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Sample records for asymmetric reactions forming

  1. Entrance channel independence in the decay of 47V formed in nearly symmetric and asymmetric reactions

    International Nuclear Information System (INIS)

    A light mass CN 47V*, produced via different reaction channels, is observed to have fully energy damped binary decay process, supported by the statistical model calculations based on the transition-state model (TSM). In the present contribution, the decay of excited CN 47V* formed in nearly symmetric and asymmetric reactions 23Na+24Mg (Elab=89.1 MeV) and 35Cl+12C (Elab=200 MeV), respectively, with the same excitation energy ECN*=64.1 MeV, is studied by using the Dynamical Cluster decay Model (DCM) of Gupta and collaborators

  2. Asymmetric reactions in continuous flow

    Directory of Open Access Journals (Sweden)

    Xiao Yin Mak

    2009-04-01

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

  3. Asymmetric Aldol Reaction with Formaldehyde: a Challenging Process.

    Science.gov (United States)

    Meninno, Sara; Lattanzi, Alessandra

    2016-08-01

    The asymmetric aldol reaction with formaldehyde is a fundamental carbon-carbon bond-forming reaction in organic synthesis, as well as in the quest of the origin of life, as it is thought to have been the first "molecular brick" involved in the synthetic path to complex sugars. Products of aldol reactions, i.e., the β-hydroxy carbonyl compounds, are versatile building blocks used to access a great variety of functionalised molecules. The employment of formaldehyde, as a C1 symmetric electrophile, in aldol reactions can be likely considered the most challenging, yet simplest, process to introduce a hydroxymethyl group in an asymmetric fashion. In this account, an overview of the progress achieved in the asymmetric metal- and organocatalysed aldol reaction, using readily available formalin or paraformaldehyde sources, is illustrated. Our recent contribution to this area, with the application of asymmetric hydroxymethylation in cascade processes for the synthesis of γ-butyrolactones, is also shown. PMID:27328802

  4. 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.

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

    Science.gov (United States)

    Node, Manabu

    2002-01-01

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

  6. 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.

  7. Asymmetric chemical reactions by polarized quantum beams

    Science.gov (United States)

    Takahashi, Jun-Ichi; Kobayashi, Kensei

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

  8. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

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

  9. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

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

  10. Novel strategies for asymmetric hydrogenation reactions

    OpenAIRE

    Chen, Dianjun

    2011-01-01

    This thesis describes two novel possibilities for asymmetric hydrogenation: enantioselective hydrogenation using chiral ionic liquid systems and metal-free hydrogenation with boranes. In the first part, asymmetric hydrogenation systems using chiral ionic liquids in combination with racemic rhodium catalyst are presented. Enantioselectivities up to 69% ee were achieved in homogeneous Rh-catalyzed hydrogenation with tropos ligand (BIPHEP, sulfonated BIPHEP) in a proline derived cation chiral io...

  11. Metal-catalyzed asymmetric aldol reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Luiz C.; Lucca Junior, Emilio C. de; Ferreira, Marco A. B.; Polo, Ellen C., E-mail: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

    2012-12-15

    The aldol reaction is one of the most powerful and versatile methods for the construction of C-C bonds. Traditionally, this reaction was developed in a stoichiometric version; however, great efforts in the development of chiral catalysts for aldol reactions were performed in recent years. Thus, in this review article, the development of metal-mediated chiral catalysts in Mukaiyama-type aldol reaction, reductive aldol reaction and direct aldol reaction are discussed. Moreover, the application of these catalysts in the total synthesis of complex molecules is discussed. (author)

  12. 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.

  13. Study of the fusion-evaporation reactions for the compound nuclei 58Ni, 60Ni, 62Ni formed by symmetrical and asymmetrical channels from energies below the Coulomb barrier

    International Nuclear Information System (INIS)

    The base of this experimental work is the study of the fusion-evaporation reactions for the compound nuclei 51Ni, 60Ni, 62Ni formed by symmetrical and asymmetrical entrance channels at energies near and below of the Coulomb barrier. The absolute cross sections were determined by means of in-beam γ-ray spectroscopy technique associated with the use of a turning target. Six fusion excitation functions have been established corresponding to the measurements of about 2000 absolute cross sections. The experimental errors are of the order of 10-20%. The excitation functions for complete fusion are analysed with a semi-classical model, and fusion barriers, radii and potential curvatures are extracted. The data are compared with the predictions of several heavy ion potentials. The enhancement of the fusion cross sections at sub-barrier energies can be reproduced either by one dimensional barrier penetration taking into account the zero point motion of the reaction partners, or by quantum mechanical calculations with two degrees of freedom indicating the presence of neck formation is sub-barrier fusion. It seems that the formation of these compound nuclei is limited neither by the entrance channels nor by the Yrast line. The Hauser-Feshbach statistical model (Cascade calculation) predictions for the deexcitation of the compound nuclei agree sufficiently with the data for the exit channels having an intensity superior to 10% of the fusion cross section. On the other hand, a systematic underestimation of the 2α decay mode is observed. A correct parametrization of the entrance channel transmission coefficients does not improve significantly the agreement between the measured and calculated evaporation residue cross sections

  14. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG; XuMu

    2001-01-01

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

  15. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

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

  16. Chiral amide from (1, 2)-(+)-norephedrine and furoic acid: An efficient catalyst for asymmetric Reformatsky reaction

    Indian Academy of Sciences (India)

    Nallamuthu Ananthi; Sivan Velmathi

    2014-01-01

    Chiral amide derived from (1, 2)-(+)-norephedrine and 2-furoic acid was found to catalyse the asymmetric Reformatsky reaction between prochiral aldehydes and α-bromo ethylacetate with diethylzinc as zinc source. The corresponding chiral -hydroxy esters were formed in 99% yield with over 80% enantiomeric excess. The presence of air was found to be essential for the effective C-C bond formation. The mechanism for the catalytic reaction was proposed.

  17. Asymmetric Aldol Reaction Catalyzed by Modularly Designed Organocatalysts

    Institute of Scientific and Technical Information of China (English)

    Sinha, Debarshi; Mandal, Tanmay; Gogoi, Sanjib; Goldman, Joshua J.; 赵从贵

    2012-01-01

    The self-assembly of the precatalyst modules, which are amino acids and cinchona alkaloid derivatives, leads to the direct formation of the desired organocatalysts without any synthesis. These modularly designed organocatalysts (MDOs) may be used for catalyzed asymmetric aldol reaction the corresponding aldol products may be obtained in mediocre diastereoselectivities (up to 79 : 21 dr). Depending on structure of the aldehyde substrates, to excellent ee values (up to 92% ee) with moderate

  18. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes.

    Science.gov (United States)

    Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael

    2014-12-01

    The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

  19. Non Heme System Asymmetric Epoxidation Reaction Made Progress

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Funded by the National Natural Science Foundation of China and the Chinese Academy of Sciences "Hundred Talents Program", the Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Oxo Synthesis and Selective Oxidation State Key Laboratory of biological and Biomimetic Catalytic task group has recently developed a new type of non heme enzyme simulation system, the system uses the benz- imidazole instead of four nitrogen ligands pyridine units, natural proline derivatives two amine instead of HMDA skeleton, the manganese complexes in asymmetric epoxidation reaction shown high activity, but in 1/10000 the amount of catalyst under conditions of high selectivity to obtain corresponding product, TON (Turnover numbers) up to 9600, TOF (Turnover frequency) up to 59000 h-1. It is currently reported the highest activity in epoxidation catalyst. Use the H202/AcOH or peracetic acid as oxidant, 180 isotope la- beling experiments, were found different degrees of 180 isotope labeling of epoxy products, won the first direct evidence of response is obtained by the high Mn O intermediates in the process, the work was pub- lished recently in Chem. Eur. J. (Chem. Eur. J. 2012, 18, 6750--6753. ).

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

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Yao, Sulan; Graven, Anette

    1998-01-01

    The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo- and...... enantioselectivities. The reaction course is dependent on several factors such as the solvent and the anions coordinated to the catalyst. The scope of the reaction is outlined by the total synthesis of a natural occurring actinidiolide....

  1. Direct asymmetric aldol reaction using MBHA resin-supported peptide containing L-proline unit

    Institute of Scientific and Technical Information of China (English)

    Liang Zhang; Wen Bo Ding; Yong Ping Yu; Hong Bin Zou

    2009-01-01

    MBHA resin-supported tripeptide catalyst system containing L-proline unit has been developed for use in the direct asymmetric aldol reaction of acetone and aldehydes,which afford the corresponding products with satisfactory isolated yields and enantiomeric excesses.

  2. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John;

    2001-01-01

    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed by...... asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  3. Preparation and Reactions of Amino Acid Ester Sulfones as New Remote Asymmetrical Induced Reagents

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Cheng-He; BAI,Xue; LI,Tan-Qing; WU,Jun; Alfred Hassner

    2004-01-01

    @@ The development of chiral auxiliary-controlled asymmetric synthesis has been receiving increasing interest in recent yearsfi,2] Various chiral auxiliary reagents have been observed[3] and a lot of results showed that variation of the chiral auxiliary could influence asymmetric induction. Recently, it has been reported the reaction of the aminated sulfones as a remote chiral auxiliary with α,β-unsaturated carbonyl compounds.[4] Here we would like to report the preparation of amino acid ester sulfones as new remote asymmetrical induced reagents and their reactions with α,β-unsaturated esters.

  4. Comparison of radial flow effects on partitions of multifragmenting sources formed in symmetric and asymmetric central collisions

    Directory of Open Access Journals (Sweden)

    Frankland J.D.

    2015-01-01

    Full Text Available The role of collective radial expansion in determining multifragmentation partition properties has previously been explored by comparing different-sized sources of the same excitation energy per nucleon formed by very different reaction mechanisms: excited quasi-projectiles from semi-peripheral Au+Au collisions and quasi-fused sources from central Xe+Sn collisions. New data has been obtained with INDRA on 181Ta+66Zn collisions in order to allow comparison of Xe+Sn data with quasi-fused systems having the same mass, charge and excitation energy per nucleon formed in mass-asymmetric reactions, for which a smaller initial compression is expected. Preliminary results confirm that, ceteris paribus, smaller radial flow leads to less fragments with more asymmetric partitions.

  5. Asymmetric Hydrogenation of α-Hydroxy Ketones: A Reaction Sensitive toward Electronic Effect of Substrates

    Institute of Scientific and Technical Information of China (English)

    XU Hui; MENG Qing-Hua; ZHANG Zhao-Guo

    2008-01-01

    An efficient asymmetric hydrogenation of a-hydroxy ketones was reported with the catalyst prepared from [RuCl2(benzene)]2 and SunPhos,chiral terminal 1,2-diols were obtained in up to 99% ee.This Ru-catalyzed asymmetric hydrogenation reaction of a-hydroxy ketones represents a new route for the synthesis of chiral terminal 1,2-diols.

  6. Excitation of the dynamical dipole in the charge asymmetric reaction 16O + 116Sn

    Science.gov (United States)

    Corsi, A.; Wieland, O.; Kravchuk, V. L.; Bracco, A.; Camera, F.; Benzoni, G.; Blasi, N.; Brambilla, S.; Crespi, F. C. L.; Giussani, A.; Leoni, S.; Million, B.; Montanari, D.; Moroni, A.; Gramegna, F.; Lanchais, A.; Mastinu, P.; Brekiesz, M.; Kmiecik, M.; Maj, A.; Bruno, M.; D'Agostino, M.; Geraci, E.; Vannini, G.; Barlini, S.; Casini, G.; Chiari, M.; Nannini, A.; Ordine, A.; Di Toro, M.; Rizzo, C.; Colonna, M.; Baran, V.

    2009-08-01

    The γ-ray emission from the dynamical dipole formed in heavy-ion collisions during the process leading to fusion was measured for the N/Z asymmetric reaction 16O + 116Sn at beam energies of 8.1 and 15.6 MeV/nucleon. High-energy γ-rays and charged particles were measured in coincidence with the heavy recoiling residual nuclei. The data are compared with those from the N/Z symmetric reaction 64Ni + 68Zn at bombarding energies of 4.7 and 7.8 MeV/nucleon, leading to the same CN with the same excitation energies as calculated from kinematics. The measured yield of the high-energy γ-rays from the 16O-induced reaction is found to exceed that of the thermalized CN and the excess yield increases with bombarding energy. The data are in rather good agreement with the predictions for the dynamical dipole emission based on the Boltzmann-Nordheim-Vlasov model. In addition, a comparison with existing data in the same mass region is performed to extract information on the dipole moment dependence.

  7. Excitation of the dynamical dipole in the charge asymmetric reaction {sup 16}O + {sup 116}Sn

    Energy Technology Data Exchange (ETDEWEB)

    Corsi, A. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy); Wieland, O. [INFN Sezione di Milano, Milano (Italy); Kravchuk, V.L. [Laboratori Nazionali INFN di Legnaro, Legnaro (Italy); Bracco, A. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy); Camera, F. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy)], E-mail: franco.camera@mi.infn.it; Benzoni, G.; Blasi, N.; Brambilla, S. [INFN Sezione di Milano, Milano (Italy); Crespi, F.C.L.; Giussani, A.; Leoni, S. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy); Million, B. [INFN Sezione di Milano, Milano (Italy); Montanari, D.; Moroni, A. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy); Gramegna, F.; Lanchais, A.; Mastinu, P. [Laboratori Nazionali INFN di Legnaro, Legnaro (Italy); Brekiesz, M.; Kmiecik, M.; Maj, A. [Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Krakow (Poland)] (and others)

    2009-08-24

    The {gamma}-ray emission from the dynamical dipole formed in heavy-ion collisions during the process leading to fusion was measured for the N/Z asymmetric reaction {sup 16}O + {sup 116}Sn at beam energies of 8.1 and 15.6 MeV/nucleon. High-energy {gamma}-rays and charged particles were measured in coincidence with the heavy recoiling residual nuclei. The data are compared with those from the N/Z symmetric reaction {sup 64}Ni + {sup 68}Zn at bombarding energies of 4.7 and 7.8 MeV/nucleon, leading to the same CN with the same excitation energies as calculated from kinematics. The measured yield of the high-energy {gamma}-rays from the {sup 16}O-induced reaction is found to exceed that of the thermalized CN and the excess yield increases with bombarding energy. The data are in rather good agreement with the predictions for the dynamical dipole emission based on the Boltzmann-Nordheim-Vlasov model. In addition, a comparison with existing data in the same mass region is performed to extract information on the dipole moment dependence.

  8. Direct Asymmetric Aldol Type Reaction with Ethyl Diazoacetate: Stereoselective Synthesis of α, β-Dihydroxy Esters

    Institute of Scientific and Technical Information of China (English)

    LIAO Ming-Yi; YAO Wen-Gang; FENG Hai-Tao; WANG Jian-Bo

    2003-01-01

    @@ Enantioselective aldol condensation under catalytic condition remains a challenging task in modern organic synthesis, and numerous efforts have been directed to this area. In particular, the direct catalytic asymmetric aldol reaction is very attractive considering the requirement of atom efficiency. This has been studied only recently, and several very practical processes have been developed. We have recently initiated a study on the direct asymmetric aldol type reaction with ethyl diazoacetate as nucleophile. Moderate enantioselectivities (65% ~91% ee ) were achieved in the condensation of aldehydes with ethyl diazoacetate catalyzed by the chiral complex of BINOL derivatives-Zr (OBu- t )4. [1

  9. Multicomponent asymmetric reactions mediated by proline lithium salt

    DEFF Research Database (Denmark)

    Renzi, Polyssena; Overgaard, Jacob; Bella, Marco

    2010-01-01

    The multicomponent reaction between proline lithium salt, 2-cyclohexen-1-one and aliphatic aldehydes affords the 4- alkylidene-2-cyclohexen-1-ones, which are interesting fragrances, and bicyclic amino acids that bear four additional stereocenters, obtained as single stereoisomer....

  10. Measurements of Dynamical Dipole in isospin asymmetric fusion reactions

    Science.gov (United States)

    Giaz, A.; Corsi, A.; Camera, F.; Bracco, A.; Crespi, F. C. L.; Leoni, S.; Nicolini, R.; Vandone, V.; Benzoni, G.; Blasi, N.; Brambilla, S.; Million, B.; Wieland, O.; Cinausero, M.; Degelier, M.; Gramegna, F.; Kravchuk, V. L.; Marchi, T.; Rizzi, V.; Bardelli, L.; Barlini, S.; Bini, M.; Carboni, S.; Casini, G.; Chiari, M.; Nannini, A.; Pasquali, G.; Piantelli, S.; Poggi, G.; Baiocco, G.; Bruno, M.; D'agostino, M.; Morelli, L.; Vannini, V.; Colonna, M.; Di Toro, M.; Rizzo, C.; Bednarcyk, P.; Ciemala, M.; Kmiecik, M.; Maj, A.; Mazurek, K.; Menczynski, W.; Alba, R.; Maiolino, C.; Santonocito, D.; Montanari, D.; Ordine, A.

    2012-05-01

    In heavy ion nuclear reactions the process leading to complete fusion is expected to produce pre-equilibrium γ-ray emission, if particular conditions are met. Indeed, when there is an N/Z asymmetry between projectile and target, charge equilibration takes place with a collective dipole oscillation, called Dynamical Dipole (DD), associated to a γ-ray emission. The existing experimental data concerning this pre-equilibrium γ-ray emission are still rather scarce and manly concentrated in the A≊132 mass region. The very preliminary results concerning the measurement of the DD γ-ray emission in the fusion reaction 16O (Elab=192 MeV) + 116Sn at 12 MeV/u will be presented and compared with the γ yield measured for the same reaction at 8.1 and 15.6 MeV/u. The present experiment aims at the measurement of the total emission yield of the DD at 12 MeV/u where the predicted theoretical yield does not completely reproduce the experimental data. The experiment has been performed at the INFN Legnaro Laboratories using the GARFIELD-HECTOR array.

  11. Asymmetric Roadmap to Diverse Polycyclic Benzopyrans via Phosphine-Catalyzed Enantioselective [4 + 2]-Annulation Reaction.

    Science.gov (United States)

    Danda, Adithi; Kesava-Reddy, Naredla; Golz, Christopher; Strohmann, Carsten; Kumar, Kamal

    2016-06-01

    The catalytic addition of the amino acid derived bifunctional N-acylaminophosphine to an α-substituted allene ester generated a zwitterionic dipole that engaged the vinylogous ester function of 3-cyano-chromones in a [4 + 2] annulation reaction to deliver tetrahydroxanthones embodying three consecutive chiral centers in high yields and with excellent enantioselectivities. The established asymmetric synthesis further paves the way to two different classes of complex, sp(3)-rich tetracyclic benzopyrans via efficient cascade reactions. PMID:27187586

  12. Zinc-prolinamide complex catalyzed direct asymmetric aldol reactions in the presence of water

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    An efficient direct asymmetric aldol reaction with zinc triflate and prolinamides as combined catalysts is reported.A series of chiral prolinamides have been designed and used in the direct aldol reaction resulting in the desired products with excellent yields(up to 94% yield) and high enantioselectivities(up to 96% ee).Water was found to play a significant role in the formation of the aldol products,which suggests a new strategy in the design of new organic catalysts.

  13. 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.

  14. Asymmetrical ClO3 - Its possible formation from ClO and O2 and its possible reactions

    Science.gov (United States)

    Prasad, S. S.; Adams, W. M.

    1980-01-01

    An analysis of recent accurate experimental studies of Cl2-photosensitized O3 decomposition, in which O3 disappearance and OClO formation were directly monitored, suggests the possibility that the suppression of the quantum yield in the presence of O2 may be due to the formation of asymmetrical chlorine trioxide (ClO.O2). Other intermediaries, such as Cl2O2, which may also form in the system are not thought to explain the observations. In addition to its capacity to oxidize, which it shares with other peroxo compounds, asymmetrical ClO3 appears to undergo an interesting class of reactions in which the loosely bound O2 adduct is relatively easily displaced by reactive atoms and radicals such as chlorine.

  15. 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.

  16. Asymmetric synthesis of tetrahydroisoquinolines by enzymatic Pictet-Spengler reaction.

    Science.gov (United States)

    Nishihachijo, Masakatsu; Hirai, Yoshinori; Kawano, Shigeru; Nishiyama, Akira; Minami, Hiromichi; Katayama, Takane; Yasohara, Yoshihiko; Sato, Fumihiko; Kumagai, Hidehiko

    2014-01-01

    Norcoclaurine synthase (NCS) catalyzes the stereoselective Pictet-Spengler reaction between dopamine and 4-hydroxyphenylacetaldehyde as the first step of benzylisoquinoline alkaloid synthesis in plants. Recent studies suggested that NCS shows relatively relaxed substrate specificity toward aldehydes, and thus, the enzyme can serve as a tool to synthesize unnatural, optically active tetrahydroisoquinolines. In this study, using an N-terminally truncated NCS from Coptis japonica expressed in Escherichia coli, we examined the aldehyde substrate specificity of the enzyme. Herein, we demonstrate the versatility of the enzyme by synthesizing 6,7-dihydroxy-1-phenethyl-1,2,3,4-tetrahydroisoquinoline and 6,7-dihydroxy-1-propyl-1,2,3,4-tetrahydroisoquinoline in molar yields of 86.0 and 99.6% and in enantiomer excess of 95.3 and 98.0%, respectively. The results revealed the enzyme is a promising catalyst that functions to stereoselectively produce various 1-substituted-1,2,3,4-tetrahydroisoquinolines. PMID:25036970

  17. Synthesis and Catalytic Asymmetric Reaction of Chiral Pyridine Prolinol Derivatives

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiao; ZHANG Yong-Xin; DU Da-Ming; HUA Wen-Ting

    2003-01-01

    @@ The enantioselective reduction of prochiral ketones with borane in the presence of a chiral ligand leading to enantiomerically pure secondary alcohols has received considerable attention in recent years. [1] Enantiomerically pure secondary alcohols are important intermediates for the synthesis of various other organic compounds such as halides, esters, ethers, ketones and amines. To the best of our knowledge, the use of pyridine prolinol derivatives in the reduction of ketones has not been reported so far. Thus, it should be of interest to investigate the catalytic a bility of such ligands. We have an ongoing project in the synthesis and application of chiral pyridine derivatives in chiral molecular recognition[2] and we want to evaluate the effect resulting from the introduction of a pyridinyl moiety onto the catalysts. We expect that the cooperation of pyridine unit and chiral prolinol unit in new ligands may result in unique properties for catalytic reaction.

  18. Isolation of microbe for asymmetric reduction of prochiral aromatic ketone and its reaction characters

    Institute of Scientific and Technical Information of China (English)

    YANG Zhonghua; ZENG Rong; WANG Yu; WANG Guanghui; YAO Shanjing

    2007-01-01

    The favorable microbes for the asymmetric reduction of prochiral aromatic ketones was isolated from soil using acetophenone as the sole carbon source,when the asymmetric reduction of acetophenone (ACP) to chiral α-phenethyl alcohol (PEA) was chosen as the model reaction.Two microbe strains with excellent catalytic activity were obtained.They were Geotrichum candidum and Pichia pastoris identified by bacteria identification.The product of the asymmetric reduction of ACP catalyzed by Pichia pastoris was mainly R-PEA and that by Geotrichum candidum was mainly S-PEA.The yield and enantiomeric excesses (e.e.) could respectively reach 75% and 90% for Pichiapastoris,and 80% and 70% for Geotrichum candidum,much higher than those catalyzed by baker's yeast.

  19. Synthesis of 7,7'-Disubstituted BINAP and Their Application in Asymmetric Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

    Yuan Wei-Cheng; Liu Hua; Mi Ai-Qiao; Gong Liu-Zhu; Jiang Yao-Zhong

    2004-01-01

    The design of new chiral ligands plays a very important role in the development of transition metal catalyzed asymmetric synthesis. Many chiral diphosphine ligands have been prepared and applied in asymmetric catalytic reactions with excellent enantioselectivities. Among the chiral diphosphine ligands reported, BINAP was found to have been the widest application in the transition metal catalyzed reaction. Recently we have developed a novel oxovanadium (Ⅳ)complex catalyst for the oxidative coupling of naphthol with high enantioselectivity.[1] And then a series of optically pure 7,7'-disubstituted BINOLs were successfully synthesized by using the catalyst,[2] on the basis of above, the 7,7'-disubstituted BINAP ligands ( 1-5 ) were easily prepared from the 7,7'-disubstituted BINOLs with high total yields (up to 64% of 5 steps from the BINOLs ).To demonstrate the efficiency of ligands 1-5, we applied their ruthenium complexes for asymmetric hydrogenation of simple ketones with high activity (S/C up to 5000 ), high converation (up to 100%) and moderate enantioselectivity (ee up to 88.3% ) under mild conditions. In addition, in the asymmetric 1,4-addition of arylboronic acids, these ligands also provide excellent enantioselectivity (ee up to 99%) and yield ( up to 99%).

  20. Pre-equilibrium dipole strength in charge asymmetric peripheral heavy-ion reactions

    International Nuclear Information System (INIS)

    We report on the results obtained from the study of the 32S+64Ni and 32S+58Ni peripheral reactions at incident energies Elab=288 MeV and Elab=320 MeV, respectively. High-energy γ-rays were detected in an array of 8 seven-pack BaF2 clusters. Coincidence with complex fragments detected in 12 three-stage telescopes ensured the selection of peripheral reaction events. All of the relevant reaction parameters were kept constant with the exception of the different initial dipole moment caused by the different entrance channel charge asymmetry. While for quasi-elastic events no N/Z effect was observed in the differential γ-ray multiplicities of the two reactions, for deep-inelastic events a larger dipole γ-ray emission occurs during the more N/Z asymmetric reaction. A theoretical interpretation based on a collective Bremsstrahlung analysis of the reaction dynamics is presented. (orig.)

  1. Fear as a medium of communication in asymmetric forms of warfare

    DEFF Research Database (Denmark)

    Harste, Gorm

    2011-01-01

    of fear evolves in asymmetric warfare. Asymmetric war induces fear in both parties, but in a communicative form that leads to very different experiences of fear. Fear is observed and analysed with Niklas Luhmann’s theory of self-referential systems of communication and well as his theory of risk....... Following Luhmann and in continuation of Clausewitz’ conceptual tools, yet with other means, the article proposes to observe war as a system that can de-ontologize itself and thereby concern moving centres of gravity such as communication lines, motivation, public fear as well as perceptions of risk...

  2. Asymmetric Electrophilic α-Amination of Silyl Enol Ether Derivatives via the Nitrosocarbonyl Hetero-ene Reaction.

    Science.gov (United States)

    Sandoval, David; Samoshin, Andrey V; Read de Alaniz, Javier

    2015-09-18

    The first example of a general asymmetric nitrosocarbonyl hetero-ene reaction is described. The procedure uses a copper-catalyzed aerobic oxidation of a commercially available chiral nitrosocarbonyl precursor (EleNOr) and is operationally simple. The transformation is both high yielding and highly diastereoselective for a range of silyl enol ether derivatives. A variety of synthetically useful postfunctionalization reactions are presented along with a mechanistic rationale that can be used as a predictive model for future asymmetric reactions with nitrosocarbonyl intermediates.

  3. 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.

  4. Novel chiral ionic liquid (CIL) assisted selectivity enhancement to (L)-proline catalyzed asymmetric aldol reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Long; Zhang, Haibo; Luo, Huadong; Zhou, Xiaohai; Cheng, Gongzhen [College of Chemistry, Wuhan University (China)

    2011-09-15

    A significant improvement of the chemical yields (up to 88%), stereoselectivity (> 99:1) and enantiomeric excesses (up to 98%) of (L)-proline catalyzed direct asymmetric aldol reaction was found when proline based chiral ionic liquids (CILs) were added as additives. Different ratios of DMSO/H{sub 2}O as solvent and chiral ionic liquids (CILs) with chiral cations of different chain length were investigated. (author)

  5. Biodiesel forming reactions using heterogeneous catalysis

    Science.gov (United States)

    Liu, Yijun

    Biodiesel synthesis from biomass provides a means for utilizing effectively renewable resources, a way to convert waste vegetable oils and animal fats to a useful product, a way to recycle carbon dioxide for a combustion fuel, and production of a fuel that is biodegradable, non-toxic, and has a lower emission profile than petroleum-diesel. Free fatty acid (FFA) esterification and triglyceride (TG) transesterification with low molecular weight alcohols constitute the synthetic routes to prepare biodiesel from lipid feedstocks. This project was aimed at developing a better understanding of important fundamental issues involved in heterogeneous catalyzed biodiesel forming reactions using mainly model compounds, representing part of on-going efforts to build up a rational base for assay, design, and performance optimization of solid acids/bases in biodiesel synthesis. As FFA esterification proceeds, water is continuously formed as a byproduct and affects reaction rates in a negative manner. Using sulfuric acid (as a catalyst) and acetic acid (as a model compound for FFA), the impact of increasing concentrations of water on acid catalysis was investigated. The order of the water effect on reaction rate was determined to be -0.83. Sulfuric acid lost up to 90% activity as the amount of water present increased. The nature of the negative effect of water on esterification was found to go beyond the scope of reverse hydrolysis and was associated with the diminished acid strength of sulfuric acid as a result of the preferential solvation by water molecules of its catalytic protons. The results indicate that as esterification progresses and byproduct water is produced, deactivation of a Bronsted acid catalyst like H2SO4 occurs. Using a solid composite acid (SAC-13) as an example of heterogeneous catalysts and sulfuric acid as a homogeneous reference, similar reaction inhibition by water was demonstrated for homogeneous and heterogeneous catalysis. This similarity together with

  6. Mechanistic insights into a BINOL-derived phosphoric acid-catalyzed asymmetric Pictet-Spengler reaction.

    Science.gov (United States)

    Overvoorde, Lois M; Grayson, Matthew N; Luo, Yi; Goodman, Jonathan M

    2015-03-01

    The reaction of tryptamine and (2-oxocyclohexyl)acetic acid can be catalyzed by 3,3'-bis(triphenylsilyl)-1,1'-bi-2-naphthol phosphoric acid to give an asymmetric β-carboline. This reaction was first studied by Holloway et al. ( Org. Lett. 2010 , 12 , 4720 - 4723 ), but their mechanistic work did not explain the high stereoselectivity achieved. This study uses density functional theory and hybrid quantum mechanics/molecular mechanics calculations to investigate this reaction and provide a model to explain its outcome. The step leading to diastereo- and enantioselectivity is an asymmetric Pictet-Spengler reaction involving an N-acyliminium ion bound to the catalyst in a bidentate fashion. This interaction occurs via hydrogen bonds between the two terminal oxygen atoms of the catalyst phosphate group and the hydrogen atoms at N and C2 of the substrate indole group. These bonds hold the transition structure rigidly and thus allow the catalyst triphenylsilyl groups to influence the enantioselectivity. PMID:25654215

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

    Institute of Scientific and Technical Information of China (English)

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

    2003-01-01

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

  8. Asymmetric Michael Reaction of Malononitrile Catalyzed by Chiral Ru(Ⅱ) Complex and Achiral Base

    Institute of Scientific and Technical Information of China (English)

    MA Ya-Ping; XING Zhi-Kui; ZHU Jin; CUI Xin; CUN Lin-Feng; DENG Jin-Gen

    2003-01-01

    @@ Michael addition reactions represent one of the most important carbon-carbon bond forming reactions in modern synthetic organic chemistry. [1 ~3] We achieved catalytic enantioselective Michael addition reactions of malononitrile with chiral vicinal diamine-Ru(Ⅱ) complex in the presence of achiral base. High yields and moderate ee were observed.

  9. Application of 3-Methyl-2-vinylindoles in Catalytic Asymmetric Povarov Reaction: Diastereo- and Enantioselective Synthesis of Indole-Derived Tetrahydroquinolines.

    Science.gov (United States)

    Dai, Wei; Jiang, Xiao-Li; Tao, Ji-Yu; Shi, Feng

    2016-01-01

    The first application of 3-methyl-2-vinylindoles in catalytic asymmetric Povarov reactions has been established via the three-component reactions of 3-methyl-2-vinylindoles, aldehydes, and anilines in the presence of chiral phosphoric acid, providing easy access to chiral indole-derived tetrahydroquinolines with three contiguous stereogenic centers at high yields (up to 99%) and with excellent diastereo- and enantioselectivities (all >95:5 dr, up to 96% ee). This mode of catalytic asymmetric three-component reaction offers a step-economic and atom-economic strategy for accessing enantioenriched indole-derived tetrahydroquinolines with structural diversity and complexity. PMID:26652222

  10. tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon-Nitrogen Bond Forming Reactions.

    Science.gov (United States)

    Ramirez Hernandez, Johana; Chemla, Fabrice; Ferreira, Franck; Jackowski, Olivier; Oble, Julie; Perez-Luna, Alejandro; Poli, Giovanni

    2016-01-01

    The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon-nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions. PMID:26931222

  11. One-Pot Synthesis of (S)-Baclofen via Aldol Condensation of Acetaldehyde with Diphenylprolinol Silyl Ether Mediated Asymmetric Michael Reaction as a Key Step.

    Science.gov (United States)

    Hayashi, Yujiro; Sakamoto, Daisuke; Okamura, Daichi

    2016-01-01

    An efficient asymmetric total synthesis of (S)-baclofen was accomplished via a one-pot operation from commercially available materials using sequential reactions, such as aldol condensation of acetaldehyde, diphenylprolinol silyl ether mediated asymmetric Michael reaction of nitromethane, Kraus-Pinnick oxidation, and Raney Ni reduction. Highly enantioenriched baclofen was obtained in one pot with a good yield over four reactions. PMID:26636719

  12. Asymmetric Construction of Benzindoloquinolizidine: Application of An Organocatalytic Enantioselective Conjugate Addition-Cyclization Cascade Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Cheolwoong; Seo, Seung Woo; Lee, Yona; Kim, Sunggon [Kyonggi Univ., Suwon (Korea, Republic of)

    2014-02-15

    We have developed the synthetic methodology of enantioenriched benzindoloquinolizidines based on the organocatalytic enantioselective conjugate addition-cyclization cascade reaction of o-N-(3-indoleacetyl)amino-cinnamaldehydes with malonates followed by an acid-catalyzed intramolecular Pictet-Spengler type cyclization. The asymmetric reaction using diphenylprolinol TMS ether as an organocatalyst produces the desired products with good to excellent yields and high enantioselectivities (up to 98% ee). The evaluation of the applications of this synthetic methodology for generating enantioenriched benzindolo-quinolizidines and studies on the biological activity of these compounds against human prostate cancer in particular are now in progress. Results of these studies will be presented in due course. Many new types of chemical reactions have been developed to facilitate easier synthesis of complex compounds. Among the strategies, domino reactions, which have been utilized for the efficient and stereoselective construction of complex molecules from simple precursors in a single process, are widely used due to their high synthetic efficiency by reducing both the number of synthetic operation required and the quantities of chemicals and solvents used.

  13. Baker's yeast catalyzed asymmetric reduction of prochiral ketones in different reaction mediums

    Directory of Open Access Journals (Sweden)

    Adi Wolfson

    2013-03-01

    Full Text Available Baker’s yeast catalyzes the asymmetric reduction of prochiral ketones in water and in various organic solvents. The reaction in water, which is the first solvent of choice for bio-reactions, led to a high product yield and enantiomeric excess, but the low miscibility of organic molecules in water resulted in lower conversions when more hydrophobic ketones were used. Petroleum-based solvents such as hexane and petroleum ether were also successfully employed as reaction mediums, but the viability of the yeast in these solvents was negligible, and they have severe environmental impacts due to their high toxicity levels. Performing the reaction in green solvents, like ionic liquids, fluorous media, and glycerol-based solvents, which have low volatilities and can be recycled, enabled dissolution of the substrates and of the energy source and also promoted isolation of the product. Among all tested green solvents, glycerol-based solvents are preferable due to their biodegradable natures and their origins from renewable sources.

  14. Asymmetric Construction of Benzindoloquinolizidine: Application of An Organocatalytic Enantioselective Conjugate Addition-Cyclization Cascade Reaction

    International Nuclear Information System (INIS)

    We have developed the synthetic methodology of enantioenriched benzindoloquinolizidines based on the organocatalytic enantioselective conjugate addition-cyclization cascade reaction of o-N-(3-indoleacetyl)amino-cinnamaldehydes with malonates followed by an acid-catalyzed intramolecular Pictet-Spengler type cyclization. The asymmetric reaction using diphenylprolinol TMS ether as an organocatalyst produces the desired products with good to excellent yields and high enantioselectivities (up to 98% ee). The evaluation of the applications of this synthetic methodology for generating enantioenriched benzindolo-quinolizidines and studies on the biological activity of these compounds against human prostate cancer in particular are now in progress. Results of these studies will be presented in due course. Many new types of chemical reactions have been developed to facilitate easier synthesis of complex compounds. Among the strategies, domino reactions, which have been utilized for the efficient and stereoselective construction of complex molecules from simple precursors in a single process, are widely used due to their high synthetic efficiency by reducing both the number of synthetic operation required and the quantities of chemicals and solvents used

  15. Chiral Borated Esters in Asymmetric Synthesis:1.The First Asymmetric Reaction Catalyzed by Chiral Spiroborated Esters with an O3BN Framework

    Institute of Scientific and Technical Information of China (English)

    LIU, De-Jun(刘德军); SHAN, Zi-Xing(单自兴); QIN, Jin-Gui(秦金贵)

    2004-01-01

    The first asymmetric reaction catalyzed by chiral spiroborated esters with an O3BN framework was reported. In the presence of 0.1 equivalent of (R,S)-1 or (S,S)-1, acetophenone was reduced by 0.6 equivalent of borane in THF at 0-5 ℃ for 2 h to give (R)-1-phenylethanol of up to 76% ee and 73% isolated yield. Influence of reaction conditions on the stereoselectivity of the reduction was investigated and a possible catalytic mechanism of the chiral spiroborated esters toward the reduction was also suggested.

  16. Study of fusion reactions forming Cf nuclei

    Directory of Open Access Journals (Sweden)

    Khuyagbaatar J.

    2013-12-01

    Full Text Available The formation of a compound nucleus in different projectile and target combinations is a powerful method for investigating the fusion process. Recently, the dominance of quasi-fission over fusion-fission has been inferred for 34S+208Pb in comparison to 36S+206Pb; both reactions lead to the compound nucleus 242Cf*.The mass and angle distributions of the fission fragments from these reactions were studied in order to further investigate the presence of quasi-fission.

  17. Non-cross-linked polystyrene-supported 2-imidazolidinone chiral auxiliary: synthesis and application in asymmetric alkylation reactions

    Science.gov (United States)

    Nguyen, Quynh Pham Bao

    2013-01-01

    Summary Asymmetric alkylation reactions using non-cross-linked polystyrene (NCPS)-supported 2-imidazolidinone chiral auxiliaries were successfully investigated with excellent diastereocontrol (>99% de). The recovery and the recycling of this soluble polymer-supported chiral auxiliary were achieved in order to produce highly optical pure carboxylic acids. PMID:24204423

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

    Science.gov (United States)

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

    2013-06-01

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

  19. An overview on the applications of `Doyle catalysts’ in asymmetric cyclopropanation, cyclopropenation and C-H insertion reactions

    Indian Academy of Sciences (India)

    Thomas J Colacot

    2000-06-01

    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.

  20. Synthesis of sulphonated mesoporous phenolic resins and their application in esterification and asymmetric aldol reactions

    Energy Technology Data Exchange (ETDEWEB)

    Muylaert, Ilke [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium); Verberckmoes, An, E-mail: an.verberckmoes@hogent.be [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium); Associated Faculty of Applied Engineering Sciences, University College Ghent, Valentin Vaerwyckweg 1, 9000 Ghent (Belgium); Spileers, Jeremy [Associated Faculty of Applied Engineering Sciences, University College Ghent, Valentin Vaerwyckweg 1, 9000 Ghent (Belgium); Demuynck, Anneleen; Peng, Li; De Clippel, Filip; Sels, Bert [Katholieke Universiteit Leuven, Centre for Surface Chemistry and Catalysis (COK), Kasteelpark Arenberg 23, 3001 Heverlee (Belgium); Van Der Voort, Pascal, E-mail: pascal.vandervoort@ugent.be [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium)

    2013-02-15

    Mesoporous phenolic resins were functionalized with sulphonic acid groups by four different types of sulphonation procedures: (i) direct sulphonation on the aromatic ring, (ii) alkyl sulphonation of the aromatic ring, and functionalizations of the phenolic hydroxyl surface by using an aryl silane, 2-(4-chlorosulphonylphenyl)ethyl trichlorosilane (iii) or a propyl silane, 3-mercaptopropyltrimethoxysilane (iv). The highest acidity loadings were obtained through direct sulphonation with fuming sulphuric acid (1.90 mmol H{sup +} g{sup −1}) or chlorosulphonic acid (1.31 mmol H{sup +} g{sup −1}) and these materials showed the highest conversion (97+ %) in Fischer esterification of acetic acid with propanol. However, the alkyl sulphonic groups, obtained through sulphonation procedure (ii) showed the highest stability in terms of maintenance of their acidity after use in consecutive catalytic runs or leaching treatments. This was demonstrated both through evaluation of the regenerated catalysts in a consecutive esterification run and during a leaching resistance test in aqueous medium. Moreover, the developed sulphonated mesoporous phenolic resins are presented as novel support for the non-covalent immobilization of an L-phenylalanine derived chiral diamine organocatalyst for asymmetric aldol reactions. The immobilization is established by an acid–base interaction between the sulphonic acid group and the amine function. The acidity and in particular the electronic withdrawing environment of the sulphonic acid groups influence enormously the catalytic performance of the non-covalent immobilized chiral diamine catalyst (aromatic > aliphatic). - Highlights: ► Different types of sulphonation procedures for mesoporous phenolic resins. ► Influence of acidity and electronic withdrawing environment. ► Novel support for non-covalent immobilization of chiral diamine catalyst. ► Catalytic performance in esterification and asymmetric aldol condensation. ► Demonstration

  1. Preparation of Poly(ionic liquid)s-Supported Recyclable Organocatalysts for the Asymmetric Nitroaldol (Henry) Reaction.

    Science.gov (United States)

    Großeheilmann, Julia; Bandomir, Jenny; Kragl, Udo

    2015-12-21

    A novel strategy for the embedding of quinine-based organocatalysts in polymerized ionic liquids-based hydrogels is presented. With this technique, the encapsulated organocatalyst was successfully recovered and reused for four cycles without any loss of enantioselectivity (up to 91% ee) for the asymmetric nitroaldol (Henry) reaction. In this study, high catalyst leaching was significantly reduced (water content. After catalyst removal, evaporation of the solvent affords the product in 98% purity without any further purification.

  2. From a Sequential to a Concurrent Reaction in Aqueous Medium: Ruthenium-Catalyzed Allylic Alcohol Isomerization and Asymmetric Bioreduction.

