewis acid catalyst that can carry out various enantioselective reactions. In this Account, we summarize our recent studies on asymmetric cycloadditions between various dienophiles and dienes, dipoles and dipolarophiles, and cascade cyclizations catalyzed by chiral N,N'-dioxide-metal complexes. In principle, these unique chiral catalysts lower the LUMO energy of electron-deficient 2π components or heterodienes by coordination with the functional groups via various binding modes. With N-Boc-3-alkenyloxindole and alkylidene malonate as the electron-deficient 2π components, N,N'-dioxide-metal complexes provided excellent catalytic activities and asymmetric inductions for a variety of transformations, including [2 + 1], [3 + 2], [4 + 2], and [8 + 2] cycloadditions. Mechanistically, these substrates could be efficiently activated through bidentate coordination. The strategy was also useful for asymmetric cascade cyclizations to form polycyclic adducts. Monodentate or bidentate coordination of other α,β-unsubstituted carbonyl compounds to metal centers enabled both normal Diels-Alder reactions and inverse-electron-demand hetero-Diels-Alder reactions as well as [2 + 2] additions. Furthermore, hetero-Diels-Alder reactions of aldehydes, ketones, and imines are well-tolerated and afford various

  19. Mechanism and an Improved Asymmetric Allylboration of Ketones Catalyzed by Chiral Biphenols**

    Science.gov (United States)

    Barnett, David S.; Moquist, Philip N.; Schaus, Scott E.

    2010-01-01

    A mechanistic study of the enantioselective asymmetric allylboration of ketones with allyldiisopropoxyborane catalyzed by chiral biphenols resulted in the development of improved reaction process. In a ligand exchange process involving the chiral biphenol and the boronate to liberate isopropanol as the key step, addition of isopropanol to the reaction was found to increase the overall rate and enantioselectivity. In the design of an improved reaction, a boronate possessing a tethered alcohol would more readily liberate catalyst at the end of a reaction. The use of allyldioxaborinane with 2 mol% (S)-3,3′-Br2-BINOL and 2 equivalents t-BuOH relative to ketone at room temperature results in high yields and enantioselectivities. Insight gathered from the mechanistic investigation resulted in the development of a reaction process that uses less catalyst (from 15 mol% to 2 mol%) at warmer temperatures (from -35 °C to room temperature). PMID:19816902

  20. A homochiral metal-organic framework as an effective asymmetric catalyst for cyanohydrin synthesis.

    Science.gov (United States)

    Mo, Ke; Yang, Yuhua; Cui, Yong

    2014-02-05

    A homochiral metal-organic framework (MOF) of an enantiopure 2,2'-dihydroxy-1,1'-biphenyl ligand was constructed. After exchanging one proton of the dihydroxyl group for Li(I) ions, the framework is shown to be a highly efficient and recyclable heterogeneous catalyst for asymmetric cyanation of aldehydes with up to >99% ee. Compared with the homogeneous counterpart, the MOF catalyst exhibits significantly enhanced catalytic activity and enantioselectivity, especially at a low catalyst/substrate ratio, due to that the rigid framework could stabilize the catalytically active monolithium salt of biphenol against its free transformation to catalytically inactive and/or less active assemblies in reactions. The synthetic utility of the cyanation was demonstrated in the synthesis of (S)-bufuralol (a nonselective β-adrenoceptor blocking agent) with 98% ee.

  1. Asymmetric PCR for good quality ssDNA generation towards DNA aptamer production

    Directory of Open Access Journals (Sweden)

    Junji Tominaga4

    2012-04-01

    Full Text Available Aptamers are ssDNA or RNA that binds to wide variety of target molecules with high affinity and specificity producedby systematic evolution of ligands by exponential enrichment (SELEX. Compared to RNA aptamer, DNA aptamer is muchmore stable, favourable to be used in many applications. The most critical step in DNA SELEX experiment is the conversion ofdsDNA to ssDNA. The purpose of this study was to develop an economic and efficient approach of generating ssDNA byusing asymmetric PCR. Our results showed that primer ratio (sense primer:antisense primer of 20:1 and sense primer amountof 10 to 100 pmol, up to 20 PCR cycles using 20 ng of initial template, in combination with polyacrylamide gel electrophoresis,were the optimal conditions for generating good quality and quantity of ssDNA. The generation of ssDNA via this approachcan greatly enhance the success rate of DNA aptamer generation.

  2. Using chiral ionic liquid additives to enhance asymmetric induction in a Diels-Alder reaction.

    Science.gov (United States)

    Goodrich, P; Nimal Gunaratne, H Q; Hall, L; Wang, Y; Jin, L; Muldoon, M J; Ribeiro, A P C; Pombeiro, A J L; Pârvulescu, V I; Davey, P; Hardacre, C

    2017-01-31

    A bis-oxazoline ligand has been complexed using Cu(ii) and Zn(ii) trifluoromethanesulfonate and a range of chiral ionic liquid (CIL) additives based on natural products were used as a co-catalyst for a Diels-Alder reaction. The catalytic performance of these systems was compared for the asymmetric Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene with and without the presence of a CIL additive. In the absence of the CIL, both catalysts resulted in low enantioselectivities in conventional solvents and ionic liquids. However, whilst only a minor effect of the CIL was observed for the Cu based catalyst, in the case of the Zn based catalyst, significant enhancements in endo enantioselectivity of up to 50% were found on the addition of a CIL.

  3. 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 ...

  4. 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.

  5. Asymmetric Uncertainty Expression for High Gradient Aerodynamics

    Science.gov (United States)

    Pinier, Jeremy T

    2012-01-01

    When the physics of the flow around an aircraft changes very abruptly either in time or space (e.g., flow separation/reattachment, boundary layer transition, unsteadiness, shocks, etc), the measurements that are performed in a simulated environment like a wind tunnel test or a computational simulation will most likely incorrectly predict the exact location of where (or when) the change in physics happens. There are many reasons for this, includ- ing the error introduced by simulating a real system at a smaller scale and at non-ideal conditions, or the error due to turbulence models in a computational simulation. The un- certainty analysis principles that have been developed and are being implemented today do not fully account for uncertainty in the knowledge of the location of abrupt physics changes or sharp gradients, leading to a potentially underestimated uncertainty in those areas. To address this problem, a new asymmetric aerodynamic uncertainty expression containing an extra term to account for a phase-uncertainty, the magnitude of which is emphasized in the high-gradient aerodynamic regions is proposed in this paper. Additionally, based on previous work, a method for dispersing aerodynamic data within asymmetric uncer- tainty bounds in a more realistic way has been developed for use within Monte Carlo-type analyses.

  6. 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 Hardy 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.

  7. [Asymmetric hypertrophy of the masticatory muscles].

    Science.gov (United States)

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

    2012-06-01

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

  8. 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.

  9. Asymmetric inheritance of cytoophidia in Schizosaccharomyces pombe

    Directory of Open Access Journals (Sweden)

    Jing Zhang

    2014-10-01

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

  10. Asymmetric Cell Divisions in the Epidermis

    Science.gov (United States)

    Poulson, Nicholas D.; Lechler, Terry

    2012-01-01

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

  11. -Pincer Ligand Family through Ligand Post-Modification

    KAUST Repository

    Huang, Mei-Hui

    2017-10-02

    A series of air-stable nickel complexes containing triazine-based PN3P-pincer ligands were synthesized and fully characterized. Complex 3 contains a de-aromatized central triazine ring from the deprotonation of one of the N–H arms. With a post-modification strategy, the Me-PN3P*NiCl complex (3) could be converted into a new class of diimine–traizine PN3P-pincer nickel complexes.

  12. Decrease in back strength in asymmetric trunk postures

    NARCIS (Netherlands)

    Vink, P.; Daanen, H. A M; Meijst, W. J.; Ligteringen, J.

    1992-01-01

    The extension force against resistance was recorded in 23 postures for 12 subjects to find explanations for the decrease in back strength in asymmetric postures. A reduction in muscle force in asymmetric postures was found up to 40%, but was strongly dependent on the plane in which asymmetry

  13. 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.

  14. Asymmetric pair distribution functions in catalysts

    DEFF Research Database (Denmark)

    Clausen, B. S.; Nørskov, Jens Kehlet

    2000-01-01

    of asymmetric pair distribution functions for nano-sized particles and how they influence the structural parameters obtained from the standard data analysis. An alternative method, which takes into account deviations from the Gaussian pair distribution function typically used in the analysis of EXAFS spectra......, will be described. The method is based on an analysis of the pair distribution functions derived from molecular dynamics simulations of small metal particles and its reliability is demonstrated by comparing structural parameters obtained from independent X-ray diffraction experiments.......The structural parameters, i.e., coordination numbers, bond distances and disorder obtained from the analysis of EXAFS spectra may sometimes be significantly influenced by errors introduced due to the inadequacy of the analysis method applied. Especially in the case of heterogeneous catalysts...

  15. 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.

  16. Optical Nonreciprocity in Asymmetric Optomechanical Couplers

    Science.gov (United States)

    Wang, Zheqi; Shi, Lei; Liu, Yi; Xu, Xinbiao; Zhang, Xinliang

    2015-03-01

    We propose an all-optical integrated nonreciprocal device on the optomechanical platform with a large nonreciprocal bandwidth and low operating power. The device is based on an asymmetric silicon coupler consisting of two branches. One of them is a conventional strip waveguide fixed on the substrate, and the other is a freestanding nanostring suspended above a groove in the substrate. When light is launched into the coupler, the optical gradient force between the freestanding nanostring and the underlying substrate leads to the deflection of the nanostring, and finally results in destruction of the initial phase-matching condition between the two branches. The suspended branch would achieve distinct deflections when light is incident from different ports. The simulation results show a nonreciprocal bandwidth of 13.1 nm with operating power of 390 μW. With the advantages of simple structure, low power consumption and large operating bandwidth, our work provides a promising solution for on-chip passive nonreciprocal device.

  17. Asymmetric adsorption in an open electrolytic cell

    Science.gov (United States)

    Bousiadi, S.; Lelidis, I.

    2018-01-01

    We investigate the effect of adsorption-desorption phenomenon of ions in an asymmetric electrolytic cell at open circuit conditions. Our approach is based on the Poisson-Nernst-Planck theory for electrolytes and the kinetic model of Langmuir for the description of adsorption-desorption phenomena on the electrodes. When the electrodes are immersed into the solution, selective ion adsorption takes place. It is shown, that the selective ion adsorption is responsible for generating an electrical potential difference between the electrodes of the cell. The analytical expressions for the potential difference and for the charge distribution are calculated. Finally, the time evolution of the system is investigated and the relaxation times of the problem are deduced numerically.

  18. Bilateral asymmetrical traumatic sternoclavicular joint dislocations.

    Science.gov (United States)

    Albarrag, Mohammed K

    2012-11-01

    Unilateral and bilateral sternoclavicular joint (SCJ) dislocations are rare injuries. The difficulty in assessing this condition often leads to delay in diagnosis and treatment. We report a rare case of bilateral asymmetrical traumatic SCJ dislocations in a 45-year-old male. The right anterior SCJ dislocation was reduced in the emergency room (ER) and resulted in residual instability. The left posterior SCJ dislocation was asymptomatic and unnoticed for six months. It is important for ER physicians and orthopaedic surgeons to be able identify and treat this condition. All suspected SCJ dislocations should be evaluated by computed tomography (CT) scan for confirmation of the diagnosis and evaluation of both SCJs. Posterior SCJ dislocation is a potentially fatal injury and should not be overlooked due to the presence of other injuries. Surgical intervention is often necessary in acute and old cases.

  19. Bilateral Asymmetrical Traumatic Sternoclavicular Joint Dislocations

    Science.gov (United States)

    Albarrag, Mohammed K.

    2012-01-01

    Unilateral and bilateral sternoclavicular joint (SCJ) dislocations are rare injuries. The difficulty in assessing this condition often leads to delay in diagnosis and treatment. We report a rare case of bilateral asymmetrical traumatic SCJ dislocations in a 45-year-old male. The right anterior SCJ dislocation was reduced in the emergency room (ER) and resulted in residual instability. The left posterior SCJ dislocation was asymptomatic and unnoticed for six months. It is important for ER physicians and orthopaedic surgeons to be able identify and treat this condition. All suspected SCJ dislocations should be evaluated by computed tomography (CT) scan for confirmation of the diagnosis and evaluation of both SCJs. Posterior SCJ dislocation is a potentially fatal injury and should not be overlooked due to the presence of other injuries. Surgical intervention is often necessary in acute and old cases. PMID:23275851

  20. Asymmetrical Integration: Lessons from a Railway Empire.

    Science.gov (United States)

    McDonald, Kate

    2015-01-01

    This article reexamines railway imperialism in Manchuria from the perspective of global network building. Through a case study of the Japanese-owned South Manchuria Railway Company (SMR), I trace how one railway empire used through traffic agreements to integrate Northeast Asian railways into a global network while at the same time installing itself as the necessary intermediary between European and Asian overland traffic. I argue that the SMR's pursuit of global reach and local dominance compels us to reconsider the traditional division of border-crossing railways into international and imperialist types, and instead to examine how border-crossing railways contributed to the uneven or "asymmetrical" integration of the global transportation infrastructure.

  1. Efficient asymmetric Baeyer–Villiger oxidation of prochiral ...

    Indian Academy of Sciences (India)

    Abstract. Two heterogeneous catalysts 4 and 5 and three homogenous complexes 1–3 were prepared and used for enantioselective .... chromatography (eluent: diethyl ether/hexanes, 1:20). Dissymmetric ligand A was prepared ... dried in vacuo to yield orange beads as Polymer-bound ligand A. Polymer-bound ligand B ...

  2. 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.

  3. 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.

  4. 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.

  5. Homogenous asymmetric hydrogenation: Recent trends and industrial applications.

    Science.gov (United States)

    Palmer, Andreas M; Zanotti-Gerosa, Antonio

    2010-01-01

    Recent advances in the field of homogeneous asymmetric hydrogenation are presented in this review. An analysis of academic literature published in the past 2 years highlights significant advances in the asymmetric hydrogenation of functional groups that previously were considered difficult to hydrogenate, as well as the emergence of novel concepts in catalysis, such as the use of non-traditional metals, phosphine-free catalysts and chiral counterions. An analysis of industry publications from 2009 and 2010 highlights more established applications of asymmetric hydrogenation reactions; these are discussed with a particular focus on practical aspects, such as catalyst selection, experimental conditions and the removal of metal residues.

  6. Coping with Asymmetric Channel Losses in CSMA/CA

    DEFF Research Database (Denmark)

    Paramanathan, Achuthan; Roetter, Daniel Enrique Lucani; Fitzek, Frank

    2013-01-01

    /CA is very sensitive to asymmetric channel losses caused by channel conditions. Leveraging this analysis, we present an adaptive channel priority protocol that copes with asymmetric channel losses while being compatible with CSMA/CA. We implement this protocol and perform real-life measurements that (i......) confirm the sensitivity of the CSMA/CA scheme in real implementations, and (ii) shows that our adaptive protocol provides a simple, yet potent mechanism to cope with asymmetric channel losses and ultimately to enhance end-to-end throughput in high-load scenarios....

  7. 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.

  8. Asymmetric Branching in Biological Resource Distribution Networks

    Science.gov (United States)

    Brummer, Alexander Byers

    There is a remarkable relationship between an organism's metabolic rate (resting power consumption) and the organism's mass. It may be a universal law of nature that an organism's resting metabolic rate is proportional to its mass to the power of 3/4. This relationship, known as Kleiber's Law, appears to be valid for both plants and animals. This law is important because it implies that larger organisms are more efficient than smaller organisms, and knowledge regarding metabolic rates are essential to a multitude of other fields in ecology and biology. This includes modeling the interactions of many species across multiple trophic levels, distributions of species abundances across large spatial landscapes, and even medical diagnostics for respiratory and cardiovascular pathologies. Previous models of vascular networks that seek to identify the origin of metabolic scaling have all been based on the unrealistic assumption of perfectly symmetric branching. In this dissertation I will present a theory of asymmetric branching in self-similar vascular networks (published by Brummer et al. in [9]). The theory shows that there can exist a suite of vascular forms that result in the often observed 3/4 metabolic scaling exponent of Kleiber's Law. Furthermore, the theory makes predictions regarding major morphological features related to vascular branching patterns and their relationships to metabolic scaling. These predictions are suggestive of evolutionary convergence in vascular branching. To test these predictions, I will present an analysis of real mammalian and plant vascular data that shows: (i) broad patterns in vascular networks across entire animal kingdoms and (ii) within these patterns, plant and mammalian vascular networks can be uniquely distinguished from one another (publication in preparation by Brummer et al.). I will also present results from a computational study in support of point (i). Namely, that asymmetric branching may be the optimal strategy to

  9. 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.

  10. Palladium-catalyzed asymmetric silaboration of allenes.

    Science.gov (United States)

    Ohmura, Toshimichi; Taniguchi, Hiroki; Suginome, Michinori

    2006-10-25

    An enantioselective silaboration of allenes was achieved using an achiral silylborane in the presence of a palladium catalyst bearing a chiral monodentate phosphine ligand. (R)-2-Bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivities in the addition of (diphenylmethylsilyl)pinacolborane to the internal C=C bond of terminal allenes at 0 degrees C, giving the corresponding beta-borylallylsilanes in high yields with high enantiomeric excesses. The enantioselectivity depended on the bulkiness of substituents of allenes: the enantiomeric excesses were found to be 91-93% ee (R = tert- and sec-alkyl), 88-90% ee (R = aryl), and 80-82% ee (R = prim-alkyl and Me) at 0 degrees C. Perfect chirality transfer was observed in the intramolecular cyclization reactions of the functionalized allylsilanes, affording highly enantioenriched cyclic alkenylboranes, which underwent Suzuki-Miyaura coupling with aryl halides.

  11. Computation in Dynamically Bounded Asymmetric Systems

    Science.gov (United States)

    Rutishauser, Ueli; Slotine, Jean-Jacques; Douglas, Rodney

    2015-01-01

    Previous explanations of computations performed by recurrent networks have focused on symmetrically connected saturating neurons and their convergence toward attractors. Here we analyze the behavior of asymmetrical connected networks of linear threshold neurons, whose positive response is unbounded. We show that, for a wide range of parameters, this asymmetry brings interesting and computationally useful dynamical properties. When driven by input, the network explores potential solutions through highly unstable ‘expansion’ dynamics. This expansion is steered and constrained by negative divergence of the dynamics, which ensures that the dimensionality of the solution space continues to reduce until an acceptable solution manifold is reached. Then the system contracts stably on this manifold towards its final solution trajectory. The unstable positive feedback and cross inhibition that underlie expansion and divergence are common motifs in molecular and neuronal networks. Therefore we propose that very simple organizational constraints that combine these motifs can lead to spontaneous computation and so to the spontaneous modification of entropy that is characteristic of living systems. PMID:25617645

  12. Asymmetric sensory reweighting in human upright stance.

    Directory of Open Access Journals (Sweden)

    David Logan

    Full Text Available To investigate sensory reweighting as a fundamental property of sensor fusion during standing, we probed postural control with simultaneous rotations of the visual scene and surface of support. Nineteen subjects were presented with pseudo-random pitch rotations of visual scene and platform at the ankle to test for amplitude dependencies in the following conditions: low amplitude vision: high amplitude platform, low amplitude vision: low amplitude platform, and high amplitude vision: low amplitude platform. Gain and phase of frequency response functions (FRFs to each stimulus were computed for two body sway angles and a single weighted EMG signal recorded from seven muscles. When platform stimulus amplitude was increased while visual stimulus amplitude remained constant, gain to vision increased, providing strong evidence for inter-modal reweighting between vision and somatosensation during standing. Intra-modal reweighting of vision was also observed as gains to vision decreased as visual stimulus amplitude increased. Such intra-modal and inter-modal amplitude dependent changes in gain were also observed in muscular activity. Gains of leg segment angle and muscular activity relative to the platform, on the other hand, showed only intra-modal reweighting. That is, changing platform motion amplitude altered the responses to both visual and support surface motion whereas changing visual scene motion amplitude did not significantly affect responses to support surface motion, indicating that the sensory integration scheme between somatosensation (at the support surface and vision is asymmetric.

  13. 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.

  14. Biomechanical reevaluation of orthodontic asymmetric headgear.

    Science.gov (United States)

    Chi, Lu; Cheng, Mulin; Hershey, H Garland; Nguyen, Tung; Ko, Ching-Chang

    2012-07-01

    To investigate the distribution of distal and lateral forces produced by orthodontic asymmetric headgear (AHG) using mathematical models to assess periodontal ligament (PDL) influence and to attempt to resolve apparent inconsistencies in the literature. Mechanical models for AHG were constructed to calculate AHG force magnitudes and direction using the theory of elasticity. The PDL was simulated by elastic springs attached to the inner-bow terminals of the AHG. The total storage energy (E(t)) of the AHG and the supporting springs was integrated to evaluate the distal and lateral forces produced by minimizing E(t) (Castigliano's theorem). All analytical solutions were derived symbolically. The spring-supported headgear model (SSHG) predicted the magnitude and distribution of distal forces consistent with our data and the published data of others. The SSHG model revealed that the lateral forces delivered to the inner-bow terminals were not equal, and the spring constant (stiffness of the PDL) affected the magnitude and direction of the resultant lateral forces. Changing the stiffness of the PDL produced a greater biomechanical effect than did altering the face-bow design. The PDL spring model appeared to help resolve inconsistencies in the literature between laboratory in vitro experiments and clinical in vivo studies. Force magnitude and direction of AHG were predicted precisely using the present model and may be applied to improve the design of AHG to minimize unwanted lateral tooth movement.

  15. Neural Network Control of Asymmetrical Multilevel Converters

    Directory of Open Access Journals (Sweden)

    Patrice WIRA

    2009-12-01

    Full Text Available This paper proposes a neural implementation of a harmonic eliminationstrategy (HES to control a Uniform Step Asymmetrical Multilevel Inverter(USAMI. The mapping between the modulation rate and the requiredswitching angles is learned and approximated with a Multi-Layer Perceptron(MLP neural network. After learning, appropriate switching angles can bedetermined with the neural network leading to a low-computational-costneural controller which is well suited for real-time applications. Thistechnique can be applied to multilevel inverters with any number of levels. Asan example, a nine-level inverter and an eleven-level inverter are consideredand the optimum switching angles are calculated on-line. Comparisons to thewell-known sinusoidal pulse-width modulation (SPWM have been carriedout in order to evaluate the performance of the proposed approach. Simulationresults demonstrate the technical advantages of the proposed neuralimplementation over the conventional method (SPWM in eliminatingharmonics while controlling a nine-level and eleven-level USAMI. Thisneural approach is applied for the supply of an asynchronous machine andresults show that it ensures a highest quality torque by efficiently cancelingthe harmonics generated by the inverters.

  16. Asymmetric evaluation promotes cooperation in network population

    Science.gov (United States)

    Shen, Chen; Li, Xiaoping; Shi, Lei; Deng, Zhenghong

    2017-05-01

    The evolution of cooperation remains a fundamental challenge in human society. Many previous studies investigated these questions via spatial reciprocity, where players obtain their payoffs by interacting with their direct neighbors. It has also been verified that environmental factors can influence the evolution of cooperation theoretically and empirically. In reality, however, individuals may have the limit knowledge about their indirect neighbors. Inspired by this fact, we consider an asymmetric fitness calculation mechanism, which only integrates the environment factors into the focal player, to explore the evolution of cooperation. Here, the environmental factor is defined as the average payoff of all individual neighbors, which is regulated by a tunable parameter u. Through numerical simulation, we find that, compared with the traditional version (u = 0), that the cooperation level can be greatly enhanced when u is positive. Interestingly, the larger the value of u, the higher the level of cooperation. Finally, to explore the generality of this finding, we have tested the results on different topologies.