    Science.gov (United States)

    Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

    2016-07-18

    The ruthenium-catalyzed redox isomerization of allylic alcohols was successfully coupled with the enantioselective enzymatic ketone reduction (mediated by KREDs) in a concurrent process in aqueous medium. The overall transformation, formally the asymmetric reduction of allylic alcohols, took place with excellent conversions and enantioselectivities, under mild reaction conditions, employing commercially and readily available catalytic systems, and without external coenzymes or cofactors. Optimization resulted in a multistep approach and a genuine cascade reaction where the metal catalyst and biocatalyst coexist from the beginning. PMID:27258838

  3. Chiral N,N'-Dioxide-Scandium(III)-Catalyzed Asymmetric Dearomatization of 2-Naphthols through an Amination Reaction.

    Science.gov (United States)

    Lian, Xiangjin; Lin, Lili; Wang, Guojin; Liu, Xiaohua; Feng, Xiaoming

    2015-11-23

    A catalytic asymmetric dearomatization of 2-naphthols with azodicarboxylates has been accomplished by using a N,N'-dioxide-scandium(III) complex as a chiral catalyst. A number of optically active β-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained in up to 99 % yield and up to 99 % ee under mild reaction conditions. The reaction could be scaled up to a gram-scale with the yield and ee maintained. Based on these experiments and on previous reports, a possible transition state was proposed. PMID:26449515

  4. Magical Power of d-block transition metals. Pd-Catalyzed Cross-Coupling and Zr-Catalyzed Asymmetric Carboalumination (Zaca reaction)

    OpenAIRE

    Año Internacional de la Quimica 2011

    2011-01-01

    Magical Porwer of d-block Transition Metals. Pd-Catalyzed Cross-Coupling and Zr-Catalyzed Asymmetric Carboalumination (Zaca Reaction). Ei-ichi Negishi (Department of Chemistry - Purdue University). Premio Nobel de Química 2010

  5. A practical new chiral controller for asymmetric Diels-Alder and alkylation reactions.

    Science.gov (United States)

    Sarakinos, G; Corey, E J

    1999-12-01

    [formula: see text] The enantiomerically pure hydroxy sulfones (+)- and (-)-2 have been prepared from 1,2-epoxycyclohexane by a simple and practical procedure. The acrylate esters of these alcohols undergo BCl3-catalyzed Diels-Alder reactions with a variety of dienes at -78 to -55 degrees C in CH2Cl2 or C7H8 with high dienophile face selectivity (Table 1). The chiral esters so formed are readily cleaved with recovery of the controllers (+)- or (-)-2. Esters of (+)- and (-)-2 can be converted to Z-potassium enolates and alkylated with high face selectivity. PMID:10836034

  6. Asymmetric aza-Morita-Baylis-Hillman reactions of chiral N-phosphonyl imines with acrylates via GAP chemistry/technology.

    Science.gov (United States)

    Yang, Bing; Ji, Xiaozhou; Xue, Yunsheng; Zhang, Haowei; Shen, Minxing; Jiang, Bo; Li, Guigen

    2016-07-01

    Chiral N-phosphonyl imines have been proven to be efficient electrophilic acceptors for asymmetric aza-Morita-Baylis-Hillman (aza-MBH) reactions with acrylates under convenient conditions. Thirty examples of β-amino acrylates were generated in high yields (up to 99.4%) and diastereoselectivity (up to >99 : 1 dr) in an atom-economical fashion. The synthesis was proved to follow the GAP (group-assisted purification) chemistry, i.e., the pure products can be obtained simply by washing the crude products with hexane/ethyl acetate (v/v, 10/1) without the use of chromatography or recrystallization. DFT calculations were also conducted to support an asymmetric induction model accounting for high diastereoselectivity. PMID:27232108

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

    Science.gov (United States)

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

    2015-12-23

    The last two decades have witnessed the emergence of direct enolization protocols providing atom-economical and operationally simple methods to use enolates for stereoselective C-C bond-forming reactions, eliminating the inherent drawback of the preformation of enolates using stoichiometric amounts of reagents. In its infancy, direct enolization relied heavily on the intrinsic acidity of the latent enolates, and the reaction scope was limited to readily enolizable ketones and aldehydes. Recent advances in this field enabled the exploitation of carboxylic acid derivatives for direct enolization, offering expeditious access to synthetically versatile chiral building blocks. Despite the growing demand for enantioenriched fluorine-containing small molecules, α- and β-fluorinated carbonyl compounds have been neglected in direct enolization chemistry because of the competing and dominating defluorination pathway. Herein we present a comprehensive study on direct and highly stereoselective Mannich-type reactions of α- and β-fluorine-functionalized 7-azaindoline amides that rely on a soft Lewis acid/hard Brønsted base cooperative catalytic system to guarantee an efficient enolization while suppressing undesired defluorination. This protocol contributes to provide a series of fluorinated analogs of enantioenriched β-amino acids for medicinal chemistry. PMID:26652911

  8. Multi-responsive physical gels formed by a biosynthetic asymmetric triblock protein polymer and a polyanion

    NARCIS (Netherlands)

    Pham, T.H.T.; Wang, J.; Werten, M.W.T.; Snijkers, F.; Wolf, de F.A.; Cohen Stuart, M.A.; Gucht, van der J.

    2013-01-01

    We report the design, production and characterization of a biosynthetic asymmetric triblock copolymer which consists of one collagen-like and one cationic block spaced by a hydrophilic random coiled block. The polymer associates into micelles when a polyanion is added due to the electrostatic intera

  9. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  10. Proline Catalyzed Asymmetric Aldol Reaction between Methyl Ketones and 1-Aryl-2,2,2-trifluoroethanones

    Institute of Scientific and Technical Information of China (English)

    QIU Li-Hua; SHEN Zong-Xuan; SHI Chang-Qing; LIU Yan-Hua; ZHANG Ya-Wen

    2005-01-01

    Direct asymmetric aldol addition of methyl ketones to 2,2,2-trifluoro-1-phenylethanone and its ring-substituted derivatives was achieved using L-proline as a chiral promoter. Various optically active β-trifluoromethyl-β-hydroxy ketones were obtained in almost quantitative yields with moderate enantioselectivities up to 64 % ee.

  11. 咪唑类离子液体及其催化有机不对称反应%Imidazolium ionic liquids and catalytic asymmetric reactions of organic

    Institute of Scientific and Technical Information of China (English)

    姜红波

    2011-01-01

    离子液体作为一种新型绿色溶剂,具有许多独特的物理化学性质,近年来逐渐被人们所认知,并发现可用在许多重要领域.本文简单介绍离子液体及其特点,重点介绍在咪唑类离子液体中典型的不对称加氢反应、不对称Michael加成反应、不对称Aldol反应、不对称烯丙基反应和不对称氟化反应.%As a new type of green solvents, ionic liquids has many unique physical and chemical properties.It has been perceived and found in many important areas available in recent years.This article briefly describes the types and characteristics of ionic liquids, focusing on the typical asymmetric hydrogenation reaction, asymmetric Michael addition reaction, asymmetric Aldol reaction, asymmetric allylation reaction and asymmetric fluorination reaction in imidazolium ionic liquids.

  12. Asymmetric Neutrino Reaction in Magnetized Proto-Neutron Stars in Fully Relativistic Approach

    Directory of Open Access Journals (Sweden)

    Yasutake Nobutoshi

    2012-02-01

    Full Text Available We calculate asymmetric neutrino absorption and scattering cross sections on hot and dense magnetized neutron-star matter including hyperons in fully relativistic mean-field theory. The absorption/scattering cross sections are suppressed/enhanced incoherently in the direction of the magnetic field B = Bẑ. The asymmetry is 2–4% at the matter density ρ0 ≤ ρB ≤ 3ρ0 and temperature T ≤ 40MeV for B = 2 × 1017G. Then we solve the Boltzmann equation for the neutrino transport in 1D attenuation approximation, and get the result that the kick velocity becomes about 300 km/s for the proto-neutron star with 168 solar mass at T = 20MeV.

  13. Asymmetric Aldol Reaction Catalyzed by L-Proline and Achiral Thiourea Fluoroboric Acid Salt

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Eun; Lee, Haney; Kim, Taek Hyeon [Chonnam National University, Gwangju (Korea, Republic of)

    2015-01-15

    Considering its ready availability and low cost, L-proline would be the first choice catalyst for preparing aldol adducts with high diastereo- and enantioselectivity. However, proline presents some major drawbacks, including poor performance in direct aldol reactions with aromatic aldehydes, limited solubility, and reactivity in nonpolar organic solvents, and side reactions that make using high catalyst loadings necessary to reach satisfactory conversions. Therefore, numerous proline-modified organo catalysts such as prolinamides, proline thioamides, sulfonamides, chiral amines, and organic salts have been designed for direct aldol reactions. An alternative is to add a readily available additive to the reactions containing proline. This last approach is clearly advantageous in avoiding tedious chemical syntheses of organo catalysts and would ultimately allow the construction of libraries of catalyst protocols by simply changing the additive. Acid additives can influence the outcome of enamine mediated reactions; however, only a few screening studies of acid additions to thiourea organo catalysts are available in the literature. The reaction between cyclohexanone and 4-nitrobenzaldehyde was selected as a standard model reaction for screening of more effective acid additives to thiourea.

  14. Engaging Allene-Derived Zwitterions in an Unprecedented Mode of Asymmetric [3+2]-Annulation Reaction.

    Science.gov (United States)

    Sankar, Muthukumar G; Garcia-Castro, Miguel; Golz, Christopher; Strohmann, Carsten; Kumar, Kamal

    2016-08-01

    Catalytic addition of chiral phosphine, that is, (R)- or (S)-SITCP, to an α-substituted allene ester generated a zwitterionic dipole. Under optimized reaction conditions, this dipole could engage isatine-derived N-Boc-ketimines in a novel mode of [3+2] annulation reaction. Pyrrolinyl spirooxindoles are thus afforded in high yields and with excellent enantioselectivities. The unprecedented annulation reaction successfully facilitated the construction of sp(3) -rich and highly substituted 3,2'-pyrrolidinyl spirooxindoles supporting many chiral centers. PMID:27345724

  15. The role of chemical reaction in waste-form performance

    International Nuclear Information System (INIS)

    The dissolution rate of waste solids in a geologic repository is a complex function of waste form geometry, chemical raction rate, exterior flow field, and chemical environment. We present here an analysis to determine the stady-state mass transfer rate, over the entire range of flow conditions relevant to geologic disposal of nuclear waste. The equations for steady-state mass transfer with a chemical-reaction-rate boundary condition are solved by three different mathematical techniques which supplement each other. This theory is illustrated with laboratory leach data for borosilicate-glass and a spherical spent-fuel waste form under typical repository conditions. For borosilicate glass waste in the temperature range of 57/degree/C to 250/degree/C, dissolution rate in a repository is determined for a wide range of chemical reaction rates and for Peclet numbers from zero to well over 100, far beyond any Peclet values expected in a repository. Spent-fuel dissolution in a repository is also investigated, based on the limited leach data now available. 10 refs., 4 figs., 1 tab

  16. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor

    Science.gov (United States)

    Bentley, Keith W.; Proano, Daysi; Wolf, Christian

    2016-08-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production.

  17. Lithium amide assisted asymmetric Mannich-type reactions of menthyl acetate with PMP-aldimines.

    Science.gov (United States)

    Hata, Seiji; Iguchi, Mayu; Iwasawa, Tetsuo; Yamada, Ken-ichi; Tomioka, Kiyoshi

    2004-05-27

    A lithium enolate of menthyl acetate added to PMP-imines, in the presence of an equimolar amount of lithium diisopropylamide, affords the Mannich-type addition products in high stereoselectivity. [reaction--see text

  18. Nitrated Confined Imidodiphosphates Enable a Catalytic Asymmetric Oxa-Pictet-Spengler Reaction.

    Science.gov (United States)

    Das, Sayantani; Liu, Luping; Zheng, Yiying; Alachraf, M Wasim; Thiel, Walter; De, Chandra Kanta; List, Benjamin

    2016-08-01

    The development of a highly enantioselective catalytic oxa-Pictet-Spengler reaction has proven a great challenge for chemical synthesis. We now report the first example of such a process, which was realized by utilizing a nitrated confined imidodiphosphoric acid catalyst. Our approach provides substituted isochroman derivatives from both aliphatic and aromatic aldehydes with high yields and excellent enantioselectivities. DFT calculations provide insight into the reaction mechanism. PMID:27457383

  19. Tandem Bond-Forming Reactions of 1-Alkynyl Ethers.

    Science.gov (United States)

    Minehan, Thomas G

    2016-06-21

    Electron-rich alkynes, such as ynamines, ynamides, and ynol ethers, are functional groups that possess significant potential in organic chemistry for the formation of carbon-carbon bonds. While the synthetic utility of ynamides has recently been expanded considerably, 1-alkynyl ethers, which possess many of the reactivity features of ynamides, have traditionally been far less investigated because of concerns about their stability. Like ynamides, ynol ethers are relatively unhindered to approach by functional groups present in the same or different molecules because of their linear geometry, and they can potentially form up to four new bonds in a single transformation. Ynol ethers also possess unique reactivity features that make them complementary to ynamides. Research over the past decade has shown that ynol ethers formed in situ from stable precursors engage in a variety of useful carbon-carbon bond-forming processes. Upon formation at -78 °C, allyl alkynyl ethers undergo a rapid [3,3]-sigmatropic rearrangement to form allyl ketene intermediates, which may be trapped with alcohol or amine nucleophiles to form γ,δ-unsaturated carboxylic acid derivatives. The process is stereospecific, takes place in minutes at cryogenic temperatures, and affords products containing (quaternary) stereogenic carbon atoms. Trapping of the intermediate allyl ketene with carbonyl compounds, epoxides, or oxetanes instead leads to complex α-functionalized β-, γ-, or δ-lactones, respectively. [3,3]-Sigmatropic rearrangement of benzyl alkynyl ethers also takes place at temperatures ranging from -78 to 60 °C to afford substituted 2-indanones via intramolecular carbocyclization of the ketene intermediate. tert-Butyl alkynyl ethers containing pendant di- and trisubstituted alkenes and enol ethers are stable to chromatographic isolation and undergo a retro-ene/[2 + 2] cycloaddition reaction upon mild thermolysis (90 °C) to afford cis-fused cyclobutanones and donor

  20. Analysis of the role of neutron transfer in asymmetric fusion reactions at subbarrier energies

    Energy Technology Data Exchange (ETDEWEB)

    Ogloblin, A. A. [National Research Center Kurchatov Institute (Russian Federation); Zhang, H. Q.; Lin, C. J.; Jia, H. M. [China Institute of Atomic Energy (China); Khlebnikov, S. V. [Khlopin Radium Institute (Russian Federation); Kuzmin, E. A.; Danilov, A. N.; Demyanova, A. S. [National Research Center Kurchatov Institute (Russian Federation); Trzaska, W. H. [University of Jyväskylä, Department of Physics (Finland); Xu, X. X. [China Institute of Atomic Energy (China); Yang, F. [National Research Center Kurchatov Institute (Russian Federation); Sargsyan, V. V., E-mail: sargsyan@theor.jinr.ru; Adamian, G. G.; Antonenko, N. V. [Joint Institute for Nuclear Research (Russian Federation); Scheid, W. [Institüt für Theoretische Physik der Justus-Liebig-Universität (Germany)

    2015-12-15

    The excitation functions were measured for the {sup 28}Si + {sup 208}Pb complete-fusion (capture) reaction at deep subbarrier energies. The results were compared with the cross sections predicted within the quantum diffusion approach. The role of neutron transfer in the case of positive Q values in the {sup 28}Si + {sup 124}Sn, {sup 208}Pb; {sup 30}Si + {sup 124}Sn, {sup 208}Pb; {sup 20}Ne + {sup 208}Pb; {sup 40}Ca + {sup 96}Zr; and {sup 134}Te + {sup 40}Ca complete-fusion (capture) reactions is discussed.

  1. Asymmetrical clustering by sex in free-forming groups: an observational field study.

    Science.gov (United States)

    Kramer-Moore, Daniela

    2010-08-01

    464 observations were carried out in public places of 3- or 4-person, mixed sex, free-forming groups who spontaneously divided into subgroups. An analysis of sex composition of the subgroups showed that significantly more single-sex subgroups were formed than expected by chance. This was significantly more pronounced among women than among men. Several explanations were considered.

  2. Solvent Effects in Asymmetric Hetero Diels-Alder and Ene Reactions

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Jørgensen, Karl Anker

    1996-01-01

    The use of polar solvents such as nitromethane or 2-nitropropane leads to a significant improvement of the catalytic properties of a cationic copper-Lewis acid in the hetero Diels-Alder reaction of alkyl glyoxylates with dienes; The scope of a newly developed copper(II)-bisoxazoline catalyst for ...

  3. Interfacial thiol-ene photoclick reactions for forming multilayer hydrogels.

    Science.gov (United States)

    Shih, Han; Fraser, Andrew K; Lin, Chien-Chi

    2013-03-13

    Interfacial visible light-mediated thiol-ene photoclick reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a noncleavage type photoinitiator eosin-Y on visible-light-mediated thiol-ene photopolymerization was first characterized using in situ photorheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using ultraviolet-visible light (UV-vis) spectrometry. It was determined that eosin-Y was able to reinitiate the thiol-ene photoclick reaction, even after light exposure. Because of its small molecular weight, most eosin-Y molecules readily leached out from the hydrogels. The diffusion of residual eosin-Y from preformed hydrogels was exploited for fabricating multilayer step-growth hydrogels. Interfacial hydrogel coating was formed via the same visible-light-mediated gelation mechanism without adding fresh initiator. The thickness of the thiol-ene gel coating could be easily controlled by adjusting visible light exposure time, eosin-Y concentration initially loaded in the core gel, or macromer concentration in the coating solution. The major benefits of this interfacial thiol-ene coating system include its simplicity and cytocompatibility. The formation of thiol-ene hydrogels and coatings neither requires nor generates any cytotoxic components. This new gelation chemistry may have great utilities in controlled release of multiple sensitive growth factors and encapsulation of multiple cell types for tissue regeneration. PMID:23384151

  4. Asymmetric Baylis-Hillman Reaction between Chiral Activated Alkenes and Aromatic Aldehydes in Me3N/H2O/Solvent Medium

    Institute of Scientific and Technical Information of China (English)

    Ke HE; Zheng Hong ZHOU; Hong Ying TANG; Guo Feng ZHAO; Chu Chi TANG

    2005-01-01

    Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide,induced asymmetric Baylis-Hillman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity (up to 99% de).

  5. Rationalization of Product Selectivities in Asymmetric Horner-Wadsworth-Emmons Reactions by Use of a New Method for Transition-State Modeling

    DEFF Research Database (Denmark)

    Norrby, Per-Ola; Brandt, Peter; Rein, Tobias

    1999-01-01

    A new method for creating a transition-state force field, based on quantum chemical normal-mode analysis, is described. The force field was used to rationalize the experimentally observed product selectivities in asymmetric Horner-Wadsworth-Emmons reactions between some chiral phosphonates...

  6. A facile approach to asymmetrical biaryls via coupling reaction of aryl halides with sodium tetraphenylborate catalyzed by MCM-41-supported sulfur palladium(O) complex

    Institute of Scientific and Technical Information of China (English)

    Qiu Hua Xu; Ping Ping Wang; Ming Zhong Cai

    2007-01-01

    Various functionalized asymmetrical biaryls can be synthesized in high to excellent yields via coupling reaction of aryl iodides or bromides with NaBPh4 catalyzed by MCM-41-supported sulfur palladium(O) complex. This palladium complex can be easily recovered and reused many times without loss of activity.

  7. Parallel Kinetic Resolution of Racemic Aldehydes by Use of Asymmetric Horner-Wadsworth-Emmons Reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Jensen, Jakob Feldthusen; Humble, Rikke Eva;

    2000-01-01

    A racemic aldehyde can undergo parallel kinetic resolution (PKR) by simultaneous reaction with two different chiral phosphonates, differing either in the structure of the chiral auxiliary or in the structure of the phosphoryl group (i.e., one (E)- and one (Z)-selective reagent). This strategy all...... allows conversion of a racemic aldehyde to two different, synthetically useful chiral products with essentially doubled material throughput and similar or improved selectivities as compared to conventional kinetic resolution....

  8. Chiral modification of copper exchanged zeolite-Y with cinchonidine and its application in the asymmetric Henry reaction.

    Science.gov (United States)

    Deka, Jogesh; Satyanarayana, L; Karunakar, G V; Bhattacharyya, Pradip Kr; Bania, Kusum K

    2015-12-28

    Chirally modified Cu(2+) exchanged zeolite-Y was synthesized by direct adsorption of cinchonidine under ambient conditions. The chirally modified materials were characterized using various spectrochemical and physicochemical techniques viz. BET, FTIR, MAS ((1)H and (13)C NMR), XPS, SEM, cyclic voltammetry and PXRD. Characteristic peaks of cinchonidine observed in the supported materials confirmed the adsorption of cinchonidine and its coordination with the Cu(2+) active site on copper exchanged zeolite-Y. (13)C SSNMR and XPS analysis however confirmed for the half encapsulation process, only the quinoline ring of cinchonidine gets coordinated to the internal metal sites via the N atom while the quinuclidine moiety extends out of the host surface. Cinchonidine supported Cu(2+)-Y zeolites were found to exhibit good catalytic performance in the asymmetric Henry reaction. (1)H SSNMR studies also confirmed the protonation of the N atom of the quinuclidine ring during the course of the Henry reaction. Heterogeneous chiral catalysts were effective for up to two consecutive cycles. Leaching of cinchonidine after the second cycle was found to have a negative result in the catalytic performance.

  9. Rhodium-Catalyzed Asymmetric Reactions Using Self-Assembled Chiral Bidentate Ligands

    Institute of Scientific and Technical Information of China (English)

    Kittichai Chaiseeda; Shin A. Moteki; D. Sahadeva Reddy; Di Wu; Kusumlata Chandra; James M. Takacs

    2005-01-01

    @@ 1 Introduction We recently described a new combinatorial strategy for modular catalyst development, one using self-assembly in the ligand scaffold-generating step to produce libraries of chiral self-assembled ligands. Metal-directed self-assembly of bifunctional subunits around a structural metal (typically zinc) can be used to form a heteroleptic complex in which a second set of ligating groups are suitably disposed to form a heterobimetallic catalyst system[1]. See Fig. 1

  10. Asymmetric crystallization during cooling and heating in model glass-forming systems.

    Science.gov (United States)

    Wang, Minglei; Zhang, Kai; Li, Zhusong; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D; O'Hern, Corey S

    2015-03-01

    We perform molecular dynamics (MD) simulations of the crystallization process in binary Lennard-Jones systems during heating and cooling to investigate atomic-scale crystallization kinetics in glass-forming materials. For the cooling protocol, we prepared equilibrated liquids above the liquidus temperature Tl and cooled each sample to zero temperature at rate Rc. For the heating protocol, we first cooled equilibrated liquids to zero temperature at rate Rp and then heated the samples to temperature T>Tl at rate Rh. We measured the critical heating and cooling rates Rh* and Rc*, below which the systems begin to form a substantial fraction of crystalline clusters during the heating and cooling protocols. We show that Rh*>Rc* and that the asymmetry ratio Rh*/Rc* includes an intrinsic contribution that increases with the glass-forming ability (GFA) of the system and a preparation-rate dependent contribution that increases strongly as Rp→Rc* from above. We also show that the predictions from classical nucleation theory (CNT) can qualitatively describe the dependence of the asymmetry ratio on the GFA and preparation rate Rp from the MD simulations and results for the asymmetry ratio measured in Zr- and Au-based bulk metallic glasses (BMG). This work emphasizes the need for and benefits of an improved understanding of crystallization processes in BMGs and other glass-forming systems.

  11. Synthesis and photoisomerization reactions of norbornadienes possessing chalcone chromophore and reactions of the formed quadricyclane derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Hasegawa, Eietsu; Mukai, Toshio; Toda, Takashi

    1988-08-10

    For efficient utilization of solar light energy, 2-aroyl-3-arylnorbornadienes derivatives (1)(with long wave absorption band) which possess a chalcone chromophore were synthesized, and the photoisomerization reactions were investigated. (1) possess the absorption band in visible light region corresponding to the kind of substitutional group introduced. Quadricyclane derivatives (2) were formed with the quantum yields of 0.06-0.60 in the photoisomerizations though they differ correspond to the substitutional group. (2) were shifted easily to (1) with heating, furthermore, isomerizations of (2) to (1) were carried out in good yields by contact with silver perchlorate, trifluoroacetic acid and even with silica gel. Photoisomerization reactions of (2) gave tricyclane derivatives (7) added ethanol in high yield, in leaving at room temperature after mixing with ethanol. (1 fig, 7 tabs, 24 refs)

  12. A Ruthenium/Phosphoramidite-Catalyzed Asymmetric Interrupted Metallo-ene Reaction.

    Science.gov (United States)

    Trost, Barry M; Ryan, Michael C

    2016-03-01

    Allylic chlorides prepared from commercially available trans-1,4-dichloro-2-butene were converted to trans-disubstituted 5- and 6-membered ring systems with perfect diastereoselectivity and high enantioselectivity under chiral ruthenium catalysis. These products contain stereodefined secondary and tertiary alcohols that originate from the trapping of an alkylruthenium intermediate with adventitious water. Key to the success of this transformation was the development of a new BINOL-based phosphoramidite ligand containing bulky substitution at its 3- and 3'-positions. As a demonstration of product utility, diastereoselective Friedel-Crafts reactions were performed on the chiral benzylic alcohols in high yield and stereoselectivity. PMID:26899551

  13. Bifunctional Brønsted Base Catalyzes Direct Asymmetric Aldol Reaction of α-Keto Amides.

    Science.gov (United States)

    Echave, Haizea; López, Rosa; Palomo, Claudio

    2016-03-01

    The first enantioselective direct cross-aldol reaction of α-keto amides with aldehydes, mediated by a bifunctional ureidopeptide-based Brønsted base catalyst, is described. The appropriate combination of a tertiary amine base and an aminal, and urea hydrogen-bond donor groups in the catalyst structure promoted the exclusive generation of the α-keto amide enolate which reacted with either non-enolizable or enolizable aldehydes to produce highly enantioenriched polyoxygenated aldol adducts without side-products resulting from dehydration, α-keto amide self-condensation, aldehyde enolization, and isotetronic acid formation. PMID:26835655

  14. Dynamical Dipole and Equation of State in N/Z Asymmetric Fusion Reactions

    Directory of Open Access Journals (Sweden)

    Giaz Agnese

    2014-03-01

    Full Text Available In heavy ion reactions, in the case of N/Z asymmetry between projectile and target, the process leading to complete fusion is expected to produce pre-equilibrium dipole γ-ray emission. It is generated during the charge equilibration process and it is known as Dynamical Dipole. A new measurement of the dynamical dipole emission was performed by studying 16O + 116Sn at 12 MeV/u. These data, together with those measured at 8.1 MeV/u and 15.6 MeV/u for the same reaction, provide the dependence on the Dynamical Dipole total emission yield with beam energy and they can be compared with theoretical expectations. The experimental results show a weak increase of the Dynamical Dipole total yield with beam energies and are in agreement with the prediction of a theoretical model based on the Boltzmann–Nordheim–Vlasov (BNV approach. The measured trend with beam energy does not confirm the rise and fall behavior previously reported for the same fused compound but with a much higher dipole moment.

  15. Theoretical calculation of the triple differential cross sections of the 2p orbital of argon in a coplanar highly asymmetric (e, 2e) reaction

    Institute of Scientific and Technical Information of China (English)

    葛自明; 周雅君; 吕志伟; 王治文

    2002-01-01

    The triple differential cross sections of the 2p electron of argon in a coplanar highly asymmetric geometry have beencalculated with the modified distorted wave Born approximation (DWBA) and the target Hartree-Fock approximationmethods. The damping polarization of the semi-classical short-range potentials and the Mee factor are included in thedistorting potentials of the modified DWBA. Theoretical results are compared with a recent experiment. The dynamicmechanism of inner shell ionization in a coplanar highly asymmetric geometry (e, 2e) reaction are also discussed.

  16. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    CERN Document Server

    Lewis, Alan M; Hore, P J

    2014-01-01

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene (CPF) triad containing considerably more nu...

  17. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor.

    Science.gov (United States)

    Bentley, Keith W; Proano, Daysi; Wolf, Christian

    2016-01-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production. PMID:27549926

  18. Asymmetric Fission in the 78Kr+40Ca reactions at 5.5 MeV/nucleon

    Directory of Open Access Journals (Sweden)

    Roy R.

    2012-02-01

    Full Text Available The cross section, kinetic energy distribution and angular distribution of fragments with atomic number 3 ≤ Z ≤ 28 emitted in the reaction 78Kr + 40Ca at the bombarding energy of 5.5 MeV/nucleon and coincidence between light charged particles and fragments were measured by means of the 4π-INDRA array to study the decay mechanism of medium mass excited nucleus. Global features indicate a high degree of relaxation and are compatible with a binary fission from compound nucleus. The mean value of the kinetic energy distributions of fragments indicates dominance of Coulomb interaction, while the width of the distribution signals large fluctuations. Inclusive cross-section distributions of fragments with charge 3 ≤ Z ≤ 28 are bell-shaped and a strong even-odd-staggering (o-es is observed for 3 ≤ Z ≤ 12. Coincidence measurements suggest that the light partners in very asymmetric fission are emitted at excitation energies below the particle emission thresholds. Data were confronted to the predictions of statistical model describing the decay of compound nuclei by emission of light particles and fragments. Calculations assuming spherical fission fragments and finite-range liquid drop fission barriers are not able to explain the experimental features. Attempts have been made to improve the agreement with experimental data. The analysis indicates the strong influence of the shape parameterization of the potential energy surface in describing the fission process of intermediate mass compound nuclei.

  19. Relative Stability of the Key Enamine,Oxazolidinone, and Imine Intermediates in Some Proline-catalyzed Asymmetric Reactions

    Institute of Scientific and Technical Information of China (English)

    HU Yi-Fan; LU Xin

    2008-01-01

    Many proline-catalyzed asymmetric addition reactions with ketones as substrates were assumed to involve a key intermediate, an enamine, produced by the condensation of proline and ketone. In this paper, the key intermediate enamines derived from L-proline and cyclohexanone (or acetone) as well as the corresponding oxazolidinone and imine tautomers have been investigated by means of density functional calculations at the B3LYP/6-311+G** level. The predicted order of stability for these tautomers is oxazolidinones > enamines > imines in gas phase and oxazolidinones > imines > enamines in aprotic THF solvent. This prediction explains why enamine intermediate can not be observed experimentally. The predicted energy/enthalpy difference between the formal oxazolidinone structure and the zwitterionic imine structures is very small in THF solvent, suggesting the oxazolidinone-to-imine tautomerization can be readily induced in solvent. 13C NMR chemical shifts of the oxazolidinone and imine structures have been computed and used to explain the experimental NMR spectra observed in oxazolidinone-to-imine tautomerization induced by protic solvent.

  20. Diastereo- and enantioselective construction of a bispirooxindole scaffold containing a tetrahydro-β-carboline moiety through an organocatalytic asymmetric cascade reaction.

    Science.gov (United States)

    Dai, Wei; Lu, Han; Li, Xin; Shi, Feng; Tu, Shu-Jiang

    2014-09-01

    The first catalytic asymmetric construction of a new class of bispirooxindole scaffold-containing tetrahydro-β-carboline moiety has been established through chiral phosphoric acid-catalyzed three-component cascade Michael/Pictet-Spengler reactions of isatin-derived 3-indolylmethanols, isatins, and amino-ester, which afforded structurally complex and diverse bispirooxindoles with one quaternary and one tetrasubstituted stereogenic centers in excellent stereoselectivities (all >95:5 diastereomeric ratio (d.r.), up to 98:2 enantiomeric ratio (e.r.)). This intriguing class of chiral bispirooxindoles integrated the two important structures of tetrahydro-β-carboline and bispirooxindole, both of them possessing significant bioactivities. This approach also combined the merits of asymmetric organocatalysis and multicomponent tandem reaction, which provided a unique strategy for the preparation of structurally rigid bispiro-architectures with concomitant creation of multiple quaternary stereogenic centers. PMID:25056997

  1. Optimisation of an asymmetric polymerase chain reaction assay for the amplification of single-stranded DNA from Wuchereria bancrofti for electrochemical detection

    OpenAIRE

    Vasuki Venkatesan; Sugeerappa Laxmanappa Hoti; Nagalakshmi Kamaraj; Somnath Ghosh; Kaushik Rajaram

    2013-01-01

    Single-stranded DNA (ssDNA) is a prerequisite for electrochemical sensor-based detection of parasite DNA and other diagnostic applications. To achieve this detection, an asymmetric polymerase chain reaction method was optimised. This method facilitates amplification of ssDNA from the human lymphatic filarial parasite Wuchereria bancrofti. This procedure produced ssDNA fragments of 188 bp in a single step when primer pairs (forward and reverse) were used at a 100:1 molar ratio in the presence ...

  2. Comparison of radial flow effects on partitions of multifragmenting sources formed in symmetric and asymmetric central collisions

    OpenAIRE

    Frankland J.D.; Gruyer D.; Bonnet E.; Chbihi A.

    2015-01-01

    The role of collective radial expansion in determining multifragmentation partition properties has previously been explored by comparing different-sized sources of the same excitation energy per nucleon formed by very different reaction mechanisms: excited quasi-projectiles from semi-peripheral Au+Au collisions and quasi-fused sources from central Xe+Sn collisions. New data has been obtained with INDRA on 181Ta+66Zn collisions in order to allow comparison of Xe+Sn data with quasi-fused system...

  3. Consumer reactions to different forms of CSR communication

    OpenAIRE

    Buden, Ivana; Connett, Louise

    2016-01-01

    Aim Companies around the world are making sizeable investments into CSR initiatives, but ensuring appropriate returns on these investments remains challenging. Therefore, it is of value to study the communication of corporate CSR efforts. The purpose of this study is to investigate how consumers react to rational versus emotional message strategies in CSR communication. Two categories of consumer reactions were considered: trust and purchase intention. Methods Qualitative research with four f...

  4. Quality check of spontaneous adverse drug reaction reporting forms of different countries.

    Science.gov (United States)

    Bandekar, M S; Anwikar, S R; Kshirsagar, N A

    2010-11-01

    Adverse drug reactions (ADRs) are considered as one of the leading causes of death among hospitalized patients. Thus reporting of adverse drug reactions become an important phenomenon. Spontaneous adverse drug reaction reporting form is an essential component and a major tool of the pharmacovigilance system of any country. This form is a tool to collect information of ADRs which helps in establishing the causal relationship between the suspected drug and the reaction. As different countries have different forms, our aim was to study, analyze the suspected adverse drug reaction reporting form of different countries, and assess if these forms can capture all the data regarding the adverse drug reaction. For this analysis we identified 18 points which are essential to make a good adverse drug reaction report, enabling proper causality assessment of adverse reaction to generate a safety signal. Adverse drug reaction reporting forms of 10 different countries were collected from the internet and compared for 18 points like patient information, information about dechallenge-rechallenge, adequacy of space and columns to capture necessary information required for its causality assessment, etc. Of the ADR forms that we analyzed, Malaysia was the highest scorer with 16 out of 18 points. This study reveals that there is a need to harmonize the ADR reporting forms of all the countries because there is a lot of discrepancy in data captured by the existing ADR reporting forms as the design of these forms is different for different countries. These incomplete data obtained result in inappropriate causality assessment.

  5. A New Approach to the Asymmetric Reaction of the Chiron 5-L-Menthyloxy-2(5H)-furanones with Horner-Emmons Reagent

    Institute of Scientific and Technical Information of China (English)

    李学强; 王凤荣; 何兰; 陈庆华

    2003-01-01

    The asymmetric reaction of the chiron 2(5H )-furanones (4a-4c) with the Horner-Emmons reagents (5a-5b) has been investigated. The newly chirai organophosphorus derivatives 6 and 7 were obtained using the phosphoryl-stabilized carbanion as a building block in DMSO under mild conditions. Through the asymmetric introduction, the Horner-Emmons reagent could be transformed to a chiral building block to afford the novel functionalized phosphorus derivatives. The structures of the synthesized compounds 6 and 7 were identified on the basis of their elementary and spectroscopic data, such as IR,1H NMR, 13C NMR, MS and X-ray crystallography. These resuits provided a valuable approach to the synthesis of potentially interesting chirai organophosphorus derivatives and probing their biological activities.

  6. On Combined Effects of Heat Transfer and Chemical Reaction for the Flow through an Asymmetric Channel with Orthogonally Deformable Porous Walls

    Directory of Open Access Journals (Sweden)

    Syed Tauseef Mohyud-Din

    2016-01-01

    Full Text Available The combined effects of heat transfer and chemical reaction are studied for the flow through a semi-infinite asymmetric channel with orthogonally deformable porous walls. The similarity transforms have been used to reduce the conservation laws to a corresponding system of nonlinear ordinary differential equations. The resulting equations are solved, both analytically and numerically, by using Homotopy Analysis Method (HAM and the fourth-order Runge-Kutta (RK-4 method, respectively. The convergence of the analytical solution is assured through the so-called total squared residual error analysis. The optimal values of auxiliary parameters are obtained by minimizing the total squared residual error.

  7. An Environmentally Benign System for Synthesis of β-Hydroxylketones: L-Histidine Asymmetrically Catalyzed Direct Aldol Reactions in Aqueous Micelle and Water-like Media

    Institute of Scientific and Technical Information of China (English)

    PENG Yi-Yuan; PENG Shu-Jun; DING Qiu-Ping; WANG Qi; CHENG Jin-Pei

    2007-01-01

    The first histidine catalyzed direct aldol reactions of ketones with nitrobenzaldehydes in water and in poly(ethylene glycol) (PEG) were reported. It reveals that histidine is a good aldol catalyst for synthesis of β-hydroxylketones in water and in PEG, giving good to excellent yields of the respective products. Better enantioand regioselectivity were achieved using low molecular weight PEG as the media. The results show that histidine and PEG-200 or -300 may constitute a promising environmentally benign system for asymmetric synthesis of β-hydroxylketones.

  8. 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...... reactions constitute the first organocatalytic asymmetric higher order cycloadditions and a rational for the periselectivity and stereoselectivity is provided based on experimental and computational investigations....

  9. Developments in catalytic asymmetric Strecker reaction of aldimines%醛亚胺的不对称Strecker反应研究进展

    Institute of Scientific and Technical Information of China (English)

    唐贝; 李高伟

    2013-01-01

    α-Aminonitriles can be easily converted to α-amino acids, and is an important intermediate for the synthesis of many biologically active natural products and drugs. The asymmetric Strecker reaction of the aldimine as a direct and affective method of synthesis of optically active α-aminonitriles has been widely accepted. In this current paper, the developments in catalytic asymmetric Strecker reaction of aldimines is introduced.%α-氨基腈不仅可以很容易地转化为α-氨基酸,而且是合成许多具有生物活性的天然产物和药物的重要中间体.醛亚胺的不对称Strecker反应作为制备光学活性α-氨基腈的直接而有效的方法之一,已被广泛接受.作者介绍了醛亚胺的不对称Strecker反应研究进展.

  10. An Asymmetric Organocatalytic Quadruple Domino Reaction Employing a Vinylogous Friedel–Crafts/Michael/Michael/Aldol Condensation Sequence

    OpenAIRE

    Philipps, Arne R.; Fritze, Lars; Erdmann, Nico; Enders, Dieter

    2015-01-01

    An organocatalytic quadruple cascade initiated by a Friedel–Crafts-type reaction is described. The (S)-diphenylprolinol trimethylsilyl ether catalyzed reaction yields highly functionalized cyclohexenecarbaldehydes bearing a 1,1-bis[4-(dialkylamino)phenyl]ethene moiety and three contiguous stereogenic centers. The reaction tolerates various functional groups and all products are obtained with very good diastereoselectivity and with virtually complete enantiomeric excess.

  11. 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.

  12. Reactions to Discrimination, Stigmatization, Ostracism, and Other Forms of Interpersonal Rejection: A Multimotive Model

    OpenAIRE

    Richman, Laura Smart; Leary, Mark R.

    2009-01-01

    This article describes a new model that provides a framework for understanding people’s reactions to threats to social acceptance and belonging as they occur in the context of diverse phenomena such as rejection, discrimination, ostracism, betrayal, and stigmatization. People’s immediate reactions are quite similar across different forms of rejection in terms of negative affect and lowered self-esteem. However, following these immediate responses, people’s reactions are influenced by construa...

  13. Terahertz optical asymmetric demultiplexer based tree-net architecture for all-optical conversion scheme from binary to its other 2n radix based form

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    To exploit the parallelism of optics in data processing,a suitable number system and an efficient encoding/decoding scheme for handling the data are very essential.In the field of optical computing and parallel information processing,several number systems like binary,quaternary,octal,hexadecimal,etc.have been used for different arithmetic and algebraic operations.Here,we have proposed an all-optical conversion scheme from its binary to its other 2n radix based form with the help of terahertz optical asymmetric demultiplexer (TOAD) based tree-net architecture.

  14. Reactions to Discrimination, Stigmatization, Ostracism, and Other Forms of Interpersonal Rejection: A Multimotive Model

    Science.gov (United States)

    Richman, Laura Smart; Leary, Mark R.

    2009-01-01

    This article describes a new model that provides a framework for understanding people's reactions to threats to social acceptance and belonging as they occur in the context of diverse phenomena such as rejection, discrimination, ostracism, betrayal, and stigmatization. People's immediate reactions are quite similar across different forms of…

  15. Ultrasound-Accelerated Synthesis of Asymmetrical Thiosulfonate S-Esters by Base-Promoted Reaction of Sulfonyl Chlorides with Thiols

    DEFF Research Database (Denmark)

    Pham, Hien Thi; Nguyen, Ngoc-Lan Thi; Duus, Fritz;

    2015-01-01

    Amberlyst A-26, Mg-Al hydrotalcite, potassium fluoride absorbed on alumina, triethylamine and pyridine have been tested as base catalysts and reagents for the reaction of sulfonyl chlorides with thiols to prepare thiosulfonate S-esters. The reactions were performed under solvent-free conditions or...

  16. Application of Aromatic Nitroso Compounds in Asymmetric Reactions%芳香性亚硝基化合物在不对称反应中的应用(下)

    Institute of Scientific and Technical Information of China (English)

    王剑峰; 章迟啸; 刘雪粉

    2012-01-01

    综述了近年来芳香性亚硝基化合物在α-氨氧化、α-羟胺化和Diels-Alder等不对称反应中的研究进展。%The recently application of aromatic nitroso compounds as active agents in asymmetric reactions (such as α-aminoxylation reaction, α-oxyamination reaction and the Diels-Alder reaction)was reviewed.

  17. Tropospheric reactions of the haloalkyl radicals formed from hydroxyl radical reaction with a series of alternative fluorocarbons

    Science.gov (United States)

    Atkinson, Roger

    1990-01-01

    In the present assessment, the hydrogen containing halocarbons being considered as alternatives to the the presently used chlorofluorocarbons are the hydrochlorofluorocarbons (HCFCs) 123 (CF3CHCl2), 141b (CFCl2CH3), 142b (CF2ClCH3), 22 (CHF2Cl) and 124 (CF3CHFCl) and the hydrofluorocarbons (HFCs) 134a (CF3CH2F), 152a (CHF2CH3) and 125 (CF3CHF2). All of these HCFCs and HFCs will react with the hydroxyl (OH) radical in the troposphere, giving rise to haloalkyl radicals which then undergo a complex series of reactions in the troposphere. These reactions of the haloalkyl radicals formed from the initial OH radical reactions with the HCFCs and HFCs under tropospheric conditions are the focus here.

  18. Simulating Some Complex Phenomena in Hydrothermal Ore-Forming Processes by Reaction-Diffusion CNN

    Institute of Scientific and Technical Information of China (English)

    Xu Deyi; Yu Chongwen; Bao Zhengyu

    2003-01-01

    Complexity phenomena like dynamic and static patterns, order from disorder, chaos and catastrophe were simulated by the application of 2-D reaction-diffusion CNN of two state variables and two diffusion coefficients transformed from Zhabotinksii model. They revealed somehow the mechanism of hydrothermal ore-forming processes, and answered several questions about the onset of ore forming.

  19. A-T linker adapter polymerase chain reaction for determining flanking sequences by rescuing inverse PCR or thermal asymmetric interlaced PCR products.

    Science.gov (United States)

    Trinh, Quoclinh; Zhu, Pengyu; Shi, Hui; Xu, Wentao; Hao, Junran; Luo, Yunbo; Huang, Kunlun

    2014-12-01

    The polymerase chain reaction (PCR)-based genome walking method has been extensively used to isolate unknown flanking sequences, whereas nonspecific products are always inevitable. To resolve these problems, we developed a new strategy to isolate the unknown flanking sequences by combining A-T linker adapter PCR with inverse PCR (I-PCR) or thermal asymmetric interlaced PCR (TAIL-PCR). The result showed that this method can be efficiently achieved with the flanking sequence from the Arabidopsis mutant and papain gene. Our study provides researchers with an additional method for determining genomic DNA flanking sequences to identify the target band from bulk of bands and to eliminate the cloning step for sequencing.

  20. Asymmetric synthesis of α-amino-1,3-dithianes via chiral N-phosphonyl imine-based Umpolung reaction without using chromatography and recrystallization.

    Science.gov (United States)

    Kattamuri, Padmanabha V; Ai, Teng; Pindi, Suresh; Sun, Yinwei; Gu, Peng; Shi, Min; Li, Guigen

    2011-04-15

    A series of α-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (group-assistant-purification chemistry) process, which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral α-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or a mixture of hexane-ethyl acetate.

  1. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 3: Michael addition reactions and miscellaneous transformations.

    Science.gov (United States)

    Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim

    2014-09-01

    The major goal of this review is a critical discussion of the literature data on asymmetric synthesis of α-amino acids via Michael addition reactions involving Ni(II)-complexes of amino acids. The material covered is divided into two conceptually different groups dealing with applications of: (a) Ni(II)-complexes of glycine as C-nucleophiles and (b) Ni(II)-complexes of dehydroalanine as Michael acceptors. The first group is significantly larger and consequently subdivided into four chapters based on the source of stereocontrolling element. Thus, a chiral auxiliary can be used as a part of nucleophilic glycine Ni(II) complex, Michael acceptor or both, leading to the conditions of matching vs. mismatching stereochemical preferences. The particular focus of the review is made on the practical aspects of the methodology under discussion and mechanistic considerations.

  2. Some Remarks on Asymmetric Syntheses from Recent Studies

    OpenAIRE

    Baba, Naomichi

    1990-01-01

    Some asymmetric syntheses were presented here and discussed briefly including NADH model reactions, phase transfer-catalyzed asymmetric epoxidation, enantiotopic group-selective hydrolysis of a malonic anhydride with alkoxide anion, intramolecular acid-catalyzed lactonizations, catalytic asymmetric Diels-Alder synthesis, asymmetric aldol condensation, chiral homoallyl alcohol synthesis, asymmetric addition of diethylzinc to aldehyde, kinetic resolution of racemic hydroperoxides and binaphthol...

  3. Millimeter and Submillimeter Studies of O(^1D) Insertion Reactions to Form Molecules of Astrophysical Interest

    Science.gov (United States)

    Hays, Brian; Wehres, Nadine; Deprince, Bridget Alligood; Roy, Althea A. M.; Laas, Jacob; Widicus Weaver, Susanna L.

    2015-06-01

    While both the number of detected interstellar molecules and their chemical complexity continue to increase, understanding of the processes leading to their formation is lacking. Our research group combines laboratory spectroscopy, observational astronomy, and astrochemical modeling for an interdisciplinary examination of the chemistry of star and planet formation. This talk will focus on our laboratory studies of O(^1D) insertion reactions with organic molecules to produce molecules of astrophysical interest. By employing these reactions in a supersonic expansion, we are able to produce interstellar organic reaction intermediates that are unstable under terrestrial conditions; we then probe the products using millimeter and submillimeter spectroscopy. We benchmarked this setup using the well-studied O(^1D) + methane reaction to form methanol. After optimizing methanol production, we moved on to study the O(^1D) + ethylene reaction to form vinyl alcohol (CH_2CHOH), and the O(^1D) + methyl amine reaction to form aminomethanol (NH_2CH_2OH). Vinyl alcohol measurements have now been extended up to 450 GHz, and the associated spectral analysis is complete. A possible detection of aminomethanol has also been made, and continued spectral studies and analysis are underway. We will present the results from these experiments and discuss future applications of these molecular and spectroscopic techniques.

  4. Characterization of SiC (SCS-6) Fiber Reinforced Reaction-Formed Silicon Carbide Matrix Composites

    Science.gov (United States)

    Singh, Mrityunjay; Dickerson, Robert M.

    1995-01-01

    Silicon carbide (SCS-6) fiber reinforced-reaction formed silicon carbide matrix composites were fabricated using NASA's reaction forming process. Silicon-2 at a percent of niobium alloy was used as an infiltrant instead of pure silicon to reduce the amount of free silicon in the matrix after reaction forming. The matrix primarily consists of silicon carbide with a bi-modal grain size distribution. Minority phases dispersed within the matrix are niobium disilicide (NbSi2), carbon and silicon. Fiber push-out tests on these composites determined a debond stress of approx. 67 MPa and a frictional stress of approx. 60 MPa. A typical four point flexural strength of the composite is 297 MPa (43.1 KSi). This composite shows tough behavior through fiber pull out.

  5. Characterization of SiC Fiber (SCS-6) Reinforced-Reaction-Formed Silicon Carbide Matrix Composites

    Science.gov (United States)

    Singh, M.; Dickerson, R. M.

    1996-01-01

    Silicon carbide fiber (SCS-6) reinforced-reaction-formed silicon carbide matrix composites were fabricated using a reaction-forming process. Silicon-2 at.% niobium alloy was used as an infiltrant instead of pure silicon to reduce the amount of free silicon in the matrix after reaction forming. The matrix primarily consists of silicon carbide with a bimodal grain size distribution. Minority phases dispersed within the matrix are niobium disilicide (NbSi2), carbon, and silicon. Fiber pushout tests on these composites determined a debond stress of approximately 67 MPa and a frictional stress of approximately 60 MPa. A typical four-point flexural strength of the composite is 297 MPa (43.1 KSi). This composite shows tough behavior through fiber pullout.

  6. One-pot multiple reactions: asymmetric synthesis of 2,6-cis-disubstituted piperidine alkaloids from chiral aziridine.

    Science.gov (United States)

    Yadav, Nagendra Nath; Choi, Jihye; Ha, Hyun-Joon

    2016-07-01

    A divergent, new, and highly stereoselective synthesis of cis-2,6-disubstituted piperidine natural products including isosolenopsins, deoxocassine, and spectaline was achieved from chiral aziridine decorated with appropriate alkyl chains for isosolenopsins or alkynyl groups for deoxocassine and spectaline at C2. The characteristic feature of this synthesis is one-pot sequential reactions under atmospheric hydrogen including the reduction of alkyne (for deoxocassine and spectaline), reductive ring-opening of aziridine, debenzylation, and intramolecular reductive amination in high yields. The prerequisite aziridines were elaborated from commercially available (2S)-hydroxymethylaziridine through oxidation, Wittig olefination, and the Grignard reaction for isosolenopsins or substrate-controlled lithium alkynylate addition for deoxocassine and spectaline. PMID:27189444

  7. 1,6-asymmetric induction in boron-mediated aldol reactions: application to a practical total synthesis of (+)-discodermolide.

    Science.gov (United States)

    Paterson, Ian; Delgado, Oscar; Florence, Gordon J; Lyothier, Isabelle; Scott, Jeremy P; Sereinig, Natascha

    2003-01-01

    By relying solely on substrate-based stereocontrol, a practical total synthesis of the microtubule-stabilizing anticancer agent (+)-discodermolide has been realized. This exploits a novel aldol bond construction with 1,6-stereoinduction from the boron enolate of (Z)-enone 3 in addition to aldehyde 2. The 1,3-diol 7 is employed as a common building block for the C(1)-C(5), C(9)-C(16), and C(17)-C(24) subunits. [reaction--see text

  8. Thin film solid-state reactions forming carbides as contact materials for carbon-containing semiconductors

    Science.gov (United States)

    Leroy, W. P.; Detavernier, C.; Van Meirhaeghe, R. L.; Lavoie, C.

    2007-03-01

    Metal carbides are good candidates to contact carbon-based semiconductors (SiC, diamond, and carbon nanotubes). Here, we report on an in situ study of carbide formation during the solid-state reaction between thin films. The solid-state reaction was examined between 11 transition metals (W, Mo, Fe, Cr, V, Nb, Mn, Ti, Ta, Zr, and Hf) and an amorphous carbon layer. Capping layers (C or TiN) of different thicknesses were applied to prevent oxidation. Carbide formation is evidenced for nine metals and the phases formed have been identified (for a temperature ranging from 100to1100°C). W first forms W2C and then WC; Mo forms Mo2C; Fe forms Fe3C; Cr first forms metastable phases Cr2C and Cr3C2-x, and finally forms Cr3C2; V forms VCx; Nb transforms into Nb2C followed by NbC; Ti forms TiC; Ta first forms Ta2C and then TaC; and Hf transforms into HfC. The activation energy for the formation of the various carbide phases has been obtained by in situ x-ray diffraction.

  9. Studies of reductive elimination reactions to form carbon-oxygen bonds from Pt(IV) complexes.

    Science.gov (United States)

    Williams, B S; Goldberg, K I

    2001-03-21

    The platinum(IV) complexes fac-L(2)PtMe(3)(OR) (L(2) = bis(diphenylphosphino)ethane, o-bis(diphenylphosphino)benzene, R = carboxyl, aryl; L = PMe(3), R = aryl) undergo reductive elimination reactions to form carbon-oxygen bonds and/or carbon-carbon bonds. The carbon-oxygen reductive elimination reaction produces either methyl esters or methyl aryl ethers (anisoles) and L(2)PtMe(2), while the carbon-carbon reductive elimination reaction affords ethane and L(2)PtMe(OR). Choice of reaction conditions allows the selection of either type of coupling over the other. A detailed mechanistic study of the reductive elimination reactions supports dissociation of the OR(-) ligand as the initial step for the C-O bond formation reaction. This is followed by a nucleophilic attack of OR(-) upon a methyl group bound to the Pt(IV) cation to produce the products MeOR and L(2)PtMe(2). C-C reductive elimination proceeds from L(2)PtMe(3)(OR) by initial L (L = PMe(3)) or OR(-) (L(2) = dppe, dppbz) dissociation, followed by C-C coupling from the resulting five-coordinate intermediate. Our studies demonstrate that both C-C and C-O reductive elimination reactions from Pt(IV) are more facile in polar solvents, in the presence of Lewis acids, and for OR(-) groups that contain electron withdrawing substituents. PMID:11456927

  10. The aluminium and iodine pentoxide reaction for the destruction of spore forming bacteria.

    Science.gov (United States)

    Clark, Billy R; Pantoya, Michelle L

    2010-10-21

    The threat of biological weapons is a major concern in the present day and has led to studying methods to neutralize spore forming bacteria. A new technique involves the use of a thermite reaction that exhibits biocidal properties to limit bacterial growth. The objective was to examine the influence on bacteria growth upon spore exposure to thermite reactions with and without biocidal properties. Three thermites are considered: two that have biocidal properties (aluminium (Al) combined with iodine pentoxide (I(2)O(5)) and Al combined with silver oxide (Ag(2)O)); and, one that produces a highly exothermic reaction but has no biocidal properties (Al combined with iron oxide (Fe(2)O(3))). Results show that Al + I(2)O(5) is extremely effective at neutralizing spores after only one hour of exposure. The temperature generated by the reaction was not determined to be an influential factor affecting spore growth kinetics. Further analysis of the thermite reactions revealed that the Al + I(2)O(5) reaction produces iodine gas that effectively interacts with the spores and neutralizes bacteria growth, while the Al + Ag(2)O reaction temperature does not vaporize silver. In the condensed phase silver does not interact with the spores enough to neutralize bacteria growth. This study gives evidence that a thermite can be used as a stable transportation and delivery system for biocidal gas. PMID:20730185

  11. A polystyrene-supported 9-amino(9-deoxy)epi quinine derivative for continuous flow asymmetric Michael reactions.

    Science.gov (United States)

    Izquierdo, Javier; Ayats, Carles; Henseler, Andrea H; Pericàs, Miquel A

    2015-04-14

    A polystyrene (PS)-supported 9-amino(9-deoxy)epi quinine derivative catalyzes Michael reactions affording excellent levels of conversion and enantioselectivity using different nucleophiles and structurally diverse enones. The highly recyclable, immobilized catalyst has been used to implement a single-pass, continuous flow process (residence time: 40 min) that can be operated for 21 hours without significant decrease in conversion and with improved enantioselectivity with respect to batch operation. The flow process has also been used for the sequential preparation of a small library of enantioenriched Michael adducts.

  12. Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

    KAUST Repository

    Zhu, Bo

    2013-05-03

    6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3-hydroxy-2-oxindole derivatives (e.g., CPC-1). Computational studies indicated that the observed stereoselectivity is a result of favorable secondary π-π* and H-bonding interactions in the transition state. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Institute of Scientific and Technical Information of China (English)

    QU Zhi-Rong; XIONG Ren-Gen

    2008-01-01

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

  14. Asymmetric allylic substitution catalyzed by C1-symmetrical complexes of molybdenum: structural requirements of the ligand and the stereochemical course of the reaction.

    Science.gov (United States)

    Malkov, Andrei V; Gouriou, Laure; Lloyd-Jones, Guy C; Starý, Ivo; Langer, Vratislav; Spoor, Paul; Vinader, Victoria; Kocovský, Pavel

    2006-09-01

    Application of new chiral ligands (R)-(-)-12 a and (S)-(+)-12 c (VALDY), derived from amino acids, to the title reaction, involving cinnamyl (linear) and isocinnamyl (branched) type substrates (4 and 5 --> 6), led to excellent regio- and enantioselectivities (>30:1, < or =98 % ee), showing that ligands with a single chiral center are capable of high asymmetric induction. The structural requirements of the ligand and the mechanism are discussed. The application of single enantiomers of deuterium-labeled substrates (both linear 38 c and branched 37 c) and analysis of the products (41-43) by (2)H{(1)H} NMR spectroscopy in a chiral liquid crystal matrix allowed the stereochemical pathways of the reaction to be distinguished. With ligand (S)-(+)-12 c, the matched enantiomer of branched substrate was found to be (S)-5, which was converted into (R)-6 with very high regio- and stereoselectivity via a process that involves net retention of stereochemistry. The mismatched enantiomer of the branched substrate was found to be (R)-5, which was also converted into (R)-6, that is, with apparent net inversion, but at a lower rate and with lower overall enantioselectivity. This latter feature, which may be termed a "memory effect", reduced the global enantioselectivity in the reaction of the racemic substrate (+/-)-5. The stereochemical pathway of the mismatched manifold has been shown also to be one of net retention, the apparent inversion occurring through equilibration via an Mo-allyl intermediate prior to nucleophilic attack. Incomplete equilibration leads to the memory effect and thus to lower enantioselectivity. Analysis of the mismatched manifold over the course of the reaction revealed that the memory effect is progressively attenuated with the nascent global selectivity increasing substantially as the reaction proceeds. The origin of this effect is suggested to be the depletion of CO sources in the reaction mixture, which attenuates turnover rate and thus facilitates

  15. 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

  16. Intermediates Formed in the Reactions of Organocuprates with α,β-Unsaturated Nitriles.

    Science.gov (United States)

    Putau, Aliaksei; Brand, Harald; Koszinowski, Konrad

    2016-08-26

    Conjugate additions of organocuprates are of outstanding importance for organic synthesis. To improve our mechanistic understanding of these reactions, we have used electrospray ionization mass spectrometry for the identification of the ionic intermediates formed upon the treatment of LiCuR2 ⋅LiCN (R=Me, Bu, Ph) with a series of α,β-unsaturated nitriles. Acrylonitrile, the weakest Michael acceptor included, did not afford any detectable intermediates. Fumaronitrile (FN) yielded adducts of the type Lin-1 Cun R2n (FN)n (-) , n=1-3. When subjected to fragmentation in the gas phase, these adducts were not converted into the conjugate addition products, but re-dissociated into the reactants. In contrast, the reaction with 1,1-dicyanoethylene furnished the products of the conjugate addition without any observable intermediates. Tri- and tetracyanoethylene proved to be quite reactive as well. The presence of several cyano groups in these substrates opened up reaction pathways different from simple conjugate additions, however, and led to dimerization and substitution reactions. Moreover, the gas-phase fragmentation behavior of the species formed from these substrates indicated the occurrence of single-electron transfer processes. Additional quantum-chemical calculations provided insight into the structures and stabilities of the observed intermediates and their consecutive reactions. PMID:27461093

  17. Reexamining closed-form formulae for inclusive breakup: Application to deuteron and $^6$Li induced reactions

    CERN Document Server

    Lei, Jin

    2015-01-01

    The problem of the calculation of inclusive breakup cross sections in nuclear reactions is reexamined. For that purpose, the post-form theory proposed by Ichimura, Austern and Vincent [Phys. Rev. C32, 431 (1985) is revisited, and an alternative derivation of the non-elastic breakup part of the inclusive breakup is presented, making use of the coupled-channels optical theorem. Using the DWBA version of this model, several applications to deuteron and $^6$Li reactions are presented and compared with available data. The validity of the zero-range approximation of the DWBA formula is also investigated by comparing zero-range with full finite-range calculations.

  18. Light Charged Particles Emission and the Giant Dipole Resonance in Highly Excited Ce Nucleus Formed in Reactions with Different Mass Asymmetries

    Science.gov (United States)

    Barlini, S.; Kravchuk, V. L.; Wieland, O.; Bracco, A.; Gramegna, F.; Airoldi, A.; Benzoni, G.; Blasi, N.; Brambilla, S.; Brekiesz, M.; Bruno, M.; Camera, F.; Casini, G.; Chiari, M.; D'Agostino, M.; De Sanctis, J.; Geraci, E.; Kmiecik, M.; Lanchais, A.; Leoni, S.; Maj, A.; Mastinu, P. F.; Million, B.; Moroni, A.; Nannini, A.; Ordine, A.; Sacchi, R.; Vannini, G.

    2006-08-01

    Recent measurements have been performed at the National Laboratoty of Legnaro using mass-symmetric (400, 500 MeV 64Ni + 68Zn) and mass-asymmetric (250 MeV 16O + 116Sn) entrance channel reactions to form 132Ce compound nucleus at different excitation energies (E*=150, 200 and 200 MeV, respectively). The decay of the composite system has been followed studying the γ-rays and Light Charged Particles (LCP) spectra emitted in coincidence with the Evaporation Residues (ER). In this way the emission mechanism of the LCP, depending on the mass-asymmetry at the entrance channel and on the projectile energy, and the results of the Full Width Half-Maximum (FWHM) of the Giant Dipole Resonance as a function of the nuclear temperature have been studied.

  19. Effect of an organoclay on the reaction-induced phase-separation in a dynamically asymmetric epoxy/PCL system

    Directory of Open Access Journals (Sweden)

    J. Rotrekl

    2013-12-01

    Full Text Available The addition of layered silicates can significantly affect the phase behaviour of both immiscible thermoplastic blends and partially miscible thermoset systems that undergo reaction-induced phase separation (RIPS during curing. This study focuses on the phase behaviour of polycaprolactone (PCL/epoxy in the presence of organically modified montmorillonite (oMMT. Due to the high dynamic asymmetry caused by the differences in the molecular weights and viscosities of the PCL and the uncured epoxy, the critical point is localised at low PCL concentrations, as indicated by the pseudophase diagram. The addition of oMMT to the system led to the marked shift of the critical point towards higher concentrations of PCL, with an increase in the oMMT content occurring as a consequence of the preferential localisation of the clay in the epoxy phase, making this phase more dynamically slow. Significant changes in morphology, including phase inversion of the PCL/epoxy systems caused by the presence of oMMT, were recorded for PCL concentrations ranging from 10 to 30%.

  20. Influence of induced magnetic field and heat transfer on the peristaltic motion of a Jeffrey fluid in an asymmetric channel: Closed form solutions

    Energy Technology Data Exchange (ETDEWEB)

    Akram, Safia, E-mail: safia_akram@yahoo.com [Department of Humanities and Basic Sciences, Military College of Signals, National University of Sciences and Technology, Rawalpindi 46000 (Pakistan); Department of Mathematics, Quaid-i-Azam University 45320, Islamabad 44000 (Pakistan); Nadeem, S. [Department of Mathematics, Quaid-i-Azam University 45320, Islamabad 44000 (Pakistan)

    2013-02-15

    We discuss the peristaltic motion of a two dimensional Jeffrey fluid in an asymmetric channel under the effects of induced magnetic field and heat transfer. The problem is simplified by using long wave length and low Reynolds approximations. Exact and closed form Adomian solutions are presented. Expressions for the velocity, stream function, magnetic force function, temperature, pressure gradient and pressure rise are computed. The results of pertinent parameters are discussed. Finally, the trapping phenomena for different wave shapes are discussed. It is observed that the pressure rise for sinusoidal wave is less than trapezoidal wave and greater than triangular in a Jeffrey fluid. - Highlights: Black-Right-Pointing-Pointer The effects of induced magnetic field and heat transfer in peristaltic motion of a two dimensional Jeffrey fluid are discussed. Black-Right-Pointing-Pointer In this paper exact and closed form Adomian solutions are presented. Black-Right-Pointing-Pointer Different wave shapes are considered to observe the behavior of pressure rise and trapping phenomena.

  1. Excitation energy dependence of fragment-mass distributions from fission of 180,190Hg formed in fusion reactions of 36Ar + 144,154Sm

    Directory of Open Access Journals (Sweden)

    K. Nishio

    2015-09-01

    Full Text Available Mass distributions of fission fragments from the compound nuclei 180Hg and 190Hg formed in fusion reactions 36Ar + 144Sm and 36Ar + 154Sm, respectively, were measured at initial excitation energies of E⁎(Hg180=33–66 MeV and E⁎(Hg190=48–71 MeV. In the fission of 180Hg, the mass spectra were well reproduced by assuming only an asymmetric-mass division, with most probable light and heavy fragment masses A¯L/A¯H=79/101. The mass asymmetry for 180Hg agrees well with that obtained in the low-energy β+/EC-delayed fission of 180Tl, from our earlier ISOLDE(CERN experiment. Fission of 190Hg is found to proceed in a similar way, delivering the mass asymmetry of A¯L/A¯H=83/107, throughout the measured excitation energy range. The persistence as a function of excitation energy of the mass-asymmetric fission for both proton-rich Hg isotopes gives strong evidence for the survival of microscopic effects up to effective excitation energies of compound nuclei as high as 40 MeV. This behavior is different from fission of actinide nuclei and heavier mercury isotope 198Hg.

  2. Reaction mixtures formed by nitrite and selected sulfa-drugs showed mutagenicity in acidic medium

    Directory of Open Access Journals (Sweden)

    Claudia Trossero

    2009-01-01

    Full Text Available Nitrite, which is present in preserved meat and can be produced in the oral cavity by reduction of nitrate taken from vegetables, could react in stomach with nitrosatable drugs, giving genotoxic-carcinogenic N-nitroso compounds (NOC. The mutagenicity of reaction mixtures formed by sodium nitrite and selected sulfa-drugs (sulfathiazole, HST; phtalylsulfathiazole, PhST; complex Co(II-sulfathiazole, Co(II-ST in acidic medium was evaluated using the Salmonella typhimurium reverse mutation assay (Ames test, with TA98 and TA 100 strains. The reactions were carried out at room temperature, with a mole ratio [nitrite]/[sulfa-drug] > 1. The three reaction mixtures showed mutagenic effects in the considered range.

  3. Optimisation of an asymmetric polymerase chain reaction assay for the amplification of single-stranded DNA from Wuchereria bancrofti for electrochemical detection

    Directory of Open Access Journals (Sweden)

    Vasuki Venkatesan

    2013-09-01

    Full Text Available Single-stranded DNA (ssDNA is a prerequisite for electrochemical sensor-based detection of parasite DNA and other diagnostic applications. To achieve this detection, an asymmetric polymerase chain reaction method was optimised. This method facilitates amplification of ssDNA from the human lymphatic filarial parasite Wuchereria bancrofti. This procedure produced ssDNA fragments of 188 bp in a single step when primer pairs (forward and reverse were used at a 100:1 molar ratio in the presence of double-stranded template DNA. The ssDNA thus produced was suitable for immobilisation as probe onto the surface of an Indium tin oxide electrode and hybridisation in a system for sequence-specific electrochemical detection of W. bancrofti. The hybridisation of the ssDNA probe and target ssDNA led to considerable decreases in both the anodic and the cathodic currents of the system's redox couple compared with the unhybridised DNA and could be detected via cyclic voltammetry. This method is reproducible and avoids many of the difficulties encountered by conventional methods of filarial parasite DNA detection; thus, it has potential in xenomonitoring.

  4. Optimisation of an asymmetric polymerase chain reaction assay for the amplification of single-stranded DNA from Wuchereria bancrofti for electrochemical detection.

    Science.gov (United States)

    Venkatesan, Vasuki; Hoti, Sugeerappa Laxmanappa; Kamaraj, Nagalakshmi; Ghosh, Somnath; Rajaram, Kaushik

    2013-09-01

    Single-stranded DNA (ssDNA) is a prerequisite for electrochemical sensor-based detection of parasite DNA and other diagnostic applications. To achieve this detection, an asymmetric polymerase chain reaction method was optimised. This method facilitates amplification of ssDNA from the human lymphatic filarial parasite Wuchereria bancrofti. This procedure produced ssDNA fragments of 188 bp in a single step when primer pairs (forward and reverse) were used at a 100:1 molar ratio in the presence of double-stranded template DNA. The ssDNA thus produced was suitable for immobilisation as probe onto the surface of an Indium tin oxide electrode and hybridisation in a system for sequence-specific electrochemical detection of W. bancrofti. The hybridisation of the ssDNA probe and target ssDNA led to considerable decreases in both the anodic and the cathodic currents of the system's redox couple compared with the unhybridised DNA and could be detected via cyclic voltammetry. This method is reproducible and avoids many of the difficulties encountered by conventional methods of filarial parasite DNA detection; thus, it has potential in xenomonitoring. PMID:24037206

  5. Role of radiolytically formed protonating agents in gas phase competitive reactions

    International Nuclear Information System (INIS)

    Radiolytically formed O2H+, N2H+, and CO2H+ ions were allowed to react with gaseous p-cymene. Dealkylation and isomerization reactions were observed with O2H+ and N2H+ ions, while only the first process occured when CO2H+ ions were employed. The results show that dealkylation is favored with respect to isomerization as the protonation exothermicity decreases. (author) 9 refs.; 2 figs.; 1 tab

  6. Product-form stationary distributions for deficiency zero chemical reaction networks

    OpenAIRE

    Anderson, David F.; Craciun, Gheorghe; Kurtz, Thomas G.

    2008-01-01

    We consider stochastically modeled chemical reaction systems with mass-action kinetics and prove that a product-form stationary distribution exists for each closed, irreducible subset of the state space if an analogous deterministically modeled system with mass-action kinetics admits a complex balanced equilibrium. Feinberg's deficiency zero theorem then implies that such a distribution exists so long as the corresponding chemical network is weakly reversible and has a deficiency of zero. The...

  7. On Peritectic Reactions and Transformations and Hot Forming of Cast Structures

    OpenAIRE

    Nassar, Hani

    2009-01-01

    This thesis deals with peritectic reactions and transformations that occur during the solidification of many alloys. Peritectics are believed to be a major cause of crack-formation in many steels, thus, good knowledge of the mechanisms by which these phenomena occur is essential for preventing such defects. The thesis also handles the behaviour of metals, in particular cast structures, during hot forming. Grain size and microstructure are of most importance in determining the strength, toughn...

  8. A non-scale-invariant form for coarse-grained diffusion-reaction equations

    Science.gov (United States)

    Ostvar, Sassan; Wood, Brian D.

    2016-09-01

    The process of mixing and reaction is a challenging problem to understand mathematically. Although there have been successes in describing the effective properties of mixing and reaction under a number of regimes, process descriptions for early times have been challenging for cases where the structure of the initial conditions is highly segregated. In this paper, we use the method of volume averaging to develop a rigorous theory for diffusive mixing with reactions from initial to asymptotic times under highly segregated initial conditions in a bounded domain. One key feature that arises in this development is that the functional form of the averaged differential mass balance equations is not, in general, scale invariant. Upon upscaling, an additional source term arises that helps to account for the initial configuration of the reacting chemical species. In this development, we derive the macroscopic parameters (a macroscale source term and an effectiveness factor modifying the reaction rate) defined in the macroscale diffusion-reaction equation and provide example applications for several initial configurations.

  9. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    Science.gov (United States)

    Cortright, Randy D.; Dumesic, James A.

    2011-01-18

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  10. Reaction sintered glass: a durable matrix for spinel-forming nuclear waste compositions

    International Nuclear Information System (INIS)

    Glass formation by reaction sintering under isostatic pressure is an innovative process to vitrify refractory-rich high-level radioactive waste. We used a typical defense waste composition, containing spinel-forming components such as ∼4 wt% of Cr2O3, ∼23 wt% Al2O3, ∼13 wt% Fe2O3, and ∼9 wt% UO2, with CeO2 simulating UO2. Reaction sintered silicate glasses with waste loading up to 45 wt% were prepared within three hours, by hot pressing at 800 deg. C. The glass former was amorphous silica. Simulated waste was added as calcined oxides. The reaction sintered glass samples were characterized using scanning and analytical electron microscopy. The results show that extensive reaction sintering took place and a continuous glass phase formed. Waste components such as Na2O, CaO, MnO2, and Fe2O3, dissolved completely in the continuous glass phase. Cr2O3, Al2O3, and CeO2 were only partially dissolved due to incomplete dissolution (Al2O3) or super-saturation and reprecipitation (Cr2O3 and CeO2). The precipitation mechanism is related to a time dependent alkali content in the developing glass phase. Short-term corrosion tests in water showed that the glasses are chemically more durable than melted nuclear waste glasses. Based on hydration energies calculations, the long-term chemical durability of our reaction sintered glasses is expected to be comparable to that of rhyolitic and tektite glasses

  11. Abnormal Nucleophilic Reaction of Ethyl Crotonate: An Easy Way to Form Novel Imidazo[1,5-a] pyridine derivatives

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    An abnormal intramolecular nucleophilic reaction of α-carbon of α,β-unsaturated ester was discovered and the reaction makes it very easy to form imidazo[1,5-a]pyridine derivatives. The mechanism of the reaction was discussed.

  12. Sequence Analysis of Trimer Isomers Formed by Montmorillonite Catalysis in the Reaction of Binary Monomer Mixtures

    Science.gov (United States)

    Ertem, Gözen; Hazen, Robert M.; Dworkin, Jason P.

    2007-10-01

    Oligonucleotides are structurally similar to short RNA strands. Therefore, their formation via non-enzymatic reactions is highly relevant to Gilbert's RNA world scenario (1986) and the origin of life. In laboratory synthesis of oligonucleotides from monomers, it is necessary to remove the water molecules from the reaction medium to shift the equilibrium in favor of oligonucleotide formation, which would have been impossible for reactions that took place in dilute solutions on the early Earth. Model studies designed to address this problem demonstrate that montmorillonite, a phyllosilicate common on Earth and identified on Mars, efficiently catalyzes phosphodiester-bond formation between activated mononucleotides in dilute solutions and produces RNA-like oligomers. The purpose of this study was to examine the sequences and regiospecificity of trimer isomers formed in the reaction of 5'-phosphorimidazolides of adenosine and uridine. Results demonstrated that regiospecificity and sequence specificity observed in the dimer fractions are conserved in their elongation products. With regard to regiospecificity, 61% of the linkages were found to be RNA-like 3',5'-phosphodiester bonds. With regard to sequence specificity, we found that 88% of the linear trimers were hetero-isomers with 61% A-monomer and 39% U-monomer incorporation. These results lend support to Bernal's hypothesis that minerals may have played a significant role in the chemical processes that led to the origin of life by catalyzing the formation of phosphodiester bonds in RNA-like oligomers.

  13. Asymmetric synthesis of pedamide using I2-induced heterocyclization to construct the skeleton

    Institute of Scientific and Technical Information of China (English)

    De Gang Liu; Ji Jun Xue; Zhi Xiang Xie; Li Ping Wei; Hua Bing Zhang; Ying Li

    2009-01-01

    An alternative approach to synthesize pedamide, a key building block of pederin was described. Iodine-induced asymmetric heterocyclization was used as the key step to construct the skeleton, a tetrahydropyran ring with three chiral centers. Brown's asymmetric allylation and Lewis acid-mediated allylation were investigated to introduce chains and chiral alcohols. Sharpless dihydroxylation decorated the side chain. And high optically pure target was obtained by removing the epimers formed in these reactions on column chromatography.

  14. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin

    2014-08-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations. © 2014 American Chemical Society.

  15. Micromechanical modeling of sulphate corrosion in concrete: Influence of ettringite forming reaction

    Directory of Open Access Journals (Sweden)

    Basista M.

    2008-01-01

    Full Text Available Two micromechanical models are developed to simulate the expansion of cementitious composites exposed to external sulphate attack. The difference between the two models lies in the form of chemical reaction of the ettringite formation (through-solution vs. topochemical. In both models the Fick's second law with reaction term is assumed to govern the transport of the sulphate ions. The Eshelby solution and the equivalent inclusion method are used to determine the eigenstrain of the expanding ettringite crystals in microcracked hardened cement paste. The degradation of transport properties is studied in the effective medium and the percolation regime. An initial-boundary value problem (2D of expansion of a mortar specimen immersed in a sodium sulphate solution is solved and compared with available test data. The obtained results indicate that the topochemical mechanism is the one capable of producing the experimentally observed amount of expansion.

  16. Innovative Catalysis in Organic Synthesis Oxidation, Hydrogenation, and C-X Bond Forming Reactions

    CERN Document Server

    Andersson, Pher G

    2012-01-01

    Authored by a European team of leaders in the field, this book compiles innovative approaches for C-X bond forming processes frequently applied in organic synthesis. It covers all key types of catalysis, including homogeneous, heterogeneous, and organocatalysis, as well as mechanistic and computational studies. Special attention is focused on the improvement of efficiency and sustainability of important catalytic processes, such as selective oxidations, hydrogenation and cross-coupling reactions.The result is a valuable resource for both advanced researchers in academia and industry, as well a

  17. 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.

  18. Synthesis of Prolinamide and Its Application in Asymmetric Aldol Reaction%脯胺酰胺衍生物的合成及在催化不对称aldol反应的应用

    Institute of Scientific and Technical Information of China (English)

    熊亚平; 金云舟; 代金玲

    2011-01-01

    Prolinamide was synthesized from natural amino acids, which has been used as a catalyst in the asymmetric aldol condensation reaction between aromatic aldehyde and acetone. The addition of acid can obviously enhance the reaction rate and enantioselectivity.%以天然氨基酸为原料合成了一种脯胺酰胺衍生物,并研究了它在催化芳香醛与丙酮的不对称羟醛缩合反应中的应用.酸的添加能够提高反应速率及产物的对应选择性.

  19. Interfacial thiol-ene photo-click reactions for forming multilayer hydrogels

    Science.gov (United States)

    Shih, Han; Fraser, Andrew K.; Lin, Chien-Chi

    2014-01-01

    Interfacial visible light-mediated thiol-ene photo-click reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a non-cleavage type photoinitiator eosin-Y on visible light-mediated thiol-ene photopolymerization was first characterized using in situ photo-rheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using UV/Vis spectrometry. It was determined that eosin-Y was able to re-initiate thiol-ene photo-click reaction even after light exposure. Due to its small molecular weight, most eosin-Y molecules readily leached out from the hydrogels. The diffusion of residual eosin-Y from pre-formed hydrogels was exploited for fabricating multilayer step-growth hydrogels. Interfacial hydrogel coating was formed via the same visible light-mediated gelation mechanism without adding fresh initiator. The thickness of the thiol-ene gel coating could be easily controlled by adjusting visible light exposure time, eosin-Y concentration initially loaded in the core gel, or macromer concentration in the coating solution. The major benefits of this interfacial thiol-ene coating system include its simplicity and cytocompatibility. The formation of thiol-ene hydrogels and coatings neither requires nor generates any cytotoxic components. This new gelation chemistry may have great utilities in controlled release of multiple sensitive growth factors and encapsulation of multiple cell types for tissue regeneration. PMID:23384151

  20. Designing a national combined reporting form for adverse drug reactions and medication errors.

    Science.gov (United States)

    Tanti, A; Serracino-Inglott, A; Borg, J J

    2015-06-09

    The Maltese Medicines Authority was tasked with developing a reporting form that captures high-quality case information on adverse drug reactions (ADRs) and medication errors in order to fulfil its public-health obligations set by the European Union (EU) legislation on pharmacovigilance. This paper describes the process of introducing the first combined ADR/medication error reporting form in the EU for health-care professionals, the analysis of reports generated by it and the promotion of the system. A review of existing ADR forms was carried out and recommendations from the European Medicines Agency and World Health Organization audits integrated. A new, combined ADR/medication error reporting form was developed and pilot tested based on case studies. The Authority's quality system (ISO 9001 certified) was redesigned and a promotion strategy was deployed. The process used in Malta can be useful for countries that need to develop systems relative to ADR/medication error reporting and to improve the quality of data capture within their systems.

  1. Effects of Water Regime and Reaction of Soil on Properties of Newly—Formed Humic Substances

    Institute of Scientific and Technical Information of China (English)

    CHENGLI-LI; WENQI-XIAO; 等

    1992-01-01

    The effects of soil water regime and soil reaction on nitrogen distribution and fractional composition of newly-formed humus (decayed products) and the structural characteristics of the newly-formed humic acids(HAs) were studied in an incubation experiment,with the following results obtained: 1.The humus newly formed under submerged conditions was higher in the relative content of α-amino acid-N and the humic acid/fulvic acid (HA/FA) ratio than that under upland conditions.The HAs extracted from the former were also higher in C/O ratio,aromaticity and the contents of methoxyl groups and lignin-like components,but lower in the content of carboxyl groups than the HAs from the latter. 2.Under upland conditions,the C/ organic N ratio and the relative content of mobile HA of newly-formed humus were lower,but the HA/FA ratio was higher in the CaCO2-amended treatment than in non-amended treatment.The presence of CaCO3 also resulted in a decrease of C/N ratio of HA and a slight increase of its carboxyl group content.On the other hand,there was no significant change in the composition and properties of the newly-formed humus with the addition of CaCO3 under submerged conditions. 3.Compared with soil HAs,the newly-formed HAs contained more carbohydrates,polypeptides and lignin-like components,and were in lower degrees of oxidation and humification.

  2. Fission characteristics of 216Ra formed in heavy-ion induced reactions

    Indian Academy of Sciences (India)

    Hadi Eslamizadeh

    2013-11-01

    A Kramers-modified statistical model is used to calculate the cross-section of the evaporation residue, fission cross-section, average pre-fission multiplicities of protons and -particles for 216Ra formed in 19F + 197Au reactions and results are compared with the experimental data. To calculate these quantities, the effects of temperature and spin K about the symmetry axis have been considered in the calculations of the potential energy surfaces and the fission widths. It is shown that the results of the calculations using values of the temperature coefficient of the effective potential = 0.008 ± 0.003 MeV−2 and scaling factor of the fission-barrier height $r_{s} = 1.004 ± 0.002$ are in good agreement with the experimental data.

  3. Reasons of Aggressive Behaviour Against School Fellows, Its Frequency, Forms: Reaction of Schoolchildren, Teachers and Parents

    Directory of Open Access Journals (Sweden)

    Valdas Pruskus

    2011-12-01

    Full Text Available The present article, which is based on conducted research data, analyzes an attitude of schoolchildren, teachers and parents towards the reasons of schoolchildren’s aggressive behaviour, its frequency and forms. Different factors and motives that stimulate the aggressiveness of schoolchildren, who go to the city, village and different professional (arts and technology schools are examined. Schoolchildren’s approach towards violence against school fellows and themselves is being discussed, as well as reaction of teachers and parents to this phenomenon. The article reveals opinion of schoolchildren, teachers, and parents about the means used to prevent violence towards schoolchildren and existing ways that can be used to make preventive means to be more effective.

  4. Microstructural Characterization of Reaction-Formed Silicon Carbide Ceramics. Materials Characterization

    Science.gov (United States)

    Singh, M.; Leonhardt, T. A.

    1995-01-01

    Microstructural characterization of two reaction-formed silicon carbide ceramics has been carried out by interference layering, plasma etching, and microscopy. These specimens contained free silicon and niobium disilicide as minor phases with silicon carbide as the major phase. In conventionally prepared samples, the niobium disilicide cannot be distinguished from silicon in optical micrographs. After interference layering, all phases are clearly distinguishable. Back scattered electron (BSE) imaging and energy dispersive spectrometry (EDS) confirmed the results obtained by interference layering. Plasma etching with CF4 plus 4% O2 selectively attacks silicon in these specimens. It is demonstrated that interference layering and plasma etching are very useful techniques in the phase identification and microstructural characterization of multiphase ceramic materials.

  5. DIFLUORPHOS and SYNPHOS in asymmetric catalysis: Synthetic applications

    Indian Academy of Sciences (India)

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

    2014-03-01

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

  6. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

    2013-11-01

    This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

  7. Asymmetric collider

    International Nuclear Information System (INIS)

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

  8. Fission dynamics of 240Cf* formed in 34,36S induced reactions

    Directory of Open Access Journals (Sweden)

    Jain Deepika

    2015-01-01

    Full Text Available We have studied the entrance channel effects in the decay of Compound nucleus 240Cf* formed in 34S+206Pb and 36S+204Pb reactions by using energy density dependent nuclear proximity potential in the framework of dynamical cluster-decay model (DCM. At different excitation energies, the fragmentation potential and preformation probability of decaying fragments are almost identical for both the entrance channels, which seem to suggest that decay is independent of its formation and entrance channel excitation energy. It is also observed that, with inclusion of deformation effects upto quadrupole within the optimum orientation approach, the fragmentation path governing potential energy surfaces gets modified significantly. Beside this, the fission mass distribution of Cf* isotopes is also investigated. The calculated fission cross-sections using SIII force for both the channels find nice agreement with the available experimental data for deformed choice of fragments, except at higher energies. In addition to this, the comparative analysis with Blocki based nuclear attraction is also worked out. It is observed that Blocki proximity potential accounts well for the CN decay at all energies whereas the use of EDF based nuclear potential suggests the presence of some non-compound nucleus process (such as quasi-fission (qf at higher energies.

  9. Photochemical reactions of chlorophyll in dehydrated photosystem II: two chlorophyll forms (680 and 700 nm).

    Science.gov (United States)

    Heber, Ulrich; Shuvalov, Vladimir A

    2005-06-01

    Lichens and phototolerant poikilohydric mosses differ from spinach leaves, fern fronds or photosensitive mosses in that they show strongly decreased Fo chlorophyll fluorescence after drying. This desiccation-induced fluorescence loss is rapidly reversible under rehydration. Fluorescence emission from Photosystem II at 685 nm was decreased more strongly by dehydration than 720 nm emission. Reaction centers of Photosystem II lose activity on dehydration and regain it on hydration. Heating of desiccated lichens increased Fo chlorophyll fluorescence. The activation energy for the reversible part of the temperature-dependent fluorescence increase was 0.045 eV, which corresponds to the energy difference between the 680 and 697 nm absorption bands. In desiccated chlorolichens such as Parmelia sulcata, heating induces the appearance of positive variable fluorescence related to the reversible reduction of QA due to overcoming the energy barrier. This is interpreted to provide information on the mechanism of photoprotection: energy is dissipated by changing Chl680 or P680 into a chlorophyll form, which absorbs at 700 nm and emits light at 720 nm (Chl-720 or P680(700)) with a low quantum yield. Dissipation of light energy in this trap is activated by desiccation. PMID:16049759

  10. Asymmetric Michael Addition Reaction under the Control of the Evans Chiral Auxiliary (Ⅱ)%Evans手性助剂控制的不对称Michael加成立体选择性研究(Ⅱ)

    Institute of Scientific and Technical Information of China (English)

    樊会丹; 张从海; 严胜骄; 林军

    2012-01-01

    Chiral auxiliaries controlled asymmetric reaction is one of the main methods in asymmetric synthesis. Under the control of the Evans auxiliary and catalyzed by FeCl13, different Grignard reagents were added asymmetrically to the substrates 1 by the way of 1,4-Michael addition reaction, and a series of Michael addition products 2a~2h which containing two chiral centers have been synthesized with higher stereoselectivity. Among them, compounds 2d and 2e achieved high diastereospeci-fically up to 98% de. The results showed that the steric hindrance of the Grignard reagents is the main factor which influences the stereoselectivity of Micheal addition.%手性助剂控制的不对称反应是不对称合成的重要方法之一.以Evans手性助剂控制的Michael受体1为底物,在FeCl3催化下,通过不同格式试剂对其进行Michael加成,一步反应得到了一系列含两个手性中心的Michael加成产物2a~2h.获得了较高的立体选择性,其中化合物2d和2e得到了de值高达98%的非对映选择性.研究结果表明,亲核试剂的空间位阻是影响产物立体选择性的主要因素.