  17. Catalytic Asymmetric Synthesis of Butenolides and Butyrolactones.

    Science.gov (United States)

    Mao, Bin; Fañanás-Mastral, Martín; Feringa, Ben L

    2017-08-09

    γ-Butenolides, γ-butyrolactones, and derivatives, especially in enantiomerically pure form, constitute the structural core of numerous natural products which display an impressive range of biological activities which are important for the development of novel physiological and therapeutic agents. Furthermore, optically active γ-butenolides and γ-butyrolactones serve also as a prominent class of chiral building blocks for the synthesis of diverse biological active compounds and complex molecules. Taking into account the varying biological activity profiles and wide-ranging structural diversity of the optically active γ-butenolide or γ-butyrolactone structure, the development of asymmetric synthetic strategies for assembling such challenging scaffolds has attracted major attention from synthetic chemists in the past decade. This review offers an overview of the different enantioselective synthesis of γ-butenolides and γ-butyrolactones which employ catalytic amounts of metal complexes or organocatalysts, with emphasis focused on the mechanistic issues that account for the observed stereocontrol of the representative reactions, as well as practical applications and synthetic potentials.

  18. Asymmetrically coupled resonators for mass sensing

    Science.gov (United States)

    Marquez, S.; Alvarez, M.; Plaza, J. A.; Villanueva, L. G.; Dominguez, C.; Lechuga, L. M.

    2017-09-01

    Mechanically coupled resonators have been applied in the last years to the development of nanomechanical mass-sensors based on the detection of the different vibration modes of the system by measuring on a single resonator. Their sensitivity and capability for detecting multiple analytes strongly depends on the design and coupling strength between the mechanically coupled resonators in an array format. We present a theoretical and experimental study of the behavior of an asymmetrically coupled array of four different resonators. These doubly clamped beam resonators are elastically coupled by an overhang region of varying length along the transversal axis of the array. The results show that parameters such as the gap between microbeams and the overhang length affect the coupling strength, tuning the system from highly disordered and highly localized (weak coupling) to highly delocalized (strong coupling). In the strong coupling and partially localized case, the distances between resonant peaks are larger, reaching higher eigenfrequency values. In this case, relative changes in a specific eigenstate, due to an added mass, can be markedly large due to the energy distribution over a single microbeam. A strong coupling also facilitates performing the detection on the relative frequency shift mode, which can usually be resolved with better precision than the amplitude changes.

  19. Performance of an AGATA asymmetric detector

    Energy Technology Data Exchange (ETDEWEB)

    Boston, A.J. [Department of Physics, University of Liverpool, Liverpool L69 7ZE (United Kingdom)], E-mail: ajboston@liv.ac.uk; Dimmock, M.R.; Unsworth, C.; Boston, H.C.; Cooper, R.J.; Grint, A.N.; Harkness, L.J. [Department of Physics, University of Liverpool, Liverpool L69 7ZE (United Kingdom); Lazarus, I.H. [STFC Daresbury Laboratory, Daresbury, Warrington WA4 4AD (United Kingdom); Jones, M.; Nolan, P.J.; Oxley, D.C. [Department of Physics, University of Liverpool, Liverpool L69 7ZE (United Kingdom); Simpson, J. [STFC Daresbury Laboratory, Daresbury, Warrington WA4 4AD (United Kingdom); Slee, M. [Department of Physics, University of Liverpool, Liverpool L69 7ZE (United Kingdom)

    2009-06-01

    High-resolution gamma-ray detectors based on high-purity germanium crystals (HPGe) are one of the key workhorses of experimental nuclear science. The technical development of such detector technology has been dramatic in recent years. Large volume, high-granularity, electrically segmented HPGe detectors have been realised and a methodology to improve position sensitivity using pulse-shape analysis coupled with the novel technique of gamma-ray tracking has been developed. Collaborations have been established in Europe (Advanced GAmma Tracking Array (AGATA)) [J. Simpson, Acta Phys. Pol. B 36 (2005) 1383] and the USA (GRETA/GRETINA) [C.W. Beausang, Nucl. Instr. and Meth. B 204 (2003)] to build gamma-ray tracking spectrometers. This paper discusses the performance of the first AGATA asymmetric detector that has been tested at the University of Liverpool. The use of a fully digital data acquisition system has allowed detector charge pulse shapes from a selection of well-defined photon interaction positions to be analysed, yielding important information on the position sensitivity of the detector.

  20. Micromagnetic simulation of Fe asymmetric nanorings

    Energy Technology Data Exchange (ETDEWEB)

    Palma, J.L.; Morales-Concha, C.; Leighton, B. [Departamento de Fisica, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Altbir, D. [Departamento de Fisica, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Center for the Development of Nanoscience and Nanotechnology (CEDENNA), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Escrig, J., E-mail: jescrigm@gmail.com [Departamento de Fisica, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Center for the Development of Nanoscience and Nanotechnology (CEDENNA), Avda. Ecuador 3493, 917-0124 Santiago (Chile)

    2012-02-15

    During the last decade several methods to control the vortex chirality in nanodots have been proposed. One of them, the introduction of asymmetry in the geometry of the dots, originates interesting effects on the magnetic behavior of the particle. However, asymmetry in core-free structures is also interesting to investigate because of the reproducibility of their magnetic properties. In this work we report systematic changes in the coercivity and remanence in asymmetric nanorings. The angular dependence is also addressed. For specific geometries and magnetic field direction newly reversal modes appear associated with important changes in the coercivity and remanence of the rings. - Highlights: > We report that the existence of asymmetry strongly influences the coercivity and the remanence. > Magnetization reversal is driven by the nucleation of a C state and propagation of a vortex state. > We also conclude that the lack of a core contributes to the stability of the vortex state. > Asymmetry can be useful for tailoring specific magnetic characteristics of these systems.

  1. Trade Credit Insurance and Asymmetric Information Problem

    Directory of Open Access Journals (Sweden)

    Sokolovska Olena

    2017-03-01

    Full Text Available The presence of different risk factors in international trade gives evidence of the necessity of support in gaps that may affect exporters’ activity. To maximize the trade volumes and in the same time to minimize the exporters’ risks the stakeholders use trade credit insurance. The paper provides analysis of conceptual background of the trade credit insurance in the world. We analyzed briefly the problems, arising in insurance markets due to asymmetric information, such as adverse selection and moral hazard. Also we discuss the main stages of development of trade credit insurance in countries worldwide. Using comparative and graphical analysis we provide a brief evaluation of the dynamics of claims and recoveries for different forms of trade credit insurance. We found that the claims related to the commercial risk for medium and long trade credits in recent years exceed the recoveries, while with the political risk the reverse trend holds. And we originally consider these findings in terms of information asymmetry in the trade credit insurance differentiated by type of risk.

  2. High sensitivity field asymmetric ion mobility spectrometer.

    Science.gov (United States)

    Chavarria, Mario A; Matheoud, Alessandro V; Marmillod, Philippe; Liu, Youjiang; Kong, Deyi; Brugger, Jürgen; Boero, Giovanni

    2017-03-01

    A high sensitivity field asymmetric ion mobility spectrometer (FAIMS) was designed, fabricated, and tested. The main components of the system are a 10.6 eV UV photoionization source, an ion filter driven by a high voltage/high frequency n-MOS inverter circuit, and a low noise ion detector. The ion filter electronics are capable to generate square waveforms with peak-to-peak voltages up to 1000 V at frequencies up to 1 MHz with adjustable duty cycles. The ion detector current amplifier has a gain up to 10 12 V/A with an effective equivalent input noise level down to about 1 fA/Hz 1/2 during operation with the ion filter at the maximum voltage and frequency. The FAIMS system was characterized by detecting different standard chemical compounds. Additionally, we investigated the use of a synchronous modulation/demodulation technique to improve the signal-to-noise ratio in FAIMS measurements. In particular, we implemented the modulation of the compensation voltage with the synchronous demodulation of the ion current. The analysis of the measurements at low concentration levels led to an extrapolated limit of detection for acetone of 10 ppt with an averaging time of 1 s.

  3. 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...

  4. High sensitivity field asymmetric ion mobility spectrometer

    Science.gov (United States)

    Chavarria, Mario A.; Matheoud, Alessandro V.; Marmillod, Philippe; Liu, Youjiang; Kong, Deyi; Brugger, Jürgen; Boero, Giovanni

    2017-03-01

    A high sensitivity field asymmetric ion mobility spectrometer (FAIMS) was designed, fabricated, and tested. The main components of the system are a 10.6 eV UV photoionization source, an ion filter driven by a high voltage/high frequency n-MOS inverter circuit, and a low noise ion detector. The ion filter electronics are capable to generate square waveforms with peak-to-peak voltages up to 1000 V at frequencies up to 1 MHz with adjustable duty cycles. The ion detector current amplifier has a gain up to 1012 V/A with an effective equivalent input noise level down to about 1 fA/Hz1/2 during operation with the ion filter at the maximum voltage and frequency. The FAIMS system was characterized by detecting different standard chemical compounds. Additionally, we investigated the use of a synchronous modulation/demodulation technique to improve the signal-to-noise ratio in FAIMS measurements. In particular, we implemented the modulation of the compensation voltage with the synchronous demodulation of the ion current. The analysis of the measurements at low concentration levels led to an extrapolated limit of detection for acetone of 10 ppt with an averaging time of 1 s.

  5. 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.

  6. Experimental study of asymmetric heart valve prototype

    Science.gov (United States)

    Vukicevic, M.; Fortini, S.; Querzoli, G.; Cenedese, A.; Pedrizzetti, G.

    2011-11-01

    The mechanical heart valves (MHVs) are extremely important medical devices, commonly used for diseased heart valves replacement. Despite the long term of use and constant design refinement, the MHVs are very far from ideal and their performance is very diverse from that of the native ones. It has been approved that small variations in geometry of valvular leaflets influence the significant change in the intraventricular vortical flow, known as one of the most important factors for the overall functionality of the heart. We have experimentally examined the home-made heart valve prototypes, exclusively modeled for the mitral valve replacement. The performance and energetic properties of the prototypes have been compared with those in the presence of standard MHVs. The analysis was based on the testing of intraventricular fluid dynamics, usually missing criteria for the quality of the valve performance. It has been shown that the asymmetric prototype, with unequal leaflets and D-shaped orifice produces flow patterns and energetic properties close to those found in the healthy subjects. Thus, the break of symmetry in the standard bi-leaflet MHV prosthesis, at least from the fluid dynamics point of view, is worthwhile to be considered for the design of MHVs for the mitral valve replacement.

  7. Cooperative Supply Chain Management Under Asymmetric Information

    Directory of Open Access Journals (Sweden)

    W.Y. Xu

    2014-04-01

    Full Text Available This study investigates supply chain cooperative management problem. In this study, based on principal-agent, firstly we analyses cooperative management factors in supply chain including leading enterprise expected utilities, subsidiary enterprise expected incomes and leading enterprise agency cost, then the incentive contract model is constructed; Secondly the model is solved in the case of symmetric information and asymmetric information; At last, in order to make clear of the model, this paper does mathematical analysis of leading enterprise expected utilities, subsidiary enterprise expected incomes and leading enterprise agency cost. Some important conclusions are obtained: subsidiary enterprise ability, cost coefficient, absolute risk aversion factor and output variance has the same influence on leading enterprise expected utilities and subsidiary enterprise expected incomes; subsidiary enterprise ability, cost coefficient has the same influence on leading enterprise expected utilities, subsidiary enterprise expected incomes and leading enterprise agency cost; leading enterprise expected utilities and subsidiary enterprise expected incomes become bigger and bigger, but leading enterprise agency cost becomes smaller and smaller with absolute risk aversion factor and output variance decreased. etc. Leading enterprise can take on incentive measures (improving subsidiary enterprise ability, decreasing subsidiary enterprise cost coefficient.etc to optimize supply chain management based on the common factors.

  8. Crystallization in mass and charge asymmetric bilayers

    Science.gov (United States)

    Bonitz, Michael; Ludwig, Patrick; Filinov, Alexei; Lozovik, Yurii; Stolz, Heinrich

    2007-11-01

    We consider Coulomb crystal formation in quantum electron-ion (hole) bilayers. Varying the mass ratio M of ions and electrons between 1 and 100 for a fixed layer separation d at low temperature and high density, one can tune the hole behavior from delocalized (quantum) to localized (quasi-classical) while the electrons remain delocalized all the time. While in 3D plasmas [1], ions crystallize if the mass ratio exceeds a critical value of Mcr˜80, in bilayers Mcr can be drastically reduced by properly choosing d and the in-layer particle density. The complicated overlap of correlation and quantum effects of both, electrons and holes, is fully taken care of by performing first-principle path integral Monte Carlo simulations. [1] M. Bonitz, V.S. Filinov, V.E. Fortov. P.R. Levashov, and H. Fehske, Phys. Rev. Lett. 95, 235006 (2005) and J. Phys. A: Math. Gen. 39, 4717 (2006). [2] P. Ludwig, A. Filinov, Yu. Lozovik, H. Stolz, and M. Bonitz, Crystallization in mass-asymmetric electron-hole bilayers, Contrib. Plasma Phys. (2007), ArXiv: cond-mat/0611556

  9. Bitopic Ligands and Metastable Binding Sites

    DEFF Research Database (Denmark)

    Fronik, Philipp; Gaiser, Birgit I; Sejer Pedersen, Daniel

    2017-01-01

    G protein-coupled receptors (GPCRs) belong to a large superfamily of membrane receptors mediating a variety of physiological functions. As such they are attractive targets for drug therapy. However, it remains a challenge to develop subtype selective GPCR ligands due to the high conservation...... sites. Computational studies on ligand binding to GPCRs have revealed transient, low-affinity binding sites, termed metastable binding sites. Metastable binding sites may provide a new source of allosteric binding sites that could be exploited in the design of bitopic ligands. Unlike the bitopic ligands...

  10. Clinical Use of PPARγ Ligands in Cancer

    Directory of Open Access Journals (Sweden)

    Jennifer L. Hatton

    2008-01-01

    Full Text Available The role of PPARγ in adipocyte differentiation has fueled intense interest in the function of this steroid nuclear receptor for regulation of malignant cell growth and differentiation. Given the antiproliferative and differentiating effects of PPARγ ligands on liposarcoma cells, investigation of PPARγ expression and ligand activation in other solid tumors such as breast, colon, and prostate cancers ensued. The anticancer effects of PPARγ ligands in cell culture and rodent models of a multitude of tumor types suggest broad applicability of these agents to cancer therapy. This review focuses on the clinical use of PPARγ ligands, specifically the thiazolidinediones, for the treatment and prevention of cancer.

  11. 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.

  12. 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.

  13. 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.

  14. 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...

  15. 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...... 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...... sediments, the diapir extruded an overhang. Using the asymmetric Klodawa Salt Structure (KSS) in central Poland as a prototype, a series of analogue models were carried out to investigate the evolution history and salt supply driven by asymmetric differential loading. During extension of the model, a daipir...

  16. Luminosity lifetime at an asymmetric e +e - collider

    Science.gov (United States)

    Porter, Frank C.

    1991-04-01

    The dependence of the luminosity on time is discussed for an asymmetric e +e - storage ring collider, with emphasis on single-particle scattering mechanisms for beam loss. The "optimal" filling strategy and average luminosity obtainable are also reviewed.

  17. 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.

  18. Asymmetric wave transmission in a diatomic acoustic/elastic metamaterial

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bing; Tan, K. T., E-mail: ktan@uakron.edu [Department of Mechanical Engineering, The University of Akron, Akron, Ohio 44325-3903 (United States)

    2016-08-21

    Asymmetric acoustic/elastic wave transmission has recently been realized using nonlinearity, wave diffraction, or bias effects, but always at the cost of frequency distortion, direction shift, large volumes, or external energy. Based on the self-coupling of dual resonators, we propose a linear diatomic metamaterial, consisting of several small-sized unit cells, to realize large asymmetric wave transmission in low frequency domain (below 1 kHz). The asymmetric transmission mechanism is theoretically investigated, and numerically verified by both mass-spring and continuum models. This passive system does not require any frequency conversion or external energy, and the asymmetric transmission band can be theoretically predicted and mathematically controlled, which extends the design concept of unidirectional transmission devices.

  19. Asymmetric MRI Systems: Shim and RF Coil Designs

    National Research Council Canada - National Science Library

    Crozier, S

    2001-01-01

    We have recently introduced the concept of asymmetric clinical MRI systems. The potential advantages of these systems include a reduced perception of claustrophobia by patients and better physician access to the patient...

  20. Pseudo-Goldstone modes in isospin-asymmetric nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, T.D. [Univ. of Washington, Seattle, WA (United States); Broniowski, W. [H. Niewodniczanski Institute of Nuclear Physics, Cracow (Poland)

    1995-01-01

    The authors analyze the chiral limit in dense isospin-asymmetric nuclear matter. It is shown that the pseudo-Goldstone modes in this system are qualitatively different from the case of isospin-symmetric matter.

  1. Pseudo-Goldstone modes in isospin-asymmetric nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, T.D. [Washington Univ., Seattle, WA (United States). Dept. of Physics; Broniowski, W. [Institute of Nuclear Physics, Cracow (Poland)

    1994-12-01

    We analyze the chiral limit in dense isoptin-asymmetric nuclear matter. It is shown that the pseudo-Goldstone modes in this system are qualitatively different from the case of isospin-symmetric matter. (author). 20 refs.

  2. Influence of temperature gradients on charge transport in asymmetric nanochannels

    NARCIS (Netherlands)

    Benneker, Anne M.; Wendt, Hans David; Lammertink, Rob G.H.; Wood, Jeffery A.

    2017-01-01

    Charge selective asymmetric nanochannels are used for a variety of applications, such as nanofluidic sensing devices and energy conversion applications. In this paper, we numerically investigate the influence of an applied temperature difference over tapered nanochannels on the resulting charge

  3. Non-stationary probabilities for the asymmetric exclusion process on ...

    Indian Academy of Sciences (India)

    stationary probabilities for the asymmetric exclusion process on a ring. V B Priezzhev. Invited Talks:- Topic 4: Pattern formation in systems out of equilibrium (growth processes, fracture, hydrodynamic instabilities, chemical reactions, granular flows, etc ...

  4. Catalytic asymmetric alkylation of ketones using organometallic reagents

    NARCIS (Netherlands)

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

    2013-01-01

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

  5. Optical detection of asymmetric bacteria utilizing electro orientation

    OpenAIRE

    Choi, Jae-Woo; Pu, Allen; Psaltis, Demetri

    2006-01-01

    We propose a bacterial detection scheme which uses no biochemical markers and can be applied in a Point-of-Care setting. The detection scheme aligns asymmetric bacteria with an electric field and detects the optical scattering.

  6. Loss aversion and the asymmetric transmission of monetary policy

    NARCIS (Netherlands)

    Gaffeo, E.; Petrella, I.; Pfajfar, D.; Santoro, E.

    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

  7. Asymmetric continuum extreme processes in solids and fluids

    CERN Document Server

    Teisseyre, Roman

    2014-01-01

    This book deals with a class of basic deformations in asymmetric continuum theory. It describes molecular deformations and transport velocities in fluids, strain deformations in solids as well as the molecular transport, important in fracture processes.

  8. Asymmetric radiation transfer based on linear light-matter interaction

    Science.gov (United States)

    Jia, Zi-xun; Shuai, Yong; Zhang, Jia-hui; Tan, He-ping

    2017-11-01

    In this paper, asymmetric radiation transfer based on linear light-matter interaction has been proposed. Two naturally different numerical methods, finite difference time domain (FDTD) and rigorous coupled wave analysis (RCWA), are utilized to verify that asymmetric radiation transfer can exist for linear plasmonic meta-material. The overall asymmetry has been introduced to evaluate bifacial transmission. Physics for the asymmetric optical responses have been understood via electromagnetic field distributions. Dispersion relation for surface plasmon polariton (SPP) and temporal coupled mode theory (TCMT) have been employed to verify the physics discussed in the paper. Geometric effects and the disappearing of asymmetric transmission have also been investigated. The results gained herein broaden the cognition of linear optical system, facilitate the design of novel energy harvesting device.

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

    OpenAIRE

    Zawar V

    2003-01-01

    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.

  10. Hodge operator and asymmetric fluid in unbounded domains

    Directory of Open Access Journals (Sweden)

    I. Kondrashuk

    2009-01-01

    Full Text Available A system of equations modeling the stationary flow of an incompressible asymmetric fluid is studied for bounded domains of an arbitrary form. Based on the methods of Clifford analysis, we write the system of asymmetric fluid in the hypercomplex formulation and represent its solution in Clifford operator terms. We have significantly used Clifford algebra, and in particular the Hodge operator of the Clifford algebra to demonstrate the existence and uniqueness of the strong solution for arbitrary unbounded domains.

  11. Hodge operator and asymmetric fluid in unbounded domains

    Directory of Open Access Journals (Sweden)

    I. kondrashuk

    2009-06-01

    Full Text Available A system of equations modeling the stationary flow of an incompressible asymmetric fluid is studied for bounded domains of an arbitrary form. Based on the methods of Clifford analysis, we write the system of asymmetric fluid in the hypercomplex formulation and represent its solution in Clifford operator terms. We have significantly used Clifford algebra, and in particular the Hodge operator of the Clifford algebra to demonstrate the existence and uniqueness of the strong solution for arbitrary unbounded domains.

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

    Directory of Open Access Journals (Sweden)

    Jarmila VOJTKOVÁ

    2015-12-01

    Full Text Available 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.

  13. Oil prices and economic activity: An asymmetric cointegration approach

    Energy Technology Data Exchange (ETDEWEB)

    Lardic, Sandrine [EconomiX-CNRS, University of Paris 10 (France); Mignon, Valerie [EconomiX-CNRS, University of Paris 10 (France); CEPII, Paris (France)

    2008-05-15

    The aim of this paper is to study the long-term relationship between oil prices and economic activity, proxied by GDP. To account for asymmetries existing in the links between the two variables, we propose an approach based on asymmetric cointegration. Our empirical analysis concerns the U.S. economy, but also the G7, Europe and Euro area economies. Results indicate that, while standard cointegration is rejected, there is evidence for asymmetric cointegration between oil prices and GDP. (author)

  14. Circular motion of asymmetric self-propelling particles.

    Science.gov (United States)

    Kümmel, Felix; ten Hagen, Borge; Wittkowski, Raphael; Buttinoni, Ivo; Eichhorn, Ralf; Volpe, Giovanni; Löwen, Hartmut; Bechinger, Clemens

    2013-05-10

    Micron-sized self-propelled (active) particles can be considered as model systems for characterizing more complex biological organisms like swimming bacteria or motile cells. We produce asymmetric microswimmers by soft lithography and study their circular motion on a substrate and near channel boundaries. Our experimental observations are in full agreement with a theory of Brownian dynamics for asymmetric self-propelled particles, which couples their translational and orientational motion.

  15. Dynamic and Asymmetric Adjustment in Beef and Pork Prices

    OpenAIRE

    Hahn, William F.

    2010-01-01

    Beef and pork prices at farm, wholesale and retail are examined for evidence of a dynamic and asymmetric price transmission using an endogenous switching model. Dynamic adjustment means that it take time for prices to adjust to changes in the market. Price transmission is asymmetric if the speed or completeness of price adjustment depends on the direction that the price or a related price is moving. Some of the previous research on price transmission in agricultural markets attempts to use ma...

  16. Asymmetric dominance and the stability of constructed preferences

    OpenAIRE

    Anyuan Shen; Shuguang Liu

    2016-01-01

    In this research, we explore how experience with an "attraction set" of options, designed to elicit an asymmetric-dominance (attraction) effect, affects choice making in a second "compromise set" designed to elicit a compromise effect. In Experiment 1, when a compromise set was presented, subjects who had chosen an asymmetrically dominating option from an attraction set were less likely to surrender to the compromise heuristic than their counterparts who had chosen the equiv...

  17. Asymmetric strand segregation: epigenetic costs of genetic fidelity?

    Directory of Open Access Journals (Sweden)

    Diane P Genereux

    2009-06-01

    Full Text Available Asymmetric strand segregation has been proposed as a mechanism to minimize effective mutation rates in epithelial tissues. Under asymmetric strand segregation, the double-stranded molecule that contains the oldest DNA strand is preferentially targeted to the somatic stem cell after each round of DNA replication. This oldest DNA strand is expected to have fewer errors than younger strands because some of the errors that arise on daughter strands during their synthesis fail to be repaired. Empirical findings suggest the possibility of asymmetric strand segregation in a subset of mammalian cell lineages, indicating that it may indeed function to increase genetic fidelity. However, the implications of asymmetric strand segregation for the fidelity of epigenetic information remain unexplored. Here, I explore the impact of strand-segregation dynamics on epigenetic fidelity using a mathematical-modelling approach that draws on the known molecular mechanisms of DNA methylation and existing rate estimates from empirical methylation data. I find that, for a wide range of starting methylation densities, asymmetric -- but not symmetric -- strand segregation leads to systematic increases in methylation levels if parent strands are subject to de novo methylation events. I found that epigenetic fidelity can be compromised when enhanced genetic fidelity is achieved through asymmetric strand segregation. Strand segregation dynamics could thus explain the increased DNA methylation densities that are observed in structured cellular populations during aging and in disease.

  18. Formation of asymmetric vesicles via phospholipase D-mediated transphosphatidylation.

    Science.gov (United States)

    Takaoka, Rina; Kurosaki, Haruko; Nakao, Hiroyuki; Ikeda, Keisuke; Nakano, Minoru

    2018-02-01

    Most biomembranes have an asymmetric structure with regard to phospholipid distribution between the inner and outer leaflets of the lipid bilayers. Control of the asymmetric distribution plays a pivotal role in several cellular functions such as intracellular membrane fusion and cell division. The mechanism by which membrane asymmetry and its alteration function in these transformation processes is not yet clear. To understand the significance of membrane asymmetry on trafficking and metabolism of intracellular vesicular components, a system that experimentally reproduces the asymmetric nature of biomembranes is essential. Here, we succeeded in obtaining asymmetric vesicles by means of transphosphatidylation reactions with phospholipase D (PLD), which acts exclusively on phosphatidylcholine (PC) present in the outer leaflet of vesicles. By treating PC vesicles with PLD in the presence of 1.7M serine and 0.3M ethanolamine, we obtained asymmetric vesicles that are topologically similar to intracellular vesicles containing phosphatidylserine and phosphatidylethanolamine in the cytosolic leaflet. PLD and other unwanted compounds could be removed by trypsin digestion followed by dialysis. Our established technique has a great advantage over conventional methods in that asymmetric vesicles can be provided at high yield and high efficiency, which is requisite for most physicochemical assays. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Macrocyclic ligands for uranium complexation

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.

    1991-04-01

    A highly preorganized 24-macrocycle containing biuret, thiobiuret and pyridine subunits has been prepared by high dilution ring-closure procedures. Intermediate products to this macrocycle have been utilized to extend this synthetic route to include further representatives where solubility and stability will be influenced by substituent variation. A 1:1 complex has been formed from uranyl acetate and a quinquepyridine derivative, this representing a new type of ligand for the uranyl ion. A very convenient synthetic procedure that will allow the incorporation of these macrocycles into polymeric systems has been developed for the introduction of a vinyl substituent into the 4-position of the pyridine ring. Using triflate, vinyltributyltin and Pd{sup 0} chemistry, this procedure should make a variety of substituted 4-vinylpyridines available for the first time. 3 refs.

  20. Affective privilege: Asymmetric interference by emotional distracters

    Directory of Open Access Journals (Sweden)

    Crystal eReeck

    2011-09-01

    Full Text Available Numerous theories posit that affectively salient stimuli are privileged in their capacity to capture attention and disrupt ongoing cognition. Two underlying assumptions in this theoretical position are that the potency of affective stimuli transcends task boundaries (i.e., emotional distracters do not have to belong to a current task-set to disrupt processing and that there is an asymmetry between emotional and cognitive processing (i.e., emotional distracters disrupt cognitive processing, but not vice versa. These assumptions have remained largely untested, as common experimental probes of emotion-cognition interaction rarely manipulate task-relevance and only examine one side of the presumed asymmetry of interference. To test these propositions directly, a face-word Stroop protocol was adapted to independently manipulate (a the congruency between target and distracter stimulus features, (b the affective salience of distracter features, and (c the task-relevance of emotional compared to non-emotional target features. A three-way interaction revealed interdependent effects of distracter relevance, congruence, and affective salience. Compared to task-irrelevant distracters, task-relevant congruent distracters facilitated performance and task-relevant incongruent distracters impaired performance, but the latter effect depended on the nature of the target feature and task. Specifically, task-irrelevant emotional distracters resulted in equivalent performance costs as task-relevant non-emotional distracters, whereas task-irrelevant non-emotional distracters did not produce performance costs comparable to those generated by task-relevant emotional distracters. These results document asymmetric cross-task interference effects for affectively salient stimuli, supporting the notion of affective prioritization in human information processing.

  1. 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.

  2. 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.

  3. Ligand-binding kinetics on histamine receptors

    NARCIS (Netherlands)

    Bosma, Reggie; Mocking, T.A.M.; Leurs, R.; Vischer, H.F.

    2017-01-01

    Equilibrium-binding affinities of ligands for a drug target do not always accurately reflect the success of drug candidates in the clinic. Affinity-based predictions concerning competitive antagonism on the target will only be accurate if equilibrium binding of both ligands is allowed. Unless

  4. Ligand based pharmacophore modelling of anticancer histone ...

    African Journals Online (AJOL)

    USER

    2010-06-21

    Jun 21, 2010 ... deacetylases (HDAC) have emerged as an important class of anticancer agents. Various side effects like myocardium damage and ... calculated through the software Jmol. The proposed model has been .... The study was carried out using the software Ligand Scout (version. 2.03[i2_001]). Ligand Scout is a ...

  5. Simple tertiary phosphines to hexaphosphane ligands: Syntheses ...

    Indian Academy of Sciences (India)

    Abstract. Designing efficient phosphorus-based ligands to make catalysts for homogeneous catalysis has been a great challenge for chemists. Despite a plethora of phosphorus ligands ranging from simple tertiary phosphines to polyphosphines are known, the enthusiasm to generate new ones is mainly due to the demand.

  6. Organotellurium ligands – designing and complexation reactions

    Indian Academy of Sciences (India)

    Unknown

    Abstract. 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 ...

  7. CXCR4 Ligands : The Next Big Hit?

    NARCIS (Netherlands)

    Walenkamp, Annemiek M. E.; Lapa, Constantin; Herrmann, Ken; Wester, Hans-Juergen

    2017-01-01

    The G protein-coupled protein receptor C-X-C chemokine receptor 4 (CXCR4) is an attractive target for cancer diagnosis and treatment, as it is overexpressed in many solid and hematologic cancers. Binding of its ligand, C-X-C chemokine ligand 12 (CXCL12), results in receptor internalization and

  8. Flexible ligand docking using a genetic algorithm

    Science.gov (United States)

    Oshiro, C. M.; Kuntz, I. D.; Dixon, J. Scott

    1995-04-01

    Two computational techniques have been developed to explore the orientational and conformational space of a flexible ligand within an enzyme. Both methods use the Genetic Algorithm (GA) to generate conformationally flexible ligands in conjunction with algorithms from the DOCK suite of programs to characterize the receptor site. The methods are applied to three enzyme-ligand complexes: dihydrofolate reductase-methotrexate, thymidylate synthase-phenolpthalein and HIV protease-thioketal haloperidol. Conformations and orientations close to the crystallographically determined structures are obtained, as well as alternative structures with low energy. The potential for the GA method to screen a database of compounds is also examined. A collection of ligands is evaluated simultaneously, rather than docking the ligands individually into the enzyme.

  9. 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.

  10. Vanadium Complexes with Hydrazone or Thiosemicarbazone Ligands as Potential Anti-Mycobacterium tuberculosis Agents.

    Science.gov (United States)

    de Souza, Paula C; Maia, Pedro I S; de Barros, Heloisa B; Leite, Clarice Q F; Deflon, Victor M; Pavan, Fernando R

    2015-01-01

    Tuberculosis (TB) is an infectious disease caused mainly by Mycobacterium tuberculosis (MTB) and still an important public health problem worldwide. Some factors like the emergence of multidrug resistant (MDR) and extensively drug-resistant (XDR) strains make urgent the research of new active compounds. Searching for new inorganic compounds against TB, three new dioxovanadium(V) complexes were obtained upon reaction of [VO(acac)2] with hydrazone and thiosemicarbazone ligands derived from di-2-pyridyl ketone. Spectroscopic studies and X-ray crystallography revealed asymmetrically oxo bridged binuclear complexes of the type [{VO(L(1,2))}2(μ-O)2], involving the hydrazone ligands, while a mononuclear square pyramidal complex of the type [VO2(L(3))] was formed with the thiosemicarbazone ligand. The compounds were tested against M. tuberculosis and three of them, with MICs values between 2.00 and 3.76 μM were considered promising for TB treatment. Such MIC values are comparable or better than those found for some drugs currently used in TB treatment.

  11. 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.

  12. Asymmetrical dimethylarginine level in atrial fibrillation.

    Science.gov (United States)

    Cengel, Atiye; Sahinarslan, Asife; Biberoğlu, Gursel; Hasanoğlu, Alev; Tavil, Yusuf; Tulmaç, Murat; Ozdemir, Murat

    2008-02-01

    Atrial fibrillation (AF) is known to be related with increased risk of thromboembolic events. Asymmetrical dimethylarginine (ADMA), which is an endogenous inhibitor of nitric oxide synthase (NOS), can cause endothelial dysfunction by decreasing nitric oxide (NO) and lead to increased risk of thrombosis. In the present study our aim was to compare plasma levels of ADMA in patients with acute onset ( 1 year) to determine the risk of thrombosis. 17 patients with the first detected attack of AF within the first 24 hours of presentation (group 1), 25 patients who had permanent chronic AF lasting at least 1 year or more (group II) and 18 healthy persons as the control group (group III) were included in the study. For each patient the plasma ADMA, L-arginine, symmetrical dimethylarginine (SDMA) concentrations were measured by high-performance liquid chromatography in venous blood samples collected before cardioversion. We compared the plasma ADMA, L-arginine and SDMA concentrations between the groups. Plasma L-arginine (78.18 +/- 28.29 vs. 73.14 +/- 14.11 vs. 71.03 +/- 21.31, P = 0.549) and plasma SDMA concentrations (0.38 +/-0.18 vs. 0.42 +/- 0.21 vs. 0.32 +/- 0.24, P = 0.224) were similar in all groups. There was a significant difference between plasma ADMA concentrations (0.76 +/- 0.27 vs. 0.50 +/- 0.26 vs. 0.36 +/- 0.20, P < 0.001) among the groups. When we compared plasma ADMA levels between the subgroups, we also found a significant difference (P = 0.002 when comparing group I and group II, P < 0.001 when comparing of group I and group III, P = 0.042 when compareng of group II and group III). ADMA levels in patients with acute onset AF were significantly increased when compared with patients with chronic AF and the healthy control group indicating the presence of endothelial dysfunction and a prothrombotic state even in a very early phase of AF.

  13. Asymmetric dimethylarginine and coronary collateral vessel development.

    Science.gov (United States)

    Kocaman, Sinan Altan; Sahinarslan, Asife; Biberoglu, Gursel; Hasanoglu, Alev; Akyel, Ahmet; Timurkaynak, Timur; Cengel, Atiye

    2008-11-01

    Nitric oxide (NO) plays a major role in collateral vessel development. Asymmetric dimethylarginine (ADMA) that is an endogenous inhibitor of NO synthesis may impair the effective coronary collateral vessel development. The aim of this study was to evaluate the relationship between plasma ADMA level and coronary collateral vessel development. The patients with a greater than or equal to 95% obstruction in at least one epicardial coronary artery were included in the study. Degree of coronary collateral development was determined according to Rentrop method. Patients with grade 2-3 collateral development were regarded as good collateral group and formed group I. The patients with grade 0-1 collateral development were regarded as poor collateral group and were included in group II. Group III that had been formed as a control group included the patients with a normal coronary angiogram. We compared the plasma ADMA, symmetric dimethylarginine, L-arginine/ADMA ratio among three groups. Seventy-four patients have been included in the study. Patients with good collateral development had lower plasma ADMA level in comparison with patients with poor collateral development (0.41+/-0.25 micromol/l vs. 0.70+/-0.23 micromol/l, P=0.001) and had similar plasma ADMA levels with the patients who have normal coronary arteries. When we compared L-arginine/ADMA ratio between good and poor collateral groups, we found that the patients with higher L-arginine/ADMA ratio have significantly better collateral development (270.8+/-168.0 vs. 120.9+/-92.1, P<0.001). In the analyses comparing Rentrop score with ADMA level and L-arginine/ADMA ratio, there were significant correlations (r=-0.444, P=0.008 and r=0.553, P=0.001, respectively). In multivariate analysis, ADMA level (odds ratio, 0.009; 95% confidence interval, 0.000-0.466, P=0.020) and L-arginine/ADMA ratio (odds ratio, 1.010; 95% confidence interval, 1.001-1.020, P=0.032) were independent predictors of collateral development. Increased

  14. 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

  15. Necessary and sufficient conditions for the asymmetric synthesis of chiral amines using ω-aminotransferases.

    Science.gov (United States)

    Seo, Joo-Hyun; Kyung, Dohyun; Joo, Keehyoung; Lee, Jooyoung; Kim, Byung-Gee

    2011-02-01

    The half reactions of ω-aminotransferase (ω-AT) from Vibrio fluvialis JS17 (ω-ATVf) were carried out using purified pyridoxal 5'-phosphate-enzyme (PLP-Enz) and pyridoxamine 5'-phosphate-enzyme (PMP-Enz) complexes to investigate the relative activities of substrates. In the reaction generating PMP-Enz from PLP-Enz using L-alanine as an amine donor, L-alanine showed about 70% of the initial reaction rate of (S)-α-methylbenzylamine ((S)-α-MBA). However, in the subsequent half reaction recycling PLP-Enz from PMP-Enz using acetophenone as an amine acceptor, acetophenone showed nearly negligible reactivity compared to pyruvate. These results indicate that the main bottleneck in the asymmetric synthesis of (S)-α-MBA lies not in the amination of PLP by alanine, but in the amination of acetophenone by PMP-Enz, where conformational restraints of the enzyme structure is likely to be the main reason for limiting the amine group transfer from PMP-Enz to acetophenone. Based upon those half reaction experiments using the two amino acceptors of different activity, it appears that the relative activities of the two amine donors and the two acceptors involved in the ω-AT reactions can roughly determine the asymmetric synthesis yield of the target chiral amine compound. Predicted conversion yields of several target chiral amines were calculated and compared with the experimental conversion yields. Approximately, a positive linear correlation (Pearson's correlation coefficient = 0.92) was observed between the calculated values and the experimental conversion yields. To overcome the low (S)-α-MBA productivity of ω-ATVf caused by the possible disadvantageous structural constraints for acetophenone, new ω-ATs showing higher affinity to benzene ring of acetophenone than ω-ATVf were computationally screened using comparative modeling and protein-ligand docking. ω-ATs from Streptomyces avermitilis MA-4680 (SAV2612) and Agrobacterium tumefaciens str. C58 (Atu4761) were

  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. Chemistry of marine ligands and siderophores.

    Science.gov (United States)

    Vraspir, Julia M; Butler, Alison

    2009-01-01

    Marine microorganisms are presented with unique challenges to obtain essential metal ions required to survive and thrive in the ocean. The production of organic ligands to complex transition metal ions is one strategy to both facilitate uptake of specific metals, such as iron, and to mitigate the potential toxic effects of other metal ions, such as copper. A number of important trace metal ions are complexed by organic ligands in seawater, including iron, cobalt, nickel, copper, zinc, and cadmium, thus defining the speciation of these metal ions in the ocean. In the case of iron, siderophores have been identified and structurally characterized. Siderophores are low molecular weight iron-binding ligands produced by marine bacteria. Although progress has been made toward the identity of in situ iron-binding ligands, few compounds have been identified that coordinate the other trace metals. Deciphering the chemical structures and production stimuli of naturally produced organic ligands and the organisms they come from is fundamental to understanding metal speciation and bioavailability. The current evidence for marine ligands, with an emphasis on siderophores, and discussion of the importance and implications of metal-binding ligands in controlling metal speciation and cycling within the world's oceans are presented.

  18. 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.

  19. Distribution of quantum Fisher information in asymmetric cloning machines.

    Science.gov (United States)

    Xiao, Xing; Yao, Yao; Zhou, Lei-Ming; Wang, Xiaoguang

    2014-12-08

    An unknown quantum state cannot be copied and broadcast freely due to the no-cloning theorem. Approximate cloning schemes have been proposed to achieve the optimal cloning characterized by the maximal fidelity between the original and its copies. Here, from the perspective of quantum Fisher information (QFI), we investigate the distribution of QFI in asymmetric cloning machines which produce two nonidentical copies. As one might expect, improving the QFI of one copy results in decreasing the QFI of the other copy. It is perhaps also unsurprising that asymmetric phase-covariant cloning outperforms universal cloning in distributing QFI since a priori information of the input state has been utilized. However, interesting results appear when we compare the distributabilities of fidelity (which quantifies the full information of quantum states), and QFI (which only captures the information of relevant parameters) in asymmetric cloning machines. Unlike the results of fidelity, where the distributability of symmetric cloning is always optimal for any d-dimensional cloning, we find that any asymmetric cloning outperforms symmetric cloning on the distribution of QFI for d ≤ 18, whereas some but not all asymmetric cloning strategies could be worse than symmetric ones when d > 18.

  20. 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.

  1. 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.

  2. Asymmetric MRI Magnet Design Using a Hybrid Numerical Method

    Science.gov (United States)

    Zhao, Huawei; Crozier, Stuart; Doddrell, David M.

    1999-12-01

    This paper describes a hybrid numerical method for the design of asymmetric magnetic resonance imaging magnet systems. The problem is formulated as a field synthesis and the desired current density on the surface of a cylinder is first calculated by solving a Fredholm equation of the first kind. Nonlinear optimization methods are then invoked to fit practical magnet coils to the desired current density. The field calculations are performed using a semi-analytical method. A new type of asymmetric magnet is proposed in this work. The asymmetric MRI magnet allows the diameter spherical imaging volume to be positioned close to one end of the magnet. The main advantages of making the magnet asymmetric include the potential to reduce the perception of claustrophobia for the patient, better access to the patient by attending physicians, and the potential for reduced peripheral nerve stimulation due to the gradient coil configuration. The results highlight that the method can be used to obtain an asymmetric MRI magnet structure and a very homogeneous magnetic field over the central imaging volume in clinical systems of approximately 1.2 m in length. Unshielded designs are the focus of this work. This method is flexible and may be applied to magnets of other geometries.

  3. A NOVEL CHIRAL GALLIUM LEWIS ACID CATALYST WITH SEMI-CROWN LIGAND IN AQUEOUS ASYMMETRIC MUKAIYAMA ALDOL REACTIONS. (R828129)

    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...

  4. 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.

  5. 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

  6. 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 ...... 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.......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...

  7. Solitary waves in asymmetric electron-positron-ion plasmas

    Science.gov (United States)

    Lu, Ding; Li, Zi-Liang; Xie, Bai-Song

    2015-10-01

    > By solving the coupled equations of the electromagnetic field and electrostatic potential, we investigate solitary waves in an asymmetric electron-positron plasma and/or electron-positron-ion plasmas with delicate features. It is found that the solutions of the coupled equations can capture multipeak structures of solitary waves in the case of cold plasma, which are left out by using the long-wavelength approximation. By considering the effect of ion motion with respect to non-relativistic and ultra-relativistic temperature plasmas, we find that the ions' mobility can lead to larger-amplitude solitary waves; especially, this becomes more obvious for a high-temperature plasma. The effects of asymmetric temperature between electrons and positrons and the ion fraction on the solitary waves are also studied and presented. It is shown that the amplitudes of solitary waves decrease with positron temperature in asymmetric temperature electron-positron plasmas and decrease also with ion concentration.

  8. 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.

  9. Left-Right Asymmetrical Development of the Proepicardium

    Directory of Open Access Journals (Sweden)

    Jan Schlueter

    2013-07-01

    Full Text Available The proepicardium (PE is a cluster of cells that forms on the cardiac inflow tract and gives rise to the epicardium and connective tissue and largely contributes to the coronary vasculature. In many vertebrates, the PE undergoes left-right asymmetrical development. While PE cells and marker genes can be initially found on both sides, only the right-sided PE will fully develop and ultimately deliver cells to the heart. Several signalling inputs, like FGF and BMP signals, are involved in PE induction in the lateral plate mesoderm, as well as during inflow tract formation and, also, control asymmetric PE development. These signalling events will be put into the context of embryonic left-right asymmetry determination. Finally, it will be discussed whether PE development may serve as a readout for asymmetric inflow tract morphogenesis.

  10. 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.

  11. Abel inversion of asymmetric plasma density profile at Aditya tokamak

    Science.gov (United States)

    Joshi, N. Y.; Atrey, P. K.; Pathak, S. K.

    2010-02-01

    In Aditya tokamak, at Institute for Plasma Research, till now, multi-channel microwave interferometer system is used to measure the cord averaged plasma density at predefined radial position. An inversion code is developed to determine the local density profile from the chord average density measurement of radially asymmetric plasma. The radial density profile is interpolated using Spline interpolation analytical technique for symmetric plasma density profile. Code implements the Slice and Stack method to determine localized density from asymmetric averaged plasma density measurement from interferometer. Inverted results are tested with various monotonically varying asymmetric radial density profiles of the plasma shots. It also provides the poloidal picture of plasma density distribution with circular constant density surfaces. Localized density measurements, which is very important for successful operation of tokamak, is in agreement with observation of other diagnostics.

  12. Asymmetric microscope; Fusho no kenbisho {exclamation_point}?

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Tadashi. [Tokyo Institute of Technology, Tokyo (Japan)

    1999-07-01

    It is difficult for a conventional optical analysis means to determine the configuration of a substance with an ultra low optical purity. Recently, an asymmetric microscope has been reported as a new concept for solving the above-mentioned problem. Specifically, a product with slight asymmetry is obtained by using the substance with an ultra low optical purity as the chiral initiation, and then the asymmetry of the product is amplified dramatically due to the asymmetric autocatalysis, thus obtaining a product having a high optical purity. A new means is to determine the configuration of the original substance having the low optical purity from the configuration of the substance having the high optical purity. According to this method, the chirality of the substance having the low optical purity is transcribed to alkanol, and the chirality is amplified due to the asymmetric autocatalysis, thus the absolute configuration of the original compound can be determined from the absolute configuration of the final product. (NEDO)

  13. 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

    2014-06-03

    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.

  14. Ligand based pharmacophore modelling of anticancer histone ...

    African Journals Online (AJOL)

    USER

    2010-06-21

    Jun 21, 2010 ... for designing the pharmacophore onto the set of 70 compounds of three different classes and two subclasses. ... More effective anticancer drug production with novel modes of action .... with Ligand Scout using default settings.

  15. Controlling Signal Transduction with Synthetic Ligands

    Science.gov (United States)

    Spencer, David M.; Wandless, Thomas J.; Schreiber, Stuart L.; Crabtree, Gerald R.

    1993-11-01

    Dimerization and oligomerization are general biological control mechanisms contributing to the activation of cell membrane receptors, transcription factors, vesicle fusion proteins, and other classes of intra- and extracellular proteins. Cell permeable, synthetic ligands were devised that can be used to control the intracellular oligomerization of specific proteins. To demonstrate their utility, these ligands were used to reduce intracellular oligomerization of cell surface receptors that lacked their transmembrane and extracellular regions but contained intracellular signaling domains. Addition of these ligands to cells in culture resulted in signal transmission and specific target gene activation. Monomeric forms of the ligands blocked the pathway. This method of ligandregulated activation and termination of signaling pathways has the potential to be applied wherever precise control of a signal transduction pathway is desired.