  11. Reactions of the alkoxy radicals formed following OH-addition to alpha-pinene and beta-pinene. C-C bond scission reactions.

    Science.gov (United States)

    Dibble, T S

    2001-05-01

    The atmospheric degradation pathways of the atmospherically important terpenes alpha-pinene and beta-pinene are studied using density functional theory. We employ the correlation functional of Lee, Yang, and Parr and the three-parameter HF exchange functional of Becke (B3LYP) together with the 6-31G(d) basis set. The C-C bond scission reactions of the beta-hydroxyalkoxy radicals that are formed after OH addition to alpha-pinene and beta-pinene are investigated. Both of the alkoxy radicals formed from the alpha-pinene-OH adduct possess a single favored C-C scission pathway with an extremely low barrier (approximately 3 kcal/mol) leading to the formation of pinonaldehyde. Neither of these pathways produces formaldehyde, and preliminary computational results offer some support for suggestions that 1,5 or 1,6 H-shift (isomerization) reactions of alkoxy radicals contribute to formaldehyde production. In the case of the alkoxy radical formed following OH addition to the methylene group of beta-pinene, there exists two C-C scission reactions with nearly identical barrier heights (approximately 7.5 kcal/mol); one leads to known products (nopinone and formaldehyde) but the ultimate products of the competing reaction are unknown. The single C-C scission pathway of the other alkoxy radical from beta-pinene possesses a very low (approximately 4 kcal/mol) barrier. The kinetically favored C-C scission reactions of all four alkoxy radicals appear to be far faster than expected rates of reaction with O2. The rearrangement of the alpha-pinene-OH adduct, a key step in the proposed mechanism of formation of acetone from alpha-pinene, is determined to possess a barrier of 11.6 kcal/mol. This value is consistent with another computational result and is broadly consistent with the modest acetone yields observed in product yield studies.

  12. Antioxidative, Antibacterial, and Food Functional Properties of the Half-Fin Anchovy Hydrolysates-Glucose Conjugates Formed via Maillard Reaction

    OpenAIRE

    Ru Song; Peiyu Yang; Rongbian Wei; Guanqiang Ruan

    2016-01-01

    The antioxidative, antibacterial, and food functional properties of the half-fin anchovy hydrolysates (HAHp)-glucose conjugates formed by Maillard reaction (MR) were investigated, respectively. Results of sugar and amino acid contents loss rates, browning index, and molecular weight distribution indicated that the initial pH of HAHp played an important role in the process of MR between HAHp and glucose. HAHp-glucose Maillard reaction products (HAHp-G MRPs) demonstrated enhanced antioxidative ...

  13. When the mind forms fear: embodied fear knowledge potentiates bodily reactions

    NARCIS (Netherlands)

    S. Oosterwijk; M. Topper; M. Rotteveel; A.H. Fischer

    2010-01-01

    In the present study, the authors tested whether conceptual fear knowledge can (a) evoke bodily reactions and (b) enhance subsequent bodily reactions to fearful stimuli. Participants unscrambled neutral or fear sentences and subsequently viewed fearful and neutral pictures in combination with startl

  14. Aerosol-Forming Reactions of Glyoxal, Methylglyoxal and Amino Acids in Clouds

    Science.gov (United States)

    de Haan, D. O.; Smith, K. W.; Stroik, D. R.; Corrigan, A. L.; Lee, F. E.; Phan, J. T.; Conley, A. C.

    2008-12-01

    Glyoxal and methylglyoxal are two common aldehydes present in fog and cloud water. Amino acids are present in clouds at similar concentrations. Here we present bulk and aerosol mass spectroscopic data demonstrating that irreversible reactions between glyoxal and amino acids, triggered by droplet evaporation, produce N-derivatized imidazole compounds along with deeply colored Maillard reaction products. These reactions can occur in the dark and in the absence of oxidants. Reactions between methylglyoxal and amino acids produce analogous methylated products plus oligomers with masses up to m/z = 1000. These reactions, which go to completion on the 10-min-timescale of cloud processing, could be significant sources of secondary organic aerosol and humic-like substances (HULIS or brown carbon).

  15. Asymmetric Michael Addition of Activated Alkenes to Nitro Alkenes Catalyzed by Organic Catalyst

    Institute of Scientific and Technical Information of China (English)

    XUE Dong; CHEN Yong-Chun; CUI Xin; WANG Qi-Wei; ZHU Jin; DENG Jin-Gen

    2003-01-01

    @@ Enantioselective Michael addition is one of the most powerfulbond-forming reaction in organic synthesis. [1] A mong the Michael acceptors, nitro alkenes are very attractive, because the nitro group is the most electron-withdrawing group known and it can serve as masked functionality to be further transformed after the addition has taken place. [2] Recently, asymmetric Michael reactions catalyzed by organic catalyst have draw much attention.[3

  16. Liquid composition having ammonia borane and decomposing to form hydrogen and liquid reaction product

    Science.gov (United States)

    Davis, Benjamin L; Rekken, Brian D

    2014-04-01

    Liquid compositions of ammonia borane and a suitably chosen amine borane material were prepared and subjected to conditions suitable for their thermal decomposition in a closed system that resulted in hydrogen and a liquid reaction product.

  17. Disassembly of hot nuclear matter formed in Au-induced reactions near the Fermi energy

    Energy Technology Data Exchange (ETDEWEB)

    Delis, D.N.

    1993-09-01

    Complex fragment emission has been studied in the 60 MeV/A {sup 197}Au + {sup 12}C, {sup 27}Al, {sup 51}V, {sup nat}Cu, and {sup 197}Au reactions. Velocity spectra, angular distributions and cross sections have been constructed for each target from the inclusive data. Coincidence data including 2-, 3-, 4-, and 5-fold events have also been examined. Furthermore neutron multiplicity distributions have been obtained for the above reactions by utilizing a novel neutron calorimetric approach.

  18. Electrocatalysis of the Oxygen Evolution Reaction: A Comparative Study of Anodically Formed and Nanostructured Iridium Oxides

    OpenAIRE

    Lervik, Ingrid Anne

    2010-01-01

    The thesis deals with electrocatalysts for the oxygen evolution reaction for proton-exchange membrane (PEM) water electrolysis. Water electrolysis is considered the only viable option for large-scale hydrogen production. Hydrogen is a relevant storage medium for renewable energy technologies.The oxygen-evolution reaction (OER) is a major source of loss in PEM water electrolysis, and currently costly catalysts such as iridium oxide, an oxide with a rutile structure, are employed. Optimum use o...

  19. A novel asymmetric membrane osmotic pump capsule with in situ formed delivery orifices for controlled release of gliclazide solid dispersion system.

    Science.gov (United States)

    Yang, Yue; Zhao, Zhinan; Wang, Yongfei; Yang, Lu; Liu, Dandan; Yang, Xinggang; Pan, Weisan

    2016-06-15

    In this study, a novel asymmetric membrane osmotic pump capsule of gliclazide (GLC) solid dispersion was developed to achieve a controlled drug release. The capsule shells were obtained by wet phase inversion process using cellulose acetate as semi-permeable membrane, glycerol and kolliphor P188 as pore formers, then filled with the mixture of GLC solid dispersion and pH modifiers. Differentiate from the conventional formulations, sodium carbonate was chosen as the osmotic agent and effervescent agent simultaneously to control the drug release, instead of the polymer materials. The ternary solid dispersion of GLC, with polyethylene glycol 6000 and kolliphor P188 as carriers, was prepared by solvent-evaporation method, realizing a 2.09-fold increment in solubility and dissolution rate in comparison with unprocessed GLC. Influence of the composition of the coating solution and pH modifiers on the drug release from the asymmetric membrane capsule (AMC) was investigated. The ultimate cumulative release of the optimal formulation reached 91.32% in an approximately zero-order manner. The osmotic pressure test and dye test were conducted to validate the drug release mechanism from the AMC. The in vivo pharmacokinetic study of the AMC indicated a 102.66±10.95% relative bioavailability compared with the commercial tablet, suggesting the bioequivalence between the two formulations. Consequently, the novel controlled delivery system with combination of solid dispersion and AMC system is capable of providing a satisfactory alternative to release the water-insoluble drugs in a controlled manner. PMID:27132166

  20. Carbon dioxide as a carbon source in organic transformation: carbon-carbon bond forming reactions by transition-metal catalysts.

    OpenAIRE

    Tsuji, Yasushi; Fujihara, Tetsuaki

    2012-01-01

    Recent carbon-carbon bond forming reactions of carbon dioxide with alkenes, alkynes, dienes, aryl zinc compounds, aryl boronic esters, aryl halides, and arenes having acidic C-H bonds are reviewed in which transition-metal catalysts play an important role.

  1. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli

    2015-06-02

    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  2. Asymmetric Ashes

    Science.gov (United States)

    2006-11-01

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

  3. 醇腈酶促不对称合成手性氰醇反应条件的研究%Study on the Reaction Conditions for Asymmetric Synthesis of Optically Active Cyanohydrin Catalyzed by Oxynitrilase

    Institute of Scientific and Technical Information of China (English)

    刘森林; 宗敏华; 涂然; 周番; 娄文勇

    2001-01-01

    利用气相色谱手性分析, 对醇腈酶促不对称合成手性氰醇中的pH值、温度、底物浓度和水含量对酶反应速度和非酶反应速度的影响作了研究. 结果表明, 上述因素对酶反应和非酶反应速度均有显著影响. 在水含量较低的非水相酶反应体系中, pH值在4.0以下或反应温度为0~5 ℃时, 非酶反应受到较大程度的抑制, 而酶反应仍具有相对较快的反应速度. 故可获得高光学纯度的产物.%The effects of pH value, temperature, substrate concentration and water content on the enzymatic and non-enzymatic reactions in the asymmetric synthesis of optically active cyanohydrin catalyzed by (R)-oxynitrilase from bitter almond were studied using GC chiral analysis. The conclusion is in non-aqueous organic solvent system with low water content, when pH value is below 4.0 or reaction temperature is 0~5 ℃, the non-enzymatic reaction is greatly inhibited, but oxynitrilase reaction still has relatively high rate. Therefore, the reaction can achieve high enantiomeric purity of the product.

  4. Dynamical decay process of {sup 219,} {sup 220}Ra{sup *} formed in {sup 10,} {sup 11}B+{sup 209}Bi reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawhney, G.; Sharma, M.K. [Thapar University, School of Physics and Materials Science, Punjab (India)

    2012-05-15

    The excitation functions for both the evaporation residue and fission have been calculated for {sup 10}B +{sup 209}Bi and {sup 11}B+{sup 209}Bi reactions forming compound systems {sup 219,220}Ra{sup *}, using the dynamical cluster-decay model (DCM) with effects of deformations and orientations of the nuclei included in it. In addition to this, the excitation functions for complete fusion (CF) are obtained by summing the fission cross-sections, neutron evaporation and charged particle evaporation residue cross-sections produced through the {alpha}xn and pxn (x = 2, 3, 4) emission channels for the {sup 219}Ra system at various incident centre-of-mass energies. Experimentally the CF cross-sections are suppressed and the observed suppression is attributed to the low binding energy of {sup 10,11}B which breaks up into charged fragments. The reported complete fusion (CF) and incomplete fusion (ICF) excitation functions for the {sup 219}Ra system are found to be nicely fitted by the calculations performed in the framework of DCM, without invoking a significant contribution from quasi-fission. Although DCM has been applied for a number of compound nucleus decay studies in the recent past, the same is being used here in reference to ICF and subsequent decay processes along with the CF process. Interestingly the main contribution to complete fusion cross-section comes from the fission cross-section at higher incident energies, which in DCM is found to consist of an asymmetric fission window, shown to arise due to the deformation and orientation effects of formation and decay fragments. (orig.)

  5. Flexible Epoxy Resin Formed Upon Blending with a Triblock Copolymer through Reaction-Induced Microphase Separation

    OpenAIRE

    Wei-Cheng Chu; Wei-Sheng Lin; Shiao-Wei Kuo

    2016-01-01

    In this study, we used diglycidyl ether bisphenol A (DGEBA) as a matrix, the ABA block copolymer poly(ethylene oxide–b–propylene oxide–b–ethylene oxide) (Pluronic F127) as an additive, and diphenyl diaminosulfone (DDS) as a curing agent to prepare flexible epoxy resins through reaction-induced microphase separation (RIMPS). Fourier transform infrared spectroscopy confirmed the existence of hydrogen bonding between the poly(ethylene oxide) segment of F127 and the OH groups of the DGEBA resin. ...

  6. Interfacial thiol-ene photo-click reactions for forming multilayer hydrogels

    OpenAIRE

    Shih, Han; Fraser, Andrew K.; Lin, Chien-Chi

    2013-01-01

    Interfacial visible light-mediated thiol-ene photo-click reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a non-cleavage type photoinitiator eosin-Y on visible light-mediated thiol-ene photopolymerization was first characterized using in situ photo-rheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using UV/Vis spectrome...

  7. Purification of hydrogen under a free or combined form in a gaseous mixture, by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Within the framework of the european fusion program, we are dealing with the purification of hydrogen (tritium) under a free or combined form, from a H2, N2, NH3, CH4, O2, gaseous mixture. The process consists in cracking the hydrogenated molecules and absorbing the impurities by chemical reactions with uranium, without holding back hydrogen. In the temperature range: 950 K < T < 1200 K hydrides are indeed fully decomposed for hydrogen partial pressures lower than ten atmospheres while uranium oxides, nitrides and carbides formation reactions are promoted. The experiments are carried out with massive uranium heated at 973 K in a closed reactor. They confirm that such a process may satisfy our goals, but they point out the importance of interactions occurring between the gaseous and solids systems and interfere with the conversion rates. Gaseous pressure decreases with time according to two successive phases: the first one is governed by a surface kinetic law, while after a short transition time, gas diffusion in the solid products arises and becomes the limiting step of the reactions. Experimental results with pure gases and mixtures, prove that solid products have different structures. An illustrative example is given by nitrogen and methane reactions with uranium: the solid layers are compactely formed with each pure gas and they slow down the chemical kinetic rates; on the contrary the chemical kinetic rates of the mixed gases reactions are clearly increased and the diffusional rates are postponed. Then, the compacity of the solid products merely depends on the operating conditions and the influence of the reactional surface state on the chemical kinetic rates is here pointed out

  8. (Salen)Ti(Ⅳ)-Catalyzed Asymmetric Ring-opening of meso Epoxides Using Dithiophosphorus Acid as the Nucleophile

    Institute of Scientific and Technical Information of China (English)

    Zheng Hong ZHOU; Zhao Ming LI; Bing LIU; Kang Ying LI; Li Xin WANG; Guo Feng ZHAO; Qi Lin ZHOU; Chu Chi TANG

    2006-01-01

    The asymmetric ring-opening of epoxides with dithiophosphorus acids catalyzed by a (salen)Ti(Ⅳ) complex formed in situ from the reaction of Ti(OPr-i)4 and the chiral Schiff base derived from (1R,2R)-(+)-diaminocyclohexane was realized. The resulting products were obtained with low to good enantioselectivity (up to 73% ee).

  9. Solid-state Asymmetric Reduction of (S)-1, l'-Bi-2-naphtholAcetylferrocene Molecular Compound with Sodium Borohydride

    Institute of Scientific and Technical Information of China (English)

    MENG, Ji-Ben; DU, Hai-Feng; DING, Kui-Ling

    2001-01-01

    A novel molecular crystal formed between enanteopure 1,l'bi-2-naphthoi and acetylferrocene has been prepared andcharacterized in this communication. The examination on itsreducton with soditma borohydride showed that the asymnetric inducton was observed in the solid state but not in the solution phase. The asymmetric induction in the solid-state reaction may be attributed to the chiral microenviromnent ofmolecular crystal.

  10. Autologous rosette-forming T cells as the responding cells in human autologous mixed-lymphocyte reaction.

    OpenAIRE

    Palacios, R; Llorente, L; Alarcón-Segovia, D; Ruíz-Arguelles, A; Díaz-Jouanen, E

    1980-01-01

    Autologous rosette-forming cells (Tar cells) have surface and functional characteristics of post-thymic precursors and among these characteristics there are some that have been identified in the responsive cell of the autologous mixed-lymphocyte reaction (AMLR). We therefore did AMLR with circulating mononuclear cells from normal subjects using as responding cells either total T cells, T cells depleted of Tar cells, or purified Tar cells. The response of Tar cells in AMLR was significantly gr...

  11. Observation of Organometallic and Radical Intermediates Formed during the Reaction of Methyl-Coenzyme M Reductase with Bromoethanesulfonate†

    OpenAIRE

    Li, Xianghui; Telser, Joshua; Hoffman, Brian M.; Gerfen, Gary; Ragsdale, Stephen W.

    2010-01-01

    Methyl-coenzyme M reductase (MCR) from methanogenic archaea catalyzes the final step of methane formation, in which methyl-coenzyme M (2-methylthioethane sulfonate, methyl-SCoM) is reduced with coenzyme B (N-7-mercaptoheptanolyl-threonine phosphate, CoBSH) to form methane and the heterodisulfide CoBS-SCoM. The active dimeric form of MCR contains two Ni(I)-F430 prosthetic groups, one in each monomer. This manuscript describes studies of the reaction of the active Ni(I) state of MCR (MCRred1) w...

  12. Entrance channel effects in fusion reactions near the barrier: Reaction dynamics or nuclear structure?

    International Nuclear Information System (INIS)

    The origin of previously reported entrance channel effects by symmetric and asymmetric fusion reactions leading to rare earth nuclei near the Coulomb barrier is critically reviewed. Possible influences of reaction dynamics or structure effects due to the proximity of superdeformation are discussed using new charged-particle spectra and angular distributions associated with specific axn exit channels. For axn channels, nonstatistical effects in the fusion of the asymmetric entrance channel are responsible for the large difference in the spin distributions in the evaporation residues formed by symmetric and asymmetric entrance channels. Whereas GDR spectra show significant entrance channel effects, the authors find no influence on the subbarrier α spectra from possible elongated shapes associated with early reaction dynamics. New data and analyses of γ-ray multiplicity distributions from the xn exit channels show that previously reported entrance channel effects are due to mapping from l to residue spin and then to γ-ray multiplicity

  13. A Brønsted Acid-Amino Acid as a Synergistic Catalyst for Asymmetric List-Lerner-Barbas Aldol Reactions.

    Science.gov (United States)

    Ramachary, Dhevalapally B; Shruthi, Kodambahalli S

    2016-03-18

    Herein, for the first time, a combination of L-amino acid, (R)-5,5-dimethyl thiazolidinium-4-carboxylate (L-DMTC) with simple Brønsted acid TFA is reported as the suitable synergistic catalyst for the List-Lerner-Barbas aldol (LLB-A) reaction of less reactive 2-azidobenzaldehydes with various ketones at ambient temperature to furnish the optically active functionalized (2-azidophenyl)alcohols with very good yields, dr's, and ee's. This method gives first time access to the novel azido-containing multifunctional compounds, which are applicable in material to medicinal chemistry. Chiral functionalized (2-azidophenyl)alcohols were transformed into different molecular scaffolds in good yields with high selectivity through Lewis acid mediated NaBH4 reduction, aza-Wittig and Staudinger reaction (azide reduction), followed by oxidative cyclizations, allenone synthesis, and click reaction, respectively. Chiral LLB-A products might become suitable starting materials for the total synthesis of natural products, ingredients, and inhibitors in medicinal chemistry. The mechanistic synergy of L-DMTC with TFA to increase the rate and selectivity of LLB-A reaction in DMSO-D6 is explained with the controlled and online NMR experiments. PMID:26907463

  14. Linear relations in microbial reaction systems: a general overview of their origin, form, and use.

    Science.gov (United States)

    Noorman, H J; Heijnen, J J; Ch A M Luyben, K

    1991-09-01

    In microbial reaction systems, there are a number of linear relations among net conversion rates. These can be very useful in the analysis of experimental data. This article provides a general approach for the formation and application of the linear relations. Two type of system descriptions, one considering the biomass as a black box and the other based on metabolic pathways, are encountered. These are defined in a linear vector and matrix algebra framework. A correct a priori description can be obtained by three useful tests: the independency, consistency, and observability tests. The independency are different. The black box approach provides only conservations relations. They are derived from element, electrical charge, energy, and Gibbs energy balances. The metabolic approach provides, in addition to the conservation relations, metabolic and reaction relations. These result from component, energy, and Gibbs energy balances. Thus it is more attractive to use the metabolic description than the black box approach. A number of different types of linear relations given in the literature are reviewed. They are classified according to the different categories that result from the black box or the metabolic system description. Validation of hypotheses related to metabolic pathways can be supported by experimental validation of the linear metabolic relations. However, definite proof from biochemical evidence remains indispensable. PMID:18604879

  15. Functional properties of nisin–carbohydrate conjugates formed by radiation induced Maillard reaction

    International Nuclear Information System (INIS)

    Nisin–carbohydrate conjugates were prepared by irradiating nisin either with glucose or dextran. Increase in browning and formation of intermediate products was observed with a concomitant decrease in free amino and reducing sugar groups indicating occurrence of the Maillard reaction catalyzed by irradiation. Nisin–carbohydrate conjugates showed a broad spectrum antibacterial activity against Gram negative bacteria (Escherichia coli, Pseudomonas fluorescence) as well as Gram positive bacteria (Staphylococcus aureus, Bacillus cereus). Results of antioxidant assays, including that of DPPH radical-scavenging activity and reducing power, showed that the nisin–dextran conjugates possessed better antioxidant potential than nisin–glucose conjugate. These results suggested that it was possible to enhance the functional properties of nisin by preparing radiation induced conjugates suitable for application in food industry. - Highlights: ► Nisin–carbohydrate conjugates were prepared using radiation induced Maillard reaction. ► Conjugation of nisin with dextran/glucose resulted in improvement of antibacterial spectrum. ► Conjugates of nisin with dextran/glucose had significant radical scavenging activity.

  16. Identification of secondary phases formed during unsaturated reaction of UO2 with EJ-13 water

    International Nuclear Information System (INIS)

    A set of experiments, wherein UO2 has been contacted by dripping water, has been conducted over a period of 182.5 weeks. The experiments are being conducted to develop procedures to study spent fuel reaction under unsaturated conditions that are expected to exist over the lifetime of the proposed Yucca Mountain repository site. One half of the experiments have been terminated, while one half are ongoing. Analyses of solutions that have dripped from the reacted UO2 have been performed for all experiments, while the reacted UO2 surfaces have been examined for the terminated experiments. A pulse of uranium release from the UO2 solid, combined with the formation of schoepite on the surface of the UO2, was observed between 39 and 96 weeks of reaction. Thereafter, the uranium release decreased and a second set of secondary phases was observed. The latter phases incorporated cations from the EJ-13 water and included boltwoodite, uranophane, sklodowskite, compreignacite, and schoepite. The experiments are continuing to monitor whether additional changes in solution chemistry or secondary phase formation occurs. 6 refs., 2 figs., 2 tabs

  17. Asymmetric Diels–Alder reaction with >C=P– functionality of the 2-phosphaindolizine-η1-P-aluminium(O-menthoxy dichloride complex: experimental and theoretical results

    Directory of Open Access Journals (Sweden)

    Rajendra K. Jangid

    2013-02-01

    Full Text Available The Diels–Alder reaction of the 2-phosphaindolizine-η1-P-aluminium(O-menthoxy dichloride complex with dimethylbutadiene was investigated experimentally and computationally. The >C=P– functionality of the complex reacts with 2,3-dimethylbutadiene with complete diastereoselectivity to afford [2 + 4] cycloadducts. Calculation of the model substrate, 3-methoxycarbonyl-1-methyl-2-phosphaindolizine-P-aluminium(O-menthoxy dichloride (7a, at the DFT (B3LYP/6-31+G* level reveals that the O-menthoxy moiety blocks the Re face of the >C=P– functionality, due to which the activation barrier of the Diels–Alder reaction of 7a with 1,3-butadiene, involving its attack from the Si face, is lower. It is found that in this case, the exo approach of the diene is slightly preferred over the endo approach.

  18. The direct asymmetric vinylogous aldol reaction of furanones with α-ketoesters: Access to chiral γ-Butenolides and glycerol derivatives

    KAUST Repository

    Luo, Jie

    2011-01-11

    Twice as good: The title reaction using the tryptophan-derived bifunctional organic catalyst 1 has been developed. The reported method led to the synthesis of chiral γ-substituted butenolides in excellent yields, with high diastereo- and enantioselectivities. Facile synthesis of chiral glycerol derivatives containing a tertiary hydroxy group has also been demonstrated. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Functional properties of nisin-carbohydrate conjugates formed by radiation induced Maillard reaction

    Science.gov (United States)

    Muppalla, Shobita R.; Sonavale, Rahul; Chawla, Surinder P.; Sharma, Arun

    2012-12-01

    Nisin-carbohydrate conjugates were prepared by irradiating nisin either with glucose or dextran. Increase in browning and formation of intermediate products was observed with a concomitant decrease in free amino and reducing sugar groups indicating occurrence of the Maillard reaction catalyzed by irradiation. Nisin-carbohydrate conjugates showed a broad spectrum antibacterial activity against Gram negative bacteria (Escherichia coli, Pseudomonas fluorescence) as well as Gram positive bacteria (Staphylococcus aureus, Bacillus cereus). Results of antioxidant assays, including that of DPPH radical-scavenging activity and reducing power, showed that the nisin-dextran conjugates possessed better antioxidant potential than nisin-glucose conjugate. These results suggested that it was possible to enhance the functional properties of nisin by preparing radiation induced conjugates suitable for application in food industry.

  20. Reduced quasifission competition in fusion reactions forming neutron-rich heavy elements

    CERN Document Server

    Hammerton, K; Hinde, D J; Dasgupta, M; Wakhle, A; Williams, E; Oberacker, V E; Umar, A S; Carter, I P; Cook, K J; Greene, J; Jeung, D Y; Luong, D H; McNeil, S D; Palshetkar, C S; Rafferty, D C; Simenel, C; Stiefel, K

    2015-01-01

    Measurements of mass-angle distributions (MADs) for Cr + W reactions, providing a wide range in the neutron-to-proton ratio of the compound system, (N/Z)CN, have allowed for the dependence of quasifission on the (N/Z)CN to be determined in a model-independent way. Previous experimental and theoretical studies had produced conflicting conclusions. The experimental MADs reveal an increase in contact time and mass evolution of the quasifission fragments with increasing (N/Z)CN, which is indicative of an increase in the fusion probability. The experimental results are in agreement with microscopic time-dependent Hartree-Fock calculations of the quasifission process. The experimental and theoretical results favor the use of the most neutron-rich projectiles and targets for the production of heavy and superheavy nuclei.

  1. Recoil properties of radionuclides formed in the photonuclear reactions on natCu at intermediate energies

    International Nuclear Information System (INIS)

    The recoil properties of 26 radionuclides produced in the photonuclear reactions on Cu at bremsstrahlung end-point energies (E0) of 250 to 1000 MeV have been investigated using the thick-target thick-catcher method. Kinematic properties of the product nuclei were calculated by the two-step vector velocity model. The calculated mean kinetic energies, T, of product nuclei increase with increase of the mass difference between products and target, reflecting the resonance natures and absorption mechanisms. The T at E0 ≥ 600 MeV were well reproduced by a calculation performed by PICA code by GABRIEL and ALSMILLER at E0 = 400 MeV, except for (γ,xn) products by giant-resonance. (author)

  2. Determination of the antiepileptics vigabatrin and gabapentin in dosage forms and biological fluids using Hantzsch reaction.

    Science.gov (United States)

    al-Zehouri, J; al-Madi, S; Belal, F

    2001-02-01

    A selective and sensitive method was developed for the determination of the anticonvulsants vigabatrin (I) (CAS 60643-86-9) and gabapentin (II) (CAS 60142-96-3). The method is based on the condensation of the drugs through their amino groups with acetylacetone and formaldehyde according to Hantzsch reaction yeilding the highly fluorescent dihydropyridine derivatives. The yellowish-orange color was also measured spectrophotometrically at 410 nm and 415 nm for I and II, respectively. The absorbance-concentration plots were rectilinear over the ranges 10-70 micrograms/ml and 20-140 micrograms/ml for I and II, respectively. As for the fluorescence-concentration plots, they were linear over the ranges 0.5-10 micrograms/ml and 2.5-20 micrograms/ml with minimum detection limits (S/N = 2) of 0.05 microgram/ml (approximately 2.1 x 10(-8) mol/l) and 0.1 microgram/ml (approximately 5.8 x 10(-7) mol/l) for I and II, respectively. The spectrophotometric method was applied to the determination of I and II in their tablets. The percentage recoveries +/- SD (n = 6) were 99.45 +/- 0.13 and 98.05 +/- 0.53, respectively. The spectrofluorimetric method was successfully applied to the determination of I and II in spiked human urine and plasma. The % recoveries +/- SD (n = 5) were 98.77 +/- 0.29 and 98.39 +/- 0.53 for urine and 99.32 +/- 0.74 and 98.90 +/- 0.96 for plasma, for I and II, respectively. No interference was encountered with the co-administered drugs: valproic acid (CAS 99-66-1), diphenylhydantoin (CAS 57-41-0), phenobarbital (CAS 50-06-6), carbamazepine (CAS 298-46-4), clonazepam (CAS 1622-61-3), clobazam (CAS 22316-47-8) or cimetidine (CAS 51481-61-9). A proposal of the reaction pathway is suggested. The advantages of the proposed methods over existing method are discussed. PMID:11258050

  3. Moderate Hypoxia Exhibits Increased Endothelial Progenitor Vessel-forming Ability However Gestational Diabetes Caused to Impede Compensatory Defense Reaction.

    Science.gov (United States)

    Dincer, U Deniz

    2016-05-30

    Endothelium represents a defense barrier and responds and integrates neuro humoral stimulus which describes as a compensatory mechanism. Endothelium formed with endothelial cells (ECs) and their progenitors. Endothelial progenitor cells (EPCs) represent minor subpopulation of mononuclear cells in the blood. During acute hypoxia, larger amount of EPCs mobilize into the peripheral blood and they directly contribute revascularization process. One of the subtypes of EPC is termed endothelial colony forming cells (ECFCs) which they possess de novo vessel-forming ability. The present study aims to investigate the role of hypoxia in EPCs functional and vessel-forming ability. Furthermore, it was investigated whether fetal exposure to a diabetic intrauterine environment influence EPCs adaptation ability. Human umbilical cord blood (HUCB) derived ECFCs were selected in all experimental procedures obtained from normal and gestational diabetes mellitus (GDM) subjects via in vitro cell culture methods. Early passage (assay conducted onto HUCB ECFCs to investigate their functional clonogenic ability. To quantify their vessel forming ability matrigel assay was applied. These data demonstrates that moderate hypoxia results increased vessel-forming ability and VEGFA expression in HUCB ECFCs obtained from control subjects. However, GDM caused to impede compensatory defense reaction against hypoxia which observed in control subjects. Thus, it illuminates beneficial information related future therapeutic modalities. PMID:27426097

  4. Moderate Hypoxia Exhibits Increased Endothelial Progenitor Vessel-forming Ability However Gestational Diabetes Caused to Impede Compensatory Defense Reaction

    Science.gov (United States)

    Dincer, U. Deniz

    2016-01-01

    Endothelium represents a defense barrier and responds and integrates neuro humoral stimulus which describes as a compensatory mechanism. Endothelium formed with endothelial cells (ECs) and their progenitors. Endothelial progenitor cells (EPCs) represent minor subpopulation of mononuclear cells in the blood. During acute hypoxia, larger amount of EPCs mobilize into the peripheral blood and they directly contribute revascularization process. One of the subtypes of EPC is termed endothelial colony forming cells (ECFCs) which they possess de novo vessel-forming ability. The present study aims to investigate the role of hypoxia in EPCs functional and vessel-forming ability. Furthermore, it was investigated whether fetal exposure to a diabetic intrauterine environment influence EPCs adaptation ability. Human umbilical cord blood (HUCB) derived ECFCs were selected in all experimental procedures obtained from normal and gestational diabetes mellitus (GDM) subjects via in vitro cell culture methods. Early passage (hypoxia associated gene specific primers designed to perform Real-time PCR. Senescenes assay conducted onto HUCB ECFCs to investigate their functional clonogenic ability. To quantify their vessel forming ability matrigel assay was applied. These data demonstrates that moderate hypoxia results increased vessel-forming ability and VEGFA expression in HUCB ECFCs obtained from control subjects. However, GDM caused to impede compensatory defense reaction against hypoxia which observed in control subjects. Thus, it illuminates beneficial information related future therapeutic modalities. PMID:27426097

  5. Role of pseudoephedrine as chiral auxiliary in the "acetate-type" aldol reaction with chiral aldehydes; asymmetric synthesis of highly functionalized chiral building blocks.

    Science.gov (United States)

    Ocejo, Marta; Carrillo, Luisa; Vicario, Jose L; Badía, Dolores; Reyes, Efraim

    2011-01-21

    We have studied in depth the aldol reaction between acetamide enolates and chiral α-heterosubstituted aldehydes using pseudoephedrine as chiral auxiliary under double stereodifferentiation conditions, showing that high diastereoselectivities can only be achieved under the matched combination of reagents and provided that the α-heteroatom-containing substituent of the chiral aldehyde is conveniently protected. Moreover, the obtained highly functionalized aldols have been employed as very useful starting materials for the stereocontrolled preparation of other interesting compounds and chiral building blocks such as pyrrolidines, indolizidines, and densely functionalized β-hydroxy and β-amino ketones using simple and high-yielding methodologies. PMID:21188970

  6. Heavy Residues with A<90 in the Asymmetric Reaction of 20 AMeV 124Sn+27Al as a Sensitive Probe of the Onset of Multifragmentation

    OpenAIRE

    Veselsky, M; Souliotis, G. A.; Chubarian, G.; Trache, L.; Keksis, A.; martin, E.; Ruangma, A.; Winchester, E; Yennello, S. J.

    2002-01-01

    The cross sections and velocity distributions of heavy residues from the reaction of 20 AMeV 124Sn + 27Al have been measured at forward angles using the MARS recoil separator at Texas A&M in a wide mass range. A consistent overall description of the measured cross sections and velocity distributions was achieved using a model calculation employing the concept of deep-inelastic transfer for the primary stage of peripheral collisions, pre-equilibrium emission and incomplete fusion for the prima...

  7. Decay Mechanism of 290,292114* Superheavy Nuclei Formed in 48Ca-Induced Reactions

    Science.gov (United States)

    Sandhu, Kirandeep; Sharma, Manoj K.

    2013-10-01

    We calculate the neutron-evaporation residue cross sections σ 3n , σ 4n , and σ 5n in the hot-fusion reactions 48Ca+242,244Pu →290,292114 ∗ over a wide range of compound-nucleus excitation energies (E_{{CN}}^{*} = 34-53 MeV). We work with the dynamical cluster-decay model (DCM), with a single parameter, the neck-length parameter ΔR. To calculate neutron-evaporation cross sections, we choose the superheavy proton magic Z = 126 and neutron magic N = 184. Among the 3n, 4n, and 5n production cross sections for 290, 292114∗, only the 3n decay cross sections of 292114∗ correspond to spherical fragmentation. The 4n and 5n cross sections of 292114∗ and 3n, 4n, and 5n cross sections of 290114∗ could only be fitted after the inclusion of quadrupole deformations β 2i within the optimum orientation approach. Changes in the angular momentum and N/Z ratio do not significantly influence the fragmentation paths of 290, 292114∗ superheavy nuclei. Larger barrier modification is required for the lower angular momentum states and lighter neutron clusters. The contribution of the fusion-fission component is also computed for the compound nucleus 292114∗ in the energy range E_{{CN}}^{*} = 27-47 MeV.

  8. Flexible Epoxy Resin Formed Upon Blending with a Triblock Copolymer through Reaction-Induced Microphase Separation

    Directory of Open Access Journals (Sweden)

    Wei-Cheng Chu

    2016-06-01

    Full Text Available In this study, we used diglycidyl ether bisphenol A (DGEBA as a matrix, the ABA block copolymer poly(ethylene oxide–b–propylene oxide–b–ethylene oxide (Pluronic F127 as an additive, and diphenyl diaminosulfone (DDS as a curing agent to prepare flexible epoxy resins through reaction-induced microphase separation (RIMPS. Fourier transform infrared spectroscopy confirmed the existence of hydrogen bonding between the poly(ethylene oxide segment of F127 and the OH groups of the DGEBA resin. Small-angle X-ray scattering, atomic force microscopy, and transmission electron microscopy all revealed evidence for the microphase separation of F127 within the epoxy resin. Glass transition temperature (Tg phenomena and mechanical properties (modulus were determined through differential scanning calorimetry and dynamic mechanical analysis, respectively, of samples at various blend compositions. The modulus data provided evidence for the formation of wormlike micelle structures, through a RIMPS mechanism, in the flexible epoxy resin upon blending with the F127 triblock copolymer.

  9. Colloid formation during waste form reaction: implications for nuclear waste disposal

    Science.gov (United States)

    Bates, J. K.; Bradley, J.; Teetsov, A.; Bradley, C. R.; ten Brink, Marilyn Buchholtz

    1992-01-01

    Insoluble plutonium- and americium-bearing colloidal particles formed during simulated weathering of a high-level nuclear waste glass. Nearly 100 percent of the total plutonium and americium in test ground water was concentrated in these submicrometer particles. These results indicate that models of actinide mobility and repository integrity, which assume complete solubility of actinides in ground water, underestimate the potential for radionuclide release into the environment. A colloid-trapping mechanism may be necessary for a waste repository to meet long-term performance specifications.

  10. Forming mechanism of nitrogen doped graphene prepared by thermal solid-state reaction of graphite oxide and urea

    Energy Technology Data Exchange (ETDEWEB)

    Mou Zhigang [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Chen Xiaoye [Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou 215123 (China); Du Yukou; Wang Xiaomei [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Yang Ping, E-mail: pyang@suda.edu.cn [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Wang Suidong, E-mail: wangsd@suda.edu.cn [Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou 215123 (China)

    2011-12-15

    Nitrogen doped graphene was synthesized from graphite oxide and urea by thermal solid-state reaction. The samples were characterized by transmission electron microscopy, atomic force microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectra, element analysis, and electrical conductivity measurement. The results reveal that there is a gradual thermal transformation of nitrogen bonding configurations from amide form nitrogen to pyrrolic, then to pyridinic, and finally to 'graphitic' nitrogen in graphene sheets with increasing annealing temperature from 200 to 700 Degree-Sign C. The products prepared at 600 Degree-Sign C and 700 Degree-Sign C show that the quantity of nitrogen incorporated into graphene lattice is {approx}10 at.% with simultaneous reduction of graphite oxide. Oxygen-containing functional groups in graphite oxide are responsible for the doping reaction to produce nitrogen doped graphene.

  11. A G-rich sequence within the c-kit oncogene promoter forms a parallel G-quadruplex having asymmetric G-tetrad dynamics.

    Science.gov (United States)

    Hsu, Shang-Te Danny; Varnai, Peter; Bugaut, Anthony; Reszka, Anthony P; Neidle, Stephen; Balasubramanian, Shankar

    2009-09-23

    Guanine-rich DNA sequences with the ability to form quadruplex structures are enriched in the promoter regions of protein-coding genes, particularly those of proto-oncogenes. G-quadruplexes are structurally polymorphic and their folding topologies can depend on the sample conditions. We report here on a structural study using solution state NMR spectroscopy of a second G-quadruplex-forming motif (c-kit2) that has been recently identified in the promoter region of the c-kit oncogene. In the presence of potassium ions, c-kit2 exists as an ensemble of structures that share the same parallel-stranded propeller-type conformations. Subtle differences in structural dynamics have been identified using hydrogen-deuterium exchange experiments by NMR spectroscopy, suggesting the coexistence of at least two structurally similar but dynamically distinct substates, which undergo slow interconversion on the NMR timescale. PMID:19705869

  12. Selective Homogeneous Catalysis in Asymmetric Synthesis

    DEFF Research Database (Denmark)

    Fristrup, Peter

    The subject of this thesis is selectivity in homogeneous asymmetric transition metalcatalyzed reactions. Four different reactions within organic chemistry have been studied by kinetic measurements, computational chemistry (modelling) or both of them in parallel. A Hammett study was performed....... A thorough computational study succeeded in explaining the observed results, although other significant results were also obtained during this study. Finally, an intramolecular reaction was studied computationally, and the rate increase observed under phase transfer catalysis conditions could be related...

  13. Thermodynamic and Kinetic Study of Crystallization Reaction of Fe/Dy Multilayers Form Amorphous State

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    To give further insight into the behavior of Fe/Dy multilayers in the crystallization from as-deposited amorphous state, free energy diagram of Fe/Dy system was constructed based on Miedema semiempirical theory. It is shown that the crystallization of amorphous films is controlled by both thermodynamic and kinetic conditions. The calculated free energies of crystalline Fe and Dy are significantly lower than those in the amorphous states, which provide thermodynamic driving force for crystallization. During annealing, the kinetic phase evolution of the multilayers is controlled by free energy barrier of nucleation and critical-size of new phase nucleus. Thus it explains the experimental results that Fe crystallites formed first followed by Dy grains, whereas crystalline Fe-Dy intermetallic compounds were not observed during annealing at moderate temperatures.

  14. The d(e, e'p)n reaction and the nuetron electric form factor

    International Nuclear Information System (INIS)

    An accurate determination of the electric form factor of the neutron, Gsub(En), is important both for our understanding of the structure of the nucleons, and for the description of electron scattering on nuclear many-body systems. At present only reliable model-independent information on Gsub(En) is available for four-momentum transfer (qsub(μ))2→0 from the scattering of thermal neutrons off atoms. Electron scattering offers the possibility to obtain information at higher (qsub(μ))2. However, since electrons can only be scattered off neutrons embedded in a many-body target the extraction of Gsub(En) will in general be affected by nuclear structure uncertainties. Some methods to obtain information on Gsub(En) in e-d experiments are discussed. (Auth.)

  15. Novel chiral N4S2- and N6S3-donor macrocyclic ligands: synthesis, protonation constants, metal-ion binding and asymmetric catalysis in the Henry reaction.

    Science.gov (United States)

    Gao, Jian; Martell, A E

    2003-08-01

    New hydrophobic chiral macrocyclic ligands L1-L3 with chiral diamino and thiophene moieties have been synthesized by the Schiff base condensation approach. Protonation constants of L1 and L2 were determined by potentiometry titration. Metal-ion binding experiments exhibited that L1 and L3 are pronounced in selective recognition, Ag+, Cu2+ and Ca2+ ions among the surveyed metal ions (Cu2+, Co2+, Ni2+, Zn2+, Cd2+, Pb2+, Ag+, Li+, Na+, K+, and Ca2+). L1 was found to spectroscopically detect the presence of Cu2+ and Ca2+ to function as a multiple readout sensor. The detection limit for Ca2+ ions was found to be 9.8 x 10(-5) M in CH2Cl2-MeOH solution. The trimeric chiral ligand L3 has been shown to be an efficient auxiliary in a Zn(II)-mediated enantioselective Henry reaction. PMID:12948208

  16. Mechanistic Insights into Homogeneous and Heterogeneous Asymmetric Iron Catalysis

    Science.gov (United States)

    Sonnenberg, Jessica

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

  17. A Convenient Method for Asymmetric Reduction of Acetophenone using Lithium Hydroxide

    OpenAIRE

    NISHIKORI, Hisashi; Mizuno, Tomofumi; 錦織, 寿

    2010-01-01

    Optically active lithium-alkoxide catalyzes asymmetric reduction of ketones and imines with alkoxyhydrosilane as a Lewis base. Lithium salt is generally formed by a mixture of optically active alcohol and n-butyllithium as a metal source, which is too sensitive to moisture to handle in air. However, if n-butyllithium is replaced by another lithium source which is stable in air, a more convenient reaction system results. In this study, we examined the enantioselective reduction of acetophenone...