  16. Organometallic chemistry of chiral diphosphazane ligands ...

    Indian Academy of Sciences (India)

    Unknown

    Organometallic chemistry of chiral diphosphazane ligands: Synthesis and structural characterisation. KANNAN RAGHURAMAN, SWADHIN K MANDAL,. T S VENKATAKRISHNAN, SETHARAMPATTU S. KRISHNAMURTHY* and MUNIRATHINAM NETHAJI. Department of Inorganic and Physical Chemistry, Indian Institute of ...

  17. EGFR Activation by Spatially Restricted Ligands

    National Research Council Canada - National Science Library

    Goodrich, Jennifer S

    2005-01-01

    ...) activity has been associated with an increased prognosis of breast cancer. During oogenesis in Drosophila melanogaster, local EGFR activation by the spatially restricted TGF alpha-like ligand, Gurken (Grk...

  18. Efficient Algorithms with Asymmetric Read and Write Costs

    OpenAIRE

    Blelloch, Guy E.; Fineman, Jeremy T.; Gibbons, Phillip B.; Gu, Yan; Shun, Julian

    2016-01-01

    In several emerging technologies for computer memory (main memory), the cost of reading is significantly cheaper than the cost of writing. Such asymmetry in memory costs poses a fundamentally different model from the RAM for algorithm design. In this paper we study lower and upper bounds for various problems under such asymmetric read and write costs. We consider both the case in which all but O(1) memory has asymmetric cost, and the case of a small cache of symmetric memory. We model both ...

  19. Asymmetric Cerebral Lesion Pattern in X-linked Adrenoleukodystrophy

    Directory of Open Access Journals (Sweden)

    Shuang Wang

    2006-08-01

    Full Text Available X-linked adrenoleukodystrophy (X-ALD is an inherited disease caused by peroxisomal dysfunction. X-ALD usually involves the cerebral white matter in an approximately symmetric way. We report a 10-year-old boy with the cerebral form of X-ALD who presented with cognitive impairment and left spastic hemiparesis. Brain magnetic resonance imaging (MRI showed asymmetric lesions, and the lesions in the right hemisphere were predominant. In the late stage of the disease, bilateral limbs were involved. The cerebral lesions enlarged and appeared approximately symmetric on MRI. The purpose of our report is to highlight asymmetric demyelination in initial presentation of X-ALD.

  20. Asymptotic behavior of observables in the asymmetric quantum Rabi model

    Science.gov (United States)

    Semple, J.; Kollar, M.

    2018-01-01

    The asymmetric quantum Rabi model with broken parity invariance shows spectral degeneracies in the integer case, that is when the asymmetry parameter equals an integer multiple of half the oscillator frequency, thus hinting at a hidden symmetry and accompanying integrability of the model. We study the expectation values of spin observables for each eigenstate and observe characteristic differences between the integer and noninteger cases for the asymptotics in the deep strong coupling regime, which can be understood from a perturbative expansion in the qubit splitting. We also construct a parent Hamiltonian whose exact eigenstates possess the same symmetries as the perturbative eigenstates of the asymmetric quantum Rabi model in the integer case.

  1. 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.

  2. 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.

  3. 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.

  4. Ratchet effect of the domain wall by asymmetric magnetostatic potentials

    Science.gov (United States)

    Piao, Hong-Guang; Choi, Hyeok-Cheol; Shim, Je-Ho; Kim, Dong-Hyun; You, Chun-Yeol

    2011-11-01

    We investigate a ratchet effect of magnetic domain wall motion in a ferromagnetic nanowire under AC magnetic fields using micromagnetic simulation. The ratchet effect for a transverse domain wall is achieved using an asymmetric magnetic potential generated by stray fields from non-contact trapezoidal ferromagnetic stubs near the straight nanowire. The ratchet phenomenon has been examined with various combinations of amplitude and frequency of the driving AC field. Interestingly, we find that the domain wall propagates along a preferential direction by the diode-like ratchet effect under AC field. The propagation of the domain wall strongly depends on the profile of the asymmetrical magnetic potentials and the driving AC field characteristics.

  5. 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 topology that the asymmetric metric L induces on Teichmüller space is the same as the usual topology. Furthermore, we show that L satisfies the axioms of a (not necessarily symmetric) metric in the sense of Busemann and conclude that L is complete in the sense of Busemann....

  6. 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....

  7. 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.

  8. Asymmetric salivary gland uptake: Potential pitfall following radioiodide therapy

    Energy Technology Data Exchange (ETDEWEB)

    Slavin, J.D. Jr.; Mack, J.M.; Spencer, R.P.

    1987-10-01

    A 67-year old woman, with prior radioiodide (/sup 131/I) therapy for differentiated thyroid carcinoma, had a follow-up scan that revealed asymmetric accumulation in the left upper neck and cheek regions. This resembled functioning metastatic tissue. An immediate /sup 99m/Tc-pertechnetate image demonstrated accumulation in the same areas. This corresponded to activity in the left submandibular gland and parotid. Hence, asymmetric salivary gland uptake was mimicking functional thyroid metastases. Possible causes of the disparate salivary gland function were discussed.

  9. Analysis of the HIV-2 protease's adaptation to various ligands: characterization of backbone asymmetry using a structural alphabet.

    Science.gov (United States)

    Triki, Dhoha; Cano Contreras, Mario Enrique; Flatters, Delphine; Visseaux, Benoit; Descamps, Diane; Camproux, Anne-Claude; Regad, Leslie

    2018-01-15

    The HIV-2 protease (PR2) is a homodimer of 99 residues with asymmetric assembly and binding various ligands. We propose an exhaustive study of the local structural asymmetry between the two monomers of all available PR2 structures complexed with various inhibitors using a structural alphabet approach. On average, PR2 exhibits asymmetry in 31% of its positions-i.e., exhibiting different backbone local conformations in the two monomers. This asymmetry was observed all along its structure, particularly in the elbow and flap regions. We first differentiated structural asymmetry conserved in most PR2 structures from the one specific to some PR2. Then, we explored the origin of the detected asymmetry in PR2. We localized asymmetry that could be induced by PR2's flexibility, allowing transition from the semi-open to closed conformations and the asymmetry potentially induced by ligand binding. This latter could be important for the PR2's adaptation to diverse ligands. Our results highlighted some differences between asymmetry of PR2 bound to darunavir and amprenavir that could explain their differences of affinity. This knowledge is critical for a better description of PR2's recognition and adaptation to various ligands and for a better understanding of the resistance of PR2 to most PR2 inhibitors, a major antiretroviral class.

  10. Ligand Interface Chemistry of Lead Chalcogenide Nanocrystals

    Science.gov (United States)

    Liu, Kun; Bealing, Clive; Hennig, Richard; Hennig Group Team

    2013-03-01

    Lead chalcogenides nanocrystals (NCs) have shown promise in photovoltaic applications. Surface chemistry is one of the most important, yet least understood aspects of NC synthesis and functionalization controlling their properties. For example, an incomplete surface passivation could create trap states that enhance undesired exciton recombination. Clever choices of ligands ensure that neighboring NCs are electronically coupled while maintaining their quantum size effects. These two barriers limiting performance of NC solar cells illustrate the importance of fundamental studies for the interaction between ligands and NC surfaces. We use density functional theory to determine the binding sites and energies of ligands commonly used in NC synthesis and functionalization. Specifically we study amine-, carboxyl-, and thiol-ligands on different PbSe and PbS surfaces. For methylamine ligands we find a similar binding energy on the (100) and (111) facet while carboxylic acid ligands strongly prefer the (111) facet leading to different effective NC shapes. This work was supported in part by Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST) and by the Energy Materials Center at Cornell (EMC2) funded by the U.S. Department of Energy under Award Number DE-SC0001086

  11. 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.

  12. Semiconductor Quantum Dots with Photoresponsive Ligands.

    Science.gov (United States)

    Sansalone, Lorenzo; Tang, Sicheng; Zhang, Yang; Thapaliya, Ek Raj; Raymo, Françisco M; Garcia-Amorós, Jaume

    2016-10-01

    Photochromic or photocaged ligands can be anchored to the outer shell of semiconductor quantum dots in order to control the photophysical properties of these inorganic nanocrystals with optical stimulations. One of the two interconvertible states of the photoresponsive ligands can be designed to accept either an electron or energy from the excited quantum dots and quench their luminescence. Under these conditions, the reversible transformations of photochromic ligands or the irreversible cleavage of photocaged counterparts translates into the possibility to switch luminescence with external control. As an alternative to regulating the photophysics of a quantum dot via the photochemistry of its ligands, the photochemistry of the latter can be controlled by relying on the photophysics of the former. The transfer of excitation energy from a quantum dot to a photocaged ligand populates the excited state of the species adsorbed on the nanocrystal to induce a photochemical reaction. This mechanism, in conjunction with the large two-photon absorption cross section of quantum dots, can be exploited to release nitric oxide or to generate singlet oxygen under near-infrared irradiation. Thus, the combination of semiconductor quantum dots and photoresponsive ligands offers the opportunity to assemble nanostructured constructs with specific functions on the basis of electron or energy transfer processes. The photoswitchable luminescence and ability to photoinduce the release of reactive chemicals, associated with the resulting systems, can be particularly valuable in biomedical research and can, ultimately, lead to the realization of imaging probes for diagnostic applications as well as to therapeutic agents for the treatment of cancer.

  13. 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.

  14. Characterization of quinoxolinol salen ligands as selective ligands for chemosensors for uranium

    Energy Technology Data Exchange (ETDEWEB)

    DeVore, Michael A. II; Kerns, Spencer A.; Gorden, Anne E.V. [Department of Chemistry and Biochemistry, Auburn University, Auburn, AL (United States)

    2015-12-15

    Quinoxalinol salen ligands have been characterized as selective ligands for the rapid identification of uranyl. The absorption maximum of ligand 1 presented a hypsochromic (blue) shift with the addition of UO{sub 2}{sup 2+} (as the acetate salt), and a bathochromic (red) shift in the presence of Cu{sup 2+} or Co{sup 2+} acetate salts, resulting in distinct, visible color changes for all three metal ions. The absorption maximum of ligand 2 was not observed to change with the addition of UO{sub 2}{sup 2+}; however, it does present a bathochromic shift with the addition of Cu{sup 2+}, and a hypsochromic shift with Co{sup 2+} added. Using TDDFT calculations, it was demonstrated that the hypsochromic shift for UO{sub 2}{sup 2+} ion complexation with ligand 1 is caused by a ligand-to-metal charge transfer, while the bathochromic shift observed with Cu{sup 2+} ion addition was caused by a metal-to-ligand charge transfer. Finally, it was found that the addition of Cu{sup 2+} (as metal salts) to either ligand resulted in rapid, complete quenching of the ligand fluorescence. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Asymmetric activation spreading in the multiplication associative network due to asymmetric overlap between numerosities semantic representations?

    Science.gov (United States)

    Didino, Daniele; Knops, André; Vespignani, Francesco; Kornpetpanee, Suchada

    2015-08-01

    Simple multiplication facts are thought to be organised in a network structure in which problems and solutions are associated. Converging evidence suggests that the ability for solving symbolic arithmetic problems is based on an approximate number system (ANS). Most theoretical stances concerning the metric underlying the ANS converge on the assumption that the representational overlap between two adjacent numbers increases as the numerical magnitude of the numbers increases. Given a number N, the overlap between N and N+1 is larger than the overlap between N and N-1. Here, we test whether this asymmetric overlap influences the activation spreading within the multiplication associative network (MAN). When verifying simple multiplication problems such as 8×4 participants were slower in rejecting false but related outcomes that were larger than the actual outcome (e.g., 8×4=36) than rejecting smaller related outcomes (e.g., 8×4=28), despite comparable numerical distance from the correct result (here: 4). This effect was absent for outcomes which are not part of either operands table (e.g., 8×4=35). These results suggest that the metric of the ANS influences the activation spreading within the MAN, further substantiating the notion that symbolic arithmetic is grounded in the ANS. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. An Asymmetrical Space Vector Method for Single Phase Induction Motor

    DEFF Research Database (Denmark)

    Cui, Yuanhai; Blaabjerg, Frede; Andersen, Gert Karmisholt

    2002-01-01

    the motor torque performance is not good enough. This paper addresses a new control method, an asymmetrical space vector method with PWM modulation, also a three-phase inverter is used for the main winding and the auxiliary winding. This method with PWM modulation is implemented to control the motor speed...

  1. Asymmetric Threat Assessment Using Electro-Optical Image Systems

    NARCIS (Netherlands)

    Schwering, P.B.W.; Schutte, K.

    2010-01-01

    Asymmetric threat assessment from military platforms, including early detection and classification by electro-optical means, is a complicated matter. These threats can be for instance explosives-packed rubber boats, minecarrying swimmers and divers in a marine environment or terrorists, improvised

  2. The catalystic asymmetric synthesis of optically active epoxy ketones

    NARCIS (Netherlands)

    Marsman, Bertha Gerda

    1981-01-01

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

  3. Efficient asymmetric Baeyer-Villiger oxidation of prochiral ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 124; Issue 4. Efficient asymmetric Baeyer-Villiger oxidation of prochiral cyclobutanones using new polymer-supported and unsupported chiral co(salen) complexes. Reza Sandaroos Mohammad Taghi Goldani Saman Damavandi Ali Mohammadi. Volume 124 Issue 4 ...

  4. 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.

  5. Novel Cinchona derived organocatalysts: new asymmetric transformations and catalysis

    NARCIS (Netherlands)

    Breman, A.C.

    2014-01-01

    Cinchona alkaloids have a long history as being a powerful medicine against malaria. Since a relative short period (about 50 years) chemist have also used these alkaloids as chiral catalyst for a wide variety of asymmetric transformations. Especially since the beginning of this century, when strong

  6. 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...

  7. Welfare-Improving Asymmetric Information in Dynamic Insurance Markets.

    Science.gov (United States)

    de Garidel-Thoron, Thomas

    2005-01-01

    This article presents a two-period asymmetric learning model of insurance markets. When information about past accidents is not shared by insurers, asymmetries of information develop through time. Equilibrium contracts exist, are payoff unique, and display a realistic bonus-malus pattern. Eliminating asymmetries through information sharing is…

  8. Asymmetric total synthesis of (-)-azaspirene, a novel angiogenesis inhibitor.

    Science.gov (United States)

    Hayashi, Yujiro; Shoji, Mitsuru; Yamaguchi, Junichiro; Sato, Kenji; Yamaguchi, Shinpei; Mukaiyama, Takasuke; Sakai, Ken; Asami, Yukihiro; Kakeya, Hideaki; Osada, Hiroyuki

    2002-10-16

    The asymmetric total synthesis of (-)-azaspirene, an angiogenesis inhibitor, has been accomplished, establishing its absolute stereochemistry. The key steps are a MgBr2.OEt2-mediated, diastereoselective Mukaiyama aldol reaction, a NaH-promoted, intramolecular cyclization of an alkynylamide, and the aldol reaction of a ketone containing functionalized gamma-lactam moiety without protection of tert-alcohol and amide functionalities.

  9. The Asymmetric Simple Exclusion Process: An Exactly Solvable ...

    Indian Academy of Sciences (India)

    Arvind Ayyer, Indian Institute of Science

    2017-06-30

    Jun 30, 2017 ... Introduction. Multispecies ASEP. Affine Weyl Groups. Table of Contents. 1 Introduction. Motivation. Toy Model. 2 Multispecies ASEP. 3 Affine Weyl Groups. Arvind Ayyer, IISc. 28th Mid Year Meeting Faculty Hall, Indian Institute of Science. Asymmetric Simple Exclusion Process ...

  10. Water-accelerated tandem Claisen rearrangement-catalytic asymmetric carboalumination.

    Science.gov (United States)

    Wipf, P; Ribe, S

    2001-05-17

    [reaction: see text] The addition of stoichiometric quantities of water accelerates both the trimethylaluminum-mediated aromatic Claisen reaction and the chiral zirconocene-catalyzed asymmetric carboalumination of terminal alkenes. The two reactions occur in a tandem sequence resulting in the selective formation of two new C-C and one C-O bond after oxidative quench of the intermediate trialkylalane.

  11. Pulse generation and compression using an asymmetrical porous ...

    Indian Academy of Sciences (India)

    We propose an asymmetrical Mach–Zehnder interferometer (MZI) for efficient pulse generation and compression using porous silicon (PS) waveguide, fibre delay line and couplers. We show a pulse compression of about 0.4 ns at the output port with third-order super-Gaussian input pulse in ∼2 ns time duration and ∼40.3 ...

  12. Linguistic Correlates of Asymmetric Motor Symptom Severity in Parkinson's Disease

    Science.gov (United States)

    Holtgraves, Thomas; McNamara, Patrick; Cappaert, Kevin; Durso, Raymond

    2010-01-01

    Asymmetric motor severity is common in Parkinson's Disease (PD) and provides a method for examining the neurobiologic mechanisms underlying cognitive and linguistic deficits associated with the disorder. In the present research, PD participants (N = 31) were assessed in terms of the asymmetry of their motor symptoms. Interviews with the…

  13. Current Topics in the Asymmetric Transfer Hydrogenation of Imines

    Czech Academy of Sciences Publication Activity Database

    Januščák, J.; Václavík, Jiří; Šot, P.; Pecháček, J.; Vilhanová, B.; Kuzma, Marek; Kačer, P.

    2015-01-01

    Roč. 109, č. 7 (2015), s. 492-498 ISSN 0009-2770 R&D Projects: GA ČR GAP106/12/1276; GA MŠk(CZ) LO1509 Institutional support: RVO:61388971 Keywords : asymmetric transfer hydrogenation * ruthenium * isoquinoline Subject RIV: EE - Microbiology, Virology Impact factor: 0.279, year: 2015

  14. The SU(2)-Higgs model on asymmetric lattices

    CERN Document Server

    Csikor, Ferenc

    1996-01-01

    We calculate the {\\cal O}(g^2,\\lambda) corrections to the coupling anisotropies of the SU(2)-Higgs model on lattices with asymmetric lattice spacings. These corrections are obtained by a one-loop calculation requiring the rotational invariance of the gauge- and Higgs-boson propagators in the continuum limit.

  15. Physics at a 10{sup 36} Asymmetric B Factory

    Energy Technology Data Exchange (ETDEWEB)

    Roodman, Aaron

    2001-08-28

    The physics opportunities at an asymmetric B Factory operating at the unprecedented luminosity of 10{sup 36} cm{sup -2}s{sup -1} are unique and attractive. The accelerator appears to be practical and the challenges of performing a sensitive experiment in this environment can be met.

  16. Luminosity lifetime at an asymmetric e sup + e sup - collider

    Energy Technology Data Exchange (ETDEWEB)

    Porter, F.C. (California Inst. of Tech., Pasadena (USA). Lauritsen Lab. of High Energy Physics)

    1991-04-15

    The dependence of the luminosity on time is discussed for an asymmetric e{sup +}e{sup -} storage ring collider, with emphasis on single-particle scattering mechanisms for beam loss. The 'optimal' filling strategy and average luminosity obtainable are also reviewed. (orig.).

  17. An EMG technique for measuring spinal loading during asymmetric lifting

    NARCIS (Netherlands)

    Dolan, P.; Kingma, I.; De Looze, M. P.; Van Dieen, J. H.; Toussaint, H. M.; Baten, C.T.M.; Adams, M.A.

    2001-01-01

    Objective. To compare two methods of calibrating the erector spinae electromyographic signal against moment generation in order to predict extensor moments during asymmetric lifting tasks, and to compare the predicted moments with those obtained using a linked-segment model. Methods. Eight men

  18. Bound states in a hyperbolic asymmetric double-well

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, R. R., E-mail: richard.hartmann@dlsu.edu.ph [Physics Department, De La Salle University, 2401 Taft Avenue, Manila (Philippines)

    2014-01-15

    We report a new class of hyperbolic asymmetric double-well whose bound state wavefunctions can be expressed in terms of confluent Heun functions. An analytic procedure is used to obtain the energy eigenvalues and the criterion for the potential to support bound states is discussed.

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

    NARCIS (Netherlands)

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

    2007-01-01

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

  20. Plasmonic Terahertz Amplification in Graphene-Based Asymmetric Hyperbolic Metamaterial

    Directory of Open Access Journals (Sweden)

    Igor Nefedov

    2015-05-01

    Full Text Available We propose and theoretically explore terahertz amplification, based on stimulated generation of plasmons in graphene asymmetric hyperbolic metamaterials (AHMM, strongly coupled to terahertz radiation. In contrast to the terahertz amplification in resonant nanocavities, AHMM provides a wide-band THz amplification without any reflection in optically thin graphene multilayers.

  1. An overview on the applications of 'Doyle catalysts' in asymmetric ...

    Indian Academy of Sciences (India)

    The chiral dirhodium(II) carboxamidates are a unique class of chiral catalysts useful for asymmetric inter- and intramolecular cyclopropanation, cyclopropenation and C-H insertion reactions with excellent enantioselectivities. The broad applications of these catalysts in organic syntheses are briefly reviewed.

  2. Purcell effect of asymmetric dipole source distributions in nanowire resonators

    DEFF Research Database (Denmark)

    Filonenko, Konstantin; Duggen, Lars; Adam, Jost

    of the asymmetric source distributions in proximity to the metal nanowire in two configurations: a metal cylinder truncated by the PEC plates and finite metal cylinder in free-space. In order to evaluate Purcell factor the mode eigenvalues are precalculated using Comsol Multiphysics radio frequency module. We...

  3. Purcell effect of asymmetric dipole source distributions in nanowire resonators

    DEFF Research Database (Denmark)

    Filonenko, Konstantin; Duggen, Lars; Adam, Jost

    2015-01-01

    of the asymmetric source distributions in proximity to the metal nanowire in two configurations: a metal cylinder truncated by the PEC plates and finite metal cylinder in free-space. In order to evaluate Purcell factor the mode eigenvalues are precalculated using Comsol Multiphysics radio frequency module. We...

  4. Free asymmetric transverse vibration of polar orthotropic annular ...

    Indian Academy of Sciences (India)

    R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

    Abstract. In the present paper, free asymmetric transverse vibrations of a non- uniform polar orthotropic annular sector plate, with parabolically varying thickness in the radial direction, have been studied on the basis of classical plate theory. The circular edges of the plate are elastically restrained against translation and.

  5. Asymmetric gold-catalyzed lactonizations in water at room temperature**

    Science.gov (United States)

    Handa, Sachin; Lippincott, Daniel J.; Slack, Eric D.; Aue, Donald H.

    2014-01-01

    Asymmetric gold-catalyzed hydrocarboxylations are reported that show broad substrate scope. The hydrophobic effect associated with in situ-formed aqueous nanomicelles leads to good-to-excellent ee’s of product lactones. In-flask product isolation, along with recycling of the catalyst and reaction medium, combine to arrive at an especially environmentally friendly process. PMID:25124085

  6. Ion pumping in nanochannels using an asymmetric electrode array

    NARCIS (Netherlands)

    Sparreboom, Wouter; Cucu, C.F.; Eijkel, Jan C.T.; van den Berg, Albert; Locascio, L.E.; Gaitan, M.; Paegel, B.M.; Ross, D.J.; Vreeland, W.N.

    2008-01-01

    We demonstrate an ion pump, consisting of a nanochannel with an AC driven asymmetric electrode array. Our system enables us to actively pump ions using a low driving voltage. In all experiments the electrical double layers are overlapping. Via viscous coupling ion pumping is accompanied by liquid

  7. 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.

  8. 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...

  9. Effect of entry bending moment on exit curvature in asymmetrical ...

    African Journals Online (AJOL)

    user

    In practice, rolling of plate and sheet asymmetry arises due to inequality in roll radii, roll velocity and interface friction. These ... used modified slab method to analyze the asymmetrical plate rolling and to predict strip curvature. Knight et al. ...... This relative motion makes the rotation toward the rougher roll. By applying ...

  10. Interactional Dimension of Online Asynchronous Exchange in an Asymmetric Telecollaboration

    Science.gov (United States)

    Loizidou, Dora; Mangenot, François

    2016-01-01

    The telecollaborative project under study involves, on the one hand, Masters students who are studying to become teachers and who design the tasks as well as tutor them, and, on the other hand, French language students. The relationship in this type of telecollaboration has been shown to be both asymmetric and symmetric. The hypothesis this paper…

  11. Market Efficiency and Price Formation When Dealers are Asymmetrically Informed

    NARCIS (Netherlands)

    Calcagno, R.; Lovo, S.M.

    2002-01-01

    We consider the effect of asymmetric information on the price formation process in a quote-driven market where one market maker receives a private signal on the security fundamental.A model is presented where market makers repeatedly compete in prices: at each stage a bid-ask auction occurs and the

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

    NARCIS (Netherlands)

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

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

  13. The asymmetric leader election algorithm: number of survivors near ...

    African Journals Online (AJOL)

    The following classical asymmetric leader election algorithm has obtained quite a bit of attention lately. Starting with n players, each one throws a coin, and the k of them which have each thrown a head (with probability q) go on, and the leader will be found amongst them, using the same strategy. Should nobody advance ...

  14. Eigenstate localization in an asymmetric coupled quantum well pair

    DEFF Research Database (Denmark)

    Mialitsin, Aleksej; Schmult, Stefan; Solov'yov, Ilia

    2012-01-01

    Optical pumping of a type-I/type-II coupled asymmetric quantum well pair induces a spatially separated two dimensional charge carriers plasma in the well’s wide and narrow parts. Treating the two coupled wells as a single system we find that the eigenstate probability distribution localizes...

  15. Proline-catalysed asymmetric ketol cyclizations: The template ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. A modified template mechanism based on modelling studies of energy minimised complexes is presented for the asymmetric proline-catalysed cyclization of triketones 1, 2 and 3 to the 2S,3S-ketols. 1a, 2a and 3a respectively. The template model involves a three-point contact as favoured in enzyme– substrate ...

  16. Proline-catalysed asymmetric ketol cyclizations: The template ...

    Indian Academy of Sciences (India)

    A modified template mechanism based on modelling studies of energy minimised complexes is presented for the asymmetric proline-catalysed cyclization of triketones 1, 2 and 3 to the 2, 3-ketols 1a, 2a and 3a respectively. The template model involves a three-point contact as favoured in enzyme-substrate interactions.

  17. Symmetrical and asymmetrical growth restriction in preterm-born children

    NARCIS (Netherlands)

    Bocca-Tjeertes, Inger; Bos, Arend; Kerstjens, Jorien; de Winter, Andrea; Reijneveld, Sijmen

    OBJECTIVE: To determine how symmetric (proportionate; SGR) and asymmetric (disproportionate; AGR) growth restriction influence growth and development in preterms from birth to 4 years. METHODS: This community-based cohort study of 810 children comprised 86 SGR, 61 AGR, and 663 non-growth restricted

  18. Measurement of mode splitting in asymmetric Y-junctions

    NARCIS (Netherlands)

    van der Tol, J.J.G.M.; Laarhuis, J.H.; Laarhuis, Jan

    1992-01-01

    A measurement procedure is presented for the determination of mode splitting (or mode sorting) in asymmetric Y-junctions. This procedure avoids measurement errors introduced by bends, tapers, small damages in the waveguides outside the coupling region, variation in fiber-chip coupling, etc. It is

  19. Asymmetric block copolymers confined in a thin film

    NARCIS (Netherlands)

    Huinink, HP; Brokken-Zijp, JCM; van Dijk, MA; Sevink, GJA

    2000-01-01

    We have used a dynamic density functional theory (DDFT) for polymeric systems, to simulate the formation of micro phases in a melt of an asymmetric block copolymer, A(n)B(m)(f(A) = 1/3), both in the bulk and in a thin film. In the DDFT model a polymer is represented as a chain of springs and beads.

  20. Baseline-dependent neutrino oscillations in asymmetrically-warped spacetimes

    CERN Document Server

    Hollenberg, S; Pas, H; Weiler, J T

    2010-01-01

    We study the possibility to explain the LSND anomaly by means of resonant active-sterile neutrino oscillations in an asymmetrically-warped spacetime. In such extra-dimensional scenarios sterile neutrinos take shortcuts through the extra dimension, which results in new types of resonances in the oscillation probability.

  1. Water transport and purification in nanochannels controlled by asymmetric wettability.

    Science.gov (United States)

    Chen, Qinwen; Meng, Lingyi; Li, Qikai; Wang, Dong; Guo, Wei; Shuai, Zhigang; Jiang, Lei

    2011-08-08

    Biomimetic asymmetric nanochannels have recently attracted increasing attention from researchers, especially in the aspect of the asymmetric wettability (a hydrophilic-hydrophobic system), which can be utilized to control the wetting behavior of aqueous media and to offer a means for guiding water motion. By using molecular dynamics simulations, a design for a potentially efficient water filter is presented based on (n, n) single-walled carbon nanotubes, where n = 6, 8, 10 and 12, asymmetrically modified with hydrophilic groups (carboxyl, -COOH) at one tip and hydrophobic groups (trifluoromethyl, -CF(3) ) at the other. The reduced water density on the hydrophobic sides of the functionalized nanotubes are observed in both pure water and aqueous electrolyte solution, except for the functionalized (6, 6) tube, due to the change of dipole orientation of the single-file water wire within it. The functionalized (8, 8) tube can significantly maintain the low water density on the hydrophobic side. Both (6, 6) and (8, 8) tubes have relatively high energy barriers at their tips for ion permeation, which can be obtained by calculating the potential of mean force. Such tip functionalization of a nanotube therefore suggests the great possibilities of water transport and filtration, dominated by asymmetric wettability. The functionalized (8, 8) tube could act as a nanofluidic channel for water purification, not only for ion exclusion but also as a stable water column structure. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The impact of asymmetric flows on pathological speech

    Science.gov (United States)

    Erath, Byron D.; Peterson, Sean D.; Plesniak, Michael W.

    2010-11-01

    In voiced speech the vocal folds form a divergent glottal passage during the closing phases of the phonatory cycle. Due to the adverse pressure gradient, asymmetric flow develops within the glottis causing the glottal jet to separate from one vocal fold wall, and fully-attach to the opposing wall. The asymmetric pressures that arise from this flow configuration directly influence the vocal fold energy exchange process, and are expected to have the greatest influence on vocal fold motion when pathologies that affect the vocal fold musculature are present. A theoretical flow solution that produces the pressure distributions arising from asymmetric glottal flows is implemented into a two-mass model of speech. The impact of flow asymmetries on pathological vocal fold motion is investigated by modifying the tissue parameters of the speech model to represent unilateral paralysis. The influence of asymmetric flow behavior on pathological vocal fold motion is quantified and compared to the commonly-reported simplified case involving symmetric flow behavior.

  3. Switching the Interpenetration of Confined Asymmetric Polymer Brushes

    NARCIS (Netherlands)

    Abbott, Stephen B.; de Vos, Wiebe Matthijs; Mears, Laura L.E.; Skoda, Maximilian W.A.; Dalgliesh, Robert; Edmondson, Steve; Richardson, Robert M.; Prescott, Stuart W.

    2016-01-01

    The interpenetration of two polymer brushes on approaching flat surfaces has been investigated. When compacting polymer brushes with an asymmetric charge on each surface, one neutral and the other weakly charged, we find that the brush interpenetration becomes a parameter that can be controlled by

  4. Study on Warm Forging Prosess of 45 Steel Asymmetric Gear

    Science.gov (United States)

    Qi, Yushi; Du, Zhiming; Sun, Hongsheng; Chen, Lihua; Wang, Changshun

    2017-09-01

    Asymmetric gear has complex structure, so using plastic forming technology to process the gear has problems of large forming load, short die life, bad tooth filling, and so on. To solve these problems, this paper presents a radial warm extrusion process of asymmetric gear to reduce the forming load and improve the filling in the toothed corner portion. Using the new mold and No. 45 steel to conducting forming experiments under the optimal forming parameters: billet temperature is 800°C, mold temperature is 250°C, the forming speed is 30mm/s, and the friction coefficient is 0.15, we can obtain the complete asymmetric gear with better surface and tooth filling. Asymmetric gears’ microstructure analysis and mechanical testing showed that the small grain evenly distributed in the region near the addendum circle with high strength; the area near the central portion of the gear had a coarse grain size, uneven distribution and low strength. Significant metal flow lines at the corner part of the gear indicated that a large number of late-forming metal flowed into the tooth cavity filling the corner portion.

  5. GaAs-Based Nanowire Devices with Multiple Asymmetric Gates for Electrical Brownian Ratchets

    OpenAIRE

    Tanaka, Takayuki; Nakano, Yuki; Kasai, Seiya

    2013-01-01

    GaAs-based nanowire devices having multiple asymmetric gates for electrical Brownian ratchets were fabricated and characterized. From three-dimensional potential simulation results and current–voltage characteristics, we confirmed the formation of the asymmetric potential in our device design. Direct current was generated at room temperature by repeatedly switching the potential in a multiple-asymmetric-gate device on and off. Such current was not observed in either a single-asymmetric-gate d...

  6. A new crystal form of human tear lipocalin reveals high flexibility in the loop region and induced fit in the ligand cavity

    Energy Technology Data Exchange (ETDEWEB)

    Breustedt, Daniel A.; Chatwell, Lorenz; Skerra, Arne, E-mail: skerra@wzw.tum.de [Munich Center for Integrated Protein Science, CIPS-M, and Lehrstuhl für Biologische Chemie, Technische Universität München, 85350 Freising-Weihenstephan (Germany)

    2009-10-01

    The crystal structure of tear lipocalin determined in space group P2{sub 1} revealed large structural deviations from the previously solved X-ray structure in space group C2, especially in the loop region and adjoining parts of the β-barrel which give rise to the ligand-binding site. These findings illustrate a novel mechanism for promiscuity in ligand recognition by the lipocalin protein family. Tear lipocalin (TLC) with the bound artificial ligand 1,4-butanediol has been crystallized in space group P2{sub 1} with four protein molecules in the asymmetric unit and its X-ray structure has been solved at 2.6 Å resolution. TLC is a member of the lipocalin family that binds ligands with diverse chemical structures, such as fatty acids, phospholipids and cholesterol as well as microbial siderophores and the antibiotic rifampin. Previous X-ray structural analysis of apo TLC crystallized in space group C2 revealed a rather large bifurcated ligand pocket and a partially disordered loop region at the entrace to the cavity. Analysis of the P2{sub 1} crystal form uncovered major conformational changes (i) in β-strands B, C and D, (ii) in loops 1, 2 and 4 at the open end of the β-barrel and (iii) in the extended C-terminal segment, which is attached to the β-barrel via a disulfide bridge. The structural comparison indicates high conformational plasticity of the loop region as well as of deeper parts of the ligand pocket, thus allowing adaptation to ligands that differ vastly in size and shape. This illustrates a mechanism for promiscuity in ligand recognition which may also be relevant for some other physiologically important members of the lipocalin protein family.

  7. 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.

  8. Asymmetric Aldol Additions: A Guided-Inquiry Laboratory Activity on Catalysis

    Science.gov (United States)

    King, Jorge H. Torres; Wang, Hong; Yezierski, Ellen J.

    2018-01-01

    Despite the importance of asymmetric catalysis in both the pharmaceutical and commodity chemicals industries, asymmetric catalysis is under-represented in undergraduate chemistry laboratory curricula. A novel guided-inquiry experiment based on the asymmetric aldol addition was developed. Students conduct lab work to compare the effectiveness of…

  9. Asymmetric catalysis at the mesoscale: gold nanoclusters embedded in chiral self-assembled monolayer as heterogeneous catalyst for asymmetric reactions.

    Science.gov (United States)

    Gross, Elad; Liu, Jack H; Alayoglu, Selim; Marcus, Matthew A; Fakra, Sirine C; Toste, F Dean; Somorjai, Gabor A

    2013-03-13

    Research to develop highly versatile, chiral, heterogeneous catalysts for asymmetric organic transformations, without quenching the catalytic reactivity, has met with limited success. While chiral supramolecular structures, connected by weak bonds, are highly active for homogeneous asymmetric catalysis, their application in heterogeneous catalysis is rare. In this work, asymmetric catalyst was prepared by encapsulating metallic nanoclusters in chiral self-assembled monolayer (SAM), immobilized on mesoporous SiO2 support. Using olefin cyclopropanation as an example, it was demonstrated that by controlling the SAM properties, asymmetric reactions can be catalyzed by Au clusters embedded in chiral SAM. Up to 50% enantioselectivity with high diastereoselectivity were obtained while employing Au nanoclusters coated with SAM peptides as heterogeneous catalyst for the formation of cyclopropane-containing products. Spectroscopic measurements correlated the improved enantioselectivity with the formation of a hydrogen-bonding network in the chiral SAM. These results demonstrate the synergetic effect of the catalytically active metallic sites and the surrounding chiral SAM for the formation of a mesoscale enantioselective catalyst.

  10. 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.

  11. PPARα Ligands as Antitumorigenic and Antiangiogenic Agents

    Directory of Open Access Journals (Sweden)

    Ambra Pozzi

    2008-01-01

    Full Text Available Peroxisome proliferator-activated receptors (PPARs belong to the nuclear receptor family of ligand-activated transcription factors. This subfamily is composed of three members—PPARα, PPARδ, and PPARγ—that differ in their cell and tissue distribution as well as in their target genes. PPARα is abundantly expressed in liver, brown adipose tissue, kidney, intestine, heart, and skeletal muscle; and its ligands have been used to treat diseases such as obesity and diabetes. The recent finding that members of the PPAR family, including the PPARα, are expressed by tumor and endothelial cells together with the observation that PPAR ligands regulate cell growth, survival, migration, and invasion, suggested that PPARs also play a role in cancer. In this review, we focus on the contribution of PPARα to tumor and endothelial cell functions and provide compelling evidence that PPARα can be viewed as a new class of ligand activated tumor “suppressor” gene with antiangiogenic and antitumorigenic activities. Given that PPAR ligands are currently used in medicine as hypolipidemic drugs with excellent tolerance and limited toxicity, PPARα activation might offer a novel and potentially low-toxic approach for the treatment of tumor-associated angiogenesis and cancer.

  12. A screening cascade to identify ERβ ligands.

    Science.gov (United States)

    Filgueira, Carly S; Benod, Cindy; Lou, Xiaohua; Gunamalai, Prem S; Villagomez, Rosa A; Strom, Anders; Gustafsson, Jan-Åke; Berkenstam, Anders L; Webb, Paul

    2014-01-01

    The establishment of effective high throughput screening cascades to identify nuclear receptor (NR) ligands that will trigger defined, therapeutically useful sets of NR activities is of considerable importance. Repositioning of existing approved drugs with known side effect profiles can provide advantages because de novo drug design suffers from high developmental failure rates and undesirable side effects which have dramatically increased costs. Ligands that target estrogen receptor β (ERβ) could be useful in a variety of diseases ranging from cancer to neurological to cardiovascular disorders. In this context, it is important to minimize cross-reactivity with ERα, which has been shown to trigger increased rates of several types of cancer. Because of high sequence similarities between the ligand binding domains of ERα and ERβ, preferentially targeting one subtype can prove challenging. Here, we describe a sequential ligand screening approach comprised of complementary in-house assays to identify small molecules that are selective for ERβ. Methods include differential scanning fluorimetry, fluorescence polarization and a GAL4 transactivation assay. We used this strategy to screen several commercially-available chemical libraries, identifying thirty ERβ binders that were examined for their selectivity for ERβ versus ERα, and tested the effects of selected ligands in a prostate cancer cell proliferation assay. We suggest that this approach could be used to rapidly identify candidates for drug repurposing.

  13. Effects of PPARγ Ligands on Leukemia

    Directory of Open Access Journals (Sweden)

    Yoko Tabe

    2012-01-01

    Full Text Available Peroxisome proliferator-activated receptors (PPARs and retinoic acid receptors (RARs, members of the nuclear receptor superfamily, are transcription factors that regulate a variety of important cellular functions. PPARs form heterodimers retinoid X receptor (RXR, an obligate heterodimeric partner for other nuclear receptors. Several novel links between retinoid metabolism and PPAR responses have been identified, and activation of PPAR/RXR expression has been shown to increase response to retinoids. PPARγ has emerged as a key regulator of cell growth and survival, whose activity is modulated by a number of synthetic and natural ligands. While clinical trials in cancer patients with thiazolidinediones (TZD have been disappointing, novel structurally different PPARγ ligands, including triterpenoids, have entered clinical arena as therapeutic agents for epithelial and hematopoietic malignancies. Here we shall review the antitumor advances of PPARγ, alone and in combination with RARα ligands in control of cell proliferation, differentiation, and apoptosis and their potential therapeutic applications in hematological malignancies.

  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...... search spaces effectively and is one of the commonly used methods for flexible ligand docking. During the last decade, several EAs using different variation operators have been introduced, such as the ones provided with the AutoDock program. In this paper we evaluate the performance of different EA...... settings such as choice of variation operators, population size, and usage of local search. The comparison is performed on a suite of six docking problems previously used to evaluate the performance of search algorithms provided with the AutoDock program package. The results from our investigation confirm...

  15. A Numerical Comparison of Symmetric and Asymmetric Supersonic Wind Tunnels

    Science.gov (United States)

    Clark, Kylen D.

    Supersonic wind tunnels are a vital aspect to the aerospace industry. Both the design and testing processes of different aerospace components often include and depend upon utilization of supersonic test facilities. Engine inlets, wing shapes, and body aerodynamics, to name a few, are aspects of aircraft that are frequently subjected to supersonic conditions in use, and thus often require supersonic wind tunnel testing. There is a need for reliable and repeatable supersonic test facilities in order to help create these vital components. The option of building and using asymmetric supersonic converging-diverging nozzles may be appealing due in part to lower construction costs. There is a need, however, to investigate the differences, if any, in the flow characteristics and performance of asymmetric type supersonic wind tunnels in comparison to symmetric due to the fact that asymmetric configurations of CD nozzle are not as common. A computational fluid dynamics (CFD) study has been conducted on an existing University of Michigan (UM) asymmetric supersonic wind tunnel geometry in order to study the effects of asymmetry on supersonic wind tunnel performance. Simulations were made on both the existing asymmetrical tunnel geometry and two axisymmetric reflections (of differing aspect ratio) of that original tunnel geometry. The Reynolds Averaged Navier Stokes equations are solved via NASAs OVERFLOW code to model flow through these configurations. In this way, information has been gleaned on the effects of asymmetry on supersonic wind tunnel performance. Shock boundary layer interactions are paid particular attention since the test section integrity is greatly dependent upon these interactions. Boundary layer and overall flow characteristics are studied. The RANS study presented in this document shows that the UM asymmetric wind tunnel/nozzle configuration is not as well suited to producing uniform test section flow as that of a symmetric configuration, specifically one

  16. Nanoparticles at fluid interfaces: exploiting capping ligands to control adsorption, stability and dynamics.

    Science.gov (United States)

    Garbin, Valeria; Crocker, John C; Stebe, Kathleen J

    2012-12-01

    Nanoparticle self-assembly at fluid-fluid interfaces has been traditionally exploited in emulsification, encapsulation and oil recovery, and more recently in emerging applications including functional nanomaterials and biphasic catalysis. We provide a review of the literature focusing on the open challenges that still hamper the broader applicability of this potentially transformative technology, and we outline strategies to achieve improved control over interfacial self-assembly of nanoparticles. First, we discuss means to promote spontaneous adsorption by tuning the interfacial energies of the nanoparticles with the fluids using capping ligands, and the occurrence of energy barriers. We then examine the interactions between interfacial nanoparticles and how they affect the formation of equilibrium interfacial suspensions versus non-equilibrium two-dimensional phases, such as weakly attractive glasses and gels. Important differences with colloidal interactions in a bulk suspension arise due to the discontinuity in solvent properties at the interface. For instance, ligand brushes rearrange in asymmetric configurations, and thus play a significant role in determining interparticle interactions. Finally, we briefly discuss the link between interfacial microstructure and the dynamic response of particle-laden interfaces, including interfacial rheology and the fate of nanoparticle monolayers upon out-of-plane deformation. Copyright © 2012 Elsevier Inc. All rights reserved.

  17. Asymmetric nonlinear response of the quantized Hall effect

    Science.gov (United States)

    Siddiki, A.; Horas, J.; Kupidura, D.; Wegscheider, W.; Ludwig, S.

    2010-11-01

    An asymmetric breakdown of the integer quantized Hall effect (IQHE) is investigated. This rectification effect is observed as a function of the current value and its direction in conjunction with an asymmetric lateral confinement potential defining the Hall bar. Our electrostatic definition of the Hall bar via Schottky gates allows a systematic control of the steepness of the confinement potential at the edges of the Hall bar. A softer edge (flatter confinement potential) results in more stable Hall plateaus, i.e. a breakdown at a larger current density. For one soft and one hard edge, the breakdown current depends on its direction, resembling rectification. This nonlinear magneto-transport effect confirms the predictions of an emerging screening theory of the IQHE.

  18. Gamma ray constraints on flavor violating asymmetric dark matter

    DEFF Research Database (Denmark)

    Masina, I.; Panci, P.; Sannino, F.

    2012-01-01

    We show how cosmic gamma rays can be used to constrain models of asymmetric Dark Matter decaying into lepton pairs by violating flavor. First of all we require the models to explain the anomalies in the charged cosmic rays measured by PAMELA, Fermi and H.E.S.S.; performing combined fits we...... determine the allowed values of the Dark Matter mass and lifetime. For these models, we then determine the constraints coming from the measurement of the isotropic gamma-ray background by Fermi for a complete set of lepton flavor violating primary modes and over a range of DM masses from 100 GeV to 10 Te......V. We find that the Fermi constraints rule out the flavor violating asymmetric Dark Matter interpretation of the charged cosmic ray anomalies....

  19. Asymmetric excitation of surface plasmons by dark mode coupling

    KAUST Repository

    Zhang, X.

    2016-02-19

    Control over surface plasmons (SPs) is essential in a variety of cutting-edge applications, such as highly integrated photonic signal processing systems, deep-subwavelength lasing, high-resolution imaging, and ultrasensitive biomedical detection. Recently, asymmetric excitation of SPs has attracted enormous interest. In free space, the analog of electromagnetically induced transparency (EIT) in metamaterials has been widely investigated to uniquely manipulate the electromagnetic waves. In the near field, we show that the dark mode coupling mechanism of the classical EIT effect enables an exotic and straightforward excitation of SPs in a metasurface system. This leads to not only resonant excitation of asymmetric SPs but also controllable exotic SP focusing by the use of the Huygens-Fresnel principle. Our experimental findings manifest the potential of developing plasmonic metadevices with unique functionalities.

  20. Multidisciplinary approach to an asymmetric traumatic occlusion: a case report.

    Science.gov (United States)

    Pinho, T; Coutinho-Alves, C; Neves, M

    2013-01-01

    The case of a 47-year-old female patient with an asymmetric traumatic occlusion, great alveolar destruction in the mandibular left central incisor, gingival recession with attachment loss and lack o fkeratinized tissue more accentuated in the crossbite teeth is described. This situation was caused by the traumatic position of the teeth, aggravated by a forced asymmetric anterior position of the mandible and aggravated by mandibular movements. After the extraction of the left central mandibular incisor, keratinized tissue reconstruction and alveolar bone regeneration were performed to obtain enough bone to move the adjacent teeth in this direction and allow the correct placement of an implant at the end of orthodontic treatment. The orthodontic treatment achieved general stable occlusal contacts and esthetic results that were finalized with a definitive prosthetic treatment. This interdisciplinary management was important to solve in the present case the seriously compromised function and esthetics that would never be achieved without this combination.

  1. Left-Right Asymmetric Morphogenesis in the Xenopus Digestive System

    Science.gov (United States)

    Muller, Jennifer K.; Prather, D.R.; Nascone-Yoder, N. M.