  18. Optimal glass-forming composition and its correlation with eutectic reaction in the Ti-Ni-Al ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Lu Baochen [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academic of Sciences, 72 Wenhua Road, Shenyang 110016 (China); Li Yi [Department of Materials Science and Engineering, National University of Singapore, Engineering Drive 1, Singapore 117675 (Singapore); Xu Jian [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academic of Sciences, 72 Wenhua Road, Shenyang 110016 (China)], E-mail: jianxu@imr.ac.cn

    2009-01-07

    The composition dependence of glass-forming ability was investigated for the Ti-Ni-Al ternary alloys. Glassy ribbons were fabricated via single-roller melt spinning. The optimal glass-forming composition was located at Ti{sub 54}Ni{sub 32}Al{sub 14}, with a critical thickness of about 90 {mu}m for complete glass formation. With respect to the Ti-Ni binary alloy, Al addition in the system only marginally improves the glass-forming ability. It is attributed to a small atomic size difference between Ti and Al. For the Ti{sub 54}Ni{sub 32}Al{sub 14} alloy, together with the binary eutectic Ti{sub 76}Ni{sub 24} and hypereutectic Ti{sub 68}Ni{sub 32} alloys for comparison, phase selection in the arc-melted ingots was investigated. The optimal glass-forming composition, Ti{sub 54}Ni{sub 32}Al{sub 14}, is near the univariant eutectic groove of [L {yields} Ti(Al){sub 2}Ni + {beta}-Ti(Al)] in the phase diagram. It is suggested that if the primary crystallization of the Ti{sub 2}Ni intermetallic can be suppressed, solidification of deeply undercooled melt will undergo such a eutectic reaction prior to glass formation.

  19. Asymmetric Membrane Osmotic Capsules for Terbutaline Sulphate

    OpenAIRE

    Gobade, N. G.; Marina Koland; K H Harish

    2012-01-01

    The aim of the present study was to design an asymmetric membrane capsule, an osmotic pump-based drug delivery system of ethyl cellulose for controlled release of terbutaline sulphate. asymmetric membrane capsules contains pore-forming water soluble additive, sorbitol in different concentrations in the capsule shell membrane, which after coming in contact with water, dissolves, resulting in an in situ formation of a microporous structure. The terbutaline sulphate is a β-adrenoreceptor agonist...

  20. The effects of density-dependent form factors for (e, e'p) reaction in quasi-elastic region

    Energy Technology Data Exchange (ETDEWEB)

    Kim, K.S. [Korea Aerospace University, School of Liberal Arts and Science, Goyang (Korea, Republic of); Cheoun, Myung-Ki [Soongsil University, Department of Physics, Seoul (Korea, Republic of); Kim, Hungchong [Kookmin University, Department of General Education, Seoul (Korea, Republic of); So, W.Y. [Kangwon National University at Dogye, Department of Radiological Science, Samcheok (Korea, Republic of)

    2016-04-15

    Within the framework of a relativistic single particle model, the effects of density-dependent electromagnetic form factors on the exclusive (e, e'p) reaction are investigated in the quasi-elastic region. The density-dependent electromagnetic form factors are generated from a quark-meson coupling model and used to calculate the cross sections in two different densities, either at the normal density of ρ{sub 0} ∝ 0.15 fm{sup -3} or at the lower density, 0.5ρ{sub 0}. Then these cross sections are analyzed in the two different kinematics: One is that the momentum of the outgoing nucleon is along the momentum transfer. The other is that the angle between the momentum of the outgoing nucleon and the momentum transfer is varied at fixed magnitude of the momentum of the outgoing nucleon. Our theoretical differential reduced cross sections are compared with the NIKHEF data for the {sup 208}Pb(e, e'p) reaction, which is related to the probability that a bound nucleon from a given orbit can be knocked-out of the nucleus. The effects of the density-dependent form factors increase the differential cross sections for both knocked-out proton and neutron by an amount of a few percent. Moreover they are shown to be almost the same within only a few percent, i.e., nearly independent of the shell location of knockout nucleons. These results are quite consistent with the characteristics of double magic nuclei which have relatively sharp smearing in the density distribution. (orig.)

  1. Design and Synthesis of Chiral Zn2+ Complexes Mimicking Natural Aldolases for Catalytic C–C Bond Forming Reactions in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Susumu Itoh

    2014-01-01

    Full Text Available Extending carbon frameworks via a series of C–C bond forming reactions is essential for the synthesis of natural products, pharmaceutically active compounds, active agrochemical ingredients, and a variety of functional materials. The application of stereoselective C–C bond forming reactions to the one-pot synthesis of biorelevant compounds is now emerging as a challenging and powerful strategy for improving the efficiency of a chemical reaction, in which some of the reactants are subjected to successive chemical reactions in just one reactor. However, organic reactions are generally conducted in organic solvents, as many organic molecules, reagents, and intermediates are not stable or soluble in water. In contrast, enzymatic reactions in living systems proceed in aqueous solvents, as most of enzymes generally function only within a narrow range of temperature and pH and are not so stable in less polar organic environments, which makes it difficult to conduct chemoenzymatic reactions in organic solvents. In this review, we describe the design and synthesis of chiral metal complexes with Zn2+ ions as a catalytic factor that mimic aldolases in stereoselective C–C bond forming reactions, especially for enantioselective aldol reactions. Their application to chemoenzymatic reactions in aqueous solution is also presented.

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

    Science.gov (United States)

    Trost, Barry M; Quintard, Adrien

    2012-09-01

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

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

    OpenAIRE

    Trost, Barry M.; Quintard, Adrien

    2012-01-01

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

  4. Reaction Characteristics of Asymmetric Synthesis of (2S,5S)-2,5-Hexanediol Catalyzed with Baker's Yeast Number 6%面包酵母No.6催化不对称合成(2S,5S)-2,5-已二醇反应特性

    Institute of Scientific and Technical Information of China (English)

    肖美添; 叶静; 张亚武; 黄雅燕

    2009-01-01

    Baker's yeast number 6 was selected by screening. It showed good catalytic activity and enantioselec-tivity for asymmetric reduction of 2,5-hexancdione to produce (2S,5S)-2,5-hexanediol. Gas chromatography-mass spectrometry (GC-MS) revealed that the intermediate was (S)-5-hydroxyhexane-2-one. Reduction of 2,5-hexanedione proceeded in a two-step reaction. The hydroxyketone was initially formed, and this intermediate was further re-duced to the diol. Factors influencing the product yield and the enantiomeric excess of the reduction of 2,5-hexandione catalyzed by baker's yeast number 6 were investigated. Higher concentration (≤100 mmol·L-1) of 2,5-hexandione did not influence 5-hydroxyhexane-2-one production, but 2,5-hexanediol production was inhibited by excess accumulation (>30 mmol·L-1) of intermediate. The optimal conditions were glucose as the co-substrate at an initial glucose concentration of 20 g·L-1, 34℃, pH 7.0 and cell concentration 60 g-L"1 (cell dry mass). Under the optimal condition and an initial substrate concentration of 30 mmol·L-1, the yield of 2,5-hexandiol was 78.7% and the enantiomeric excess of (2S,5S)-2,5-hexandiol was 94.4% for 24-h reduction.

  5. Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis.

    Science.gov (United States)

    Paek, Seung-Mann; Jeong, Myeonggyo; Jo, Jeyun; Heo, Yu Mi; Han, Young Taek; Yun, Hwayoung

    2016-07-21

    Chiral pool α-amino acids have been used as powerful tools for the total synthesis of structurally diverse natural products. Some common naturally occurring α-amino acids are readily available in both enantiomerically pure forms. The applications of the chiral pool in asymmetric synthesis can be categorized prudently as chiral sources, devices, and inducers. This review specifically examines recent advances in substrate-controlled asymmetric reactions induced by the chirality of α-amino acid templates in natural product synthesis research and related areas.

  6. STUDY OF INFLUENCE OF PREVIOUS ORAL APPLICATION OF DIPHTHERIA ANTIGENIC PREPARATIONS ON RABBIT ALLERGIC REACTION FORMING AFTER SKIN TEST

    Directory of Open Access Journals (Sweden)

    Babych YeM

    2013-03-01

    Full Text Available It’s studied an influence of previous oral application of diphtheria antigenic preparations on allergic inflammation forming after skin test. It’s used destroyed by ultrasonic microbe cells C.diphtheriae var. gravis tox+ massachusets, free from destroyed cells by the use of centrifugation supernatant and refined concentrated diphteria toxoid. Experimental rabbits are fed to 3,5 ml of one of antigenic preparations (the total protein dose is 33,6 mg, control ones are fed to saline. In a week all animals were injected intracutaneously 0,2 ml each of corresponding antigenic preparation. The findings testify to decreasing manifestation tendency of rabbit skin reactions on antigenic preparations.

  7. Catalytic asymmetric synthesis of mycocerosic acid

    NARCIS (Netherlands)

    ter Horst, B.; Feringa, B.L.; J. Minnaard, A.

    2007-01-01

    The first catalytic asymmetric total synthesis of mycocerosic acid was achieved via the application of iterative enantioselective 1,4-addition reactions and allows for the efficient construction of 1,3-polymethyl arrays with full stereocontrol; further exemplified by the synthesis of tetramethyl-dec

  8. Microstructural characterization and wear behavior of in situ TiC/7075 composites synthesized by displacement reactions and spray forming

    International Nuclear Information System (INIS)

    Highlights: → This article presents novel processing routs for TiC/7075 composites. → The formation of deleterious second phases can be suppressed with careful control of the Ti/C ratio. → At higher applied loads, the 7075 alloy exhibited superior wear resistance to the composites. → We present careful XRD, SEM, TEM results that appear to be self-consistent. - Abstract: A novel in situ reaction technique is developed to prepare TiC/7075 composites. This technique provides a new approach overcoming the problems of loss and agglomeration of reinforcement particles when they are in situ formed in a molten metal first and then injected into the spray cone of molten droplets during the spray forming process. Experimental results have shown that the presence of strip or rectangular-like Al3Ti, which is detrimental not only to the fracture toughness, but also to the stability of the microstructure, can be avoided completely from the final product by using a proper Ti:C molar ratio in the Ti-C-Al performs. The mechanisms of formation or absence of Al3Ti phase in the TiC/7075 composites are explained based on thermodynamics of the system. The modification of the microstructure of the spray-formed 7075 alloy can be understood in the light of atomic diffusion. The wear results showed that the wear rates of the spray-formed 7075 alloy and its composites increased with applied loads. At higher applied loads, the 7075 alloy exhibited superior wear resistance than that of the composites. This is attributed to increased microcracking tendency of the composites than the matrix alloy.

  9. Chiral Brønsted Acids for Asymmetric Organocatalysis

    Science.gov (United States)

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

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

  10. 不对称有机催化Michael加成/半缩醛胺化/酰亚胺正离子环化串联反应研究进展%Progress in Asymmetric Organocatalyzed Michael Addition/Hemi-aminoacetalization/Acylimminium-Cyclization Cascade Reactions

    Institute of Scientific and Technical Information of China (English)

    陈杰; 刘钦; 戴小鸯; 聂凛凛; 房辉辉; 吴小余

    2013-01-01

    During the last decades along with the development of asymmetric organocatalysis, tremendous achievements have been made in asymmetric organocatalytic domino or cascade reactions. Herein, the examples of domino or cascade reactions based on asymmetric organocatalyzed Michael addition are described. More specifically, this review aims to cover and discuss the hemi-aminoacetalyzation/acylimminium-cyclization initiated by Michael addition, and the application of this type of reactions in the synthesis of alkaloids.%随着近十多年来不对称有机小分子催化的发展,以这类催化为基础的串联反应也取得了很大的进展.综述了近几年来不对称有机催化Michael加成/半缩醛胺化/酰亚胺正离子环化串联反应构建手性氮杂多环结构的研究进展,介绍了国内外多个课题组对这一类反应的研究结果以及该类反应在生物碱合成中的应用.

  11. Crystal structure of a nucleoside model for the interstrand cross-link formed by the reaction of 2′-deoxyguanosine and an abasic site in duplex DNA

    Directory of Open Access Journals (Sweden)

    Michael J. Catalano

    2016-05-01

    Full Text Available The title compound, 9-[(2R,4S,5R-4-hydroxy-5-(hydroxymethyltetrahydrofuran-2-yl]-2-{[(2R,4S,5R-4-methoxy-5-(methoxymethyltetrahydrofuran-2-yl]amino}-1H-purin-6(9H-one, C17H25N5O7, crystallizes with two independent molecules (A and B in the asymmetric unit. In the crystal, the guanosine moieties of molecules A and B are linked by N—H...N and O—H...N hydrogen-bonding interactions, forming ribbons which are stacked to form columns along [100]. These columns are then linked by O—H...O hydrogen bonds between the ribose moieties and numerous C—H...O interactions to complete the three-dimensional structure.

  12. Antioxidative, Antibacterial, and Food Functional Properties of the Half-Fin Anchovy Hydrolysates-Glucose Conjugates Formed via Maillard Reaction.

    Science.gov (United States)

    Song, Ru; Yang, Peiyu; Wei, Rongbian; Ruan, Guanqiang

    2016-01-01

    The antioxidative, antibacterial, and food functional properties of the half-fin anchovy hydrolysates (HAHp)-glucose conjugates formed by Maillard reaction (MR) were investigated, respectively. Results of sugar and amino acid contents loss rates, browning index, and molecular weight distribution indicated that the initial pH of HAHp played an important role in the process of MR between HAHp and glucose. HAHp-glucose Maillard reaction products (HAHp-G MRPs) demonstrated enhanced antioxidative activities of reducing power and scavenging DPPH radicals compared to control groups. HAHp-G MRPs produced from the condition of pH 9.6 displayed the strongest reducing power. The excellent scavenging activity on DPPH radicals was found for HAHp(5.6)-G MRPs which was produced at pH 5.6. Additionally, HAHp(5.6)-G MRPs showed variable antibacterial activities against Escherichia coli, Pseudomonas fluorescens, Proteus vulgaris, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, Bacillus megaterium, and Sarcina lutea, with the MIC values ranging from 8.3 to 16.7 μg/mL. Result of scanning electron microscopy (SEM) on E. coli suggested that HAHp(5.6)-G MRPs exhibited antibacterial activity by destroying the cell integrity through membrane permeabilization. Moreover, HAHp(5.6)-G MRPs had excellent foaming ability and stability at alkaline conditions of pH 8.0, and showed emulsion properties at acidic pH 4.0. These results suggested that specific HAHp-G MRPs should be promising functional ingredients used in foods. PMID:27331806

  13. Antioxidative, Antibacterial, and Food Functional Properties of the Half-Fin Anchovy Hydrolysates-Glucose Conjugates Formed via Maillard Reaction

    Directory of Open Access Journals (Sweden)

    Ru Song

    2016-06-01

    Full Text Available The antioxidative, antibacterial, and food functional properties of the half-fin anchovy hydrolysates (HAHp-glucose conjugates formed by Maillard reaction (MR were investigated, respectively. Results of sugar and amino acid contents loss rates, browning index, and molecular weight distribution indicated that the initial pH of HAHp played an important role in the process of MR between HAHp and glucose. HAHp-glucose Maillard reaction products (HAHp-G MRPs demonstrated enhanced antioxidative activities of reducing power and scavenging DPPH radicals compared to control groups. HAHp-G MRPs produced from the condition of pH 9.6 displayed the strongest reducing power. The excellent scavenging activity on DPPH radicals was found for HAHp(5.6-G MRPs which was produced at pH 5.6. Additionally, HAHp(5.6-G MRPs showed variable antibacterial activities against Escherichia coli, Pseudomonas fluorescens, Proteus vulgaris, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, Bacillus megaterium, and Sarcina lutea, with the MIC values ranging from 8.3 to 16.7 μg/mL. Result of scanning electron microscopy (SEM on E. coli suggested that HAHp(5.6-G MRPs exhibited antibacterial activity by destroying the cell integrity through membrane permeabilization. Moreover, HAHp(5.6-G MRPs had excellent foaming ability and stability at alkaline conditions of pH 8.0, and showed emulsion properties at acidic pH 4.0. These results suggested that specific HAHp-G MRPs should be promising functional ingredients used in foods.

  14. Homogeneous asymmetric catalysis in fragrance chemistry.

    Science.gov (United States)

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

    2008-06-01

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

  15. Asymmetric catalysis with short-chain peptides.

    Science.gov (United States)

    Lewandowski, Bartosz; Wennemers, Helma

    2014-10-01

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

  16. Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry

    Directory of Open Access Journals (Sweden)

    Y. Sun

    2010-02-01

    Full Text Available Recent work has shown that aqueous-phase reactions of phenolic compounds – phenol (C6H6O, guaiacol (C7H8O2, and syringol (C8H10O3 – can form secondary organic aerosol (SOA at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS, an Ion Chromatograph (IC, and a Total Organic Carbon (TOC analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C ratios in the range of 0.80–1.06 and carbon oxidation states (=2×O/C–H/C between −0.14 and +0.47. The organic mass-to-carbon (OM/OC ratios determined by the HR-AMS (=2.21���2.55 agree well with values determined based on the SOA mass measured gravimetrically and the OC mass from the TOC analyzer. Both the O/C and OM/OC ratios of the phenolic SOA are similar to the values observed for ambient low-volatility oxygenated/secondary OA (LV-OOA. Oxalate is a minor, but ubiquitous, component of the SOA formed from all three phenolic precursors, accounting for 1.4–5.2% of the SOA mass, with generally higher yields in experiments with H2O2 added as an ·OH source compared to without. The AMS spectra show evidence for the formation of syringol and guaiacol dimers and higher oligomers via C–C and C–O coupling of phenoxyl radicals, which are formed through oxidation pathways such as abstraction of the phenolic hydrogen atom or ·OH addition to the aromatic ring. This latter pathway leads to hydroxylation of the aromatic ring, which is one mechanism that increases the degree of oxidation of the SOA products. Compared to direct photochemical reactions of the phenols, ·OH-initiated reactions favor the formation of smaller oxidation products but less dimers or higher oligomers. Two unique and prominent ions in the syringol and guaiacol SOA spectra,

  17. Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry

    Directory of Open Access Journals (Sweden)

    Y. L. Sun

    2010-05-01

    Full Text Available Recent work has shown that aqueous-phase reactions of phenolic compounds – phenol (C6H6O, guaiacol (C7H8O2, and syringol (C8H10O3 – can form secondary organic aerosol (SOA at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS, an Ion Chromatography system (IC, and a Total Organic Carbon (TOC analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C ratios in the range of 0.80–1.06 and carbon oxidation states (=2×O/C-H/C between −0.14 and +0.47. The organic mass-to-carbon (OM/OC ratios determined by the HR-AMS (=2.21–2.55 agree well with values determined based on the SOA mass measured gravimetrically and the OC mass from the TOC analyzer. Both the O/C and OM/OC ratios of the phenolic SOA are similar to the values observed for ambient low-volatility oxygenated/secondary OA (LV-OOA. Oxalate is a minor, but ubiquitous, component of the SOA formed from all three phenolic precursors, accounting for 1.4−5.2% of the SOA mass, with generally higher yields in experiments with H2O2 added as an OH source compared to without. The AMS spectra show evidence for the formation of syringol and guaiacol dimers and higher oligomers via C-C and C-O coupling of phenoxyl radicals, which are formed through oxidation pathways such as abstraction of the phenolic hydrogen atom or OH addition to the aromatic ring. This latter pathway leads to hydroxylation of the aromatic ring, which is one mechanism that increases the degree of oxidation of the SOA products. Compared to direct photochemical reactions of the phenols, OH-initiated reactions favor the formation of smaller oxidation products but less dimers or higher oligomers. Two unique and prominent ions in the syringol and guaiacol SOA spectra, m/z 306 (C

  18. Decay of 202Pb* formed in 48Ca+154Sm reaction using the dynamical cluster-decay model

    International Nuclear Information System (INIS)

    The decay of compound nucleus 202Pb*, formed in entrance channel reaction 48Ca+154Sm at different incident energies, is studied by using the dynamical cluster-decay model (DCM) where all decay products are calculated as emissions of preformed clusters through the interaction barriers. The calculated results show an excellent agreement with experimental data for the fusion-evaporation residue cross-section σER together with the fusion-fission cross-section σFF (taken as a sum of the energetically favored symmetric ACN*/2 ± 20 and near symmetric A=65–75 plus complementary fragments), and the competing, non-compound-nucleus quasi-fission cross-section σQF where the entrance channel is considered not to lose its identity (and hence with preformation factor P0=1). The interesting feature of this study is that the three decay processes (ER, FF and QF) are quite comparable at low energies, ER being the most dominant, whereas at higher energies FF becomes most probable followed by ER and QF. The prediction of two fission windows, the symmetric fission (SF) and the near symmetric fission (nSF) whose contribution is more at lower incident energies, suggests the presence of a fine structure effect in the fusion-fission of 202Pb*. This result is attributed to the shell effects (magic shells) playing effective role in the fragment preformation yields for 48Ca+154Sm reaction at lower excitation energies, giving rise to shoulders, to an otherwise Gaussian FF mass distribution, responsible for the QF process. As a further verification of this result, absence of "shoulders" (hence, the QF component) in the decay of 192Pb* due to 48Ca+144Sm reaction is also shown to be given by the calculations, in agreement with experiments. The only parameter of the model is the neck-length ΔR which shows that the ER occurs first, having the largest values of ΔR, and the FF and QF processes occur almost simultaneously at lower incident energies but the FF takes over QF at higher incident

  19. Decay studies of 59Cu* formed in the 35Cl + 24Mg reaction using the dynamical cluster-decay model

    Science.gov (United States)

    Karthikraj, C.; Balasubramaniam, M.

    2013-02-01

    The reformulated dynamical cluster-decay model (DCM) is applied to study the decay of odd-A and non-α structured 59Cu* formed in the 35Cl+24Mg reaction at Elab=275 MeV. Here, the temperature (T)-dependent binding energies due to Krappe are used. The roles of Wigner and pairing energies in the fragmentation potential are explicitly shown in this work. For the temperature T=4.1898 MeV corresponding to Elab=275 MeV, the contribution of pairing vanishes and the resulting structure of the fragmentation potential due to Wigner term is shown. In addition to this, we have studied the role of factor α appearing in the inertia part of the equation of motion dictating the mass-transfer process. It is shown that this factor has significant effect in the structure of preformation probability values and hence in turn we see significant changes in the cross sections. We compare the cross sections of the measured charge distributions of the fission fragments for two limiting values of the parameter α with the experimental data. In order to fit the total cross-section values, a linear relation is obtained between the free parameter of the model ▵R and the factor α appearing in the hydrodynamical mass.

  20. Development of a polymerase chain reaction (PCR) test for the detection of virulent forms of Vibrio parahaemolyticus.

    Science.gov (United States)

    Kadhim, H M; Miah, A; Munn, C B; Gilpin, M L

    2012-04-01

    Vibrio parahaemolyticus is a marine bacterium and some strains cause gastroenteritis in humans. Clinical isolates are thought to possess virulence factors that are absent from the majority of environmental isolates. Use of randomly amplified polymorphic DNA (RAPD)-PCR produced a unique 600 bp amplicon (band Y) in the majority of clinical isolates and rarely in environmental isolates tested. The DNA from band Y was cloned and sequenced and found to code for an outer membrane protein (OMP). Two polymerase chain reaction (PCR) primers were designed to specifically amplify a 200 bp unique sequence from presumptive virulent strains (PCR-OMP). The virulence of 23 clinical and 32 environmental isolates was assessed in cytotoxicity tests by treatment of Caco-2 cells with extracellular products (ECPs). All but two of the clinical isolates (91%) were positive for the 200 bp PCR-OMP and their ECPs produced a significantly higher (p PCR-OMP is strongly correlated with virulence, as determined by the cytotoxicity assay, and identified virulent forms better than current PCR tests for tdh, trh or T3SS2.

  1. Bimolecular recombination reactions: K-adiabatic and K-active forms of the bimolecular master equations and analytic solutions

    Science.gov (United States)

    Ghaderi, Nima

    2016-03-01

    Expressions for a K-adiabatic master equation for a bimolecular recombination rate constant krec are derived for a bimolecular reaction forming a complex with a single well or complexes with multiple well, where K is the component of the total angular momentum along the axis of least moment of inertia of the recombination product. The K-active master equation is also considered. The exact analytic solutions, i.e., the K-adiabatic and K-active steady-state population distribution function of reactive complexes, g(EJK) and g(EJ), respectively, are derived for the K-adiabatic and K-active master equation cases using properties of inhomogeneous integral equations (Fredholm type). The solutions accommodate arbitrary intermolecular energy transfer models, e.g., the single exponential, double exponential, Gaussian, step-ladder, and near-singularity models. At the high pressure limit, the krec for both the K-adiabatic and K-active master equations reduce, respectively, to the K-adiabatic and K-active bimolecular Rice-Ramsperger-Kassel-Marcus theory (high pressure limit expressions). Ozone and its formation from O + O2 are known to exhibit an adiabatic K. The ratio of the K-adiabatic to the K-active recombination rate constants for ozone formation at the high pressure limit is calculated to be ˜0.9 at 300 K. Results on the temperature and pressure dependence of the recombination rate constants and populations of O3 will be presented elsewhere.

  2. 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.

  3. Microbial transformations 59: first kilogram scale asymmetric microbial Baeyer-Villiger oxidation with optimized productivity using a resin-based in situ SFPR strategy.

    Science.gov (United States)

    Hilker, Iris; Wohlgemuth, Roland; Alphand, Véronique; Furstoss, Roland

    2005-12-20

    This study is demonstrating the scale up of asymmetric microbial Baeyer-Villiger oxidation of racemic bicyclo[3.2.0]hept-2-en-6-one (1) to the kilogram scale using a 50 L bioreactor. The process has been optimized with respect to bottlenecks identified in downscaled experiments. A high productivity was obtained combining a resin-based in situ substrate feeding and product removal methodology (in situ SFPR), a glycerol feed control, and an improved oxygenation device (using a sintered-metal sparger). As expected both regioisomeric lactones [(-)-(1S,5R)-2 and (-)-(1R,5S)-3] were obtained in nearly enantiopure form (ee > 98%) and good yield. This represents the first example of such an asymmetric Baeyer-Villiger biooxidation reaction ever operated at that scale. This novel resin-based in situ SFPR technology therefore clearly opens the way to further (industrial) upscaling of this highly valuable (asymmetric) reaction.

  4. A Novel and Optimized Method for Electro-focusing and Moving Neutralization Reaction Boundary Formed by HCl and NaOH

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel method is developed for electro-focusing and moving neutralization reaction boundary (MNRB) created with HCl and NaOH. The optimized conditions are screened out. By using this method, the experiments are performed on MNRB formed with HCl and NaOH in agarose gel. The experiments are quantitatively in coincidence with the predictions with the theory of moving chemical reaction boundary (MCRB).

  5. A quantitative method to characterize the Al_{4}C_{3}-formed interfacial reaction : the case study of MWCNT/Al composites

    OpenAIRE

    Yan, Laipeng; Tan, Zhanqiu; Ji, Gang; Li, Zhiqiang; Fan, Genlian; Schryvers, D.; Shan, Aidang; Zhang, Di

    2016-01-01

    Abstract: The Al4C3-formed interfacial reaction plays an important role in tuning the mechanical and thermal properties of carbon/aluminum (C/Al) composites reinforced with carbonaceous materials such as multi-wall carbon nanotube (MWCNT) and graphene nanosheet. In terms of the hydrolysis nature of Al4C3, an electrochemical dissolution method was developed to quantitatively characterize the extent of C/Al interfacial reaction, which involves dissolving the composite samples in alkaline soluti...

  6. Asymmetric membrane osmotic capsules for terbutaline sulphate

    Directory of Open Access Journals (Sweden)

    N G Gobade

    2012-01-01

    Full Text Available The aim of the present study was to design an asymmetric membrane capsule, an osmotic pump-based drug delivery system of ethyl cellulose for controlled release of terbutaline sulphate. asymmetric membrane capsules contains pore-forming water soluble additive, sorbitol in different concentrations in the capsule shell membrane, which after coming in contact with water, dissolves, resulting in an in situ formation of a microporous structure. The terbutaline sulphate is a β-adrenoreceptor agonist widely used in the treatment of asthma. The oral dosage regimen of terbutaline sulphate is 5 mg twice or thrice daily, the plasma half-life is approximate 3-4 h and it produces GI irritation with extensive first pass metabolism. Hence, terbutaline sulphate was chosen as a model drug with an aim to develop controlled release system. Different formulations of ethyl cellulose were prepared by phase inversion technique using different concentrations of sorbitol as pore forming agent. It was found that the thickness of the prepared asymmetric membrane capsules was increased with increase in concentration of ethyl cellulose and pore forming agent, i.e. sorbitol. The dye release study in water and 10% sodium chloride solution indicates that, the asymmetric membrane capsules follow osmotic principle to release content. The pores formed due to sorbitol were confirmed by microscopic observation of transverse section of capsule membrane. Data of in vitro release study of terbutaline sulphate from asymmetric membrane capsules indicated that, the capsules prepared with 10% and 12.5% of ethyl cellulose and 25% of sorbitol released as much as 97.44% and 76.27% in 12 h, respectively with zero order release rate. Hence asymmetric membrane capsule of 10% ethyl cellulose and 25% of sorbitol is considered as optimum for controlled oral delivery of terbutaline sulphate.

  7. Asymmetric membrane osmotic capsules for terbutaline sulphate.

    Science.gov (United States)

    Gobade, N G; Koland, Marina; Harish, K H

    2012-01-01

    The aim of the present study was to design an asymmetric membrane capsule, an osmotic pump-based drug delivery system of ethyl cellulose for controlled release of terbutaline sulphate. asymmetric membrane capsules contains pore-forming water soluble additive, sorbitol in different concentrations in the capsule shell membrane, which after coming in contact with water, dissolves, resulting in an in situ formation of a microporous structure. The terbutaline sulphate is a β-adrenoreceptor agonist widely used in the treatment of asthma. The oral dosage regimen of terbutaline sulphate is 5 mg twice or thrice daily, the plasma half-life is approximate 3-4 h and it produces GI irritation with extensive first pass metabolism. Hence, terbutaline sulphate was chosen as a model drug with an aim to develop controlled release system. Different formulations of ethyl cellulose were prepared by phase inversion technique using different concentrations of sorbitol as pore forming agent. It was found that the thickness of the prepared asymmetric membrane capsules was increased with increase in concentration of ethyl cellulose and pore forming agent, i.e. sorbitol. The dye release study in water and 10% sodium chloride solution indicates that, the asymmetric membrane capsules follow osmotic principle to release content. The pores formed due to sorbitol were confirmed by microscopic observation of transverse section of capsule membrane. Data of in vitro release study of terbutaline sulphate from asymmetric membrane capsules indicated that, the capsules prepared with 10% and 12.5% of ethyl cellulose and 25% of sorbitol released as much as 97.44% and 76.27% in 12 h, respectively with zero order release rate. Hence asymmetric membrane capsule of 10% ethyl cellulose and 25% of sorbitol is considered as optimum for controlled oral delivery of terbutaline sulphate. PMID:23204625

  8. Asymmetric total synthesis of vindoline.

    Science.gov (United States)

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

    2010-03-24

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

  9. Asymmetrical international attitudes

    NARCIS (Netherlands)

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

    2002-01-01

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

  10. An asymmetric Kadison's inequality

    CERN Document Server

    Bourin, Jean-Christophe

    2010-01-01

    Some inequalities for positive linear maps on matrix algebras are given, especially asymmetric extensions of Kadison's inequality and several operator versions of Chebyshev's inequality. We also discuss well-known results around the matrix geometric mean and connect it with complex interpolation.

  11. The form of the rate constant for elementary reactions at equilibrium from MD: framework and proposals for thermokinetics

    CERN Document Server

    Jesudason, C G

    2006-01-01

    The rates or formation and concentration distributions of a dimer reaction showing hysteresis behavior are examined in an ab initio chemical reaction designed as elementary and where the hysteresis structure precludes the formation of transition states (TS) with pre-equilibrium and internal sub-reactions. It was discovered that the the reactivity coefficients, defined as a measure of departure from the zero density rate constant for the forward and backward steps had a ratio that was equal to the activity coefficient ratio for the product and reactant species. From the above observations, a theory is developed with the aid of some proven elementary theorems in thermodynamics, and expressions are derived whereby a feasible experimental and computational method for determining the activity coefficients from the rate constants may be obtained The theory developed is applied to ionic reactions where the standard Bronsted-Bjerrum rate equation and exceptions to this are rationalized, and by viewing ion association...

  12. Asymmetric catalysis with helical polymers

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    2011-01-01

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

  13. Towards the development of a cyclisation-release screening methodology for new C-C bond forming reactions

    OpenAIRE

    Sohail, Takmeel

    2010-01-01

    The objective of this project is primarily to develop a cyclisation-release methodology which could be applied to the investigation of Baylis-Hillman reactions, and to further develop a methodology, enzymatic or chemical, suitable to screen reaction products. The screening process will ultimately be incorporated to identify a potential Baylis-Hillmanase, developed through directed evolution by other members of the Berrisford group. This area of work is based around evolving aldolase enzymes a...

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

    Directory of Open Access Journals (Sweden)

    Carlos Magno R. Ribeiro

    2008-01-01

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

  15. 1,2- and 1,3-dihydroxylated and hydroxynitrogenated monoterpenes as chiral ligands in the asymmetric reformatsky reaction; Monoterpenos di-hidroxilados e hidroxi-nitrogenados 1,2 e 1,3 como ligantes quirais em reacao de reformatsky assimetrica

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  16. Post-column reaction for simultaneous analysis of chromatic and leuco forms of malachite green and crystal violet by high-performance liquid chromatography with photometric detection

    Science.gov (United States)

    Allen, J.L.; Meinertz, J.R.

    1991-01-01

    The chromatic and leuco forms of malachite green and crystal violet were readily separated and detected by a sensitive and selective high-performance liquid chromatographic procedure. The chromatic and leuco forms of the dyes were separated within 11 min on a C18 column with a mobile phase of 0.05 M sodium acetate and 0.05 M acetic acid in water (19%) and methanol (81%). A reaction chamber, containing 10% PbO2 in Celite 545, was placed between the column and the spectrophotometric detector to oxidize the leuco forms of the dyes to their chromatic forms. Chromatic and leuco malachite green were quantified by their absorbance at 618 nm; and chromatic and leuco Crystal Violet by their absorbance at 588 nm. Detection limits for chromatic and leuco forms of both dyes ranged from 0.12 to 0.28 ng. A linear range of 1 to 100 ng was established for both forms of the dyes.

  17. Synthesis of the 1,3-oxathiolanes using asymmetrically oxiranes

    Institute of Scientific and Technical Information of China (English)

    Faramarz Rostami-Charati; Zinatossadat Hossaini; Bita Mohtat; Mehdi Shahraki; Mohammad R. Hosseini-Tabatabaei

    2011-01-01

    An efficient synthesis of 1,3-oxathiolane-2-imin derivatives is described via one-pot reaction between arylisothiocyanats, asymmetrically substituted oxiranes and catalytic amount of methanol. The mild reaction conditions and high yields of the products exhibit the good synthetic advantage of this method.

  18. Recoil Properties of Fragments Formed in the Deuteron-Induced Reaction of Gold at Incident Energy 2.2 AGeV

    CERN Document Server

    Balabekyan, A R; Karapetyan, G S; Drnoyan, D R; Zhemenik, V I; Adam, J; Zavorka, L; Solnyshkin, A A; Tsoupko-Sitnikov, V M; Khushvaktov, J

    2013-01-01

    The thick-target recoil properties of 90 nuclides, varying from $^{24}$Na to $^{198}$Au, formed in the interaction of 4.4-GeV deuterons with $^{197}$Au, have been measured for the first time in the literature, up to our knowledge, in order to study the systematics of their variation with product mass. The products forward-to-backward ratios ($F/B$) exhibit the different behavior, which depends upon the mass region of the reaction products. There was an evidence supportive of the existence of several different mechanisms in the reaction studied. The results are analyzed by the two-step model of high-energy reactions and discussed in terms of the different reaction mechanisms, spallation, fission and fragmentation. Fission contributes appreciably to the formation of products in the mass region 65 $\\leq$ A $\\leq$ 120 amu. The kinematic features for deuteron-induced reaction have been compared to those for reactions of energetic protons with gold. The relation between forward momentum and mean deposition energy a...

  19. Quantum state-resolved differential cross sections for complex-forming chemical reactions: Asymmetry is the rule, symmetry the exception

    Energy Technology Data Exchange (ETDEWEB)

    Larrégaray, Pascal, E-mail: pascal.larregaray@u-bordeaux.fr; Bonnet, Laurent, E-mail: laurent.bonnet@u-bordeaux.fr [ISM, UMR 5255, CNRS, F-33400 Talence (France); ISM, UMR 5255, Univ. Bordeaux, F-33400 Talence (France)

    2015-10-14

    We argue that statistical theories are generally unable to accurately predict state-resolved differential cross sections for triatomic bimolecular reactions studied in beam experiments, even in the idealized limit where the dynamics are fully chaotic. The basic reason is that quenching of interferences between partial waves is less efficient than intuitively expected, especially around the poles.

  20. Asymmetric information and economics

    Science.gov (United States)

    Frieden, B. Roy; Hawkins, Raymond J.

    2010-01-01

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

  1. Engineering Chiral Catalysts through Asymmetric Activation and Super High Throughput Screening (SHTS)

    Institute of Scientific and Technical Information of China (English)

    MIKAMI,Koichi; KORENAGA,Toshinobu; MATSUKAWA,Satoru; DING,Kui-Ling; LONG,Jiang

    2001-01-01

    A conceptually new strategy for asymmetric catalysis, namely asymmetric activation, in which a chiral activator selectively activates one enantiomer of a racemic chiral catalyst, and a highly efficient screening system for finding the most effective catalysts, namely super high throughput screening (SHTS), by which the reaction can be conducted in parallel and the ee% of the product is allowed to determine within minutes, are summarized in the present account. It is reasonable to be lieve that SHTS technique combined with asymmetric activa tion or deactivation principle will provide a very powerful methodology for finding the new catalysts and the best catalyst tuning for asymmetric reactions.

  2. Technical Note: Detection and identification of radical species formed from α-pinene/ozone reaction using DMPO spin trap

    Directory of Open Access Journals (Sweden)

    J. Pavlovic

    2009-11-01

    Full Text Available The reactions of ozone with monoterpenes proceed via the formation of multiple oxygen- and carbon-centered free radical species. These radical species are highly reactive and thus, have generally not been measureable. A method for their detection and characterization is needed to preserve these radicals for a sufficiently long time to permit analyzes to be performed. Radical-addition reactions, also called spin trapping techniques, allow the detection of short-lived radicals. This approach has been applied to products from the α-pinene/ozone reaction. Secondary organic aerosol (SOA from a reaction chamber was collected on quartz fiber filters and extracted with a solution of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO (spin trap followed by analysis with ion-trap tandem mass spectrometry (MSn using electrospray ionization (ESI in the positive scan mode. The DMPO adducts with radical species appear as positive ions [DMPO−R+H]+, [DMPO−OR+H]+ and [DMPO−O−OR+H]+ in full MS spectra of the samples. Tandem mass spectrometry (MS2 was performed to identify the radical species. The DMPO adducts with the C-centered radical species [DMPO−R+H]+ are characterized by m/z 114 [DMPO+H]+ in the MS2 spectra and with peaks that represent the loss of [DMPO+H]+. The DMPO adducts with O-centered radical species (RO· and ROO· are identified by m/z 130 [DMPO−OH+H]+ and m/z 146 [DMPO−O−OH+H]+, respectively, and with peaks that correspond to the loss of those adducts. DMPO was also able to capture OH radicals from the particle phase, and the product ion fragmentation confirmed DMPO/OH structure providing evidence for particle-bound OH radicals.

  3. Processes forming Gas, Tar, and Coke in Cellulose Gasification from Gas-Phase Reactions of Levoglucosan as Intermediate.

    Science.gov (United States)

    Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro

    2015-07-01

    The gas-phase pyrolysis of levoglucosan (LG), the major intermediate species during cellulose gasification, was studied experimentally over the temperature range of 400-900 °C. Gaseous LG did not produce any dehydration products, which include coke, furans, and aromatic substances, although these are characteristic products of the pyrolysis of molten LG. Alternatively, at >500 °C, gaseous LG produced only fragmentation products, such as noncondensable gases and condensable C1 -C3 fragments, as intermediates during noncondensable gas formation. Therefore, it was determined that secondary reactions of gaseous LG can result in the clean (tar- and coke-free) gasification of cellulose. Cooling of the remaining LG in the gas phase caused coke formation by the transition of the LG to the molten state. The molecular mechanisms that govern the gas- and molten-phase reactions of LG are discussed in terms of the acid catalyst effect of intermolecular hydrogen bonding to promote the molten-phase dehydration reactions. PMID:26099988

  4. Processes forming Gas, Tar, and Coke in Cellulose Gasification from Gas-Phase Reactions of Levoglucosan as Intermediate.

    Science.gov (United States)

    Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro

    2015-07-01

    The gas-phase pyrolysis of levoglucosan (LG), the major intermediate species during cellulose gasification, was studied experimentally over the temperature range of 400-900 °C. Gaseous LG did not produce any dehydration products, which include coke, furans, and aromatic substances, although these are characteristic products of the pyrolysis of molten LG. Alternatively, at >500 °C, gaseous LG produced only fragmentation products, such as noncondensable gases and condensable C1 -C3 fragments, as intermediates during noncondensable gas formation. Therefore, it was determined that secondary reactions of gaseous LG can result in the clean (tar- and coke-free) gasification of cellulose. Cooling of the remaining LG in the gas phase caused coke formation by the transition of the LG to the molten state. The molecular mechanisms that govern the gas- and molten-phase reactions of LG are discussed in terms of the acid catalyst effect of intermolecular hydrogen bonding to promote the molten-phase dehydration reactions.

  5. Target Residues Formed in the Deuteron-Induced Reaction of Gold at Incident Energy 2.2 AGeV

    CERN Document Server

    Balabekyan, A R; Karapetyan, G S; Drnoyan, D R; Zhemenik, V I; Adam, J; Zavorka, L; Solnyshkin, A A; Tsoupko-Sitnikov, V M; Khushvaktov, J

    2013-01-01

    Cross sections of radioactive nuclides, resulting from the interactions of 4.4-GeV deuterons with $^{197}$Au, which cover all mass range of the reaction products, have been measured for the first time in the literature, up to our knowledge. The measurements were done by direct counting of the target with calibrated Ge(Li) $\\gamma$-ray spectrometer and spectral analysis with computer program. More than 60 nuclides were identified between mass numbers 22 and 199. The results have been parametrized in term of 3-parameter equation which accurately reproduces the measured isobaric distribution. Using data from charge distribution mass-yield distribution was obtained. From mass distribution the evidence supportive of the existence of several different mechanisms in the reaction was derived. The comparison of the results of this work with the data from the reactions of high energy protons, deuterons and heavy-ions has been done in order to check the concepts of factorization and limiting fragmentation. The results a...

  6. Growth behavior of LiMn2O4 particles formed by solid-state reactions in air and water vapor

    Science.gov (United States)

    Kozawa, Takahiro; Yanagisawa, Kazumichi; Murakami, Takeshi; Naito, Makio

    2016-11-01

    Morphology control of particles formed during conventional solid-state reactions without any additives is a challenging task. Here, we propose a new strategy to control the morphology of LiMn2O4 particles based on water vapor-induced growth of particles during solid-state reactions. We have investigated the synthesis and microstructural evolution of LiMn2O4 particles in air and water vapor atmospheres as model reactions; LiMn2O4 is used as a low-cost cathode material for lithium-ion batteries. By using spherical MnCO3 precursor impregnated with LiOH, LiMn2O4 spheres with a hollow structure were obtained in air, while angulated particles with micrometer sizes were formed in water vapor. The pore structure of the particles synthesized in water vapor was found to be affected at temperatures below 700 °C. We also show that the solid-state reaction in water vapor is a simple and valuable method for the large-scale production of particles, where the shape, size, and microstructure can be controlled.