    2003-01-01

    The morphogenetic mechanisms by which developing organs become left-right asymmetric entities are unknown. To investigate this issue, we compared the roles of the left and right sides of the Xenopus embryo during the development of anatomic asymmetries in the digestive system. Although both sides contribute equivalently to each of the individual digestive organs, during the initial looping of the primitive gut tube, the left side assumes concave topologies where the right side becomes convex. Of interest, the concave surfaces of the gut tube correlate with expression of the LR gene, Pitx2, and ectopic Pitx2 mRNA induces ectopic concavities in a localized manner. A morphometric comparison of the prospective concave and convex surfaces of the gut tube reveals striking disparities in their rate of elongation but no significant differences in cell proliferation. These results provide insight into the nature of symmetry-breaking morphogenetic events during left-right asymmetric organ development. ?? 2003 Wiley-Liss, Inc.

  2. Asymmetric dark matter models and the LHC diphoton excess

    Energy Technology Data Exchange (ETDEWEB)

    Frandsen, Mads T. [CP" 3-Origins & Danish Institute for Advanced Study DIAS,University of Southern Denmark,Campusvej 55, DK-5230 Odense M (Denmark); Shoemaker, Ian M. [Department of Physics, Department of Astronomy & Astrophysics,Center for Particle and Gravitational Astrophysics, The Pennsylvania State University,104 Davey Laboratory, University Park, PA 16802 (United States)

    2016-05-31

    The existence of dark matter (DM) and the origin of the baryon asymmetry are persistent indications that the SM is incomplete. More recently, the ATLAS and CMS experiments have observed an excess of diphoton events with invariant mass of about 750 GeV. One interpretation of this excess is decays of a new spin-0 particle with a sizable diphoton partial width, e.g. induced by new heavy weakly charged particles. These are also key ingredients in models cogenerating asymmetric DM and baryons via sphaleron interactions and an initial particle asymmetry. We explore what consequences the new scalar may have for models of asymmetric DM that attempt to account for the similarity of the dark and visible matter abundances.

  3. Control of Wind Turbines during Symmetrical and Asymmetrical Grid Faults

    DEFF Research Database (Denmark)

    Göksu, Ömer

    grid code requirements, which are targeting to make the WPPs operate in a closer manner to the conventional power plants. Common to most of the grid codes, WPPs are required to stay connected during short-circuit grid faults, and also inject reactive current in order to support the grid voltage...... regulation. The uninterrupted operation of WPPs is required even when the grid voltage drops down to zero; and the current injection requirement is defined as positive sequence reactive current irrespective of the fault type; symmetrical or asymmetrical. In this project, the response of full-scale converter...... type wind turbines (WTs), in an AC connected WPP, is investigated and control algorithms are designed for minimum disrupted operation and improved grid support, for both symmetrical and asymmetrical grid faults. WTs’ response with conventional control algorithms is studied regarding the impact...

  4. Multiband Printed Asymmetric Dipole Antenna for LTE/WLAN Applications

    Directory of Open Access Journals (Sweden)

    Chia-Mei Peng

    2013-01-01

    Full Text Available The ability of a single layer strip fed printed asymmetric dipole antenna, which is composed of top-loading, asymmetric coplanar waveguide (ACPW and stepped-feeding structure, to operate at three wide frequency bands (698~960 MHz, 1710~2620 MHz, and 5150~5850 MHz to cover WLAN and LTE operation has been demonstrated. A prototype of the proposed antenna with 57.5 mm in length, 0.4 mm in thickness, and 5 mm in width is fabricated and experimentally investigated. The experimental results indicate that the VSWR 2.5 : 1 bandwidths achieved were 74.3%, 40.8%, and 18.2% at 700 MHz, 2450 MHz, and 5500 MHz, respectively. Experimental results are shown to verify the validity of theoretical work.

  5. Corporate governance ratings as a means to reduce asymmetric information

    DEFF Research Database (Denmark)

    Balling, Morten; Holm, Claus; Poulsen, Thomas

    Can corporate governance ratings reduce problems of asymmetric information between companies and investors? To answer this question, we set out to examine the information basis for providing such ratings by reviewing corporate governance attributes that are required or recommended in laws...... suggest that rating providers by selecting relevant attributes in an intelligent way can improve the screening of companies according to governance quality. In contrast, it seems questionable that weighting, aggregation and classification of corporate governance attributes considerably improve...... governance ratings as a means to reduce asymmetric information in a more general manner. We propose that the rating process may be seen as consisting of two general activities, namely a data reduction phase, and a data weighting, aggregation and classification phase. Findings based on a Danish data set...

  6. Broadband terahertz metamaterial absorber based on sectional asymmetric structures

    Science.gov (United States)

    Gong, Cheng; Zhan, Mingzhou; Yang, Jing; Wang, Zhigang; Liu, Haitao; Zhao, Yuejin; Liu, Weiwei

    2016-01-01

    We suggest and demonstrate the concept and design of sectional asymmetric structures which can manipulate the metamaterial absorber’s working bandwidth with maintaining the other inherent advantages. As an example, a broadband terahertz perfect absorber is designed to confirm its effectiveness. The absorber’s each cell integrates four sectional asymmetric rings, and the entire structure composed of Au and Si3N4 is only 1.9 μm thick. The simulation results show the bandwidth with absorptivity being larger than 90% is extended by about 2.8 times comparing with the conventional square ring absorber. The composable small cell, ultra-thin, and broadband absorption with polarization and incident angle insensitivity will make the absorber suitable for the applications of focal plane array terahertz imaging. PMID:27571941

  7. Meta-$\\mathcal{PT}$ Symmetry in Asymmetric Directional Couplers

    CERN Document Server

    Ma, Chicheng; Litchinitser, Natalia M

    2015-01-01

    Despite the benefits that directional coupler based parity-time symmetric systems may offer to the field of integrated optics, the realization of such couplers relies on rather strict design constraints on the waveguide parameters. Here, we investigate directional couplers built of asymmetric waveguides that do not fulfill parity-time symmetry. Nevertheless, we demonstrate that for properly designed parameters, at least one mode of such couplers shows a behavior similar to the one observed in parity-symmetric systems. We find an analytical condition relating gain and loss that enables such a behavior. Moreover, if the individual waveguides composing the asymmetric coupler are designed such that the propagation constants of their modes are identical, the behavior of both super-modes supported by the coupler resembles that of the parity-time symmetric systems.

  8. Asymmetric trienamine catalysis: new opportunities in amine catalysis.

    Science.gov (United States)

    Kumar, Indresh; Ramaraju, Panduga; Mir, Nisar A

    2013-02-07

    Amine catalysis, through HOMO-activating enamine and LUMO-activating iminium-ion formation, is receiving increasing attention among other organocatalytic strategies, for the activation of unmodified carbonyl compounds. Particularly, the HOMO-raising activation concept has been applied to the greatest number of asymmetric transformations through enamine, dienamine, and SOMO-activation strategies. Recently, trienamine catalysis, an extension of amine catalysis, has emerged as a powerful tool for synthetic chemists with a novel activation strategy for polyenals/polyenones. In this review article, we discuss the initial developments of trienamine catalysis for highly asymmetric Diels-Alder reactions with different dienophiles and emerging opportunities for other types of cycloadditions and cascade reactions.

  9. Cosmology in time asymmetric extensions of general relativity

    CERN Document Server

    Leon, Genly

    2015-01-01

    We investigate the cosmological behavior in a universe governed by time asymmetric extensions of general relativity, which is a novel modified gravity based on the addition of new, time-asymmetric, terms on the Hamiltonian framework, in a way that the algebra of constraints and local physics remain unchanged. Nevertheless, at cosmological scales these new terms can have significant effects that can alter the universe evolution, both at early and late times, and the freedom in the choice of the involved modification function makes the scenario able to produce a huge class of cosmological behaviors. For basic ansatzes of modification, we perform a detailed dynamical analysis, extracting the stable late time solutions. Amongst others, we find that the universe can result in dark-energy dominated, accelerating solutions, even in the absence of an explicit cosmological constant, in which the dark energy can be quintessence-like, phantom-like, or behave as an effective cosmological constant. Moreover, it can result...

  10. Asymmetric molecular-orbital tomography by manipulating electron trajectories

    Science.gov (United States)

    Wang, Bincheng; Zhang, Qingbin; Zhu, Xiaosong; Lan, Pengfei; Rezvani, Seyed Ali; Lu, Peixiang

    2017-11-01

    We present a scheme for tomographic imaging of asymmetric molecular orbital based on high-order harmonic generation with a two-color orthogonally polarized multicycle laser field. With the two-dimensional manipulation of the electron trajectories, the electrons can recollide with the target molecule from two noncollinear directions, and then the dipole moment generated from the single direction can be obtained to reconstructed the asymmetric molecular orbital. The recollision is independent from the molecular structure and the angular dependence of the ionization rate in the external field. For this reason, this scheme can avoid the negative effects arising from the modification of the angle-dependent ionization rate induced by Stark shift and be applied to various molecules.

  11. Asymmetric Hardware Distortions in Receive Diversity Systems: Outage Performance Analysis

    KAUST Repository

    Javed, Sidrah

    2017-02-22

    This paper studies the impact of asymmetric hardware distortion (HWD) on the performance of receive diversity systems using linear and switched combining receivers. The asymmetric attribute of the proposed model motivates the employment of improper Gaussian signaling (IGS) scheme rather than the traditional proper Gaussian signaling (PGS) scheme. The achievable rate performance is analyzed for the ideal and non-ideal hardware scenarios using PGS and IGS transmission schemes for different combining receivers. In addition, the IGS statistical characteristics are optimized to maximize the achievable rate performance. Moreover, the outage probability performance of the receive diversity systems is analyzed yielding closed form expressions for both PGS and IGS based transmission schemes. HWD systems that employ IGS is proven to efficiently combat the self interference caused by the HWD. Furthermore, the obtained analytic expressions are validated through Monte-Carlo simulations. Eventually, non-ideal hardware transceivers degradation and IGS scheme acquired compensation are quantified through suitable numerical results.

  12. New type of asymmetric fission in proton-rich nuclei

    CERN Document Server

    Andreyev, A N; Huyse, M; Van Duppen, P; Antalic, S; Barzakh, A; Bree, N; Cocolios, T E; Comas, V F; Diriken, J; Fedorov, D; Fedosseev, V; Franchoo, S; Heredia, J A; Ivanov, O; Koster, U; Marsh, B A; Nishio, K; Page, R D; Patronis, N; Seliverstov, M; Tsekhanovich, I; Van den Bergh, P; Van De Walle, J; Venhart, M; Vermote, S; Veselsky, M; Wagemans, C; Ichikawa, T; Iwamoto, A; Moller, P; Sierk, A J

    2010-01-01

    A very exotic process of ${\\beta}$-delayed fission of $^{180}$Tl is studied in detail by using resonant laser ionization with subsequent mass separation at ISOLDE (CERN). In contrast to common expectations, the fission-fragment mass distribution of the post-${\\beta}$-decay daughter nucleus $^{180}$Hg (N/Z=1.25) is asymmetric. This asymmetry is more surprising since a mass-symmetric split of this extremely neutron-deficient nucleus would lead to two $^{90}$Zr fragments, with magic N=50 and semimagic Z=40. This is a new type of asymmetric fission, not caused by large shell effects related to fragment magic proton and neutron numbers, as observed in the actinide region. The newly measured branching ratio for $\\beta$-delayed fission of $^{180}$Tl is 3.6(7)×10$^{-3}$%, approximately 2 orders of magnitude larger than in an earlier study.

  13. Organocatalytic asymmetric arylation of indoles enabled by azo groups

    Science.gov (United States)

    Qi, Liang-Wen; Mao, Jian-Hui; Zhang, Jian; Tan, Bin

    2018-01-01

    Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.

  14. Broadband terahertz metamaterial absorber based on sectional asymmetric structures.

    Science.gov (United States)

    Gong, Cheng; Zhan, Mingzhou; Yang, Jing; Wang, Zhigang; Liu, Haitao; Zhao, Yuejin; Liu, Weiwei

    2016-08-30

    We suggest and demonstrate the concept and design of sectional asymmetric structures which can manipulate the metamaterial absorber's working bandwidth with maintaining the other inherent advantages. As an example, a broadband terahertz perfect absorber is designed to confirm its effectiveness. The absorber's each cell integrates four sectional asymmetric rings, and the entire structure composed of Au and Si3N4 is only 1.9 μm thick. The simulation results show the bandwidth with absorptivity being larger than 90% is extended by about 2.8 times comparing with the conventional square ring absorber. The composable small cell, ultra-thin, and broadband absorption with polarization and incident angle insensitivity will make the absorber suitable for the applications of focal plane array terahertz imaging.

  15. A high voltage asymmetric waveform generator for FAIMS.

    Science.gov (United States)

    Canterbury, Jesse D; Gladden, James; Buck, Lon; Olund, Roy; MacCoss, Michael J

    2010-07-01

    High field asymmetric waveform ion mobility spectrometry (FAIMS) has been used increasingly in recent years as an additional method of ion separation and selection before mass spectrometry. The FAIMS electrodes are relatively simple to design and fabricate for laboratories wishing to implement their own FAIMS designs. However, construction of the electronics apparatus needed to produce the required high magnitude asymmetric electric field oscillating at a frequency of several hundred kilohertz is not trivial. Here we present an entirely custom-built electronics setup capable of supplying the required waveforms and voltages. The apparatus is relatively simple and inexpensive to implement. We also present data acquired on this system demonstrating the use of FAIMS as a gas-phase ion filter interface to an ion trap mass spectrometer. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

  16. Asymmetric cointegration between exchange rate and trade balance in Nigeria

    Directory of Open Access Journals (Sweden)

    Alhaji Jibrilla Aliyu

    2015-12-01

    Full Text Available This paper empirically examines the long-run pass through of the official exchange rates into trade balance in Nigeria by means of threshold cointegration and asymmetric error correction modeling. The study provides evidence for non-linear cointegration between our variables of interest. The estimated asymmetric error correction models provide new evidence for slower transmission of exchange rate depreciations into the country’s trade balance, which in turn appears to offer partial support for the Dutch disease hypothesis. This finding suggests that policy-makers cannot hope to use currency devaluation to improve the trade balance. It is recommended that policy-makers focus attention on diversification of the economy away from dependence on crude oil exports into productive manufacturing and non-oil exports, which will be vital in making the economy more competitive.

  17. On Another Edge of Defocusing: Hyperbolicity of Asymmetric Lemon Billiards

    Science.gov (United States)

    Bunimovich, Leonid; Zhang, Hong-Kun; Zhang, Pengfei

    2016-02-01

    Defocusing mechanism provides a way to construct chaotic (hyperbolic) billiards with focusing components by separating all regular components of the boundary of a billiard table sufficiently far away from each focusing component. If all focusing components of the boundary of the billiard table are circular arcs, then the above separation requirement reduces to that all circles obtained by completion of focusing components are contained in the billiard table. In the present paper we demonstrate that a class of convex tables— asymmetric lemons, whose boundary consists of two circular arcs, generate hyperbolic billiards. This result is quite surprising because the focusing components of the asymmetric lemon table are extremely close to each other, and because these tables are perturbations of the first convex ergodic billiard constructed more than 40 years ago.

  18. Asymmetrical involvement of frontal lobes in social reasoning.

    Science.gov (United States)

    Goel, Vinod; Shuren, Jeffrey; Sheesley, Laura; Grafman, Jordan

    2004-04-01

    The frontal lobes are widely implicated in logical reasoning. Recent neuroimaging studies suggest that frontal lobe involvement in reasoning is asymmetric (L>R) and increases with the presence of familiar, meaningful content in the reasoning situation. However, neuroimaging data can only provide sufficiency criteria. To determine the necessity of prefrontal involvement in logical reasoning, we tested 19 patients with focal frontal lobe lesions and 19 age- and education-matched normal controls on the Wason Card Selection Task, while manipulating social knowledge. Patients and controls performed equivalently on the arbitrary rule condition. Normal controls showed the expected improvement in the social knowledge conditions, but frontal lobe patients failed to show this facilitation in performance. Furthermore, left hemisphere patients were more affected than right hemisphere patients, suggesting that frontal lobe involvement in reasoning is asymmetric (L>R) and necessary for reasoning about social situations.

  19. Asymmetric synthesis of amines using tert-butanesulfinamide.

    Science.gov (United States)

    Xu, Hai-Chao; Chowdhury, Somenath; Ellman, Jonathan A

    2013-11-01

    Chiral amines are prevalent in many bioactive molecules, including amino acids and pharmaceutical agents. tert-Butanesulfinamide (tBS) is a chiral amine reagent that has enabled the reliable asymmetric synthesis of a very broad range of different amine structures from simple, readily available starting materials. Three steps are commonly applied to the asymmetric synthesis of amines: (i) condensation of tBS with a carbonyl compound, (ii) nucleophile addition and (iii) tert-butanesulfinyl group cleavage. Here we demonstrate these steps with the preparation of a propargylic tertiary carbinamine, one of a class of amines that have been used for many different biological purposes, including click chemistry applications, diversity-oriented synthesis, the preparation of peptide isosteres and the development of protease inhibitors as drug candidates and imaging agents. The process described here can be performed in 3-4 d.

  20. Isotherm of ligand adsorption on DNA at multiplicative noise.

    Science.gov (United States)

    Arakelyan, Valeri; Harutyunyan, Sos; Andriasyan, Vardan; Arakelyan, Hakob

    2012-01-01

    Fluctuations of the number of ligands adsorbed on macromolecules are considered in the case when the number of ligands in the solution fluctuates under the action of fluctuations of the external medium (external noise). For the case of small filling, the multiplicative type of stochastic differential equation is obtained, describing the time variation of the number of ligands adsorbed on macromolecules. The isotherm of adsorption of ligands on DNA is obtained. It is shown that at small ligand concentrations, for some relations between adsorption parameters and the intensity of the external noise, no macromolecule adsorption of ligands takes place.

  1. Asymmetrical two-atom entanglement in a coated microsphere

    Energy Technology Data Exchange (ETDEWEB)

    Burlak, G.N. [Center for Research on Engineering and Applied Sciences, Autonomous State University of Morelos, Cuernavaca, Mor. 62210 (Mexico)]. E-mail: gburlak@uaem.mx; Klimov, A.B. [Departamento de Fisica, Universidad de Guadalajara, Revolucion 1500, Guadalajara, Jalisco, 44420 (Mexico)]. E-mail: klimov@cencar.udg.mx

    2006-12-25

    We study evolution of entanglement of two two-level atoms placed inside a multilayered microsphere. We show that due to inhomogeneity of the optical field modes this entanglement essentially depends on the atomic positions (asymmetrical entanglement) and also on the detuning between the atomic transitions and field frequencies. The robust and complete entanglement can be achieved even in the resonant case when the atoms have different effective coupling constants, and it can be extended in time if the detuning is large enough.

  2. Asymmetric Dark Matter Models and the LHC Diphoton Excess

    DEFF Research Database (Denmark)

    Frandsen, Mads T.; Shoemaker, Ian M.

    2016-01-01

    The existence of dark matter (DM) and the origin of the baryon asymmetry are persistent indications that the SM is incomplete. More recently, the ATLAS and CMS experiments have observed an excess of diphoton events with invariant mass of about 750 GeV. One interpretation of this excess is decays...... have for models of asymmetric DM that attempt to account for the similarity of the dark and visible matter abundances....

  3. Total harmonic distortion of an asymmetric quasi-sinusoidal current

    Directory of Open Access Journals (Sweden)

    Grebennikov Vitaliy

    2017-01-01

    Full Text Available This paper presents the correlation of factors that determine the quality of asymmetric quasi-sinusoidal output current and dynamic losses in the switches of the current generator circuit. The operating mode of the generator was obtained, especially of its power circuit elements, where combination of acceptable output current quality with relatively small dynamic losses in switches and mass-dimensional parameters of the inductor are provided. Achieved results can be used in designing this type of generators.

  4. Degrees of Freedom of Asymmetrical Multi-Way Relay Networks

    DEFF Research Database (Denmark)

    Sun, Fan; De Carvalho, Elisabeth

    2011-01-01

    In this paper, we introduce an asymmetrical multi-way relay channel where a base station conveys independent symbols to K different users while receiving independent symbols from the users. In this network, user i Shas Mi antennas (i ∈ [1, ..., K]), the base station has Σi=1K Mi antennas and the ...... with a proposed joint multiple access and broadcast precoding design using the signal space alignment concept....

  5. Comment on "Asymmetric coevolutionary networks facilitate biodiversity maintenance"

    Science.gov (United States)

    Holland, J. Nathaniel; Okuyama, Toshinori; DeAngelis, Donald L.

    2006-01-01

    Bascompte et al. (Reports, 21 April 2006, p. 431) used network asymmetries to explain mathematical conditions necessary for stability in historic models of mutualism. The Lotka-Volterra equations they used artificially created conditions in which some factor, such as asymmetric interaction strengths, is necessary for community coexistence. We show that a more realistic model incorporating nonlinear functional responses requires no such condition and is consistent with their data.

  6. Novel Asymmetric Wittig Reaction: Synthesis of Chiral Allenic Esters

    OpenAIRE

    Melo, Teresa M. V. D. Pinho e; Cardoso, Ana L.; Gonsalves, António M. D'A Rocha; Pessoa, João Costa; José A. Paixão; Beja, Ana M

    2004-01-01

    Wittig reactions between 10-(phenylsulfonyl)isobornyl (triphenylphosphoranylidene)acetates (1 and 6) and ketenes resulted in asymmetric induction, with the selective synthesis of allenes with axial chirality. Use of the (1R)-(-)-10-(phenylsulfonyl)isoborneol unit allows the synthesis of allenes with S configuration, whereas use of the (1S)-(+)-10-(phenylsulfonyl)isoborneol unit produces allenes with R configuration. The structure of (1R)-(-)-10-(phenylsulfonyl)isobornyl (S)-5,5-dimethylhexa-2...

  7. International labor migration, asymmetric information and occupational choice

    OpenAIRE

    Kar, Saibal

    2009-01-01

    We study the effect of asymmetric information in the labor market of a country on the occupational choice pattern of immigrants vis-à-vis natives. The choice is limited to self-employment and paid employment. The study is motivated by empirical observations that regular and irregular immigrants in many countries are often over-represented in entrepreneurship/small business despite substantial initial disadvantages. There are also evidences that the immigrants catch up with the native incom...

  8. Asymmetric cell division in Mycobacterium tuberculosis and its unique features.

    Science.gov (United States)

    Vijay, Srinivasan; Nagaraja, Mukkayyan; Sebastian, Jees; Ajitkumar, Parthasarathi

    2014-03-01

    Recently, several reports showed that about 80 % of mid-log phase Mycobacterium smegmatis, Mycobacterium marinum, and Mycobacterium bovis BCG cells divide symmetrically with 5-10 % deviation in the septum position from the median. However, the mode of cell division of the pathogenic mycobacterial species, Mycobacterium tuberculosis, remained unclear. Therefore, in the present study, using electron microscopy, fluorescence microscopy of septum- and nucleoid-stained live and fixed cells, and live cell time-lapse imaging, we show the occurrence of asymmetric cell division with unusually deviated septum/constriction in 20 % of the 15 % septating M. tuberculosis cells in the mid-log phase population. The remaining 80 % of the 15 % septating cells divided symmetrically but with 2-5 % deviation in the septum/constriction position, as reported for M. smegmatis, M. marinum, and M. bovis BCG cells. Both the long and the short portions of the asymmetrically dividing M. tuberculosis cells with unusually deviated septum contained nucleoids, thereby generating viable short and long cells from each asymmetric division. M. tuberculosis short cells were acid fast positive and, like the long cells, further readily underwent growth and division to generate micro-colony, thereby showing that they were neither mini cells, spores nor dormant forms of mycobacteria. The freshly diagnosed pulmonary tuberculosis patients' sputum samples, which are known for the prevalence of oxidative stress conditions, also contained short cells at the same proportion as that in the mid-log phase population. The probable physiological significance of the generation of the short cells through unusually deviated asymmetric cell division is discussed.

  9. Dynamic vergence eye movements in strabismus and amblyopia: asymmetric vergence.

    OpenAIRE

    Kenyon, R V; Ciuffreda, K J; Stark, L.

    1981-01-01

    This report investigates line-of-sight asymmetric disparity vergence in patients having either intermittent strabismus, constant strabismus with amblyopia, or amblyopia without strabismus. We find an absence of disparity vergence in all patients with strabismus and in some with amblyopia only. Accommodative vergence and saccades place the dominant eye on the targets moving in depth. These accommodative vergence responses have normal dynamic characteristics, thus indicating a properly function...

  10. Exposing asymmetric gray matter vulnerability in amyotrophic lateral sclerosis

    OpenAIRE

    Devine, Matthew S.; Pannek, Kerstin; Coulthard, Alan; Pamela A. McCombe; Rose, Stephen E; Henderson, Robert D.

    2015-01-01

    Limb weakness in amyotrophic lateral sclerosis (ALS) is typically asymmetric. Previous studies have identified an effect of limb dominance on onset and spread of weakness, however relative atrophy of dominant and non-dominant brain regions has not been investigated. Our objective was to use voxel-based morphometry (VBM) to explore gray matter (GM) asymmetry in ALS, in the context of limb dominance. 30 ALS subjects were matched with 17 healthy controls. All subjects were right-handed. Each und...

  11. Airplane automatic control force trimming device for asymmetric engine failures

    Science.gov (United States)

    Stewart, Eric C. (Inventor)

    1987-01-01

    The difference in dynamic pressure in the propeller slipstreams as measured by sensors is divided by the freestream dynamic pressure generating a quantity proportional to the differential thrust coefficient. This quantity is used to command an electric trim motor to change the position of trim tab thereby retrimming the airplane to the new asymmetric power condition. The change in position of the trim tab produced by the electric trim motor is summed with the pilot's input to produce the actual trim tab position.

  12. Asymmetric MHD outflows/jets from accreting T Tauri stars

    Science.gov (United States)

    Dyda, S.; Lovelace, R. V. E.; Ustyugova, G. V.; Lii, P. S.; Romanova, M. M.; Koldoba, A. V.

    2015-06-01

    Observations of jets from young stellar objects reveal the asymmetric outflows from some sources. A large set of 2.5D magnetohydrodynamic simulations was carried out for axisymmetric viscous/diffusive disc accretion to rotating magnetized stars for the purpose of assessing the conditions where the outflows are asymmetric relative to the equatorial plane. We consider initial magnetic fields that are symmetric about the equatorial plane and consist of a radially distributed field threading the disc (disc field) and a stellar dipole field. (1) For pure disc-fields the symmetry or asymmetry of the outflows is affected by the mid-plane plasma β of the disc. For discs with small plasma β, outflows are symmetric to within 10 per cent over time-scales of hundreds of inner disc orbits. For higher β discs, the coupling of the upper and lower coronal plasmas is broken, and quasi-periodic field motion leads to asymmetric episodic outflows. (2) Accreting stars with a stellar dipole field and no disc-field exhibit episodic, two component outflows - a magnetospheric wind and an inner disc wind. Both are characterized by similar velocity profiles but the magnetospheric wind has densities ≳ 10 times that of the disc wind. (3) Adding a disc field parallel to the stellar dipole field enhances the magnetospheric winds but suppresses the disc wind. (4) Adding a disc field which is antiparallel to the stellar dipole field in the disc suppresses the magnetospheric and disc winds. Our simulations reproduce some key features of observations of asymmetric outflows of T Tauri stars.

  13. A highly asymmetric dijet event of the ATLAS experiment

    CERN Multimedia

    ATLAS, Experiment

    2014-01-01

    A highly asymmetric dijet event, with one jet with ET > 100 GeV and no evident recoiling jet, and with high energy calorimeter cell deposits distributed over a wide azimuthal region. Only tracks with pT > 2.6 GeV are shown, and only calorimeter energy deposits with cell energy ET > 700 MeV in the electromagnetic calorimeter, and E > 1 GeV in the hadronic calorimeter.

  14. Implementation of Asymmetric Potential Fields in Real Time Strategy Game

    OpenAIRE

    Mansur-Ul-Islam, Muhammad; SAJJAD, Muhammad

    2011-01-01

    In eighties, the idea of using potential fields was first introduced in the field of the robotics. The purpose of using potential fields was to achieve the natural movement in robotics. Many researchers proceeded this idea to enhance their research. The idea of using potential fields was also introduced in real time strategy games for the better movement of objects. In this thesis we worked on the idea of using asymmetric potential fields in the game environment. The purpose of our study was ...

  15. Reflection-asymmetric nuclear deformations within the Density Functional Theory

    OpenAIRE

    Olsen, E; Erler, J; Nazarewicz, W.; Stoitsov, M.

    2013-01-01

    Within the nuclear density functional theory (DFT) we study the effect of reflection-asymmetric shapes on ground-state binding energies and binding energy differences. To this end, we developed the new DFT solver AxialHFB that uses an approximate second-order gradient to solve the Hartree-Fock-Bogoliubov equations of superconducting DFT with the quasi-local Skyrme energy density functionals. Illustrative calculations are carried out for even-even isotopes of radium and thorium.

  16. Kinematics and Dynamics of an Asymmetrical Parallel Robotic Wrist

    DEFF Research Database (Denmark)

    Wu, Guanglei

    2014-01-01

    This paper introduces an asymmetrical parallel robotic wrist, which can generate a decoupled unlimited-torsion motion and achieve high positioning accuracy. The kinematics, dexterity, and singularities of the manipulator are investigated to visualize the performance contours of the manipulator....... Using the method of Lagrange multipliers and considering all the mobile components, the equations of motion of the manipulator are derived to investigate the dynamic characteristics efficiently. The developed dynamic model is numerically illustrated and compared with its simplified formulation to show...

  17. The Influence of the Asymmetric Ionosphere on the Schumann Resonances

    Science.gov (United States)

    Yu, H.; Williams, E. R.

    2015-12-01

    The asymmetric ionosphere is known to affect the behavior of the Earth's Schumann resonances (SR). Several studies have addressed the day-night asymmetry with observation or simulation and showed the contrast in SR amplitude between day and night (Satori et.al 2007, Pechony and Price 2007, Yang et.al., 2006). And distinct perturbations in the ionosphere caused by solar proton events, x-ray emission and earthquake coupling will also produce variations in SRs (Roldugin et.al., 2004, De et al., 2010; Satori et.al., 2015). Considering all these possible variations produced by changes in ionospheric asymmetry, we simulate the SR propagation in an asymmetric cavity including the day-night contribution and the more general perturbation asymmetry using a TDTE (Two Dimensional Telegraph Equation) approach. The change of source position in the asymmetric ionosphere and the size of the perturbation will also affect the SR parameters such as amplitude and modal frequency. The central location of the source in either the daytime or nighttime zone will produce a larger amplitude than other locations in the cavity. For example, the amplitude from a source in the zone with lower electric height (like the daytime region) is larger than the situation with source in region of larger electric height (like nighttime region). The asymmetry(difference on EM amplitude between two regions) will be more distinct when the source is on the terminator between two region than on other position. And when the size of the asymmetric construction is changed, the amplitude and modal frequency will also be changed. The increased size of the zone with lower electric height will produce larger SR amplitudes and decreased modal frequency.

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

    KAUST Repository

    Mukherjee, Herschel

    2011-03-04

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

  19. Asymmetric Monotone Comparative Statics for the Industry Compositions

    DEFF Research Database (Denmark)

    Laugesen, Anders Rosenstand

    distributions of all activities across active firms. MCS for the industry composition occurs in a country which experiences a decline in its costs of serving the foreign market and meanwhile experiences an increase in its level of competition. In the other country, the industry-level implications are exactly...... opposite. These clear industry-level results hold while firms respond asymmetrically to the trade shock...

  20. Photon splitting in a strongly magnetized, charge-asymmetric plasma

    Directory of Open Access Journals (Sweden)

    Chistyakov M.V.

    2016-01-01

    Full Text Available The process of the photon splitting, γ → γγ, is investigated in the presence of strongly magnetized charge-asymmetric cold plasma. The dispersion properties of photons and the new polarization selection rules are obtained in such plasma. The absorption rate of the leading photon splitting channel are calculated with taking account of the photon dispersion and wave function renormalization. In addition, a comparison of the photon splitting and the Compton scattering processes is performed.

  1. Forecasting Performance of Asymmetric GARCH Stock Market Volatility Models

    Directory of Open Access Journals (Sweden)

    Hojin Lee

    2009-12-01

    Full Text Available We investigate the asymmetry between positive and negative returns in their effect on conditional variance of the stock market index and incorporate the characteristics to form an out-of-sample volatility forecast. Contrary to prior evidence, however, the results in this paper suggest that no asymmetric GARCH model is superior to basic GARCH(1,1 model. It is our prior knowledge that, for equity returns, it is unlikely that positive and negative shocks have the same impact on the volatility. In order to reflect this intuition, we implement three diagnostic tests for volatility models: the Sign Bias Test, the Negative Size Bias Test, and the Positive Size Bias Test and the tests against the alternatives of QGARCH and GJR-GARCH. The asymmetry test results indicate that the sign and the size of the unexpected return shock do not influence current volatility differently which contradicts our presumption that there are asymmetric effects in the stock market volatility. This result is in line with various diagnostic tests which are designed to determine whether the GARCH(1,1 volatility estimates adequately represent the data. The diagnostic tests in section 2 indicate that the GARCH(1,1 model for weekly KOSPI returns is robust to the misspecification test. We also investigate two representative asymmetric GARCH models, QGARCH and GJR-GARCH model, for our out-of-sample forecasting performance. The out-of-sample forecasting ability test reveals that no single model is clearly outperforming. It is seen that the GJR-GARCH and QGARCH model give mixed results in forecasting ability on all four criteria across all forecast horizons considered. Also, the predictive accuracy test of Diebold and Mariano based on both absolute and squared prediction errors suggest that the forecasts from the linear and asymmetric GARCH models need not be significantly different from each other.

  2. Asymmetric bursting of Taylor bubble in inclined tubes

    Science.gov (United States)

    Rana, Basanta Kumar; Das, Arup Kumar; Das, Prasanta Kumar

    2016-08-01

    In the present study, experiments have been reported to explain the phenomenon of approach and collapse of an asymmetric Taylor bubble at free surface inside an inclined tube. Four different tube inclinations with horizontal (30°, 45°, 60° and 75°) and two different fluids (water and silicon oil) are considered for the experiment. Using high speed imaging, we have investigated the approach, puncture, and subsequent liquid drainage for re-establishment of the free surface. The present study covers all the aspects in the collapse of an asymmetric Taylor bubble through the generation of two films, i.e., a cap film which lies on top of the bubble and an asymmetric annular film along the tube wall. Retraction of the cap film is studied in detail and its velocity has been predicted successfully for different inclinations and fluids. Film drainage formulation considering azimuthal variation is proposed which also describes the experimental observations well. In addition, extrapolation of drainage velocity pattern beyond the experimental observation limit provides insight into the total collapse time of bubbles at different inclinations and fluids.

  3. Asymmetric osmotic water permeation through a vesicle membrane

    Science.gov (United States)

    Su, Jiaye; Zhao, Yunzhen; Fang, Chang; Shi, Yue

    2017-05-01

    Understanding the water permeation through a cell membrane is of primary importance for biological activities and a key step to capture its shape transformation in salt solution. In this work, we reveal the dynamical behaviors of osmotically driven transport of water molecules across a vesicle membrane by molecular dynamics simulations. Of particular interest is that the water transport in and out of vesicles is highly distinguishable given the osmotic force are the same, suggesting an asymmetric osmotic transportation. This asymmetric phenomenon exists in a broad range of parameter space such as the salt concentration, temperature, and vesicle size and can be ascribed to the similar asymmetric potential energy of lipid-ion, lipid-water, lipid-solution, lipid-lipid, and the lipid-lipid energy fluctuation. Specifically, the water flux has a linear increase with the salt concentration, similar to the prediction by Nernst-Planck equation or Fick's first law. Furthermore, due to the Arrhenius relation between the membrane permeability and temperature, the water flux also exhibits excellent Arrhenius dependence on the temperature. Meanwhile, the water flux shows a linear increase with the vesicle surface area since the flux amount across a unit membrane area should be a constant. Finally, we also present the anonymous diffusion behaviors for the vesicle itself, where transitions from normal diffusion at short times to subdiffusion at long times are identified. Our results provide significant new physical insights for the osmotic water permeation through a vesicle membrane and are helpful for future experimental studies.

  4. Fault Current Characteristics of the DFIG under Asymmetrical Fault Conditions

    Directory of Open Access Journals (Sweden)

    Fan Xiao

    2015-09-01

    Full Text Available During non-severe fault conditions, crowbar protection is not activated and the rotor windings of a doubly-fed induction generator (DFIG are excited by the AC/DC/AC converter. Meanwhile, under asymmetrical fault conditions, the electrical variables oscillate at twice the grid frequency in synchronous dq frame. In the engineering practice, notch filters are usually used to extract the positive and negative sequence components. In these cases, the dynamic response of a rotor-side converter (RSC and the notch filters have a large influence on the fault current characteristics of the DFIG. In this paper, the influence of the notch filters on the proportional integral (PI parameters is discussed and the simplified calculation models of the rotor current are established. Then, the dynamic performance of the stator flux linkage under asymmetrical fault conditions is also analyzed. Based on this, the fault characteristics of the stator current under asymmetrical fault conditions are studied and the corresponding analytical expressions of the stator fault current are obtained. Finally, digital simulation results validate the analytical results. The research results are helpful to meet the requirements of a practical short-circuit calculation and the construction of a relaying protection system for the power grid with penetration of DFIGs.

  5. All conducting polymer electrodes for asymmetric solid-state supercapacitors

    KAUST Repository

    Kurra, Narendra

    2015-02-16

    In this study, we report the fabrication of solid-state asymmetric supercapacitors (ASCs) based on conducting polymer electrodes on a plastic substrate. Nanostructured conducting polymers of poly(3,4-ethylenedioxythiophene), PEDOT, and polyaniline (PANI) are deposited electrochemically over Au-coated polyethylene naphthalate (PEN) plastic substrates. Due to the electron donating nature of the oxygen groups in the PEDOT, reduction potentials are higher, allowing it to be used as a negative electrode material. In addition, the high stability of PEDOT in its oxidised state makes it capable to exhibit electrochemical activity in a wide potential window. This can qualify PEDOT to be used as a negative electrode in fabricating asymmetric solid state supercapacitors with PANI as a positive electrode while employing polyvinyl alcohol (PVA)/H2SO4 gel electrolyte. The ASCs exhibit a maximum power density of 2.8 W cm−3 at an energy density of 9 mW h cm−3, which is superior to the carbonaceous and metal oxide based ASC solid state devices. Furthermore, the tandem configuration of asymmetric supercapacitors is shown to be capable of powering a red light emitting diode for about 1 minute after charging for 10 seconds.

  6. Exposing asymmetric gray matter vulnerability in amyotrophic lateral sclerosis

    Directory of Open Access Journals (Sweden)

    Matthew S. Devine

    2015-01-01

    Full Text Available Limb weakness in amyotrophic lateral sclerosis (ALS is typically asymmetric. Previous studies have identified an effect of limb dominance on onset and spread of weakness, however relative atrophy of dominant and non-dominant brain regions has not been investigated. Our objective was to use voxel-based morphometry (VBM to explore gray matter (GM asymmetry in ALS, in the context of limb dominance. 30 ALS subjects were matched with 17 healthy controls. All subjects were right-handed. Each underwent a structural MRI sequence, from which GM segmentations were generated. Patterns of GM atrophy were assessed in ALS subjects with first weakness in a right-sided limb (n = 15 or left-sided limb (n = 15. Within each group, a voxelwise comparison was also performed between native and mirror GM images, to identify regions of hemispheric GM asymmetry. Subjects with ALS showed disproportionate atrophy of the dominant (left motor cortex hand area, irrespective of the side of first limb weakness (p < 0.01. Asymmetric atrophy of the left somatosensory cortex and temporal gyri was only observed in ALS subjects with right-sided onset of limb weakness. Our VBM protocol, contrasting native and mirror images, was able to more sensitively detect asymmetric GM pathology in a small cohort, compared with standard methods. These findings indicate particular vulnerability of dominant upper limb representation in ALS, supporting previous clinical studies, and with implications for cortical organisation and selective vulnerability.

  7. Exposing asymmetric gray matter vulnerability in amyotrophic lateral sclerosis.

    Science.gov (United States)

    Devine, Matthew S; Pannek, Kerstin; Coulthard, Alan; McCombe, Pamela A; Rose, Stephen E; Henderson, Robert D

    2015-01-01

    Limb weakness in amyotrophic lateral sclerosis (ALS) is typically asymmetric. Previous studies have identified an effect of limb dominance on onset and spread of weakness, however relative atrophy of dominant and non-dominant brain regions has not been investigated. Our objective was to use voxel-based morphometry (VBM) to explore gray matter (GM) asymmetry in ALS, in the context of limb dominance. 30 ALS subjects were matched with 17 healthy controls. All subjects were right-handed. Each underwent a structural MRI sequence, from which GM segmentations were generated. Patterns of GM atrophy were assessed in ALS subjects with first weakness in a right-sided limb (n = 15) or left-sided limb (n = 15). Within each group, a voxelwise comparison was also performed between native and mirror GM images, to identify regions of hemispheric GM asymmetry. Subjects with ALS showed disproportionate atrophy of the dominant (left) motor cortex hand area, irrespective of the side of first limb weakness (p < 0.01). Asymmetric atrophy of the left somatosensory cortex and temporal gyri was only observed in ALS subjects with right-sided onset of limb weakness. Our VBM protocol, contrasting native and mirror images, was able to more sensitively detect asymmetric GM pathology in a small cohort, compared with standard methods. These findings indicate particular vulnerability of dominant upper limb representation in ALS, supporting previous clinical studies, and with implications for cortical organisation and selective vulnerability.

  8. Baseline Testing of the Club Car Carryall With Asymmetric Ultracapacitors

    Science.gov (United States)

    Eichenberg, Dennis J.

    2003-01-01

    The NASA John H. Glenn Research Center initiated baseline testing of the Club Car Carryall with asymmetric ultracapacitors as a way to reduce pollution in industrial settings, reduce fossil fuel consumption, and reduce operating costs for transportation systems. The Club Car Carryall provides an inexpensive approach to advance the state of the art in electric vehicle technology in a practical application. The project transfers space technology to terrestrial use via non-traditional partners, and provides power system data valuable for future space applications. The work was done under the Hybrid Power Management (HPM) Program, which includes the Hybrid Electric Transit Bus (HETB). The Carryall is a state of the art, ground up, electric utility vehicle. A unique aspect of the project was the use of a state of the art, long life ultracapacitor energy storage system. Innovative features, such as regenerative braking through ultracapacitor energy storage, are planned. Regenerative braking recovers much of the kinetic energy of the vehicle during deceleration. The Carryall was tested with the standard lead acid battery energy storage system, as well as with an asymmetric ultracapacitor energy storage system. The report concludes that the Carryall provides excellent performance, and that the implementation of asymmetric ultracapacitors in the power system can provide significant performance improvements.

  9. Asymmetric Flexible MXene-Reduced Graphene Oxide Micro-Supercapacitor

    KAUST Repository

    Couly, Cedric

    2017-11-27

    Current microfabrication of micro-supercapacitors often involves multistep processing and delicate lithography protocols. In this study, simple fabrication of an asymmetric MXene-based micro-supercapacitor that is flexible, binder-free, and current-collector-free is reported. The interdigitated device architecture is fabricated using a custom-made mask and a scalable spray coating technique onto a flexible, transparent substrate. The electrode materials are comprised of titanium carbide MXene (Ti3C2Tx) and reduced graphene oxide (rGO), which are both 2D layered materials that contribute to the fast ion diffusion in the interdigitated electrode architecture. This MXene-based asymmetric micro-supercapacitor operates at a 1 V voltage window, while retaining 97% of the initial capacitance after ten thousand cycles, and exhibits an energy density of 8.6 mW h cm−3 at a power density of 0.2 W cm−3. Further, these micro-supercapacitors show a high level of flexibility during mechanical bending. Utilizing the ability of Ti3C2Tx-MXene electrodes to operate at negative potentials in aqueous electrolytes, it is shown that using Ti3C2Tx as a negative electrode and rGO as a positive one in asymmetric architectures is a promising strategy for increasing both energy and power densities of micro-supercapacitors.

  10. Experiment and numerical modeling of asymmetrically initiated hexagonal prism warhead

    Directory of Open Access Journals (Sweden)

    Yuan Li

    2017-01-01

    Full Text Available Traditional fragmentation warheads are usually initiated on the axis, producing a uniform fragment distribution around the warhead, but only little portion of them can be imposed on the targets. The aimable warhead, on the other hand, using the off-axis initiations or the structure deforming, can improve the warhead energy utilization highly. Seeking methods to both enhance the fragment velocity and density has significant value for improving the target damage probability. In this article, a warhead shaped as hexagonal prism was studied using arena experiment and numerical modeling and compared with the traditional cylindrical structure. The fragment velocities and target hit patterns of the two types of warheads under axial initiation and asymmetrical initiation are obtained. It is revealed that for the hexagonal prism warhead, the asymmetrical initiation can enhance the fragment velocities by 27.71% and enhance fragment density by 34.09% compared to the axial initiation. The fragment velocity enhancement is close to that of the cylindrical warhead, but the fragment density enhancement is far above the cylindrical warhead. This indicates that the asymmetrically initiated hexagonal prism warhead is a very effective aimable warhead.

  11. Ligand Exchange Kinetics of Environmentally Relevant Metals

    Energy Technology Data Exchange (ETDEWEB)

    Panasci, Adele Frances [Univ. of California, Davis, CA (United States)

    2014-07-15

    The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.

  12. Supramolecular architectures constructed using angular bipyridyl ligands

    CERN Document Server

    Barnett, S A

    2003-01-01

    This work details the synthesis and characterization of a series of coordination frameworks that are formed using bidentate angular N-donor ligands. Pyrimidine was reacted with metal(ll) nitrate salts. Reactions using Cd(NO sub 3) sub 2 receive particular focus and the analogous reactions using the linear ligand, pyrazine, were studied for comparison. In all cases, two-dimensional coordination networks were prepared. Structural diversity is observed for the Cd(ll) centres including metal-nitrate bridging. In contrast, first row transition metal nitrates form isostructural one-dimensional chains with only the bridging N-donor ligands generating polymeric propagation. The angular ligand, 2,4-bis(4-pyridyl)-1,3,5-triazine (dpt), was reacted with Cd(NO sub 3) sub 2 and Zn(NO sub 3) sub 2. Whereas Zn(NO sub 3) sub 2 compounds exhibit solvent mediated polymorphism, a range of structures were obtained for the reactions with Cd(NO sub 3) sub 2 , including the first example of a doubly parallel interpenetrated 4.8 sup...

  13. Flexible Ligand Docking Using Differential Evolution

    DEFF Research Database (Denmark)

    Thomsen, René

    2003-01-01

    Molecular docking of biomolecules is becoming an increasingly important part in the process of developing new drugs, as well as searching compound databases for promising drug candidates. The docking of ligands to proteins can be formulated as an optimization problem where the task is to find...

  14. A versatile dinucleating ligand containing sulfonamide groups

    DEFF Research Database (Denmark)

    Sundberg, Jonas; Witt, Hannes; Cameron, Lisa

    2014-01-01

    Copper, iron, and gallium coordination chemistries of the new pentadentate bis-sulfonamide ligand 2,6-bis(N-2-pyridylmethylsulfonamido)-4-methylphenol (psmpH3) were investigated. PsmpH3 is capable of varying degrees of deprotonation, and notably, complexes containing the fully trideprotonated...