  7. Decay analysis of compound nuclei with mass A$\\sim 30-200$ formed in the reactions involving loosely bound projectiles

    CERN Document Server

    Kaur, Mandeep; Sharma, Manoj K; Gupta, Raj K

    2015-01-01

    The dynamics of the reactions forming compound nuclei using loosely bound projectiles is analysed within the framework of dynamical cluster decay model (DCM) of Gupta and Collaborators. We have analysed different reactions with $^{7}Li$, $^{9}Be$ and $^{7}Be$ as neutron rich and neutron deficient projectiles, respectively, on different targets at the three $E_{lab}$ values, forming compound nuclei within the mass region A$\\sim 30-200$. The contributions of light particles LPs ($A\\le4$) cross sections $\\sigma_{LP}$, energetically favoured intermediate mass fragments IMFs ($5 \\le A_2 \\le 20$) cross sections $\\sigma_{IMF}$ as well as fusion-fission $\\it{ff}$ cross sections $\\sigma_{ff}$ constitute the $\\sigma_{fus}$ (=$\\sigma_{LP}$+$\\sigma_{IMF}$+$\\sigma_{ff}$) for these reactions. The contribution of the emitted LPs, IMFs and ff fragments is added for all the angular momentum upto the $\\ell_{max}$ value, for the resepctive reactions. Interestingly, we find that the $\\Delta R^{emp}$, the only parameter of model ...

  8. Gas-phase reactivity of peptide thiyl (RS•), perthiyl (RSS•), and sulfinyl (RSO•) radical ions formed from atmospheric pressure ion/radical reactions.

    Science.gov (United States)

    Tan, Lei; Xia, Yu

    2013-04-01

    In this study, we demonstrated the formation of gas-phase peptide perthiyl (RSS•) and thiyl (RS•) radical ions besides sulfinyl radical (RSO•) ions from atmospheric pressure (AP) ion/radical reactions of peptides containing inter-chain disulfide bonds. The identity of perthiyl radical was verified from characteristic 65 Da (•SSH) loss in collision-induced dissociation (CID). This signature loss was further used to assess the purity of peptide perthiyl radical ions formed from AP ion/radical reactions. Ion/molecule reactions combined with CID were carried out to confirm the formation of thiyl radical. Transmission mode ion/molecule reactions in collision cell (q2) were developed as a fast means to estimate the population of peptide thiyl radical ions. The reactivity of peptide thiyl, perthiyl, and sulfinyl radical ions was evaluated based on ion/molecule reactions toward organic disulfides, allyl iodide, organic thiol, and oxygen, which followed in order of thiyl (RS•) > perthiyl (RSS•) > sulfinyl (RSO•). The gas-phase reactivity of these three types of sulfur-based radicals is consistent with literature reports from solution studies.

  9. Asymmetric AgPd-AuNR heterostructure with enhanced photothermal performance and SERS activity

    Science.gov (United States)

    Zhang, Han; Liu, Zeke; Kang, Xiaolin; Guo, Jun; Ma, Wanli; Cheng, Si

    2016-01-01

    Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts.Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07333b

  10. Chiral N,N’-Dioxide-Ni(Ⅱ) Complex Catalyzed Asymmetric Carbonyl-Ene Reaction of Ethyl Trifluoropyruvate%手性氮氧-Ni(Ⅱ)络合物催化三氟甲基酮酸酯的不对称羰基ene反应

    Institute of Scientific and Technical Information of China (English)

    郑柯; 林丽丽; 冯小明

    2012-01-01

    本工作对手性氮氧–镍络合物催化剂在不对称羰基ene反应中的应用进行了深入研究,通过对配体结构和反应条件的优化,实现了三氟甲基酮酸酯的不对称羰基ene反应.实验发现,氮氧配体的结构对反应对映选择性有很大影响,其中酰胺结构中苯环2,6-位大位阻供电取代基对于反应立体选择性控制起着至关重要的作用.该催化体系有广泛的底物普适性,对一系列α-甲基烯烃都能得到高达80%~96%的收率和97%~〉99%ee的对映选择性.同时,通过对照实验以及对催化剂单晶结构的分析,提出了可能的反应过渡态,为该系列催化剂的拓展提供了基础.%The optically active homoallylic alcohols are widespread in natural products and have been frequently used as convenient building blocks in organic synthesis.As one of the most efficient synthetic methods to obtain chiral homoallylic alcohols,the asymmetric ene reaction of carbonyl compounds has attracted significant attentions.N,N’-dioxide-amide compounds,which could be easily prepared from chiral amino acids,have been developed into a type of privileged ligand and organocatalyst in various asymmetric reactions.On the other hand,the fluoroorganic compounds are important building blocks for the total synthesis of complex natural products,pharmaceuticals,and plant pesticides due to the unique abilities of the fluorine atom to significantly modify their physicochemical and biological properties.In recent years,the interest of the pharmaceutical industry in trifluoromethyl-containing compounds has grown significantly.In this manuscript,a series of Ni(II)-N,N’-dioxide complexes have been investigated for the asymmetric carbonyl-ene reaction of ethyl trifluoropyruvate.It was found that the electronic and steric characteristics of substituents on the amide moieties of the ligand greatly affected the reaction outcomes.The catalyst L4 with bulky and electron-donating groups at the

  11. 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

  12. Side-chain interactions form late and cooperatively in the binding reaction between disordered peptides and PDZ domains

    DEFF Research Database (Denmark)

    Haq, S Raza; Chi, Celestine N; Bach, Anders;

    2012-01-01

    used short peptides as a model system for intrinsically disordered proteins. Linear free-energy relationships based on rate and equilibrium constants for the binding of these peptides to ordered target proteins, PDZ domains, demonstrate that native side-chain interactions form mainly after the rate......-limiting barrier for binding, in a cooperative fashion. This finding suggests that these disordered peptides first form a weak encounter complex with non-native interactions. The data do not support the recent notion that the affinities of intrinsically disordered proteins towards their targets are generally...

  13. Kemp elimination in membrane mimetic reaction media : Probing catalytic properties of catanionic vesicles formed from double-tailed amphiphiles

    NARCIS (Netherlands)

    Klijn, JE; Engberts, JBFN

    2003-01-01

    The rate-determining deprotonation of 5-nitrobenzisoxazole (Kemp elimination) by hydroxide is efficiently catalyzed by vesicles formed from dimethyldioctadecylammonium chloride (C18C18+). Gradual addition of sodium didecyl phosphate (C10C10-) leads to the formation of catanionic vesicles, which were

  14. Probing the effect of different cross-sections in asymmetric collisions

    OpenAIRE

    Kaur, Deepinder; Kaur, Varinderjit; Kumar, Suneel

    2011-01-01

    We present a complete systematic theoretical study of multifragmentation for asymmetric colliding nuclei for heavy-ion reactions in the energy range between 50 MeV/nucleon and 1000 MeV/nucleon by using isospin dependent quantum molecular dynamics (IQMD) model. We have observed an interesting outcome for asymmetric colliding nuclei. The comparison between the symmetric and asymmetric colliding nuclei for the isospin independent cross section and isospin dependent cross section has been studied...

  15. The Dualism of Asymmetric Information in Agricultural Insurance

    Directory of Open Access Journals (Sweden)

    Xuemei Yang

    2013-07-01

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

  16. Asymmetric inheritance of cytoophidia in Schizosaccharomyces pombe

    OpenAIRE

    Jing Zhang; Lydia Hulme; Ji-Long Liu

    2014-01-01

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

  17. Cluster emission in superdeformed Sr isotopes in the ground state and formed in heavy-ion reaction

    Indian Academy of Sciences (India)

    K P Santhosh; Antony Joseph

    2005-01-01

    Cluster decay of superdeformed 76,78,80Sr isotopes in their ground state are studied taking the Coulomb and proximity potential as the interacting barrier for the post-scission region. The predicted 1/2 values are found to be in close agreement with those values reported by the preformed cluster model (PCM). Our calculation shows that these nuclei are stable against both light and heavy cluster emissions. We studied the decay of these nuclei produced as an excited compound system in heavy-ion reaction. It is found that inclusion of excitation energy increases the decay rate (decreases 1/2 value) considerably and these nuclei become unstable against decay. These findings support earlier observation of Gupta et al based on PCM.

  18. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    Science.gov (United States)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants - the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  19. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; Anastasio, Cort N.; Laskin, Julia; Zhang, Qi

    2014-01-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), desorption electrospray ionization mass spectrometry (DESIMS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O/C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than •OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O/C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  20. Asymmetric quantum cloning machines

    International Nuclear Information System (INIS)

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

  1. 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.

  2. Plausible mechanisms of the fenton-like reactions, M = Fe(II) and Co(II), in the presence of RCO2(-) substrates: are OH(•) radicals formed in the process?

    Science.gov (United States)

    Kornweitz, Haya; Burg, Ariela; Meyerstein, Dan

    2015-05-01

    DFT calculations concerning the plausible mechanism of Fenton-like reactions catalyzed by Fe(II) and Co(II) cations in the presence of carboxylate ligands suggest that hydroxyl radicals are not formed in these reactions. This conclusion suggests that the commonly accepted mechanisms of Fenton-like reactions induced oxidative stress and advanced oxidation processes have to be reconsidered.

  3. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

    Directory of Open Access Journals (Sweden)

    A. L. Van Wyngarden

    2014-11-01

    Full Text Available Particles in the upper troposphere and lower stratosphere (UT/LS consist mostly of concentrated sulfuric acid (40–80 wt % in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4 with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, Attenuated Total Reflectance–Fourier Transform Infrared and 1H Nuclear Magnetic Resonance spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal and 1,3,5-trimethylbenzene, which was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence for products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal

  4. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

    Science.gov (United States)

    Van Wyngarden, A. L.; Pérez-Montaño, S.; Bui, J. V. H.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.

    2015-04-01

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt%) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and

  5. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed

    Energy Technology Data Exchange (ETDEWEB)

    Gaikwad, Vaibhav [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Kennedy, Eric, E-mail: Eric.Kennedy@newcastle.edu.au [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Mackie, John [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Holdsworth, Clovia [Centre for Organic Electronics, Chemistry Building, School of Environmental and Life Sciences, University of Newcastle, Callaghan, NSW 2308 (Australia); Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Dlugogorski, Bogdan [School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150 (Australia)

    2014-09-15

    Highlights: • CCl{sub 4} remediation using non-equilibrium plasma and non-oxidative conditions is proposed. • The reaction mechanism relies on experimental data and quantum chemical analysis. • Comprehensive mass balance for the reaction is provided. • CCl{sub 4} is converted to an environmentally benign and potentially useful polymer. • Characterisation of the polymer structure based on NMR and FTIR analyses is presented. - Abstract: In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  6. Effect of the Keto Group on Yields and Composition of Organic Aerosol Formed from OH Radical-Initiated Reactions of Ketones in the Presence of NOx.

    Science.gov (United States)

    Algrim, Lucas B; Ziemann, Paul J

    2016-09-01

    Yields of secondary organic aerosol (SOA) were measured for OH radical-initiated reactions of the 2- through 6-dodecanone positional isomers and also n-dodecane and n-tetradecane in the presence of NOx. Yields decreased in the order n-tetradecane > dodecanone isomer average > n-dodecane, and the dodecanone isomer yields decreased as the keto group moved toward the center of the molecule, with 6-dodecanone being an exception. Trends in the yields can be explained by the effect of carbon number and keto group presence and position on product vapor pressures, and by the isomer-specific effects of the keto group on branching ratios for keto alkoxy radical isomerization, decomposition, and reaction with O2. Most importantly, results indicate that isomerization of keto alkoxy radicals via 1,5- and 1,6-H shifts are significantly hindered by the presence of a keto group whereas decomposition is enhanced. Analysis of particle composition indicates that the SOA products are similar for all isomers, and that compared to those formed from the corresponding reactions of alkanes the presence of a pre-existing keto group opens up additional heterogeneous/multiphase reaction pathways that can lead to the formation of new products. The results demonstrate that the presence of a keto group alters gas and particle phase chemistry and provide new insights into the potential effects of molecular structure on the products of the atmospheric oxidation of volatile organic compounds and subsequent formation of SOA. PMID:27508315

  7. Application of Ru-DPEN complex in synthesis of chiral α-benzyl ethanol via asymmetric hydrogen transfer reaction of acetophenone%Ru-DPEN配合物在苯乙酮不对称氢转移反应制备手性α-苯乙醇中的应用

    Institute of Scientific and Technical Information of China (English)

    胡明明; 李英霞; 白立光

    2012-01-01

    A novel chiral ruthenium complex RuCl[p-cymene] [ R,R-DPEN] ( R, R-DPEN - 1 ,2-diphe-nylethylenediamine) was synthesized and used as the catalyst for synthesis of chiral a-benzyl ethanol via asymmetric hydrogen transfer reaction of acetophenone. Influence of reaction temperature, reaction time, isopropanol solvent volume, n(acetophenone): n{ RuCl[p-cymene] [ R,R-DPEN] and alkalinity on conversion and ee( enantiomeric excess value) of the asymmetric hydrogen transfer reaction was investigated. The experimental results indicated that the chiral complex exhibited good catalytic activity and favorable enantioselectivity under the following condition:reaction temperature = 40℃, n ( potassium tert-butox-ide):ra(RuCl[p-cymene] [R, R-DPEN]) = 10. 3:1, n ( acetophenone): n( RuCl [p-cymene] [R,R-DPEN] ) = 23. 7: 1 , reaction for 24 h, with conversion of 99. 63% , and ee of 31. 04% .%合成一种新型钌-手性二胺三元配合物RuCl[p-cymene][R,R-DPEN](DPEN=1,2-二苯基乙二胺).利用此配合物作为催化剂催化苯乙酮的不对称氢转移反应,考察反应温度、反应时间、溶剂异丙醇用量、n(苯乙酮)∶n(RuCl[p-cymene][R,R-DPEN])和碱浓度对苯乙酮不对称氢转移反应的转化率和ee值的影响.结果表明,在反应温度40℃、n(叔丁醇钾)∶n(RuCl[p-cymene][R,R-DPEN])=10.3∶1、n(苯乙酮)∶n(RuCl[p-cymene][R,R-DPEN])=23.7∶1和反应时间24h条件下,配合物对苯乙酮不对称氢转移反应具有良好的催化性能和较好的对映选择性,苯乙酮不对称氢转移反应转化率达99.63%,ee值达31.04%.

  8. Asymmetric Bulkheads for Cylindrical Pressure Vessels

    Science.gov (United States)

    Ford, Donald B.

    2007-01-01

    Asymmetric bulkheads are proposed for the ends of vertically oriented cylindrical pressure vessels. These bulkheads, which would feature both convex and concave contours, would offer advantages over purely convex, purely concave, and flat bulkheads (see figure). Intended originally to be applied to large tanks that hold propellant liquids for launching spacecraft, the asymmetric-bulkhead concept may also be attractive for terrestrial pressure vessels for which there are requirements to maximize volumetric and mass efficiencies. A description of the relative advantages and disadvantages of prior symmetric bulkhead configurations is prerequisite to understanding the advantages of the proposed asymmetric configuration: In order to obtain adequate strength, flat bulkheads must be made thicker, relative to concave and convex bulkheads; the difference in thickness is such that, other things being equal, pressure vessels with flat bulkheads must be made heavier than ones with concave or convex bulkheads. Convex bulkhead designs increase overall tank lengths, thereby necessitating additional supporting structure for keeping tanks vertical. Concave bulkhead configurations increase tank lengths and detract from volumetric efficiency, even though they do not necessitate additional supporting structure. The shape of a bulkhead affects the proportion of residual fluid in a tank that is, the portion of fluid that unavoidably remains in the tank during outflow and hence cannot be used. In this regard, a flat bulkhead is disadvantageous in two respects: (1) It lacks a single low point for optimum placement of an outlet and (2) a vortex that forms at the outlet during outflow prevents a relatively large amount of fluid from leaving the tank. A concave bulkhead also lacks a single low point for optimum placement of an outlet. Like purely concave and purely convex bulkhead configurations, the proposed asymmetric bulkhead configurations would be more mass-efficient than is the flat

  9. Nickel-Catalyzed Carbon–Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations

    OpenAIRE

    Zultanski, Susan L.; Fu, Gregory C.

    2013-01-01

    The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr[subscript 2]·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group,...

  10. STUDY OF INFLUENCE OF PREVIOUS ORAL APPLICATION OF DIPHTHERIA ANTIGENIC PREPARATIONS ON RABBIT ALLERGIC REACTION FORMING AFTER SKIN TEST

    OpenAIRE

    Babych YeM; Yelyseyeva IV; Zhdamarova LA; Belozersky VI; Bobireva IV

    2013-01-01

    It’s studied an influence of previous oral application of diphtheria antigenic preparations on allergic inflammation forming after skin test. It’s used destroyed by ultrasonic microbe cells C.diphtheriae var. gravis tox+ massachusets, free from destroyed cells by the use of centrifugation supernatant and refined concentrated diphteria toxoid. Experimental rabbits are fed to 3,5 ml of one of antigenic preparations (the total protein dose is 33,6 mg), control ones are fed to saline. In a week ...

  11. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed.

    Science.gov (United States)

    Gaikwad, Vaibhav; Kennedy, Eric; Mackie, John; Holdsworth, Clovia; Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael; Dlugogorski, Bogdan

    2014-09-15

    In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  12. Alternative Asymmetric Stochastic Volatility Models

    NARCIS (Netherlands)

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

    2010-01-01

    textabstractThe stochastic volatility model usually incorporates asymmetric effects by introducing the negative correlation between the innovations in returns and volatility. In this paper, we propose a new asymmetric stochastic volatility model, based on the leverage and size effects. The model is

  13. Fission fragment mass distribution studies in 30Si +180Hf reaction

    Science.gov (United States)

    Shamlath, A.; Shareef, M.; Prasad, E.; Sugathan, P.; Thomas, R. G.; Jhingan, A.; Appannababu, S.; Nasirov, A. K.; Vinodkumar, A. M.; Varier, K. M.; Yadav, C.; Babu, B. R. S.; Nath, S.; Mohanto, G.; Mukul, Ish; Singh, D.; Kailas, S.

    2016-01-01

    Fission fragment mass-angle and mass ratio distributions have been measured for the 30Si + 180Hf reaction in the beam energy range 128-148 MeV. Quasifission signature is observed in this reaction, forming the compound system 210Rn. The results are compared with a very asymmetric reaction 16O + 194Pt, forming the same compound nucleus. Calculations assuming saddle point, scission point and DNS models have been performed to interpret the experimental results. The results strongly suggest the entrance channel dependence of quasifission in heavy ion collisions.

  14. Mechanisms for Two-Step Proton Transfer Reactions in the Outward-Facing Form of MATE Transporter.

    Science.gov (United States)

    Nishima, Wataru; Mizukami, Wataru; Tanaka, Yoshiki; Ishitani, Ryuichiro; Nureki, Osamu; Sugita, Yuji

    2016-03-29

    Bacterial pathogens or cancer cells can acquire multidrug resistance, which causes serious clinical problems. In cells with multidrug resistance, various drugs or antibiotics are extruded across the cell membrane by multidrug transporters. The multidrug and toxic compound extrusion (MATE) transporter is one of the five families of multidrug transporters. MATE from Pyrococcus furiosus uses H(+) to transport a substrate from the cytoplasm to the outside of a cell. Crystal structures of MATE from P. furiosus provide essential information on the relevant H(+)-binding sites (D41 and D184). Hybrid quantum mechanical/molecular mechanical simulations and continuum electrostatic calculations on the crystal structures predict that D41 is protonated in one structure (Straight) and, both D41 and D184 protonated in another (Bent). All-atom molecular dynamics simulations suggest a dynamic equilibrium between the protonation states of the two aspartic acids and that the protonation state affects hydration in the substrate binding cavity and lipid intrusion in the cleft between the N- and C-lobes. This hypothesis is examined in more detail by quantum mechanical/molecular mechanical calculations on snapshots taken from the molecular dynamics trajectories. We find the possibility of two proton transfer (PT) reactions in Straight: the 1st PT takes place between side-chains D41 and D184 through a transient formation of low-barrier hydrogen bonds and the 2nd through another H(+) from the headgroup of a lipid that intrudes into the cleft resulting in a doubly protonated (both D41 and D184) state. The 1st PT affects the local hydrogen bond network and hydration in the N-lobe cavity, which would impinge on the substrate-binding affinity. The 2nd PT would drive the conformational change from Straight to Bent. This model may be applicable to several prokaryotic H(+)-coupled MATE multidrug transporters with the relevant aspartic acids. PMID:27028644

  15. Asymmetric Hydrogenation of 3-Substituted Pyridinium Salts.

    Science.gov (United States)

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

    2016-07-01

    The use of an equivalent amount of an organic base leads to high enantiomeric excess in the asymmetric hydrogenation of N-benzylated 3-substituted pyridinium salts into the corresponding piperidines. Indeed, in the presence of Et3 N, a Rh-JosiPhos catalyst reduced a range of pyridinium salts with ee values up to 90 %. The role of the base was elucidated with a mechanistic study involving the isolation of the various reaction intermediates and isotopic labeling experiments. Additionally, this study provided some evidence for an enantiodetermining step involving a dihydropyridine intermediate. PMID:27140832

  16. Engineered Asymmetric Synthetic Vesicles

    Science.gov (United States)

    Lu, Li; Chiarot, Paul

    2013-11-01

    Synthetic vesicles are small, fluid-filled spheres that are enclosed by a bilayer of lipid molecules. They can be used as models for investigating membrane biology and as delivery vehicles for pharmaceuticals. In practice, it is difficult to simultaneously control membrane asymmetry, unilamellarity, vesicle size, vesicle-to-vesicle uniformity, and luminal content. Membrane asymmetry, where each leaflet of the bilayer is composed of different lipids, is of particular importance as it is a feature of most natural membranes. In this study, we leverage microfluidic technology to build asymmetric vesicles at high-throughput. We use the precise flow control offered by microfluidic devices to make highly uniform emulsions, with controlled internal content, that serve as templates to build the synthetic vesicles. Flow focusing, dielectrophoretic steering, and interfacial lipid self-assembly are critical procedures performed on-chip to produce the vesicles. Fluorescent and confocal microscopy are used to evaluate the vesicle characteristics.

  17. 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.

  18. Iron-, Cobalt-, and Nickel-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric Hydrogenation of Ketones.

    Science.gov (United States)

    Li, Yan-Yun; Yu, Shen-Luan; Shen, Wei-Yi; Gao, Jing-Xing

    2015-09-15

    Chiral alcohols are important building blocks in the pharmaceutical and fine chemical industries. The enantioselective reduction of prochiral ketones catalyzed by transition metal complexes, especially asymmetric transfer hydrogenation (ATH) and asymmetric hydrogenation (AH), is one of the most efficient and practical methods for producing chiral alcohols. In both academic laboratories and industrial operations, catalysts based on noble metals such as ruthenium, rhodium, and iridium dominated the asymmetric reduction of ketones. However, the limited availability, high price, and toxicity of these critical metals demand their replacement with abundant, nonprecious, and biocommon metals. In this respect, the reactions catalyzed by first-row transition metals, which are more abundant and benign, have attracted more and more attention. As one of the most abundant metals on earth, iron is inexpensive, environmentally benign, and of low toxicity, and as such it is a fascinating alternative to the precious metals for catalysis and sustainable chemical manufacturing. However, iron catalysts have been undeveloped compared to other transition metals. Compared with the examples of iron-catalyzed asymmetric reduction, cobalt- and nickel-catalyzed ATH and AH of ketones are even seldom reported. In early 2004, we reported the first ATH of ketones with catalysts generated in situ from iron cluster complex and chiral PNNP ligand. Since then, we have devoted ourselves to the development of ATH and AH of ketones with iron, cobalt, and nickel catalysts containing novel chiral aminophosphine ligands. In our study, the iron catalyst containing chiral aminophosphine ligands, which are expected to control the stereochemistry at the metal atom, restrict the number of possible diastereoisomers, and effectively transfer chiral information, are successful catalysts for enantioselective reduction of ketones. Among these novel chiral aminophosphine ligands, 22-membered macrocycle P2N4

  19. 金鸡纳生物碱-9-O-三甲基硅衍生物催化的不对称“中断”Feist-Bénary反应%Cinchona Alkaloid-9-O-trimethylsilyl Derivatives as Organocatalysts for the Asymmetric Interrupted” Feist-Bénary Reaction

    Institute of Scientific and Technical Information of China (English)

    金瑛; 张天一; 昌盛

    2012-01-01

    Cinchona alkaloid-9-0-trimethylsilyl(TMS) derivatives have been used to catalyze the asymmetric interrupted " Feist-B6nary reaction of ethyl bromopyruvate/substituted bromo-ketoesters with 1,3-cyclohexadione. The corresponding hydroxydihydrofurans have been obtained in excellent yields (85% ~ 97% ) and with up to 90% ee value.%将6种金鸡纳生物碱-9-O-三甲基硅(TMS)衍生物用于催化环己二酮与溴乙酰甲酸乙酯/β取代的溴乙酰甲酸乙酯的不对称“中断的”Feist-Bénary反应,得到了高的化学产率(85%~97%)和最高达90%ee的立体选择性.

  20. 金鸡纳生物碱-9-O-脯氨酸酯衍生物催化的不对称“中断的”Feist-Bénary反应%Cinchona alkaloid-9-O-proline ester derivatives as organocatalysts for asymmetric “ interrupted” Feist-Bénary reaction

    Institute of Scientific and Technical Information of China (English)

    张天一; 张巍; 李妍; 金瑛

    2012-01-01

    4种金鸡纳生物碱-9-O-脯氨酸酯衍生物用于催化环己二酮与溴乙酰甲酸乙酯的不对称“中断的”Feist-Bénary反应,得到了高的化学产率(>92%)和最高为72% e.e.的立体选择性.%Four cinchona alkaloid-9-O-proline ester derivatives were used to catalyze the asymmetric " interrupted " Feist-B6nary reaction of ethyl bromopyruvate bromo-ketoesters and 1,3-cyclohexadione. The corresponding hydroxydihydro-furans were obtained in excellent yields ( > 92% ) and with up to 72% e. e. .

  1. I-V-T studies on Ni-silicide/n-Si(100) contacts formed by Ti-Ni-Si solid state reaction

    Institute of Scientific and Technical Information of China (English)

    Zhu Shi-Yang; Ru Guo-Ping; Zhou Jia; Huang Yi-Ping

    2005-01-01

    The current-voltage (I-V) characteristics of Ni silicide/n-Si(100) contacts, which were formed from solid-state reaction of Ni-Si with a thin Ti capping layer at different annealing temperatures, were measured at temperatures ranging from 80K to room temperature. The low temperature I-V curves exhibit an excess current at the low bias region which is significantly larger than that predicted by the traditional thermionic emission (TE) model. A doubleSchottky barrier height (SBH) model simplified from Tung's pinch-off model is used to analyse the measured I-V curves,from which the extent of the SBH inhomogeneity can be extracted. Higher annealing temperature results in larger SBH inhomogeneity, implying the degradation of the silicide film uniformity. The thin Ti capping layer increases slightly both the NiSi phase transfer temperature and the thermal stability of the formed NiSi film.

  2. Asymmetric dynamic phase holographic grating in nematic liquid crystal

    Science.gov (United States)

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

    2016-09-01

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

  3. RESEARCH ON HETEROLOGOUS REPLAY ATTACK AIMING AT ASP.NET FORMS AUTHENTICATION AND ITS REACTION%针对 ASP.net Forms 认证的异源重放攻击研究及应对

    Institute of Scientific and Technical Information of China (English)

    孙伟; 张永; 王占

    2015-01-01

    采用 Forms 认证的 ASP.net 网站容易受到重放攻击的威胁。介绍 ASP.net Forms 认证一般性实施方法,分析 Forms 认证的原理,给出重放攻击的原理性实施方法,并对重放攻击得逞的原因进行分析。在此基础上,通过引入更加严谨的会话概念,提出基于会话识别的异源重放攻击应对方案。该方案通过对会话的严格管理,识别客户端的变化,适时地要求用户输入原始认证信息,例如,用户名和密码,进行身份认证,达到应对重放攻击的目的。最后,代码实现和理论分析均表明,所提出的应对方案能够有效地应对异源重放攻击。%ASP.net websites with Forms authentication are subject to the menace from replay attacks.In this paper,we introduce the gen-eral realisation process of ASP.net Forms authentication,analyse the principle of Forms authentication,give a principle realisation means of the replay attacks and analyse the reason why the replay attacks can be success.Based on these,we propose a session recognition-based reac-tion scheme against heterologous replay attacks through introducing the concept of more scrupulous session.This scheme achieves the goal of thwarting the replay attacks by managing sessions rigorously and identifying client changes,and duly asking the clients to input their primitive authentication information,e.g.users’name and passwords,for identities authentication.Finally,the prototype realisation and theoretical analysis both prove that the proposed reaction scheme can thwart heterologous replay attacks effectively.

  4. Study of the p(e,e'π+)n electro-production reaction: form factor and electromagnetic radius of pion

    International Nuclear Information System (INIS)

    After having recalled the definitions and theoretical knowledge on the form factor and electromagnetic radius of hadron and pion, and discussed the relationship between electro-production and form factor for the pion, this research thesis recalls some theoretical aspects of the electro-production process. The author discusses the reaction kinematics and shows how the electro-production cross section can be broken down in terms of photon polarization. Then, he focuses on the cross section dynamic structure. After having recalled the different possible choices for amplitudes, he studies their behaviour, firstly within the framework of the Born approximation, and then within the framework of commonly used models, notably to take the resonant part of the phenomenon into account. The limits of the different models are outlined. The second part addresses the study of forward electro-production. The author shows how the pion form factor can be simply optimized. The author describes the experimental arrangement: electron beam and liquid hydrogen target, detection system, normalisation device, data acquisition logics. In the next chapter, the author describes how data are recorded until the obtainment of N electro-production events. Results are then interpreted in terms of form factor and electromagnetic radius. They are also compared with published results obtained with other electro-production experiments or measurements based on other processes

  5. Twin Higgs Asymmetric Dark Matter.

    Science.gov (United States)

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

    2015-09-18

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

  6. Twin Higgs Asymmetric Dark Matter.

    Science.gov (United States)

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

    2015-09-18

    We study asymmetric dark matter (ADM) in the context of the minimal (fraternal) twin Higgs solution to the little hierarchy problem, with a twin sector with gauged SU(3)^{'}×SU(2)^{'}, a twin Higgs doublet, and only third-generation twin fermions. Naturalness requires the QCD^{'} scale Λ_{QCD}^{'}≃0.5-20  GeV, and that t^{'} is heavy. We focus on the light b^{'} quark regime, m_{b^{'}}≲Λ_{QCD}^{'}, where QCD^{'} is characterized by a single scale Λ_{QCD}^{'} with no light pions. A twin baryon number asymmetry leads to a successful dark matter (DM) candidate: the spin-3/2 twin baryon, Δ^{'}∼b^{'}b^{'}b^{'}, with a dynamically determined mass (∼5Λ_{QCD}^{'}) in the preferred range for the DM-to-baryon ratio Ω_{DM}/Ω_{baryon}≃5. Gauging the U(1)^{'} group leads to twin atoms (Δ^{'}-τ^{'}[over ¯] bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors. PMID:26430985

  7. Asymmetric Gepner Models (Revisited)

    CERN Document Server

    Gato-Rivera, B

    2010-01-01

    We reconsider a class of heterotic string theories studied in 1989, based on tensor products of N=2 minimal models with asymmetric simple current invariants. We extend this analysis from (2,2) and (1,2) spectra to (0,2) spectra with SO(10) broken to the Standard Model. In the latter case the spectrum must contain fractionally charged particles. We find that in nearly all cases at least some of them are massless. However, we identify a large subclass where the fractional charges are at worst half-integer, and often vector-like. The number of families is very often reduced in comparison to the 1989 results, but there are no new tensor combinations yielding three families. All tensor combinations turn out to fall into two classes: those where the number of families is always divisible by three, and those where it is never divisible by three. We find an empirical rule to determine the class, which appears to extend beyond minimal N=2 tensor products. We observe that distributions of physical quantities such as th...

  8. 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.

  9. 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...

  10. Catalytic Asymmetric Total Synthesis of Hedyosumins A, B, and C.

    Science.gov (United States)

    Sun, Wang-Bin; Wang, Xuan; Sun, Bing-Feng; Zou, Jian-Ping; Lin, Guo-Qiang

    2016-03-18

    The first and asymmetric total synthesis of hedyosumins A, B, and C was accomplished in 13-14 steps from simple starting materials. The essential tools that allow us to access the tetracyclic skeleton include an organocatalytic [4 + 3] cycloaddition reaction, an intramolecular aldol condensation, and an intramolecular carboxymercuration/demercuration enabled lactonization. A CBS-catalyzed asymmetric reduction was employed to boost the ee of the synthetic natural products to an excellent level. This synthesis established the absolute configurations of hedyosumins A, B, and C. PMID:26925758

  11. On Asymmetric Quantum MDS Codes

    CERN Document Server

    Ezerman, Martianus Frederic; Ling, San

    2010-01-01

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

  12. Mobile Termination with Asymmetric Networks

    OpenAIRE

    Dewenter, Ralf; Haucap, Justus

    2003-01-01

    This paper examines mobile termination fees and their regulation when networks are asymmetric in size. It is demonstrated that with consumer ignorance about the exact termination rates (a) a mobile network?s termination rate is the higher the smaller the network?s size (as measured through its subscriber base) and (b) asymmetric regulation of only the larger operators in a market will, ce-teris paribus, induce the smaller operators to increase their termination rates. The results are supporte...

  13. Asymmetric New Product Development Alliances: Win-Win or Win-Lose Partnerships?

    OpenAIRE

    Kartik Kalaignanam; Venkatesh Shankar; Rajan Varadarajan

    2007-01-01

    Interorganizational alliances are widely recognized as critical to product innovation, particularly in high-technology markets. Many new product development (NPD) alliances tend to be asymmetric, that is, they are formed between a larger firm and a smaller firm. As is the case with alliances in general, asymmetric alliances also typically result in changes in the shareholder values of the partner firms. Are the changes in shareholder values of the partner firms significant? Are asymmetric NPD...

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

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

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

  15. Antioxidant activity of the melanoidin fractions formed from DGlucose and D-Fructose with L-Asparagine in the Maillard reaction

    Directory of Open Access Journals (Sweden)

    A.P Echavarría

    2013-03-01

    Full Text Available Melanoidins formed at the last stage of the Maillard reaction have been shown to possess certain functional properties, such as antioxidant activity. In order to gain more insight into these functional properties, soluble model systems melanoidins from L‑Asparagine with D‑glucose or D‑fructose fractionating by ultrafiltration were analyzed. The fractionating/concentration sequence of the melanoidin fraction (1-300 kDa enabled five fractions to be produced.Additionally, the absorption of melanoidins was measured at different wavelengths (280, 325, 405 and browning at 420 nm. The fractionation effect of melanoidin systems on the color intensity, UV-absorbance scan wavelengths (nm, CIE, L*, a*, b* parameters and antioxidant activity were measured. For this purpose, antioxidant activity was evaluated through the free radical scavenging activity, including 1,1-diphenyl-2-picryl-hydrazil (DPPH and 2,20-azinobis (3-ethylbenothiazoline-6-sulfonic acid, diammonium salt (ABTS. The results showed that the absorption of the melanoidins formed from Glucose/L-Asn was higher than for those derived from Fructose/L-Asn. On the other hand, their antioxidant power was lower than that for melanoidins formed from Fructose/L-Asn systems.

  16. Flexible Asymmetric Encapsulation for Dehydration-Responsive Hybrid Microfibers.

    Science.gov (United States)

    Chaurasia, Ankur S; Sajjadi, Shahriar

    2016-08-01

    A new class of smart alginate microfibers with asymmetric oil encapsulates is introduced. These fibers are produced by injecting an aqueous alginate solution into an outer aqueous calcium chloride solution to form alginate fibers, which are asymmetrically loaded with oil entities through eccentrically aligned inner capillaries. The fiber morphology and its degree of asymmetry can be tuned via altering the size, location, and frequency of the oil encapsulates. These asymmetric fibers reveal significant potential for applications where conventional symmetric fibers fail to perform. It is shown how asymmetric oil-encapsulated fibers can become dehydration-sensitive, and trigger the release of encapsulates if their hydration level drops below a critical value. It is also shown how the triggered response could be switched off on demand by stabilizing the oil encapsulates. The capability of asymmetric fibers to carry and release multiple cargos in parallel is demonstrated. The fibers loaded with equal-sized spheres are more asymmetric than those containing unequal drops, have a higher tensile strength, and show better potential for a triggered response. PMID:27352241

  17. Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

    Science.gov (United States)

    Sidera, Mireia; Fletcher, Stephen P.

    2015-11-01

    Csp2-Csp2 cross-coupling reactions between arylboronic acid and aryl halides are widely used in both academia and industry and are strategically important in the development of new agrochemicals and pharmaceuticals. Csp2-Csp3 cross-coupling reactions have been developed, but enantioselective variations are rare and simply retaining the stereochemistry is a problem. Here we report a highly enantioselective Csp2-Csp3 bond-forming method that couples arylboronic acids to racemic allyl chlorides. Both enantiomers of a cyclic chloride are converted into a single enantiomer of product via a dynamic kinetic asymmetric transformation. This Rh-catalysed method uses readily available and inexpensive building blocks and is mild and broadly applicable. For electron-deficient, electron-rich or ortho-substituted boronic acids better results are obtained with racemic allyl bromides. Oxygen substitution in the allyl halide is tolerated and the products can be functionalized to provide diverse building blocks. The approach fills a significant gap in the methods for catalytic asymmetric synthesis.

  18. Rencent Advances in Asymmetric Organic Reactions Catalyzed by Bifunctional Amine- thioureas%双官能团硫脲-胺催化剂催化不对称有机反应的研究进展

    Institute of Scientific and Technical Information of China (English)

    史艳娜; 孙传智; 孙南

    2012-01-01

    双官能团硫脲-胺催化剂因在不对称催化反应中表现出的高效、高对映选择性而受到广泛关注,已成功应用于催化各种不对称有机反应中,本文简述了双官能团硫脲-胺催化剂在Michael加成、1,2加成以及Michael-type串联反应中应用的研究进展。%Bifunctional amine -thiourea has received increasing attention as a highly efficient and enantioselective catalyst. It has been used for various reactions extensively. The applications of the catalyst in asyrmnetric Michael addition, 1,2 -addition, Michael- type cascade reaction were reviewed.

  19. Niobium nitride films formed by rapid thermal processing (RTP): a study of depth profiles and interface reactions by complementary analytical techniques.

    Science.gov (United States)

    Berendes, A; Brunkahl, O; Angelkort, C; Bock, W; Hofer, F; Warbichler, P; Kolbesen, B O

    2004-06-01

    The nitridation of niobium films approximately 250 and 650 nm thick by rapid thermal processing (RTP) at 800 degrees C in molecular nitrogen or ammonia was investigated. The niobium films were deposited by electron beam evaporation on silicon substrates covered by a 100 or 300 nm thick thermally grown SiO(2) layer. In these investigations the reactivity of ammonia and molecular nitrogen was compared with regard to nitride formation and reaction with the SiO(2) substrate layer. The phases formed were characterized by X-ray diffraction (XRD). Depth profiles of the elements in the films were recorded by use of secondary neutral mass spectrometry (SNMS). Microstructure and spatial distribution of the elements were imaged by transmission electron microscopy (TEM) and energy-filtered TEM (EFTEM). Electron energy loss spectra (EELS) were taken at selected positions to discriminate between different nitride, oxynitride, and oxide phases. The results provide clear evidence of the expected higher reactivity of ammonia in nitride formation and reaction with the SiO(2) substrate layer. Outdiffusion of oxygen into the niobium film and indiffusion of nitrogen from the surface of the film result in the formation of oxynitride in a zone adjacent to the Nb/SiO(2) interface. SNMS profiles of nitrogen reveal a distinct tail which is attributed to enhanced diffusion of nitrogen along grain boundaries. PMID:15098081

  20. The Charge Form Factor of the Neutron from the Reaction $^{2}\\overrightarrow{H} (\\overrightarrow{e}, e^{'}n)p$

    CERN Document Server

    Passchier, I; Bauer, T; Boersma, D J; Van den Brand, J F J; Van Buuren, L D; Bulten, H J; Ferro-Luzzi, M; Heimberg, P; Higinbotham, D W; De Jager, C W; Klous, S; Kolster, H; Lang, J; Militsyn, B L; Nikolenko, D M; Nooren, G J L; Norum, B E; Poolman, H R; Rachek, Igor A; Simani, M C; Six, E; Szczerba, D; De Vries, H; Wang, K; Bauer, Th. S.

    1999-01-01

    We report on the first measurement of spin-correlation parameters in quasifree electron scattering from vector-polarized deuterium. Polarized electrons were injected into an electron storage ring at a beam energy of 720~MeV. A Siberian snake was employed to preserve longitudinal polarization at the interaction point. Vector-polarized deuterium was produced by an atomic beam source and injected into an open-ended cylindrical cell, internal to the electron storage ring. The spin correlation parameter A^V_{ed} was measured for the reaction \\pol{2H}(\\pol{e},e'n)p at a four-momentum transfer squared of 0.21 (GeV/c)^2 from which a value for the charge form factor of the neutron was extracted.

  1. The Charge Form Factor of the Neutron from the Reaction {sup 2}{rvec H}({rvec e},e{prime}n)p

    Energy Technology Data Exchange (ETDEWEB)

    I. Passchier; R. Alarcon; Th. S. Bauer; D. Boersma; J. F. J. van den Brand; L. D. van Buuren; H. J. Bulten; M. Ferro-Luzzi; P. Heimberg; D. W. Higinbotham; C. W. de Jager; S. Klous; H. Kolster; J. Lang; B. L. Militsyn; D. Nikolenko; G. J. L. Nooren; B. E. Norum; H. R. Poolman; I. Rachek; M. C. Simani; E. Six; D. Szczerba; H. de Vries; K. Wang

    1999-06-21

    We report on the first measurement of spin-correlation parameters in quasifree electron scattering from vector-polarized deuterium. Polarized electrons were injected into an electron storage ring at a beam energy of 720 MeV. A Siberian snake was employed to preserve longitudinal polarization at the interaction point. Vector-polarized deuterium was produced by an atomic beam source and injected into an open-ended cylindrical cell, internal to the electron storage ring. The spin correlation parameter A{sub ed}{sup V} was measured for the reaction {sup 2}{rvec H}({rvec e},e{prime}n)p at a four-momentum transfer squared of 0.21 (GeV/c){sup 2} from which a value for the charge form factor of the neutron was extracted.

  2. Adiabatic and sudden interaction potentials in the fusion-fission of heavy ion collisions: Asymmetric target-projectile combinations

    International Nuclear Information System (INIS)

    It is now well known that many reactions giving measurable fusion cross-sections also show a fission of the compound system formed, similar to the low energy fission of the known fissioning nuclei. Recently, both the fusion excitation functions and the mass equilibration in the fragmentation of the composite system were measured for a large number of systems with 94208Pb on different targets of 26Mg, 48Ca, 50Ti, 52Cr, 58Fe and 64Ni. From a theoretical point of view, it is relevant to ask the question: how do the colliding nuclei fuse and then why does the compound system formed fission instead of going to the ground state to give a stable system. In this Letter, we attempt to show that the fusion of asymmetric colliding nuclei is due to the overcoming of the interaction barriers in adiabatic potentials and the fission of the compound system should perhaps occur as a sudden process, like the one in the spontaneous fission phenomenon. We have made our calculations for the compound systems with 102<=Z<=110 and for the asymmetric target-projectile combinations of the experiments of Ref. 1, using the fragmentation theory whose basis is the asymmetric two-centre shell model

  3. The reaction between ZnO and Molten K2S2O7 forming K2Zn(SO4)2, studied by Raman and IR Spectroscopy and X-ray Diffraction

    DEFF Research Database (Denmark)

    Berg, Rolf W.; Nielsen, Kurt; Boghosian, Soghomon

    1999-01-01

    The reaction between zinc oxide and molten potassium pyrosulfate at 500 °C was shown by Raman spectroscopy to be a 1:1 reaction. By lovering the temperature, colorless crystals could be formed. The crystal structure was determined: Space group = P21/c, Z = 4, a = 5.3582(11), b = 8.7653(18), c = 1...