  15. Noncalcemic actions of vitamin D receptor ligands.

    Science.gov (United States)

    Nagpal, Sunil; Na, Songqing; Rathnachalam, Radhakrishnan

    2005-08-01

    1alpha,25-Dihydroxyvitamin D(3) [1,25-(OH)(2)D(3)], the active metabolite of vitamin D(3), is known for the maintenance of mineral homeostasis and normal skeletal architecture. However, apart from these traditional calcium-related actions, 1,25-(OH)(2)D(3) and its synthetic analogs are being increasingly recognized for their potent antiproliferative, prodifferentiative, and immunomodulatory activities. These actions of 1,25-(OH)(2)D(3) are mediated through vitamin D receptor (VDR), which belongs to the superfamily of steroid/thyroid hormone nuclear receptors. Physiological and pharmacological actions of 1,25-(OH)(2)D(3) in various systems, along with the detection of VDR in target cells, have indicated potential therapeutic applications of VDR ligands in inflammation (rheumatoid arthritis, psoriatic arthritis), dermatological indications (psoriasis, actinic keratosis, seborrheic dermatitis, photoaging), osteoporosis (postmenopausal and steroid-induced osteoporosis), cancers (prostate, colon, breast, myelodysplasia, leukemia, head and neck squamous cell carcinoma, and basal cell carcinoma), secondary hyperparathyroidism, and autoimmune diseases (systemic lupus erythematosus, type I diabetes, multiple sclerosis, and organ transplantation). As a result, VDR ligands have been developed for the treatment of psoriasis, osteoporosis, and secondary hyperparathyroidism. Furthermore, encouraging results have been obtained with VDR ligands in clinical trials of prostate cancer and hepatocellular carcinoma. This review deals with the molecular aspects of noncalcemic actions of vitamin D analogs that account for the efficacy of VDR ligands in the above-mentioned indications.

  16. CHELATING LIGANDS: ENHANCERS OF QUALITY AND PURITY ...

    African Journals Online (AJOL)

    Nwokem et al.

    ABSTRACT. The quality of biogas depends largely on the percentage of methane and hydrogen sulphide gas present. High concentration of hydrogen sulphide results in low quality biogas. This work employed the use of chelating ligands in scrubbing hydrogen sulphide gas while improving the yield of methane gas.

  17. 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...... demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)2(PCy3)2], from RuC has been examined and the reaction...... found to be quite sluggish and of first order in both RuC and cyanide with a rate constant of k = 0.0104(6) M–1 s–1. Further reaction with cyanide leads to loss of the carbide ligand and formation of trans-[Ru(CN)4(PCy3)2]2–, which was isolated and structurally characterized as its PPh4+ salt....

  18. Simple tertiary phosphines to hexaphosphane ligands: Syntheses ...

    Indian Academy of Sciences (India)

    In this context, we have developed new synthetic methodologies for making unusual inorganic ring systems containing trivalent phosphorus centres, novel phosphorus-based multidentate and hybrid ligands and explored their rich transition metal chemistry and catalytic applications. We have also fine tuned a few existing ...

  19. Multi-Nuclear NMR Investigation of Nickel(II), Palladium(II), Platinum(II) and Ruthenium(II) Complexes of an Asymmetrical Ditertiary Phosphine

    Energy Technology Data Exchange (ETDEWEB)

    Raj, Joe Gerald Jesu [Institut National de la Recherche Scientifique, Quebec (China); Pathak, Devendra Deo [Indian School of Mines, Dhanbad (India); Kapoor, Pramesh N. [Univ. of Delhi, Delhi (India)

    2013-12-15

    Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong σ-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, {sup 1}HNMR, {sup 31}PNMR and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

  20. Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand

    Science.gov (United States)

    Askevold, Bjorn; Nieto, Jorge Torres; Tussupbayev, Samat; Diefenbach, Martin; Herdtweck, Eberhardt; Holthausen, Max C.; Schneider, Sven

    2011-07-01

    Bioinspired hydrogenation of N2 to ammonia at ambient conditions by stepwise nitrogen protonation/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H2 remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N2 splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We report the synthesis of a ruthenium(IV) nitrido complex. The high nucleophilicity of the nitrido ligand is demonstrated by unusual N-C coupling with π-acidic CO. Furthermore, the terminal nitrido ligand undergoes facile hydrogenolysis with H2 at ambient conditions to produce ammonia in high yield. Kinetic and quantum chemical examinations of this reaction suggest cooperative behaviour of a phosphorus-nitrogen-phosphorus pincer ligand in rate-determining heterolytic hydrogen splitting.

  1. Quantum.Ligand.Dock: protein-ligand docking with quantum entanglement refinement on a GPU system.

    Science.gov (United States)

    Kantardjiev, Alexander A

    2012-07-01

    Quantum.Ligand.Dock (protein-ligand docking with graphic processing unit (GPU) quantum entanglement refinement on a GPU system) is an original modern method for in silico prediction of protein-ligand interactions via high-performance docking code. The main flavour of our approach is a combination of fast search with a special account for overlooked physical interactions. On the one hand, we take care of self-consistency and proton equilibria mutual effects of docking partners. On the other hand, Quantum.Ligand.Dock is the the only docking server offering such a subtle supplement to protein docking algorithms as quantum entanglement contributions. The motivation for development and proposition of the method to the community hinges upon two arguments-the fundamental importance of quantum entanglement contribution in molecular interaction and the realistic possibility to implement it by the availability of supercomputing power. The implementation of sophisticated quantum methods is made possible by parallelization at several bottlenecks on a GPU supercomputer. The high-performance implementation will be of use for large-scale virtual screening projects, structural bioinformatics, systems biology and fundamental research in understanding protein-ligand recognition. The design of the interface is focused on feasibility and ease of use. Protein and ligand molecule structures are supposed to be submitted as atomic coordinate files in PDB format. A customization section is offered for addition of user-specified charges, extra ionogenic groups with intrinsic pK(a) values or fixed ions. Final predicted complexes are ranked according to obtained scores and provided in PDB format as well as interactive visualization in a molecular viewer. Quantum.Ligand.Dock server can be accessed at http://87.116.85.141/LigandDock.html.

  2. Role of Lanthanide-Ligand bonding in the magnetization relaxation ...

    Indian Academy of Sciences (India)

    Ligand bonding. Our calculations transpire comparatively improved Single-Ion Magnet (SIM) behaviour for carbene analogues due to the more axially compressed trigonal prismatic ligand environment. Furthermore, our detailed Mulliken charge, ...

  3. Fluorescent GPCR ligands as new tools in pharmacology.

    Science.gov (United States)

    Kuder, Kamil; Kieć-Kononowicz, Katarzyna

    2008-01-01

    The expansion of fluorescent techniques for studying the ligand-receptor interaction resulted in a burst of the novel fluorescent ligands development. The discovery of the ligand, that is of high affinity to the receptor and whose localization could be easily visualized, even on the single cell level, gave the researchers a strong impulse to investigate that field of GPCR ligands. Moreover, paying attention to the "non pharmacological" advantages of these ligands, as well as the techniques to be used, fluorescent ligands are becoming treated more seriously, as the ligands themselves, and as novel, useful tools for studying GPCRs. Herein, we review results described in the literature, starting from the year 2000, in the field of the fluorescent GPCR small, non-peptide ligands according to the affinity to the selected receptors (histamine, adenosine, adrenergic, cannabinoid, muscarinie, neuropeptide Y and serotonine) as well as the fluorophores that have been used to tag the molecules.

  4. Ligand-Mediated Coating of Liposomes with Human Serum Albumin.

    Science.gov (United States)

    Sato, Hikari; Nakhaei, Elnaz; Kawano, Takahito; Murata, Masaharu; Kishimura, Akihiro; Mori, Takeshi; Katayama, Yoshiki

    2018-02-13

    Coating liposome surfaces with human serum albumin (HSA) can improve the colloidal stability and prevent opsonization. HSA coating via specific binding with alkyl ligands is promising because although the ligand-mediated coating is relatively stable it can spontaneously exchange with fresh HSA. However, to achieve surface coating with HSA, multiple hydrophobic ligands must be exposed to an aqueous medium prior to binding with HSA. This presents a challenge, as hydrophobic ligands tend to be buried in the liposomal membrane. Here we present the first HSA modification of liposome surfaces via alkyl ligands. We found that a relatively short alkyl ligand, or a long alkyl ligand with a terminal carboxylate, could be exposed on the liposome surface without causing aggregation of the liposomes and these ligands could subsequently bind HSA. The resulting HSA-coated liposomes were as inert as conventional PEGylated liposomes in terms of macrophage recognition.

  5. Investigation of Asymmetric Thrust Detection with Demonstration in a Real-Time Simulation Testbed

    Science.gov (United States)

    Chicatelli, Amy K.; Rinehart, Aidan W.; Sowers, T. Shane; Simon, Donald L.

    2016-01-01

    The purpose of this effort is to develop, demonstrate, and evaluate three asymmetric thrust detection approaches to aid in the reduction of asymmetric thrust-induced aviation accidents. This paper presents the results from that effort and their evaluation in simulation studies, including those from a real-time flight simulation testbed. Asymmetric thrust is recognized as a contributing factor in several Propulsion System Malfunction plus Inappropriate Crew Response (PSM+ICR) aviation accidents. As an improvement over the state-of-the-art, providing annunciation of asymmetric thrust to alert the crew may hold safety benefits. For this, the reliable detection and confirmation of asymmetric thrust conditions is required. For this work, three asymmetric thrust detection methods are presented along with their results obtained through simulation studies. Representative asymmetric thrust conditions are modeled in simulation based on failure scenarios similar to those reported in aviation incident and accident descriptions. These simulated asymmetric thrust scenarios, combined with actual aircraft operational flight data, are then used to conduct a sensitivity study regarding the detection capabilities of the three methods. Additional evaluation results are presented based on pilot-in-the-loop simulation studies conducted in the NASA Glenn Research Center (GRC) flight simulation testbed. Data obtained from this flight simulation facility are used to further evaluate the effectiveness and accuracy of the asymmetric thrust detection approaches. Generally, the asymmetric thrust conditions are correctly detected and confirmed.

  6. GLIDA: GPCR-ligand database for chemical genomic drug discovery

    OpenAIRE

    Okuno, Yasushi; Yang, Jiyoon; Taneishi, Kei; Yabuuchi, Hiroaki; Tsujimoto, Gozoh

    2005-01-01

    G-protein coupled receptors (GPCRs) represent one of the most important families of drug targets in pharmaceutical development. GPCR-LIgand DAtabase (GLIDA) is a novel public GPCR-related chemical genomic database that is primarily focused on the correlation of information between GPCRs and their ligands. It provides correlation data between GPCRs and their ligands, along with chemical information on the ligands, as well as access information to the various web databases regarding GPCRs. Thes...

  7. AutoSite: an automated approach for pseudo-ligands prediction—from ligand-binding sites identification to predicting key ligand atoms

    Science.gov (United States)

    Ravindranath, Pradeep Anand; Sanner, Michel F.

    2016-01-01

    Motivation: The identification of ligand-binding sites from a protein structure facilitates computational drug design and optimization, and protein function assignment. We introduce AutoSite: an efficient software tool for identifying ligand-binding sites and predicting pseudo ligand corresponding to each binding site identified. Binding sites are reported as clusters of 3D points called fills in which every point is labelled as hydrophobic or as hydrogen bond donor or acceptor. From these fills AutoSite derives feature points: a set of putative positions of hydrophobic-, and hydrogen-bond forming ligand atoms. Results: We show that AutoSite identifies ligand-binding sites with higher accuracy than other leading methods, and produces fills that better matches the ligand shape and properties, than the fills obtained with a software program with similar capabilities, AutoLigand. In addition, we demonstrate that for the Astex Diverse Set, the feature points identify 79% of hydrophobic ligand atoms, and 81% and 62% of the hydrogen acceptor and donor hydrogen ligand atoms interacting with the receptor, and predict 81.2% of water molecules mediating interactions between ligand and receptor. Finally, we illustrate potential uses of the predicted feature points in the context of lead optimization in drug discovery projects. Availability and Implementation: http://adfr.scripps.edu/AutoDockFR/autosite.html Contact: sanner@scripps.edu Supplementary information: Supplementary data are available at Bioinformatics online. PMID:27354702

  8. Integrating structural and mutagenesis data to elucidate GPCR ligand binding

    DEFF Research Database (Denmark)

    Munk, Christian; Harpsøe, Kasper; Hauser, Alexander S

    2016-01-01

    G protein-coupled receptors (GPCRs) represent the largest family of human membrane proteins, as well as drug targets. A recent boom in GPCR structural biology has provided detailed images of receptor ligand binding sites and interactions on the molecular level. An ever-increasing number of ligands...... elucidate new GPCR ligand binding sites, and ultimately design drugs with tailored pharmacological activity....

  9. New mixed ligand complexes of ruthenium (II) that incorporate a ...

    Indian Academy of Sciences (India)

    New mixed ligand complexes of ruthenium(II) that incorporate a modified phenanthroline ligand: Synthesis, spectral characterization and DNA binding. S Murali C V ... Fulltext. Click here to view fulltext PDF ... Ruthenium(II) complexes; modified phenanthroline ligand; spectroscopy; DNA binding; fluorescence enhancement.

  10. Novel peptide ligand with high binding capacity for antibody purification

    DEFF Research Database (Denmark)

    Lund, L. N.; Gustavsson, P. E.; Michael, R.

    2012-01-01

    ligands have an advantage over biological ligands; they are cheaper to produce, ligand leakage by enzymatic degradation is either eliminated or significantly reduced, and they can in general better withstand cleaning in place (CIP) conditions such as 0.1 M NaOH. Here, we present a novel synthetic peptide...

  11. Page 1 ASSESSMENT OF BINDING ENERGIES AND LIGAND ...

    African Journals Online (AJOL)

    The successive binding energies of up to six water ligands to ferric ion and the reduction in the gross binding energies by ligand-ligand repulsion are determined by electrostatic interaction. The gross binding energy is found to be both geometry and coordination nuitber dependent: whereas it increases with number of ...

  12. Differential isotopic enrichment to facilitate characterization of asymmetric multimeric proteins using hydrogen/deuterium exchange mass spectrometry.

    Science.gov (United States)

    Goswami, Devrishi; Tuske, Steve; Pascal, Bruce D; Bauman, Joseph D; Patel, Disha; Arnold, Eddy; Griffin, Patrick R

    2015-04-07

    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry has emerged as a powerful tool for analyzing the conformational dynamics of protein-ligand and protein-protein interactions. Recent advances in instrumentation and methodology have expanded the utility of HDX for the analysis of large and complex proteins; however, asymmetric dimers with shared amino acid sequence present a unique challenge for HDX because assignment of peptides with identical sequence to their subunit of origin remains ambiguous. Here we report the use of differential isotopic labeling to facilitate HDX analysis of multimers using HIV-1 reverse transcriptase (RT) as a model. RT is an asymmetric heterodimer of 51 kDa (p51) and 66 kDa (p66) subunits. The first 440 residues of p51 and p66 are identical. In this study differentially labeled RT was reconstituted from isotopically enriched ((15)N-labeled) p51 and unlabeled p66. To enable detection of (15)N-deuterated RT peptides, the software HDX Workbench was modified to follow a 100% (15)N model. Our results demonstrated that (15)N enrichment of p51 did not affect its conformational dynamics compared to unlabeled p51, but (15)N-labeled p51 did show different conformational dynamics than p66 in the RT heterodimer. Differential HDX-MS of isotopically labeled RT in the presence of the non-nucleoside reverse transcriptase inhibitor (NNRTI) efavirenz (EFV) showed subunit-specific perturbation in the rate of HDX consistent with previously published results and the RT-EFV cocrystal structure.

  13. A theoretically-guided optimization of a new family of modular P,S-ligands for iridium-catalyzed hydrogenation of minimally functionalized olefins.

    Science.gov (United States)

    Margalef, Jèssica; Caldentey, Xisco; Karlsson, Erik A; Coll, Mercè; Mazuela, Javier; Pàmies, Oscar; Diéguez, Montserrat; Pericàs, Miquel A

    2014-09-15

    A library of modular iridium complexes derived from thioether-phosphite/phosphinite ligands has been evaluated in the asymmetric iridium-catalyzed hydrogenation of minimally functionalized olefins. The modular ligand design has been shown to be crucial in finding highly selective catalysts for each substrate. A DFT study of the transition state responsible for the enantiocontrol in the Ir-catalyzed hydrogenation is also described and used for further optimization of the crucial stereodefining moieties. Excellent enantioselectivities (enantiomeric excess (ee) values up to 99 %) have been obtained for a range of substrates, including E- and Z-trisubstituted and disubstituted olefins, α,β-unsaturated enones, tri- and disubstituted alkenylboronic esters, and olefins with trifluoromethyl substituents. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Mechanics, thermodynamics, and kinetics of ligand binding to biopolymers.

    Science.gov (United States)

    Jarillo, Javier; Morín, José A; Beltrán-Heredia, Elena; Villaluenga, Juan P G; Ibarra, Borja; Cao, Francisco J

    2017-01-01

    Ligands binding to polymers regulate polymer functions by changing their physical and chemical properties. This ligand regulation plays a key role in many biological processes. We propose here a model to explain the mechanical, thermodynamic, and kinetic properties of the process of binding of small ligands to long biopolymers. These properties can now be measured at the single molecule level using force spectroscopy techniques. Our model performs an effective decomposition of the ligand-polymer system on its covered and uncovered regions, showing that the elastic properties of the ligand-polymer depend explicitly on the ligand coverage of the polymer (i.e., the fraction of the polymer covered by the ligand). The equilibrium coverage that minimizes the free energy of the ligand-polymer system is computed as a function of the applied force. We show how ligands tune the mechanical properties of a polymer, in particular its length and stiffness, in a force dependent manner. In addition, it is shown how ligand binding can be regulated applying mechanical tension on the polymer. Moreover, the binding kinetics study shows that, in the case where the ligand binds and organizes the polymer in different modes, the binding process can present transient shortening or lengthening of the polymer, caused by changes in the relative coverage by the different ligand modes. Our model will be useful to understand ligand-binding regulation of biological processes, such as the metabolism of nucleic acid. In particular, this model allows estimating the coverage fraction and the ligand mode characteristics from the force extension curves of a ligand-polymer system.

  15. Mechanics, thermodynamics, and kinetics of ligand binding to biopolymers.

    Directory of Open Access Journals (Sweden)

    Javier Jarillo

    Full Text Available Ligands binding to polymers regulate polymer functions by changing their physical and chemical properties. This ligand regulation plays a key role in many biological processes. We propose here a model to explain the mechanical, thermodynamic, and kinetic properties of the process of binding of small ligands to long biopolymers. These properties can now be measured at the single molecule level using force spectroscopy techniques. Our model performs an effective decomposition of the ligand-polymer system on its covered and uncovered regions, showing that the elastic properties of the ligand-polymer depend explicitly on the ligand coverage of the polymer (i.e., the fraction of the polymer covered by the ligand. The equilibrium coverage that minimizes the free energy of the ligand-polymer system is computed as a function of the applied force. We show how ligands tune the mechanical properties of a polymer, in particular its length and stiffness, in a force dependent manner. In addition, it is shown how ligand binding can be regulated applying mechanical tension on the polymer. Moreover, the binding kinetics study shows that, in the case where the ligand binds and organizes the polymer in different modes, the binding process can present transient shortening or lengthening of the polymer, caused by changes in the relative coverage by the different ligand modes. Our model will be useful to understand ligand-binding regulation of biological processes, such as the metabolism of nucleic acid. In particular, this model allows estimating the coverage fraction and the ligand mode characteristics from the force extension curves of a ligand-polymer system.

  16. A ligand's view of target similarity

    DEFF Research Database (Denmark)

    Garland, Stephen L; Gloriam, David E

    2011-01-01

    shows with several examples how focusing on the binding site(s) has a clear advantage when it comes to establishing sequence-correlated pharmacological profiles. By organizing and comparing sequence and structural data it is possible to "borrow" SAR from similar targets to increase the speed of lead......-finding and, potentially, to produce ligands for previously intractable receptors. Sequence motifs correlated with ligands can be applied in the design of target-specific focused libraries that are both efficient and cost-effective and should provide increased hit-rates over diversity screening. Furthermore......, in the optimization phase, the binding motif approach offers the possibility to identify quickly the most likely off-target candidates to be chosen for selectivity screening, as well as potentially characterizing those pockets which may best be exploited for improved selectivity....

  17. Sigma-2 receptor ligands QSAR model dataset

    Directory of Open Access Journals (Sweden)

    Antonio Rescifina

    2017-08-01

    Full Text Available The data have been obtained from the Sigma-2 Receptor Selective Ligands Database (S2RSLDB and refined according to the QSAR requirements. These data provide information about a set of 548 Sigma-2 (σ2 receptor ligands selective over Sigma-1 (σ1 receptor. The development of the QSAR model has been undertaken with the use of CORAL software using SMILES, molecular graphs and hybrid descriptors (SMILES and graph together. Data here reported include the regression for σ2 receptor pKi QSAR models. The QSAR model was also employed to predict the σ2 receptor pKi values of the FDA approved drugs that are herewith included.

  18. Asymmetric muscle function in patients with developmental mandibular asymmetry.

    Science.gov (United States)

    Dong, Y; Wang, X M; Wang, M Q; Widmalm, S E

    2008-01-01

    The aim was to test the hypothesis that developmental mandibular asymmetry is associated with increased asymmetry in muscle activity. Patients with mandibular condylar and/or ramus hyperplasia having unilateral cross-bite were compared with healthy subjects with normal occlusion. Muscle activity was recorded with surface electrodes in the masseter, suprahyoid, sternocleidomastoid muscle (SCM) and upper trapezius areas during jaw opening-closing-clenching, head-neck flexion-extension, and elevation-lowering of shoulders. Root mean square (RMS) and mean power frequency (MPF) values were calculated and analysed using anova and t-tests with P muscles showed co-activation during jaw and head movements, significantly more asymmetric in the patients than in the healthy subjects. The RMS and MPF values were higher in the patients than in the controls in the SCM and suprahyoid areas on both sides during jaw opening-closing movement. The results indicate that the ability to perform symmetric jaw and neck muscle activities is disturbed in patients with developmental mandibular asymmetry. This is of clinical interest because asymmetric activity may be an etiologic factor in temporomandibular joint and cervical pain. The results support that co-activation occurs between jaw and neck muscles during voluntary jaw opening and indicate that postural antigravity reflex activity occurs in the masseter area during head extension. Further studies, where EMG recordings are made from the DMA patients at early stages are motivated to verify activity sources and test if the asymmetric activity is associated with muscle and joint pain in the jaw and cervical areas.

  19. Hydrogen bonding penalty upon ligand binding.

    Directory of Open Access Journals (Sweden)

    Hongtao Zhao

    Full Text Available Ligand binding involves breakage of hydrogen bonds with water molecules and formation of new hydrogen bonds between protein and ligand. In this work, the change of hydrogen bonding energy in the binding process, namely hydrogen bonding penalty, is evaluated with a new method. The hydrogen bonding penalty can not only be used to filter unrealistic poses in docking, but also improve the accuracy of binding energy calculation. A new model integrated with hydrogen bonding penalty for free energy calculation gives a root mean square error of 0.7 kcal/mol on 74 inhibitors in the training set and of 1.1 kcal/mol on 64 inhibitors in the test set. Moreover, an application of hydrogen bonding penalty into a high throughput docking campaign for EphB4 inhibitors is presented, and remarkably, three novel scaffolds are discovered out of seven tested. The binding affinity and ligand efficiency of the most potent compound is about 300 nM and 0.35 kcal/mol per non-hydrogen atom, respectively.

  20. Palladium-Catalyzed Asymmetric Benzylic Substitution of Secondary Benzyl Carbonates with Nitrogen and Oxygen Nucleophiles.

    Science.gov (United States)

    Najib, Atifah; Hirano, Koji; Miura, Masahiro

    2017-05-05

    A Pd/(R)-BINAP-catalyzed asymmetric benzylic substitution of secondary benzyl carbonates with amides and amines proceeds to form the corresponding optically active benzylamines in good yields with a high enantiomeric ratio. The reaction occurs in a dynamic kinetic asymmetric transformation (DYKAT) manner. Additionally, the asymmetric Pd catalysis can also be applicable to phenol nucleophiles, thus delivering chiral ethers with acceptable yields and enantioselectivity.