  4. Plasma current resonance in asymmetric toroidal systems

    Energy Technology Data Exchange (ETDEWEB)

    Hazeltine, R. D. [Institute for Fusion Studies, University of Texas at Austin, Austin, Texas 78712 (United States); Catto, Peter J. [Plasma Science and Fusion Center, Massachusetts Institute of Technology, 167 Albany Street, Cambridge, Massachusetts 02139 (United States)

    2015-09-15

    The well-known singularity in the magnetic differential equation for plasma current in an asymmetric toroidal confinement system is resolved by including in the pressure tensor corrections stemming from finite Larmor radius. The result provides an estimate of the amplitude of spikes in the parallel current that occur on rational magnetic surfaces. Resolution of the singularity is shown to depend on both the ambipolarity condition—the requirement of zero surface-averaged radial current—and the form of the magnetic differential equation near the rational surface.

  5. Reaction of Pb(II) and Zn(II) with Ethyl Linoleate To Form Structured Hybrid Inorganic–Organic Complexes: A Model for Degradation in Historic Paint Films

    Energy Technology Data Exchange (ETDEWEB)

    MacDonald, Margaret G.; Palmer, Michael R.; Suchomel, Matthew R.; Berrie, Barbara H. (NGA); (Bordeaux)

    2016-09-23

    To investigate soap formation in drying oils in historic paints, the reaction between metal acetates (K+, Zn2+, Pb2+) and ethyl linoleate (EL) was studied using optical microscopy, X-ray powder diffraction, and electron microscopy. Pb(II) and Zn(II) react rapidly with EL to form highly structured, spherulitic, luminescent crystallites that aggregate. Evidence from Fourier transform infrared (FTIR) and scanning electron microscopy/energy dispersive X-ray analysis and high-resolution synchrotron powder X-ray diffraction indicates that these are organic–inorganic hybrid complexes or coordination polymers. FTIR absorbance peaks at ca. 1540 cm–1 for Pb(II) and ca. 1580 cm–1 for Zn(II) are consistent with the formation of carboxylate complexes. The complexes formed offer insight into the degradation processes observed in oil paint films, suggesting that soap formation is rapid when metal ions are solubilized and can occur with unsaturated fatty acids that are present in fresh oils. These complexes may account for the atypical luminescence observed in lead-containing cured oil paint films.

  6. Process for fabricating PBI hollow fiber asymmetric membranes for gas separation and liquid separation

    Energy Technology Data Exchange (ETDEWEB)

    Jayaweera, Indira; Krishnan, Gopala N.; Sanjurjo, Angel; Jayaweera, Palitha; Bhamidi, Srinivas

    2016-04-26

    The invention provides methods for preparing an asymmetric hollow fiber, the asymmetric hollow fibers prepared by such methods, and uses of the asymmetric hollow fibers. One method involves passing a polymeric solution through an outer annular orifice of a tube-in-orifice spinneret, passing a bore fluid though an inner tube of the spinneret, dropping the polymeric solution and bore fluid through an atmosphere over a dropping distance, and quenching the polymeric solution and bore fluid in a bath to form an asymmetric hollow fiber.

  7. Crystal structure of a nucleoside model for the inter-strand cross-link formed by the reaction of 2'-de-oxy-guanosine and an abasic site in duplex DNA.

    Science.gov (United States)

    Catalano, Michael J; Ruddraraju, Kasi Viswanatharaju; Barnes, Charles L; Gates, Kent S

    2016-05-01

    The title compound, 9-[(2R,4S,5R)-4-hy-droxy-5-(hy-droxy-meth-yl)tetra-hydro-furan-2-yl]-2-{[(2R,4S,5R)-4-meth-oxy-5-(meth-oxy-meth-yl)tetra-hydro-furan-2-yl]amino}-1H-purin-6(9H)-one, C17H25N5O7, crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. In the crystal, the guanosine moieties of mol-ecules A and B are linked by N-H⋯N and O-H⋯N hydrogen-bonding inter-actions, forming ribbons which are stacked to form columns along [100]. These columns are then linked by O-H⋯O hydrogen bonds between the ribose moieties and numerous C-H⋯O inter-actions to complete the three-dimensional structure. PMID:27308004

  8. Organizing for Asymmetric Collaboration

    DEFF Research Database (Denmark)

    Nielsen, Jørn Flohr; Sørensen, Henrik B.

    ' different motives and different situational factors appear in an interorganizational setting. We classify interfaces according to the symmetry/asymmetry in the respective parent organizations' resources, commitment, and control of representatives and indicate how  classification schemes can be used......  The vision of new organizational forms consists of less-organized networks and alliances between organizations, in which collaborative capabilities are assumed to be crucial (Miles et al., 2005). The path to such new forms may go through fragile cooperative efforts. Despite the good will of many...

  9. 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.

  10. Asymmetric Strecker-Type Reaction of alpha-Aryl Ketones. Synthesis of (S)-alphaM4CPG, (S)-MPPG, (S)-AIDA, and (S)-APICA, the Antagonists of Metabotropic Glutamate Receptors.

    Science.gov (United States)

    Ma, Dawei; Tian, Hongqi; Zou, Guixiang

    1999-01-01

    Heating a mixture of alpha-aryl ketone with (R)-phenylglycinol produces a mixture of imine and 1,3-dioxazolidine. Treatment of this mixture with trimethylsilyl cyanide followed by transformation of nitrile to ester gives Strecker-type reaction products. The diastereoselectivity of the generated alpha-amino esters is from 2/1 to 7/1, and the (R,S)isomer is found as the major product. The (R,S) and (R,R)isomers can be separated by conversion to their N-Cbz or cyclization derivatives. Using this methodology, four antagonists of metabotropic glutamate receptors, (S)-alphaM4CPG, (S)-MPPG, (S)-AIDA, and (S)-APICA, are synthesized. PMID:11674092

  11. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

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

    1996-01-01

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

  12. Ideal 3D asymmetric concentrator

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-01-15

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

  13. Incompressibility of asymmetric nuclear matter

    OpenAIRE

    Chen, Lie-Wen; Cai, Bao-Jun; Shen, Chun; Ko, Che Ming; Xu, Jun; Li, Bao-An(Department of Physics and Astronomy, Texas A&M University-Commerce, Commerce, TX, 75429-3011, USA)

    2009-01-01

    The incompressibility $K_sat(\\delta)$ of isospin asymmetric nuclear matter at its saturation density. Our results show that in the expansion of $K_sat(\\delta)$ in powers of isospin asymmetry $\\delta$, i.e., $K_sat(\\delta )$=K_{0}+K_{sat,2}\\delta^{2}+K_{sat,4}\\delta^{4}+O(\\delta^{6})$, the magnitude of the 4th-order K_{sat,4} parameter is generally small. The 2nd-order K_{sat,2} parameter thus essentially characterizes the isospin dependence of the incompressibility of asymmetric nuclear matte...

  14. Forces between asymmetric polymer brushes

    OpenAIRE

    Shim, D.F.K.; Cates, M. E.

    1990-01-01

    We study the equilibrium compression of asymmetric polymer brushes grafted on flat plates, under athermal and theta solvent conditions, using a lattice self-consistent field (SCF) approach. We find that the separation d between two plates coated asymmetrically with brushes of type 1 and 2, as a function of the force F, obeys the "bisection rule", d(F) = (d1(F) + d 2(F)) /2 where d1(F)and d 2(F) are the corresponding separations for the symmetric brushes of type 1 and 2 respectively.The bisect...

  15. Research on asymmetric "Jerusalem" unit

    Institute of Scientific and Technical Information of China (English)

    Jun Lu; Jianbo Wang

    2009-01-01

    An asymmetric Jerusalem unit and the frequency selective surface(FSS)structure composed of such units are designed.The transmittance of the designed FSS structure is calculated by mode-matching method and compared with the test results.The comparison results show that the FSS center frequency of the asymmetric structure unit drifts little with the variation of the incident angles of the electromagnetic waves and keeps relatively stable.The research offers a new choice for the application of FSS under the large scanning angle of electromagnetic waves.

  16. A Novel Asymmetric ent-Kauranoid Dimer from Isodon enanderianus

    Institute of Scientific and Technical Information of China (English)

    NA,Zhi(纳智); LI,Sheng-Hong(黎胜红); XIANG,Wei(项伟); ZHAO,Ai-Hua(赵爱华); LI,Chao-Ming(李朝明); SUN,Han-Dong(孙汉董)

    2002-01-01

    Further investigation on the aerial parts of Isodon enanderianus afforded a novel asymmetric ent-kauranoid dimer, enanuderinaninJ (1). The structure of the dimer was elucidated by means of spectroscopic methods (including 2D NMR techniques ). Enanderinanin J was a dimer of xerophilusin A and probably formed by [ 4 + 2] cycloaddition.

  17. A Nove Asymmetric ent—Kauranoid Dimer from Isodon enanderianus

    Institute of Scientific and Technical Information of China (English)

    纳智; 黎胜红; 等

    2002-01-01

    Further investigation on the aerial parts of Isodon enanderianus afforded a novel asymmetric ent-kauranoid dimer,enanderi-nanin J(1).The structure of the dimer was elucidated by means of spectroscopic methods (including 2D NMR tecniques ),Enanderinanin J was a dimer of xerophilusin A and probably formed by [4+2] cycloaddition.

  18. Bisimulation Lattice of Asymmetric Chi Calculus with Mismatch

    Institute of Scientific and Technical Information of China (English)

    Dong Xiaoju(董笑菊); Zhong Farong; Fu Yuxi

    2003-01-01

    This paper carries out a systematic investigation into the bisimulation lattice of asymmetric chi calculus with a mismatch combinator. It is shown that all the sixty three L-bisimilarities collapse to twelve distinct relations and they form a bisimulation lattice with respect to set inclusion. The top of the lattice coincides with the barbed bisimilarity.

  19. Passive vibro-acoustic detection of a sodium-water reaction in a steam generator of a sodium-cooled fast neutrons nuclear reactor by beam forming

    International Nuclear Information System (INIS)

    This thesis deals with a new method to detect a sodium-water reaction in a steam generator of a fast sodium-cooled nuclear reactor. More precisely, the objective is to detect a micro-leak of water (flow ≤ 1 g/s) in less than 10 seconds by measuring the external shell vibrations of the component. The strong background noise in operation makes impossible the use of a detection system based on a threshold overrun. A beam forming method applied to vibrations measured by a linear array of accelerometers is developed in this thesis to increase the signal-to-noise ratio and to detect and locate the leak in the steam generator. A numerical study is first realized. Two models are developed in order to simulate the signals measured by the accelerometers of the array. The performances of the beam forming are then studied in function of several parameters, such as the source location and frequency, the damping factor, the background noise considered. The first model consists in an infinite plate in contact with a heavy fluid, excited by an acoustic monopole located in this fluid. Analyzing the transverse displacements in the wavenumber domain is useful to establish a criterion to sample correctly the vibration field of the plate. A second model, more representative of the system is also proposed. In this model, an elastic infinite cylindrical shell, filled with a heavy fluid is considered. The finite dimensions in the radial and circumferential directions lead to a modal behavior of the system which impacts the beam forming. Finally, the method is tested on an experimental mock-up which consists in a cylindrical pipe made in stainless steel and filled with water connected to hydraulic circuit. The water flow speed can be controlled by varying the speed of the pump. The acoustic source is generated by a hydro-phone. The performances of the beam forming are studied for different water flow speeds and different amplitude and frequencies of the source. (author)

  20. Asymmetric Parton Distributions

    CERN Document Server

    Radyushkin, A V

    1997-01-01

    Applications of perturbative QCD to hard exclusive electroproduction processes in the Bjorken limit at small invariant momentum transfer t bring in a new type of parton distributions which have hybrid properties, resembling both the parton distribution functions and the distribution amplitudes. Their t-dependence is analogous to that of hadronic form factors. We discuss general properties of these new parton distributions, their relation to usual parton densities and the evolution equations which they satisfy.

  1. Highly Enantioselective Organocatalytic Asymmetric Mukaiyama-aldol Reaction of Difluoroenoxysilanes with β,γ-Unsaturated α-Ketoesters%高对映选择性的有机催化的二氟烯醇硅醚与β,γ-不饱和-α-酮酸酯的不对称Mukaiyama-aldol反应

    Institute of Scientific and Technical Information of China (English)

    刘运林; 周剑

    2012-01-01

    We report the first example of catalytic asymmetric reaction of difluoroenoxysilanes 1 and β,γ-unsaturated α-ketoesters 2. In the presence of tertiary amine or tertiary amine-H-bonding donor bifunctional catalysts, it was found that the reaction selectively took place at the ketone moiety of ketoesters 2, and no conjugate reaction happened. Hydronquinine derived urea catalyst 11 was identified as a powerful catalyst for this Mukaiyama-aldol reaction to finnish a-difluoroalkyl substituted tertiary alcohols in good to high yield (44%-81%), with moderate to excellent enantioselectivity (72%-96%). The optimum reaction condition was determined to run the reaction at -40 ℃ using THF as the solvent, in the presence of 10 mol% of chiral catalyst 11. The reaction possibly proceeded via the dual activation of both reaction partners: the tertiary amine moiety of catalyst 11 working as a Lewis base to activate difluoroenoxysilanes 1, while the urea part of the catalyst as a Bronsted acid to activate carbonyl group of ketoesters 2. Different aryl substituted difluoroenoxysilanes 1 and ),-aryl substi- tuted β,γ-unsaturated a-ketoesters 2 all worked well under the established reaction condition, with 15 examples provided. The thus obtained chiral α-difluoroalkyl substituted tertiary alcohols were not only valuable in the medicinal research, but also versatile building blocks for the synthesis of a variety of difluoroalkyl-substituted chiral compounds. For example, the selec- tive reduction of the ketone or ester group of product 3g has been realized by using NaBH4 or Et3SiH as the reducing agents, giving the triol 14 or diol 15 in moderate yield without the loss ofee.%首次研究了二氟烯醇硅醚1与β,γ-不饱和酮酸酯2的反应.发现不论使用叔胺或叔胺-氢键给体双功能催化剂,均专一地发生Mukaiyama-aldol反应生成相应的叔醇3.利用手性氢化奎宁衍生的双功能脲催化剂11高对映选择性地实现了这一反

  2. Generation of isolated asymmetric umbilics in light's polarization

    CERN Document Server

    Galvez, Enrique J; Kumar, Vijay; Viswanathan, Nirmal K

    2014-01-01

    Polarization-singularity C-points, a form of line singularities, are the vectorial counterparts of the optical vortices of spatial modes and fundamental optical features of polarization-spatial modes. Their generation in tailored beams has been limited to lemon and star C-points that contain symmetric dislocations in state-of-polarization patterns. In this article we present the theory and laboratory measurements of two complementary methods to generate isolated asymmetric C-points in tailored beams, of which symmetric lemons and stars are limiting cases; and we report on the generation of monstars, an asymmetric C-point with characteristics of both lemons and stars.

  3. Careful numerical study of flowfields about asymmetric external conical corners

    Science.gov (United States)

    Salas, M. D.

    1980-01-01

    A numerical study of the flowfield about asymmetrical external axial corners formed by the juncture of swept compressive wedges is presented. The geometrical configuration allows a unified treatment of external corners typical of delta wings and rectangular inlets. The study investigates how the flow transitions from a symmetrical flowfield with a cross-flow stagnation point at the corner to an asymmetrical flowfield for which the flow spills over the corner. The effects of leading-edge sweep, wedge compression, and corner radius are investigated.

  4. Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

    Science.gov (United States)

    Ryan, Michael C; Rao, Meera

    2016-01-01

    Summary A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent. PMID:27559366

  5. Development of chiral sulfoxide ligands for asymmetric catalysis.

    Science.gov (United States)

    Trost, Barry M; Rao, Meera

    2015-04-20

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

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

    Science.gov (United States)

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

    2013-02-01

    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.

  7. Asymmetric fuel share responses to relative price movements

    International Nuclear Information System (INIS)

    Following the fall in oil prices in 1986, and the lower-than-expected response of energy demand, recent work has focused upon the importance of asymmetric price elasticities of total energy demand. The irreversibility of new technology developed as a reaction to high price signals provides firm intuitive support for this idea. The unwillingness of consumers to believe that prices will remain low can also offer a basis for expecting asymmetry in lag structures: abstracting from technological development, the reactions to price movements may well be symmetrical, but will take longer to occur. Another general development, following the 1970s' price rises, has been the substantial fall in energy intensities in the OECD, leading to these economies becoming less exposed to external energy price 'shocks'. Therefore, some attention has also been focused upon asymmetric energy price impacts upon economic growth. (author)

  8. Catálise assimétrica na ciclopropanação de olefinas Asymmetric catalysis in the cyclopropanation of olefins

    Directory of Open Access Journals (Sweden)

    Raquel A. C. Leão

    2007-01-01

    Full Text Available The main methodologies in the asymmetric cyclopropanation of alkenes with emphasis on asymmetric catalysis are covered. Exemples are the Simmons-Smith reaction, the use of diazoalkanes and reactions carried out by decomposition of alpha-diazoesters in the presence of transition metals.

  9. High angular momentum decay properties of the compound systems 100Ru and 160Er formed in 50Ti-induced reactions

    International Nuclear Information System (INIS)

    The γ-decay from the evaporation residues formed in the 50Ti + 50Ti → 100Rusup(*) and 50Ti + 110Pd → 160Ersup(*) reactions with angular momentum up to the maximum these systems can sustain, has been studied utilizing a sum spectrometer in coincidence with two smaller NaI detectors. The excitation energy and average angular momentum are determined as a function of γ-ray cascade energy. Simultaneously, the structure of the γ-ray continuum and its multipolarity is obtained as a function of these two correlated parameters. From the centroid energy of quadrupole transitions between states confined to a narrow spin region an effective moment of inertia is extracted. For the products of the 100Ru compound system a large deformation, is indicated by a moment of inertia as large as 1.3 times the spherical rigid-body value for I approx. > 40 h/2π. This is considerably lower in angular momentum than the transition to triaxial shape predicted for a rotating liquid drop. The moment of inertia for the residues of the 160Er compound system is 5-15% larger than the spherical rigid body value. For both systems studied a considerable part of the decay is due to dipole transitions of rather low energy (< 1 MeV) even at the highes spins where a quadrupole bump is well developed. (orig.)

  10. Synthesis of Asymmetric Propanetriol Analogues

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

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

  11. Vertical asymmetric double quantum dots

    Science.gov (United States)

    Roßbach, R.; Reischle, M.; Beirne, G. J.; Schweizer, H.; Jetter, M.; Michler, P.

    2007-01-01

    Two layers of differently sized self-assembled InP-quantum dots (QDs) separated by a GaInP spacer layer with varying thickness were grown by metal organic vapor phase epitaxy (MOVPE). Photoluminescence measurements of the QD ensembles and of individual asymmetric double QDS show coupling due to the tunnelling of carriers.

  12. Asymmetrical Switch Costs in Children

    Science.gov (United States)

    Ellefson, Michelle R.; Shapiron, Laura R.; Chater, Nick

    2006-01-01

    Switching between tasks produces decreases in performance as compared to repeating the same task. Asymmetrical switch costs occur when switching between two tasks of unequal difficulty. This asymmetry occurs because the cost is greater when switching to the less difficult task than when switching to the more difficult task. Various theories about…

  13. Ballistic thermal rectification in asymmetric three-terminal graphene nanojunctions

    Science.gov (United States)

    Ouyang, Tao; Chen, Yuanping; Xie, Yuee; Wei, X. L.; Yang, Kaike; Yang, Ping; Zhong, Jianxin

    2010-12-01

    Graphene nanojunctions (GNJs) are important components of future nanodevices and nanocircuits. Using the nonequilibrium Green’s function method, we investigate the phononic properties of three-terminal GNJs (TGNJs). The results show that the heat flux runs preferentially along the direction from narrow to wide terminals, presenting an evident ballistic thermal rectification effect in the asymmetric TGNJs. The rectification efficiency is strongly dependent on the asymmetry of the nanojunctions, which increases rapidly with the width discrepancy between the left and right terminals. Meanwhile, the corner form of the TGNJs also plays an important role in the rectification effect. The mechanism of this thermal rectification is explained by a qualitative analysis. Compared to previous thermal rectifiers based on other materials, the asymmetric nanojunctions based on graphene possess much high rectification ratio which can approach about 200%. These indicate that asymmetric TGNJs might be a promising candidate for excellent ballistic thermal (phononic) devices.

  14. Asymmetric spindle pole formation in CPAP-depleted mitotic cells.

    Science.gov (United States)

    Lee, Miseon; Chang, Jaerak; Chang, Sunghoe; Lee, Kyung S; Rhee, Kunsoo

    2014-02-21

    CPAP is an essential component for centriole formation. Here, we report that CPAP is also critical for symmetric spindle pole formation during mitosis. We observed that pericentriolar material between the mitotic spindle poles were asymmetrically distributed in CPAP-depleted cells even with intact numbers of centrioles. The length of procentrioles was slightly reduced by CPAP depletion, but the length of mother centrioles was not affected. Surprisingly, the young mother centrioles of the CPAP-depleted cells are not fully matured, as evidenced by the absence of distal and subdistal appendage proteins. We propose that the selective absence of centriolar appendages at the young mother centrioles may be responsible for asymmetric spindle pole formation in CPAP-depleted cells. Our results suggest that the neural stem cells with CPAP mutations might form asymmetric spindle poles, which results in premature initiation of differentiation.

  15. Gravity-induced asymmetric distribution of a plant growth hormone

    Science.gov (United States)

    Bandurski, R. S.; Schulze, A.; Momonoki, Y.

    1984-01-01

    Dolk (1936) demonstrated that gravistimulation induced an asymmetric distribution of auxin in a horizontally-placed shoot. An attempt is made to determine where and how that asymmetry arises, and to demonstrate that the endogenous auxin, indole-3-acetic acid, becomes asymmetrically distributed in the cortical cells of the Zea mays mesocotyl during 3 min of geostimulation. Further, indole-3-acetic acid derived by hydrolysis of an applied transport form of the hormone, indole-3-acetyl-myo-inositol, becomes asymmetrically distributed within 15 min of geostimulus time. From these and prior data is developed a working theory that the gravitational stimulus induces a selective leakage, or secretion, of the hormone from the vascular tissue to the cortical cells of the mesocotyl.

  16. 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 < p < 2} and {x in L_p({M},τ)} one can find {a, b in L_p({M},τ)} and contractions {u_n, v_n in {M}} such that {E}_n(x) = a u_n + v_n b quad and quad max big{ |a|_p,|b|_p big} ≤ c_p |x|_p. Moreover, it turns out that {a u_n} and {v_n b} converge in the row/column 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.

  17. Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2011-06-08

    corrosion rates in water alone and in simulated sludge were near or slightly below the metal-in-water rate while nitrate-free sludge/Aquaset II decreased rates by about a factor of 3. Addition of 1 M nitrate to simulated sludge decreased the corrosion rate by a factor of ~5 while 1 M nitrate in sludge/Aquaset II mixtures decreased the corrosion rate by ~2.5 compared with the nitrate-free analogues. Mixtures of simulated sludge with Aquaset II treated with 1 M nitrate had uranium corrosion rates about a factor of 8 to 10 lower than the water-only rate law. Nitrate was found to provide substantial hydrogen mitigation for immobilized simulant sludge waste forms containing Aquaset II or Aquaset II G clay. Hydrogen attenuation factors of 1000 or greater were determined at 60°C for sludge-clay mixtures at 1 M nitrate. Hydrogen mitigation for tests with PC and Aquaset II H (which contains PC) were inconclusive because of suspected failure to overcome induction times and fully enter into anoxic corrosion. Lessening of hydrogen attenuation at ~80°C and ~95°C for simulated sludge and Aquaset II was observed with attenuation factors around 100 to 200 at 1 M nitrate. Valuable additional information has been obtained on the ability of nitrate to attenuate hydrogen gas generation from solution, simulant K Basin sludge, and simulant sludge with immobilization agents. Details on characteristics of the associated reactions were also obtained. The present testing confirms prior work which indicates that nitrate is an effective agent to attenuate hydrogen from uranium metal corrosion in water and simulated K Basin sludge to show that it is also effective in potential candidate solidified K Basin waste forms for WIPP disposal. The hydrogen mitigation afforded by nitrate appears to be sufficient to meet the hydrogen generation limits for shipping various sludge waste streams based on uranium metal concentrations and assumed waste form loadings.

  18. Selfhealing of asymmetric Bessel-like modes

    DEFF Research Database (Denmark)

    Israelsen, Stine Møller; Rishøj, Lars Søgaard; Rottwitt, Karsten

    2014-01-01

    We numerically investigate asymmetric Bessel-like modes in an aircladding fiber. The selfhealing ability of asymmetric Bessel-like modes is demonstrated and quantified including the angular dependency of this ability.......We numerically investigate asymmetric Bessel-like modes in an aircladding fiber. The selfhealing ability of asymmetric Bessel-like modes is demonstrated and quantified including the angular dependency of this ability....

  19. Asymmetric cyanation of imines via dipeptide-derived organophosphine dual-reagent catalysis

    Science.gov (United States)

    Wang, Hong-Yu; Zheng, Chang-Wu; Chai, Zhuo; Zhang, Jia-Xing; Zhao, Gang

    2016-09-01

    Over the past few decades, enantioselective phosphine organocatalysis has evolved rapidly into a highly efficient catalytic strategy for a range of useful reactions. However, as restricted by the traditional catalytic modes, some important reactions, such as asymmetric Strecker-type reactions, have thus far been out of reach of this strategy. Reported herein is an application of enantioselective phosphine organocatalysis for asymmetric Strecker-type reactions, enabled by a dual-reagent catalyst system in which the key organophosphorus zwitterion intermediate, generated in situ by mixing a chiral dipeptide-derived multifunctional organophosphine with methyl acrylate, is used as a highly efficient chiral Lewis base catalyst. The high efficiency of this catalytic system is demonstrated in the asymmetric cyanation of isatin-derived ketimines and azomethine aldimines as well as in the kinetic resolution of racemic 3-substituted azomethines. Mechanistic studies provide experimental evidence for the intermediacy of the putative zwitterion and its role as a catalytically active Lewis base.

  20. Asymmetric Imine Isomerisation in the Enantioselective Synthesis of Chiral Amines from Prochiral Ketones

    NARCIS (Netherlands)

    Willems, Johannes G.H.; Vries, Johannes G. de; Nolte, Roeland J.M.; Zwanenburg, Binne

    1995-01-01

    An asymmetric catalytic synthesis of chiral amines using a chiral base catalysed [1,3]-proton shift reaction of imines is described. The isomerisation reaction of N-benzylimines derived from prochiral ketones (benzylacetone, acetophenone) and p-substituted benzylamines, is catalysed by chiral alcoho

  1. Asymmetric synthesis of telcagepant, a CGRP receptor antagonist for the treatment of migraine.

    Science.gov (United States)

    Xu, Feng; Zacuto, Michael; Yoshikawa, Naoki; Desmond, Richard; Hoerrner, Scott; Itoh, Tetsuji; Journet, Michel; Humphrey, Guy R; Cowden, Cameron; Strotman, Neil; Devine, Paul

    2010-11-19

    A highly efficient, asymmetric synthesis of telcagepant (1), a CGRP receptor antagonist for the treatment of migraine, is described. This synthesis features the first application of iminium organocatalysis on an industrial scale. The key to the success of this organocatalytic transformation was the identification of a dual acid cocatalyst system, which allowed striking a balance of the reaction efficiency and product stability effectively. As such, via an iminium species, the necessnary C-6 stereogenicity was practically established in one operation in >95% ee. Furthermore, we enlisted an unprecedented Doebner-Knoevenagel coupling, which was also via an iminium species, to efficiently construct the C3-C4 bond with desired functionality. In order to prepare telcagepant (1) in high quality, a practical new protocol was discovered to suppress the formation of desfluoro impurities formed under hydrogenation conditions to manufacturing process and prepares telcagepant (1) with the high quality required for pharmaceutical use.

  2. Instability of asymmetric continuous shaft system

    Science.gov (United States)

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

    2016-11-01

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

  3. Updating the asymmetric osmium-catalyzed dihydroxylation (AD) mnemonic. Q2MM modeling and new kinetic measurements

    DEFF Research Database (Denmark)

    Fristrup, Peter; Tanner, David Ackland; Norrby, Per-Ola

    2003-01-01

    The mnemonic device for predicting stereoselectivities in the Sharpless asymmetric dihydroxylation (AD) reaction has been updated based on extensive computational studies. Kinetic measurements from competition reactions validate the new proposal. The interactions responsible for the high stereose......The mnemonic device for predicting stereoselectivities in the Sharpless asymmetric dihydroxylation (AD) reaction has been updated based on extensive computational studies. Kinetic measurements from competition reactions validate the new proposal. The interactions responsible for the high...... stereoselectivity in the title reaction are analyzed in detail and mapped onto the mnemonic device....

  4. Asymmetric Multilevel Diversity Coding and Asymmetric Gaussian Multiple Descriptions

    CERN Document Server

    Mohajer, Soheil; Diggavi, Suhas N

    2009-01-01

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

  5. Originally Asymmetric Dark Matter

    CERN Document Server

    Okada, Nobuchika

    2012-01-01

    We propose a scenario with a fermion dark matter, where the dark matter particle used to be the Dirac fermion, but it takes the form of the Majorana fermion at a late time. The relic number density of the dark matter is determined by the dark matter asymmetry generated through the same mechanism as leptogenesis when the dark matter was the Dirac fermion. After efficient dark matter annihilation processes have frozen out, a phase transition of a scalar field takes place and generates Majorana mass terms to turn the dark matter particle into the Majorana fermion. In order to address this scenario in detail, we propose two simple models. The first one is based on the Standard Model (SM) gauge group and the dark matter originates the $SU(2)_L$ doublet Dirac fermion, analogous to the Higgsino-like neutralino in supersymmetric models. We estimate the spin-independent/dependent elastic scattering cross sections of this late-time Majorana dark matter with a proton and find the possibility to discover it by the direct...

  6. The Practical Asymmetric Syntheses of Key Chiral Intermediates of Chiral Drug from Four-Carbon Chiral Pool

    Institute of Scientific and Technical Information of China (English)

    MI; AiQiao

    2001-01-01

    (S)-or (R)-2-Amino-4-phenylbutyric acid and (S)-or (R)-2-hydroxy-4-phenylbutyric acid and their ethyl esters are key chiral intermediates for the preparation of angiotensin converting enzyme inhibitors (ACEI) and other chiral drugs. Their practically asymmetric synthetic methods in large scale from four-carbon chiral pool, commercially available L-aspartic acid and L-malic acid, will be presented (as scheme).  (S)-2-Amino-4-phenylbutyric acid and its ethyl ester hydrochloride were prepared from the easily available L-aspartic acid via activation by forming anhydride hydrochloride, Friedel-Crafts reaction with benzene, hydrogenolysis and esterification with ethanol in the presence of thionyl chloride in overall yield of 80% and 73.6% respectively with 99% ee. We first used amino acid anhydride hydrochloride as the acylating agent in Friedel-Crafts reaction without racemization. [1]……

  7. The Practical Asymmetric Syntheses of Key Chiral Intermediates of Chiral Drug from Four-Carbon Chiral Pool

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ (S)-or (R)-2-Amino-4-phenylbutyric acid and (S)-or (R)-2-hydroxy-4-phenylbutyric acid and their ethyl esters are key chiral intermediates for the preparation of angiotensin converting enzyme inhibitors (ACEI) and other chiral drugs. Their practically asymmetric synthetic methods in large scale from four-carbon chiral pool, commercially available L-aspartic acid and L-malic acid, will be presented (as scheme). (S)-2-Amino-4-phenylbutyric acid and its ethyl ester hydrochloride were prepared from the easily available L-aspartic acid via activation by forming anhydride hydrochloride, Friedel-Crafts reaction with benzene, hydrogenolysis and esterification with ethanol in the presence of thionyl chloride in overall yield of 80% and 73.6% respectively with 99% ee. We first used amino acid anhydride hydrochloride as the acylating agent in Friedel-Crafts reaction without racemization. [1

  8. HTPB/ADN推进剂反应气孔产生机理研究%Reaction Mechanism of Forming Pore in HTPB/AND Propellants

    Institute of Scientific and Technical Information of China (English)

    胥会祥; 庞维强; 李勇宏; 张楠楠; 王晓红

    2009-01-01

    为揭示HTPB/ADN/AP/Al推进剂产生气孔的原因,制备了一系列含ADN和TEA、T-313、MAPO、HX-752等键合剂的推进剂样品,试验确定与ADN反应产生气孔的组分,并通过DSC/TG-IR/MS联用仪分析了产生气孔的反应机理.结果表明,含固化剂TDI、IPDI和醇胺类键合剂TEA、T-313的推进剂样品不产生气孔,而含氮丙啶类键合剂MAPO、HX-752的样品固化后均出现气孔.DSC法证实MAPO与ADN产生强烈的作用,使ADN的主要放热分解峰温度降低99.7 ℃.在50 ℃,MAPO与ADN混合物(质量比1:1)加热2 h的过程形成了气体产物: N_2O、NO_2,并通过质谱检测到其存在.分析认为,推进剂中氮丙啶类键合剂促使了ADN的分解,形成反应气孔.%In order to reveal the reasons of forming pore in hydroxyl terminated polybutadiene/ammonium dinitramide/ammonium perchlorate/aluminium ( HTPB/ADN/AP/Al ) composite propellants, a series of propellant samples containing ADN and triethanolamine ( TEA ) , triethanolamine trifluoroboron complex ( T-313), tris ( 2-methylaziridinyl) phosphine oxide ( MAPO ) , isoph-thaloyl-bis-(2-methylaziridine) (HX-752) were prepared,and the components of reacting with ADN and forming pore were confirmed, and the reaction mechanism was analyzed by DSC/TG-IR/MS. Results show that there are no pores in the propellant samples containing curing agents such as toluene diisocyanate(TDI) ,isophrone diisocyanate(IPDI) and ethanolamine bonding agents such as TEA, T-313 respectively, but the pores are formed in the samples containing aziridine bonding agents MAPO and HX-752. It is proved by DSC that there is a strong interaction between ADN and MAPO,which decreases the temperature of the main decomposition peak of ADN by about 99.7 ℃ . When the mixture of ADN and MAPO ( mass ratio 1:1) was heated continuously at 50 ℃ for 2 h ,the gasous products N_2O and NO_2 are farmed and detected by mass spectrum. It is considered that the aziridine bonding agents can accelerate

  9. Modelling asymmetric growth in crowded plant communities

    DEFF Research Database (Denmark)

    Damgaard, Christian

    2010-01-01

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

  10. Terahertz metamaterial with asymmetric transmission

    CERN Document Server

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

    2009-01-01

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

  11. Stable walking with asymmetric legs

    International Nuclear Information System (INIS)

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

  12. 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.

  13. Entrepreneurship, Asymmetric Information and Unemployment

    OpenAIRE

    Robin Boadway; Nicolas Marceau; Maurice Marchand; Marianne Vigneault

    1998-01-01

    We examine how three sources of asymmetric information affect the supply of entrepreneurs and unemployment. In the first case, banks cannot observe entrepreneurs' risk of failure so ration credit. This increases the number of entrepreneurs and the level of unemployment. In the second case, firms cannot observe workers' effort so offer a wage above the market clearing one. This results in unemployment and too few entrepreneurs. The final case arises when firms cannot observe workers' abilities...

  14. Asymmetric Microscopic Driving Behavior Theory

    OpenAIRE

    Yeo, Hwasoo

    2008-01-01

    Numerous theories on traffic have been developed as traffic congestion gains more and more interest in our daily life. To model traffic phenomena, many traffic theorists have adopted theories from other fields such as fluid mechanics and thermodynamics. However, their efforts to model the traffic at a microscopic level have not been successful yet. Therefore, to overcome the limitations of the existing theories we propose a microscopic asymmetric traffic theory based on analysis of individual...

  15. Asymmetric Wettability Directs Leidenfrost Droplets

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-01

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

  16. Superstructures of fluorescent cyclodextrin via click-reaction

    Directory of Open Access Journals (Sweden)

    Arkadius Maciollek

    2013-04-01

    Full Text Available Mono-(6-azido-6-deoxy-β-cyclodextrin (CD was covalently attached to an alkyne-modified 5-methyl-2-(pyridin-2-ylthiazol-4-ol yielding a fluorophore containing CD in a click-type reaction. Intermolecular complexes were formed by poly(host–guest-interactions. The supramolecular structures were characterized by 1H NMR-ROESY spectroscopy, dynamic light scattering, UV–vis spectroscopy, fluorescence spectroscopy, and asymmetric flow field-flow fractionation. By adding potassium adamantane-1-carboxylate, the thiazol dye is displaced from the CD-cavity and the elongated noncovalent polymeric structures collapse.

  17. Synthesis and infrared spectra of alkaline earth metal carbonates formed by the reaction of metal salts with urea at high temperature

    Indian Academy of Sciences (India)

    S M Teleb; D El-Sayed Nassr; E M Nour

    2004-12-01

    The metal carbonate, MCO3 (M = Ca, Sr and Ba), was synthesized by a novel method of reacting aqueous solution of each of Ca2+, Sr2+ and Ba2+ salts with urea at high temperature, ∼ 80°C. The reaction products were characterized through elemental analysis and infrared spectra. The infrared spectra of the products are the same as those of the corresponding commercially obtained carbonates. A general reaction describing the formation of MCO3 is proposed.

  18. On thermonuclear reaction rates

    OpenAIRE

    Hans J. Haubold; Mathai, Arak Mathai

    1996-01-01

    Nuclear reactions govern major aspects of the chemical evolution of galaxies and stars. Analytic study of the reaction rates and reaction probability integrals is attempted here. Exact expressions for the reaction rates and reaction probability integrals for nuclear reactions in the cases of nonresonant, modified nonresonant, screened nonresonant and resonant cases are given. These are expressed in terms of H-functions, G-functions and in computable series forms. Computational aspects are als...

  19. Transition State Models for Understanding the Origin of Chiral Induction in Asymmetric Catalysis.

    Science.gov (United States)

    Sunoj, Raghavan B

    2016-05-17

    In asymmetric catalysis, a chiral catalyst bearing chiral center(s) is employed to impart chirality to developing stereogenic center(s). A rich and diverse set of chiral catalysts is now available in the repertoire of synthetic organic chemistry. The most recent trends point to the emergence of axially chiral catalysts based on binaphthyl motifs, in particular, BINOL-derived phosphoric acids and phosphoramidites. More fascinating ideas took shape in the form of cooperative multicatalysis wherein organo- and transition-metal catalysts are made to work in concert. At the heart of all such manifestations of asymmetric catalysis, classical or contemporary, is the stereodetermining transition state, which holds a perennial control over the stereochemical outcome of the catalytic process. Delving one step deeper, one would find that the origin of the stereoselectivity is delicately dependent on the relative stabilization of one transition state, responsible for the formation of the predominant stereoisomer, over the other transition state for the minor stereoisomer. The most frequently used working hypothesis to rationalize the experimentally observed stereoselectivity places an undue emphasis on steric factors and tends to regard the same as the origin of facial discrimination between the prochiral faces of the reacting partners. In light of the increasing number of asymmetric catalysts that rely on hydrogen bonding as well as other weak non-covalent interactions, it is important to take cognizance of the involvement of such interactions in the sterocontrolling transition states. Modern density functional theories offer a pragmatic and effective way to capture non-covalent interactions in transition states. Aided by the availability of such improved computational tools, it is quite timely that the molecular origin of stereoselectivity is subjected to more intelligible analysis. In this Account, we describe interesting molecular insights into the stereocontrolling

  20. Transition State Models for Understanding the Origin of Chiral Induction in Asymmetric Catalysis.

    Science.gov (United States)

    Sunoj, Raghavan B

    2016-05-17

    In asymmetric catalysis, a chiral catalyst bearing chiral center(s) is employed to impart chirality to developing stereogenic center(s). A rich and diverse set of chiral catalysts is now available in the repertoire of synthetic organic chemistry. The most recent trends point to the emergence of axially chiral catalysts based on binaphthyl motifs, in particular, BINOL-derived phosphoric acids and phosphoramidites. More fascinating ideas took shape in the form of cooperative multicatalysis wherein organo- and transition-metal catalysts are made to work in concert. At the heart of all such manifestations of asymmetric catalysis, classical or contemporary, is the stereodetermining transition state, which holds a perennial control over the stereochemical outcome of the catalytic process. Delving one step deeper, one would find that the origin of the stereoselectivity is delicately dependent on the relative stabilization of one transition state, responsible for the formation of the predominant stereoisomer, over the other transition state for the minor stereoisomer. The most frequently used working hypothesis to rationalize the experimentally observed stereoselectivity places an undue emphasis on steric factors and tends to regard the same as the origin of facial discrimination between the prochiral faces of the reacting partners. In light of the increasing number of asymmetric catalysts that rely on hydrogen bonding as well as other weak non-covalent interactions, it is important to take cognizance of the involvement of such interactions in the sterocontrolling transition states. Modern density functional theories offer a pragmatic and effective way to capture non-covalent interactions in transition states. Aided by the availability of such improved computational tools, it is quite timely that the molecular origin of stereoselectivity is subjected to more intelligible analysis. In this Account, we describe interesting molecular insights into the stereocontrolling

  1. Asymmetric error correction models for the oil-gasoline price relationship

    International Nuclear Information System (INIS)

    The existing literature on price asymmetries does not systematically investigate the sensitivity of the empirical results to the choice of a particular econometric specification. This paper fills this gap by providing a detailed comparison of the three most popular models designed to describe asymmetric price behavior, namely asymmetric ECM, autoregressive threshold ECM and ECM with threshold cointegration. Each model is estimated on a common monthly data set for the gasoline markets of France, Germany, Italy, Spain and UK over the period 1985-2003. All models are able to capture the temporal delay in the reaction of retail prices to changes in spot gasoline and crude oil prices, as well as some evidence of asymmetric behavior. However, the type of market and the number of countries which are characterized by asymmetric oil-gasoline price relations vary across models. The asymmetric ECM prescribes that long-run price asymmetries are most likely to be found in the second stage of the transmission chain. Conversely, the ECM with threshold cointegration suggests that long-run price asymmetries vary across countries and markets. Short-run price asymmetries are captured by the asymmetric ECM specification and the TAR-ECM. The latter model suggests that all European countries are likely to be affected by asymmetries at the distribution stage, while the results obtained with the asymmetric ECM are mixed

  2. Design and fabrication of asymmetric nanopores using pulsed PECVD

    Science.gov (United States)

    Kelkar, Sanket S.

    Manipulating matter at nanometric length scales is important for many electronic, chemical and biological applications. Structures such as nanopores demonstrate a phenomenon known as hindered transport which can be exploited in analytical applications such as DNA sequencing, ionic transistors, and molecular sieving. Precisely controlling the size, geometry and surface characteristics of the nanopores is important for realizing these applications. In this work, we employ relatively large template structures (˜ 100 nm) produced by track-etching or electron beam lithography. The pore size is then reduced to the desired level by deposition of material using pulsed plasma enhanced chemical vapor deposition (PECVD). Pulsed PECVD has been developed as a high throughput alternative to atomic layer deposition (ALD) to deliver self-limiting growth of thin films. The goal of this thesis is to extend the application of pulsed PECVD to fabricate asymmetric nanopores. In contrast to ALD, pulsed PECVD does not result in perfectly conformal deposition profiles, and predicting the final nanostructure is more complicated. A two dimensional feature scale model was developed to predict film profile evolution. The model was built in COMSOL, and is based on a diffusion reaction framework with a spatially varying Knudsen diffusion coefficient to account for the molecular transport inside the features. A scaling analysis was used to account for ALD exposure limitations that commonly occur when coating these extremely high aspect ratio features. The model was verified by cross-section microscopy of deposition profiles on patterned cylinders and trenches. The model shows that it is possible to obtain unique nanopore morphologies in pulsed PECVD that are distinct from either steady state deposition processes such as physical vapor deposition (PVD) or conventional ALD. Polymeric track etched (TE) membrane supports with a nominal size of 100 nm were employed as model template structures to

  3. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.

    2014-04-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

  4. Synthetic Applications of Asymmetric Horner-Wadsworth-Emmons Condensations: Approaches to Marine Natural Products

    DEFF Research Database (Denmark)

    Tullis, Joshua S.; Helquist, Paul; Rein, Tobias

    1999-01-01

    Asymmetric HWE condensations of meso-dialdehyde 1 with chiral phosphonates containing 8-phenylmenthol very directly generate chiral moieties that are seen in a number of cytotoxic natural products. The HWE reactions proceed in good yields with synthetically useful geometric and diastereoselectivi......Asymmetric HWE condensations of meso-dialdehyde 1 with chiral phosphonates containing 8-phenylmenthol very directly generate chiral moieties that are seen in a number of cytotoxic natural products. The HWE reactions proceed in good yields with synthetically useful geometric...... and diastereoselectivities. Also, we demonstrate the applicability of the HWE products to the synthesis of biologically active marine natural products....

  5. Asymmetric Information and Consumer Demand

    OpenAIRE

    Ismagilova G. N.; Danilina E. I.; Gafurov I. R.; Ismagilov R. I.; Safiullin L. N.

    2014-01-01

    In the paper study the peculiarities of the formation the consumer demand for durable goods, the so-called «experience goods» in markets with asymmetric information. In the known literature sources studying of the demand is based on the assumption that at the moment of the purchase of goods and services people know exactly what price they are willing to pay for them and what utility they are going to obtain using those goods and services. Consider the signal model in which the initial price a...

  6. Spontaneous baryogenesis from asymmetric inflaton

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-15

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

  7. Asymmetric Formal Synthesis of Azadirachtin.

    Science.gov (United States)

    Mori, Naoki; Kitahara, Takeshi; Mori, Kenji; Watanabe, Hidenori

    2015-12-01

    An asymmetric formal synthesis of azadirachtin, a potent insect antifeedant, was accomplished in 30 steps to Ley's synthetic intermediate (longest linear sequence). The synthesis features: 1) rapid access to the optically active right-hand segment starting from the known 5-hydroxymethyl-2-cyclopentenone scaffold; 2) construction of the B and E rings by a key intramolecular tandem radical cyclization; 3) formation of the hemiacetal moiety in the C ring through the α-oxidation of the six-membered lactone followed by methanolysis. PMID:26474211

  8. Transient Stability During Asymmetrical Faults

    OpenAIRE

    Couturier, Nicolas

    2015-01-01

    This research project has been conducted at RTE in order to study the transient stability after asymmetrical faults. When three-phase short-circuits occur in a network, almost all the electrical power is lost on the relevant line(s). Among all short-circuit types, it is the most drastic event and the issue has to be solved very quickly. But oddly, it is also the easiest problem to solve mathematically speaking. This comes from the fact that the system stays balanced, and equations can be simp...

  9. Asymmetric Modeling of the Industrial Heavy Water Plant (PIAP)

    International Nuclear Information System (INIS)

    Software of asymmetric stationary simulation for the Industrial Heavy Water Plant (PIAP) was developed, based on an existing symmetric simulator (Brigitte 2.0).This software allows to turn off some of the isotopic enrichment twin units present in the plant and to simulate them asymmetrically, in other words, with different selection of parameters between twins.Other incorporations were done, such as passing flows between units and entering flows in strategic points of the plant.The iterative system in which the symmetric simulator is based was insufficient to develop the asymmetric simulator, so the system was modeled according to an implicit scheme for the units that form the simulator.This type of resolution resulted in a simulator that supports a big range of boundary conditions and internal parameters.Moreover, the time of calculus is short (∼3 minutes), making it actually useful.The asymmetric simulator is at the PIAP now, for its study and validation. It shows expected tendencies and results according to the symmetric simulator already validated

  10. Impact of the new HNO3-forming channel of the HO2+NO reaction on tropospheric HNO3, NOx, HOx and ozone

    Directory of Open Access Journals (Sweden)

    A. Kukui

    2008-07-01

    Full Text Available We have studied the impact of the recently observed reaction NO+HO2→HNO3 on atmospheric chemistry. A pressure and temperature-dependent parameterisation of this minor channel of the NO+HO2→NO2+OH reaction has been included in both a 2-D stratosphere-troposphere model and a 3-D tropospheric chemical transport model (CTM. Significant effects on the nitrogen species and hydroxyl radical concentrations are found throughout the troposphere, with the largest percentage changes occurring in the tropical upper troposphere (UT. Including the reaction leads to a reduction in NOx everywhere in the troposphere, with the largest decrease of 25% in the tropical and Southern Hemisphere UT. The tropical UT also has a corresponding large increase in HNO3 of 25%. OH decreases throughout the troposphere with the largest reduction of over 20% in the tropical UT. The mean global decrease in OH is around 13%, which is very large compared to the impact that typical photochemical revisions have on this modelled quantity. This OH decrease leads to an increase in CH4 lifetime of 5%. Due to the impact of decreased NOx on the OH:HO2 partitioning, modelled HO2 actually increases in the tropical UT on including the new reaction. The impact on tropospheric ozone is a decrease in the range 5 to 12%, with the largest impact in the tropics and Southern Hemisphere. Comparison with observations shows that in the region of largest changes, i.e. the tropical UT, the inclusion of the new reaction tends to degrade the model agreement. Elsewhere the model comparisons are not able to critically assess the impact of including this reaction. Only small changes are calculated in the minor species distributions in the stratosphere.

  11. Enhanced Asymmetric Bilinear Model for Face Recognition

    OpenAIRE

    Wenjuan Gong; Weishan Zhang; Jordi Gonzàlez; Yan Ren; Zhen Li

    2015-01-01

    Bilinear models have been successfully applied to separate two factors, for example, pose variances and different identities in face recognition problems. Asymmetric model is a type of bilinear model which models a system in the most concise way. But seldom there are works exploring the applications of asymmetric bilinear model on face recognition problem with illumination changes. In this work, we propose enhanced asymmetric model for illumination-robust face recognition. Instead of initiali...

  12. Identification of compounds formed from thermochemical reactions in U3O8-Al, U3Si2-Al and UMo-Al fuel ingot using X-ray diffractometer

    International Nuclear Information System (INIS)

    Aluminium matrix in U3O8-Al, U3Si2-Al, and UMo-Al fuel experiences melting reaction at the temperature of 630 °C to 645 °C. The melted aluminium matrix reacts thermochemically either in an exothermic or an endothermic reaction with each of the above fuels and forms new compounds which will influence the performance of the fuel in the reactor. Research reactor in effect operates at the temperature of 140 °C so the probability of energy release from the thermochemical reaction of U3O8-Al, U3Si2-Al and UMo-Al will not take place except in case of LOCA (Loss of Cooling Accident). Nevertheless, the condition must be anticipated to determine the performance of the three fuels in normal condition as well as in LOCA condition. Thermochemical reaction analysis was performed using DTA followed by identification analysis of the compounds using XRD. The analysis results showed that UO2, Al2O3 compound was formed in the U3O8-Al fuel, metastable compound U (Al,Si)x in the U3Si2-Al fuel, and U(Al,Mo)x in the UMo-Al fuel. The three fuels also produced UAlx (UAl2, UAl3 ,UAl4) as the end products of the thermochemical reactions. (author)

  13. Crystal structure of a nucleoside model for the inter­strand cross-link formed by the reaction of 2′-de­oxy­guanosine and an abasic site in duplex DNA

    Science.gov (United States)

    Catalano, Michael J.; Ruddraraju, Kasi Viswanatharaju; Barnes, Charles L.; Gates, Kent S.

    2016-01-01

    The title compound, 9-[(2R,4S,5R)-4-hy­droxy-5-(hy­droxy­meth­yl)tetra­hydro­furan-2-yl]-2-{[(2R,4S,5R)-4-meth­oxy-5-(meth­oxy­meth­yl)tetra­hydro­furan-2-yl]amino}-1H-purin-6(9H)-one, C17H25N5O7, crystallizes with two independent mol­ecules (A and B) in the asymmetric unit. In the crystal, the guanosine moieties of mol­ecules A and B are linked by N—H⋯N and O—H⋯N hydrogen-bonding inter­actions, forming ribbons which are stacked to form columns along [100]. These columns are then linked by O—H⋯O hydrogen bonds between the ribose moieties and numerous C—H⋯O inter­actions to complete the three-dimensional structure. PMID:27308004

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

    KAUST Repository

    Mukherjee, Herschel

    2011-03-04

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

  15. Bargaining with asymmetric information in non-stationary markets

    OpenAIRE

    Daniel Trefler

    1999-01-01

    The Rubinstein and Wolinsky bargaining-in-markets framework is modified by the introduction of asymmetric information and non-stationarity. Non-stationarity is introduced in the form of an arbitrary stochastic Markov process which captures the dynamics of market entry and pairwise matching. A new technique is used for establishing existence and characterizing the unique outcome of a non-stationary market equilibrium. The impact of market supply and demand on bilateral bargaining outcomes and ...

  16. Asymmetric angular dependence of domain wall motion in magnetic nanowires.

    Science.gov (United States)

    Nam, Chunghee

    2013-03-01

    An angular dependence of domain wall (DW) motion is studied in a magnetic wire consisting of a giant-magnetoresistance spin-valve. A DW pinning site is formed by a single notch, where a conventional linear one and a specially designed tilted one are compared. The asymmetric angular dependence was found in the DW depinning behavior with the tilted notch. The geometry control of the pinning site can be useful for DW diode devices using a rotating magnetic field. PMID:23755619

  17. Nuclear tracks in PADC induced by neutron, heavy ion and energetic fragments formed in the reaction {sup 54}Cr + {sup 208}Pb, at 320 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Barbui, M. [INFN Laboratori Nazionali di Legnaro, I-35020 Legnaro (Pd) (Italy); Fabris, D.; Moretto, S.; Nebbia, G. [Dipartimento di Fisica and Sezione INFN Padova, I-35131 Padova (Italy); Nemeth, P. [Departamento de Fisica, Universidad Simon Bolivar, Caracas 1080A (Venezuela, Bolivarian Republic of); Palfalvi, J. [Atomic Energy Research Institute P.O. Box 49, H-1525 Budapest (Hungary); Pesente, S. [Dipartimento di Fisica and Sezione INFN Padova, I-35131 Padova (Italy); Prete, G. [INFN Laboratori Nazionali di Legnaro, I-35020 Legnaro (Pd) (Italy); Sajo-Bohus, L., E-mail: sajobhus@gmail.co [Departamento de Fisica, Universidad Simon Bolivar, Caracas 1080A (Venezuela, Bolivarian Republic of); Viesti, G. [Dipartimento di Fisica and Sezione INFN Padova, I-35131 Padova (Italy)

    2009-10-15

    Passive nuclear track detectors in the study of multi fragmentation and compound nucleus fission in the fusion reaction {sup 54}Cr + {sup 208}Pb, leading to composite systems with Z = 106 is given. Results indicate that mostly nuclear tracks are related to fragments with low atomic number and less than 11% to beam like particles in opposition to the expected distribution.

  18. Nuclear tracks in PADC induced by neutron, heavy ion and energetic fragments formed in the reaction 54Cr + 208Pb, at 320 MeV

    International Nuclear Information System (INIS)

    Passive nuclear track detectors in the study of multi fragmentation and compound nucleus fission in the fusion reaction 54Cr + 208Pb, leading to composite systems with Z = 106 is given. Results indicate that mostly nuclear tracks are related to fragments with low atomic number and less than 11% to beam like particles in opposition to the expected distribution.

  19. Mechanism for Forming B,C,N,O Rings from NH3BH3 and CO2 via Reaction Discovery Computations.

    Science.gov (United States)

    Li, Maxwell W; Pendleton, Ian M; Nett, Alex J; Zimmerman, Paul M

    2016-03-01

    This study employs computational reaction finding tools to probe the unique biphilic reactivity between ammonia-borane (AB) and CO2. The results show that sequential reactions involving multiple equivalents of AB and CO2 can lead to the formation of stable nonplanar B,C,N,O-heterocycles (Cy-BCN). Cy-BCN is shown to emerge through boron-oxygen bond formation, hydroboration, dative bond formation, and single- or double-hydrogen transfers. The most kinetically facile reactions (computed at the coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory) result from polarized nitrogen-boron double bonds whereas thermodynamic stability results from formation of covalent boron-oxygen bonds. An important structure, HCOOBHNH2 (DHFAB), contains both of these features and is the key intermediate involved in generation of Cy-BCN. Crucially, it is shown that favorable boron-oxygen bond formation results in production of Cy-BCN species that are more stable than polyaminoboranes. These types of reaction intermediates could serve as building blocks in the formation of B,N-codoped graphene oxide (BCN). PMID:26844585

  20. LC/MS/MS structure elucidation of reaction intermediates formed during the TiO2 photocatalysis of microcystin-LR

    Science.gov (United States)

    Microcystin-LR (MC-LR), a cyanotoxin and emerging drinking water contaminant, was treated with TiO(2) photocatalysts immobilized on stainless steel plates as an alternative to nanoparticles in slurry. The reaction intermediates of MC-LR were identified with mass spectrometry (MS)...

  1. Comment on the paper: “Spectroscopic and computational study of the major oxidation products formed during the reaction of two quercetin conformers with a free radical”

    Science.gov (United States)

    Scognamiglio, Monica; Temussi, Fabio; D'Abrosca, Brigida; Fiorentino, Antonio

    2013-12-01

    The title paper reports a study on the structural elucidation by spectroscopic and computational methods of the products obtained from the reaction of two conformers of quercetin with the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH•). Many points of criticism, concerning both theoretical principles and experimental data, are highlighted in the present communication.

  2. Excitons in asymmetric quantum wells

    Science.gov (United States)

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

    2016-09-01

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

  3. 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.

  4. Asymmetric Wettability Directs Leidenfrost Droplets

    Science.gov (United States)

    Agapov, Rebecca; Boreyko, Jonathan; Briggs, Dayrl; Srijanto, Bernadeta; Retterer, Scott; Collier, C. Patrick; Lavrik, Nickolay

    2014-03-01

    Exploration of Leidenfrost droplets on nano- and microstructured surfaces are of great importance for increasing control over heat transfer in high power density systems using boiling phenomena. They also provide an elegant way to direct droplet motion in a variety of emerging fluidic systems. Here, we report the fabrication and characterization of tilted nanopillar arrays (TNPAs) that exhibit directional Leidenfrost water droplets under dynamic conditions. The batch fabrication of the TNPAs was achieved by glancing-angle anisotropic reactive ion etching of a thermally dewet platinum mask. In contrast to previously implemented macro- and microscopic Leidenfrost ratchets, our TNPAs induce no preferential directional movement of Leidenfrost droplets under conditions approaching steady-state film boiling. This suggests that the observed droplet directionality is not a result of asymmetric vapor flow. Phase diagrams were constructed for the boiling behavior upon droplet impact onto TNPAs, straight nanopillar arrays, and smooth silicon surfaces. Asymmetric wettability and directional trajectory of droplets was exclusive to the TNPAs for impacts corresponding to the transition boiling regime, revealing this to be the mechanism for the droplet directionality. This work was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Lab by the Division of Scientific User Facilities, US Dept. of Energy.

  5. Intramolecular coupling of eta/sup 2/-iminoacyl groups at group 4 metal centers: a kinetic study of the carbon-carbon double-bond-forming reaction

    Energy Technology Data Exchange (ETDEWEB)

    Durfee, L.D.; McMullen, A.K.; Rothwell, I.P.

    1988-03-02

    The series of bis(eta/sup 2/-iminoacyl) compounds of general formula M(OAr)/sub 2/(eta/sup 2/-R'NCR)/sub 2/ (M = Ti, Zr, Hf; OAr = 2,6-diisopropyl- and 2,6-di-tert-butylphenoxide; R = CH/sub 3/, CH/sub 2/Ph; R' = various substituted phenyls) undergo intramolecular coupling on thermolysis to produce the corresponding enediamide derivatives M(OAr)/sub 2/(R'NC(R) = C(R)NR'). A kinetic study of the reaction in hydrocarbon solvents has shown it to be first order. The reaction is metal dependent with the rate decreasing in the order Ti > Zr > Hf. The rate of the reaction is also dependent on the steric and electronic nature of the nitrogen substituent (R'). The use of the bulky aryl group 2,6-dimethylphenyl retards the reaction, while the use of various 3- and 4-substituted phenyls (3-F, 3-OMe, 4-OMe, 4-Cl, 4-NMe/sub 2/) shows the reaction to be accelerated by electron-withdrawing substituents. A sigma plot based on kinetic data obtained at 67/sup 0/C and 77/sup 0/C yielded rho values of 0.83 (R = 0.97) and 0.84 (R = 0.95), respectively. Both the steric and electronic dependence of the reactivity on the nitrogen substituents is discussed mechanistically and used to rationalize the much more facile intramolecular coupling observed for the related eta/sup 2/-acyl (eta/sup 2/-OCR) functionalities.

  6. Fold catastrophe model of dynamic pillar failure in asymmetric mining

    Institute of Scientific and Technical Information of China (English)

    PAN Yue; LI Ai-wu; QI Yun-song

    2009-01-01

    A rock burst disaster not only destroys the pit facilities and results in economic loss but it also threatens the life of the miners. Pillar rock burst has a higher frequency of occurrence in the pit compared to other kinds of rock burst. Understanding the cause, magnitude and prevention of pillar rock burst is a significant undertaking. Equations describing the bending moment and displacement of the rock beam in asymmetric mining have been deduced for simplified asymmetric beam-pillar systems. Using the symbolic operation software MAPLE 9.5 a catastrophe model of the dynamic failure of an asymmetric rock-beam pillar system has been established. The differential form of the total potential function deduced from the law of conservation of energy was used for this deduction. The critical conditions and the initial and final positions of the pillar during failure have been given in analytical form. The amount of elastic energy released by the rock beam at the instant of failure is determined as well as. A diagrammatic form showing the pillar failure was plotted using MATLAB software. This plot contains a wealth of information and is important for understanding the behavior during each deformation phase of the rock-beam pillar system. The graphic also aids in distinguishing the equivalent stiffness of the rock beam in different directions.

  7. Dynamics of fission and heavy ion reactions

    International Nuclear Information System (INIS)

    Recent advances in a unified macroscopic-microscopic description of large-amplitude collective nuclear motion such as occurs in fission and heavy ion reactions are discussed. With the goal of finding observable quantities that depend upon the magnitude and mechanism of nuclear dissipation, one-body dissipation and two-body viscosity within the framework of a generalized Fokker-Planck equation for the time dependence of the distribution function in phase space of collective coordinates and momenta are considered. Proceeding in two separate directions, the generalized Hamilton equations of motion for the first moments of the distribution function with a new shape parametrization and other technical innovations are first solved. This yields the mean translational fission-fragment kinetic energy and mass of a third fragment that sometimes forms between the two end fragments, as well as the energy required for fusion in symmetric heavy-ion reactions and the mass transfer and capture cross section in asymmetric heavy-ion reactions. In a second direction, we specialize to an inverted-oscillator fission barrier and use Kramers' stationary solution to calculate the mean time from the saddle point to scission for a heavy-ion-induced fission reaction for which experimental information is becoming available. 25 references

  8. Synthesis of New Chiral Phosphine Ligands and Their Application in Asymmetric Hydrogenation of Ketones

    Institute of Scientific and Technical Information of China (English)

    XIE Jian-Hua; FU Yu; WANG Li-Xin; ZHOU Qi-Lin

    2004-01-01

    The design of new chiral ligands is the key in the development of transition metal catalyzed asymmetric synthesis. Many chiral diphosphine ligands have been prepared and applied in asymmetric catalytic reactions with excellent enantioselectivities. Among the chiral diphosphine ligands that have been reported, the atropisomeric C2-symmetric phosphines with a biaryl scaffold initiated by Noyori and co-workers with BINAP were found to have the widest application in the transition metal catalyzed reactions. Planar chiral diphosphines based on ferrocene or paracyclophane backbones have also been applied to a number of reactions with a remarkable degree of success. However, the spiro diphosphine compounds, another type of axially chiral ligands, have not been synthesized yet. Recently, we designed chiral phosphoramidite ligands (SIPHOS)containing a 1, 1′-spirobiindane backbone and demonstrated that these ligands can be highly efficient for the Rh-catalyzed asymmetric hydrogenation of functionalized olefins. Especially, in the case of asymmetric hydrogenation of α-arylethenylamines, the spiro monophosphoramidite ligands provided a significantly higher level of enantiocontrol compared to that of the monophosphoramidite ligands derived from BINOL. Herein we present the synthesis of spiro diphosphines (SDP) containing 1,1′-spirobiindane as a new chiral scaffold and their application in the ruthenium-catalyzed asymmetric hydrogenation of simple ketones with high activity (S/C up to 100 000) and excellent enantioselectivity (ee up to 99.5%).

  9. Two-Dimensional Laguerre-Gaussian Asymmetric Soliton Family in Strongly Nonlocal Media

    Institute of Scientific and Technical Information of China (English)

    ZHONG Wei-Ping

    2008-01-01

    We demonstrate the existence of a broad class of higher-order Laguerre-Gaussian asymmetric spatial optical solitons in strongly nonlocal nonlinear media. Furthermore, we discuss specific values (q = 0) of the modulation depth parameter for different rational values of the topological charge in detail. Our results show that higher-order asymmetry spatial soliton family can exist in various forms, such as two-dimensional defect half-solitons, asymmetric single-layer and multi-layer necklace solitons.

  10. Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

    KAUST Repository

    Elshewy, Ahmed M.

    2013-12-01

    Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

  11. Production cross sections and isomeric ratios for sup(110m)In/sup(110g)In formed in Cd (d,xn) reactions

    International Nuclear Information System (INIS)

    Excitation functions and isomeric cross sections ratios have been measured for the 110Cd (d,2n) and 111Cd (d,3n) reactions in which the isomeric pair sup(110m)In/sup(110g)In is produced. Activation method was employed and the irradiations were performed at the synchrocyclotron of the Comision Nacional de Energia Atomica, Argentina, with an incident energy of 27.MeV. (author)

  12. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

    OpenAIRE

    Van Wyngarden, A. L.; Pérez-Montaño, S.; Bui, J. V. H.; Li, E. S. W.; Nelson, T.E.; Ha, K. T.; L. Leong; Iraci, L.T.

    2014-01-01

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric ...

  13. Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination.

    Science.gov (United States)

    Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok

    2015-04-21

    Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged as a step- and atom-economical alternative to the conventional C-N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C-H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this context, we were curious to see whether a transition-metal-catalyzed mild C-H amination protocol could be achieved using organic azides as the amino source. We envisaged that a dual role of organic azides as an environmentally benign amino source and also as an internal oxidant via N-N2 bond cleavage would be key to develop efficient C-H amination reactions employing azides. An additional advantage of this approach was anticipated: that a sole byproduct is molecular nitrogen (N2) under the perspective catalytic conditions. This Account mainly describes our research efforts on the development of rhodium- and iridium-catalyzed direct C-H amination reactions with organic azides. Under our initially optimized Rh(III)-catalyzed amination conditions, not only sulfonyl azides but also aryl- and alkyl azides could be utilized as facile amino sources in reaction with various types of C(sp(2))-H bonds bearing such directing groups as pyridine, amide, or ketoxime. More recently, a new

  14. Asymmetric Syntheses Aided by Biocatalysts

    Institute of Scientific and Technical Information of China (English)

    陈沛然; 顾建新; 魏志亮; 韩世清; 李祖义; 林国强

    2003-01-01

    This article summarizes the achievements of the authors' group in the area of biocatalyst-catalyzed organic reactions in recent 10 years. A strain of Geotrichum sp. obtained by screeninu is capable of stereoselectlvely reducing a number of carbonyl compounds. In many cases, the stermghemistry is complementary with that obtained by baker' s yeast. Therefore, this microorganism provides a useful pathway to the preparation of alcohol eompounds with specific configurations. On the other hand, a nmmber of plant sourees have been screened for oxynitrilases and the hydrocyanation reactions of various arylcarboxalde-hydes have been investigated.A"micro-aqueous reaction system" was invented,by which a serles of novel optically active cyanohydrins were prepared.On this hasis,a high through-put comtimasous reaction system has been designed.This paper also deseribes examples of the syntheses of bio-active compounds by using the optieally active compounds obtained from the above mentioned catalytic reactions as precursors.

  15. Preparation of D-Phenylalanine by Asymmetric Transformation

    Institute of Scientific and Technical Information of China (English)

    Ben Mei WEI; Li Jian JIANG; Ying Ping ZHENG; Hai Qing XU

    2004-01-01

    The method of preparing D-phenylalanine by asymmetric transformation is reported.D-phenylalanine was prepared from DL-phenylalanine by two-step reaction.D-phenylalanine(2S,3S)-tartrate was prepared by heating DL-phenylalanine, salicylaldehyde,and(2S,3S)-tartaric acid in propionic acid;the obtained D-phenylalanine(2S,3S)-tartrate was treated with triethylamine in ethanol giving D-phenylalanine with 98% optical purity in 69% yield.

  16. Condensation on Slippery Asymmetric Bumps

    CERN Document Server

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

    2015-01-01

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

  17. New asymmetric quantum codes over Fq

    Science.gov (United States)

    Ma, Yuena; Feng, Xiaoyi; Xu, Gen

    2016-07-01

    Two families of new asymmetric quantum codes are constructed in this paper. The first family is the asymmetric quantum codes with length n=qm-1 over Fq, where qge 5 is a prime power. The second one is the asymmetric quantum codes with length n=3m-1. These asymmetric quantum codes are derived from the CSS construction and pairs of nested BCH codes. Moreover, let the defining set T1=T2^{-q}, then the real Z-distance of our asymmetric quantum codes are much larger than δ _max+1, where δ _max is the maximal designed distance of dual-containing narrow-sense BCH code, and the parameters presented here have better than the ones available in the literature.

  18. In situ observation of eutectoid reaction forming a PbTe-Sb₂Te₃ thermoelectric nanocomposite by synchrotron X-ray diffraction

    OpenAIRE

    Ikeda, Teruyuki; Toberer, Eric S; Ravi, Vilupanur A.; Snyder, G. Jeffrey; Aoyagi, Shinobu; Nishibori, Eiji; Sakata, Makoto

    2009-01-01

    In situ high-temperature powder X-ray diffraction experiments have been performed on performed on Pb10.5Sb6Te57.9 using using a synchrotron X-ray source to observe the eutectoid reaction from Pb2Sb6Te11 to PbTe and Sb2Te3. Molar fractions of the constituent phases and fraction transformed were obtained as functions of time. The experimental fraction transformed vs. time curve were well fitted by the Kolmogorov–Johnson–Mehl–Avrami equation with an Avrami index n = 1.4. The small n value sugges...

  19. Fusion-fission and deep inelastic orbiting in the target-like yields from 32S formed in 20Ne+12C reaction at different excitation energies

    International Nuclear Information System (INIS)

    A strong motivation behind this work is that, though NOC model marked large σCExpt in the decay of 32S or small NOC for 20Ne+12C reaction indicating equivalently possibility of nCN contribution in it, but it does not work out the amount of contributions of σff and σorb separately in the total σC and the dynamics behind it, at different centre of mass energies, Ec.m.. We intend to address this question in the present work

  20. Atomic-Level Understanding of "Asymmetric Twins" in Boron Carbide

    Science.gov (United States)

    Xie, Kelvin Y.; An, Qi; Toksoy, M. Fatih; McCauley, James W.; Haber, Richard A.; Goddard, William A.; Hemker, Kevin J.

    2015-10-01

    Recent observations of planar defects in boron carbide have been shown to deviate from perfect mirror symmetry and are referred to as "asymmetric twins." Here, we demonstrate that these asymmetric twins are really phase boundaries that form in stoichiometric B4C (i.e., B12C3 ) but not in B13C2 . TEM observations and ab initio simulations have been coupled to show that these planar defects result from an interplay of stoichiometry, atomic positioning, icosahedral twinning, and structural hierarchy. The composition of icosahedra in B4C is B11C and translation of the carbon atom from a polar to equatorial site leads to a shift in bonding and a slight distortion of the lattice. No such distortion is observed in boron-rich B13C2 because the icosahedra do not contain carbon. Implications for tailoring boron carbide with stoichiometry and extrapolations to other hierarchical crystalline materials are discussed.

  1. Thomson scattering measurements from asymmetric interpenetrating plasma flows

    Energy Technology Data Exchange (ETDEWEB)

    Ross, J. S., E-mail: ross36@llnl.gov; Moody, J. D.; Fiuza, F.; Ryutov, D.; Divol, L.; Huntington, C. M.; Park, H.-S. [Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, California 94551 (United States)

    2014-11-15

    Imaging Thomson scattering measurements of collective ion-acoustic fluctuations have been utilized to determine ion temperature and density from laser produced counter-streaming asymmetric flows. Two foils are heated with 8 laser beams each, 500 J per beam, at the Omega Laser facility. Measurements are made 4 mm from the foil surface using a 60 J 2ω probe laser with a 200 ps pulse length. Measuring the electron density and temperature from the electron-plasma fluctuations constrains the fit of the multi-ion species, asymmetric flows theoretical form factor for the ion feature such that the ion temperatures, ion densities, and flow velocities for each plasma flow are determined.

  2. Atomic-Level Understanding of "Asymmetric Twins" in Boron Carbide.

    Science.gov (United States)

    Xie, Kelvin Y; An, Qi; Toksoy, M Fatih; McCauley, James W; Haber, Richard A; Goddard, William A; Hemker, Kevin J

    2015-10-23

    Recent observations of planar defects in boron carbide have been shown to deviate from perfect mirror symmetry and are referred to as "asymmetric twins." Here, we demonstrate that these asymmetric twins are really phase boundaries that form in stoichiometric B(4)C (i.e., B(12)C(3)) but not in B(13)C(2). TEM observations and ab initio simulations have been coupled to show that these planar defects result from an interplay of stoichiometry, atomic positioning, icosahedral twinning, and structural hierarchy. The composition of icosahedra in B(4)C is B(11)C and translation of the carbon atom from a polar to equatorial site leads to a shift in bonding and a slight distortion of the lattice. No such distortion is observed in boron-rich B(13)C(2) because the icosahedra do not contain carbon. Implications for tailoring boron carbide with stoichiometry and extrapolations to other hierarchical crystalline materials are discussed.

  3. Reactions forming C(0,+)n=2,10, Cn=2,4H(0,+) and C3H(0,+) in the gas phase: semi empirical branching ratios

    CERN Document Server

    Chabot, M; Gratier, P; Jallat, A; Wakelam, V

    2013-01-01

    The aim of this paper is to provide a new set of branching ratios for interstellar and planetary chemical networks based on a semi empirical model. We applied, instead of zero order theory (i.e. only the most exoergic decaying channel is considered), a statistical microcanonical model based on the construction of breakdown curves and using experimental high velocity collision branching ratios for their parametriza- tion. We applied the model to ion-molecule, neutral-neutral, and ion-pair reactions implemented in the few popular databases for astrochemistry such as KIDA, OSU and UMIST. We studied the reactions of carbon and hydrocarbon species with electrons, He+, H+, CH+, CH, C, and C+ leading to intermediate complexes of the type Cn=2,10, Cn=2,4 H, C3 H2, C+n=2,10, Cn=2,4 H+, or C3 H+2 . Comparison of predictions with measurements supports the validity of the model. Huge deviations with respect to database values are often obtained. Effects of the new branching ratios in time dependant chemistry for dark clo...

  4. Development of chiral metal amides as highly reactive catalysts for asymmetric [3 + 2] cycloadditions

    Science.gov (United States)

    Yamashita, Yasuhiro; Yoshimoto, Susumu; Dutton, Mark J

    2016-01-01

    Summary Highly efficient catalytic asymmetric [3 + 2] cycloadditions using a chiral copper amide are reported. Compared with the chiral CuOTf/Et3N system, the CuHMDS system showed higher reactivity, and the desired reactions proceeded in high yields and high selectivities with catalyst loadings as low as 0.01 mol %. PMID:27559396

  5. Rhodium-catalyzed asymmetric hydroformylation with Taddol-based IndolPhos ligands

    NARCIS (Netherlands)

    J. Wassenaar; B. de Bruin; J.N.H. Reek

    2010-01-01

    A small library of Taddol-based IndolPhos ligands 2a−g and their use in asymmetric hydroformylation (AHF) reactions are reported. Moderate to good enantioselectivities are obtained for styrene, vinyl acetate, and allyl cyanide up to 72%, 74%, and 63% ee, respectively. High b/l ratios are obtained, w

  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

    2015-03-01

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

  7. Preparation of 6,6'-Bisperfluoroalkylated BINOLs and Their Application in Asymmetric Alkylation of Benzaldehyde

    Institute of Scientific and Technical Information of China (English)

    YIN,Yue-Yan(尹月燕); ZHAO,Gang(赵刚); YANG,Gao-Sheng(杨高升); YIN,Wei-Xing(殷卫星)

    2002-01-01

    6,6'-Bis(1H,1H,2H,2H-perfluorooctyl)-BINOL and 6,6'-bis(1H ,1H , 2 H , 2 H- perfluorodecyl ) -BINOL were synthesized through Suzuki coupling reaction and used in fluorous biphase asymmetric alkylation of benzaldehyde. Good enantioselectivity was obtained and the catalysts could be recovered by liquid-liquid extraction.

  8. Organocatalytic One-Pot Asymmetric Synthesis of Thiolated Spiro-γ-lactam Oxindoles Bearing Three Stereocenters.

    Science.gov (United States)

    Huang, Xin; Liu, Miao; Pham, Kenny; Zhang, Xiaofeng; Yi, Wen-Bin; Jasinski, Jerry P; Zhang, Wei

    2016-07-01

    The first asymmetric synthesis of spiro-γ-lactam oxindoles bearing three stereocenters is reported. One-pot thiol-Michael/Mannich/lactamization reactions promoted by a recyclable fluorous bifunctional cinchona alkaloid/thiourea organocatalyst afford products in moderate to good yields with up to 95% ee and 6:1 dr. PMID:27258150

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

    Science.gov (United States)

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

    2015-03-01

    Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment. PMID:25656548

  10. The Nonlinear Phillips Curve and Inflation Forecast Targeting - Symmetric Versus Asymmetric Monetary Policy Rules

    NARCIS (Netherlands)

    Schaling, E.

    1998-01-01

    We extend the Svensson (1997a) inflation forecast targeting framework with a convex Phillips curve. We derive an asymmetric target rule, that implies a higher level of nominal interest rates than the Svensson (1997a) forward looking version of the reaction function popularised by Taylor (1993). Exte

  11. An Asymmetric Synthetic Approach to the A-ring of the Taxol Family of Anti-Cancer Compounds

    Directory of Open Access Journals (Sweden)

    M. L. Marin

    1998-02-01

    Full Text Available A synthetic route developed for the preparation of the A-ring of Taxol family of molecules is reported. By means of an intramolecular Diels-Alder reaction an asymmetric approach to this ring has been accomplished. Also, initial studies to prepare the A ring using an intramolecular Diels-Alder reaction have been successful.

  12. Evaluation of a barley core collection for spot form net blotch reaction reveals distinct genotype specific pathogen virulence and host susceptibility

    Science.gov (United States)

    Spot form net blotch (SFNB) caused by Pyrenophora teres Drechs. f. maculata Smedeg., (anamorph Drechslera teres [Sacc.] Shoem.) is a major foliar disease of barley (Hordeum vulgare L.) worldwide. SFNB epidemics have recently been observed in major barley producing countries, suggesting that the loca...

  13. Synthesis of New Bifunctional Bis(oxazolines) and Their Application in the Asymmetric Cyanosilylation of Aromatic Ketones

    Institute of Scientific and Technical Information of China (English)

    LUO,Mei; DU,Da-Ming

    2004-01-01

    @@ Catalytic asymmetric synthesis of tertiary cyanohydrins by the addition of cyanide to a wide range of ketones has important synthetic utility, since the resulting optically active cyanohydrins are important intermediates for the synthesis of a variety of valuable classes of chiral compounds. The application of oxazoline in asymmetric cyanosilylation has seldom reported in comparation with other reactions.[1] Recently, polymer-supported pyridine-bis(oxazoline) ytterbium complex was reported to catalyze cyanosilylation of benzaldehyde.

  14. Reexamination of the mechanism of hydroxyl radical adducts formed from the reaction between familial amyotrophic lateral sclerosis-associated Cu,Zn superoxide dismutase mutants and H2O2

    Science.gov (United States)

    Singh, Ravinder J.; Karoui, Hakim; Gunther, Michael R.; Beckman, Joseph S.; Mason, Ronald P.; Kalyanaraman, B.

    1998-01-01

    Amyotrophic lateral sclerosis (ALS) involves the progressive degeneration of motor neurons in the spinal cord and motor cortex. Mutations to Cu,Zn superoxide dismutase (SOD) linked with familial ALS are reported to increase hydroxyl radical adduct formation from hydrogen peroxide as measured by spin trapping with 5,5′-dimethyl-1-pyrrolline N-oxide (DMPO). In the present study, we have used oxygen-17-enriched water and H2O2 to reinvestigate the mechanism of DMPO/⋅OH formation from the SOD and SOD mutants. The relative ratios of DMPO/⋅17OH and DMPO/⋅16OH formed in the Fenton reaction were 90% and 10%, respectively, reflecting the ratios of H217O2 to H216O2. The reaction of the WT SOD with H217O2 in bicarbonate/CO2 buffer yielded 63% DMPO/⋅17OH and 37% DMPO/⋅16OH. Similar results were obtained from the reaction between familial ALS SOD mutants and H217O2: DMPO/⋅17OH (64%); DMPO/⋅16OH (36%) from A4V and DMPO/⋅17OH (62%); and DMPO/⋅16OH (38%) from G93A. These results were confirmed further by using 5-diethoxyphosphoryl-5-methyl-1-pyrroline N-oxide spin trap, a phosphorylated analog of DMPO. Contrary to earlier reports, the present results indicate that a significant fraction of DMPO/⋅OH formed during the reaction of SOD and familial ALS SOD mutants with H2O2 is derived from the incorporation of oxygen from water due to oxidation of DMPO to DMPO/⋅OH presumably via DMPO radical cation. No differences were detected between WT and mutant SODs, neither in the concentration of DMPO/⋅OH or DEPMPO/⋅OH formed nor in the relative incorporation of oxygen from H2O2 or water. PMID:9618471

  15. Expressions for Form Factors for Inelastic Scattering and Charge Exchange in Plane-Wave, Distorted-Wave, and Coupled-Channels Reaction Formalisms

    Energy Technology Data Exchange (ETDEWEB)

    Dietrich, F S

    2006-09-25

    This document is intended to facilitate calculation of inelastic scattering and charge-exchange cross sections in a variety of reaction models, including the plane-wave and distorted-wave approximations and the full coupled-channels treatments. Expressions are given for the coupling potentials between the relevant channels in both coordinate and momentum space. In particular, it is expected that the plane-wave calculations should be useful as a check on the correctness of coupled-channels calculations. The Fourier transform methods used to calculate the plane-wave approximation cross sections are also intended to be used to generate the transition potentials for coupled-channels codes, using a folding model with local effective interactions. Specific expressions are given for calculating transition densities for the folding model in the random phase approximation (RPA).

  16. Recyclable fluorous cinchona alkaloid ester as a chiral promoter for asymmetric fluorination of β-ketoesters

    Directory of Open Access Journals (Sweden)

    Wen-Bin Yi

    2012-08-01

    Full Text Available A fluorous cinchona alkaloid ester has been developed as a chiral promoter for the asymmetric fluorination of β-ketoesters. It has comparable reactivity and selectivity to the nonfluorous versions of cinchona alkaloids and can be easily recovered from the reaction mixture by simple fluorous solid-phase extraction (F-SPE and used for the next round of reaction without further purification.

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

    Science.gov (United States)

    Zhao, Hua; Shen, Kai

    2016-03-01

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

  18. Regenerating a symmetry in asymmetric dark matter.

    Science.gov (United States)

    Buckley, Matthew R; Profumo, Stefano

    2012-01-01

    Asymmetric dark matter theories generically allow for mass terms that lead to particle-antiparticle mixing. Over the age of the Universe, dark matter can thus oscillate from a purely asymmetric configuration into a symmetric mix of particles and antiparticles, allowing for pair-annihilation processes. Additionally, requiring efficient depletion of the primordial thermal (symmetric) component generically entails large annihilation rates. We show that unless some symmetry completely forbids dark matter particle-antiparticle mixing, asymmetric dark matter is effectively ruled out for a large range of masses, for almost any oscillation time scale shorter than the age of the Universe. PMID:22304253

  19. Asymmetric dark matter in braneworld cosmology

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-01

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

  20. Regenerating a symmetry in asymmetric dark matter.

    Science.gov (United States)

    Buckley, Matthew R; Profumo, Stefano

    2012-01-01

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

  1. Asymmetric Dark Matter and Effective Operators

    CERN Document Server

    Buckley, Matthew R

    2011-01-01

    In order to annihilate in the early Universe to levels well below the measured dark matter density, asymmetric dark matter must possess large couplings to the Standard Model. In this paper, we consider effective operators which allow asymmetric dark matter to annihilate into quarks. In addition to a bound from requiring sufficient annihilation, the energy scale of such operators can be constrained by limits from direct detection and monojet searches at colliders. We show that the allowed parameter space for these operators is highly constrained, leading to non-trivial requirements that any model of asymmetric dark matter must satisfy.

  2. ADMonium: Asymmetric Dark Matter Bound State

    CERN Document Server

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

    2016-01-01

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

  3. Why Do Nucleosomes Unwrap Asymmetrically?

    Science.gov (United States)

    de Bruin, Lennart; Tompitak, Marco; Eslami-Mossallam, Behrouz; Schiessel, Helmut

    2016-07-01

    Nucleosomes, DNA spools with a protein core, engage about three-quarters of eukaryotic DNA and play a critical role in chromosomal processes, ranging from gene regulation, recombination, and replication to chromosome condensation. For more than a decade, micromanipulation experiments where nucleosomes are put under tension, as well as the theoretical interpretations of these experiments, have deepened our understanding of the stability and dynamics of nucleosomes. Here we give a theoretical explanation for a surprising new experimental finding: nucleosomes wrapped onto the 601 positioning sequence (the sequence used in most laboratories) respond highly asymmetrically to external forces by always unwrapping from the same end. Using a computational nucleosome model, we show that this asymmetry can be explained by differences in the DNA mechanics of two very short stretches on the wrapped DNA portion. Our finding suggests that the physical properties of nucleosomes, here the response to forces, can be tuned locally by the choice of the underlying base-pair sequence. This leads to a new view of nucleosomes: a physically highly varied set of DNA-protein complexes whose properties can be tuned on evolutionary time scales to their specific function in the genomic context. PMID:26991771

  4. Twin Higgs Asymmetric Dark Matter

    CERN Document Server

    García, Isabel García; March-Russell, John

    2015-01-01

    We study Asymmetric Dark Matter (ADM) in the context of the minimal (Fraternal) Twin Higgs solution to the little hierarchy problem, with a twin sector with gauged $SU(3)' \\times SU(2)'$, a twin Higgs, and only third generation twin fermions. Naturalness requires the QCD$^\\prime$ scale $\\Lambda'_{\\rm QCD} \\simeq 0.5 - 20 \\ {\\rm GeV}$, and $t'$ to be heavy. We focus on the light $b'$ quark regime, $m_{b'} \\lesssim \\Lambda'_{\\rm QCD}$, where QCD$^\\prime$ is characterised by a single scale $\\Lambda'_{\\rm QCD}$ with no light pions. A twin baryon number asymmetry leads to a successful DM candidate: the spin-3/2 twin baryon, $\\Delta' \\sim b'b'b'$, with a dynamically determined mass ($\\sim 5 \\Lambda'_{\\rm QCD}$) in the preferred range for the DM-to-baryon ratio $\\Omega_{\\rm DM}/\\Omega_{\\rm baryon} \\simeq 5$. Gauging the $U(1)'$ group leads to twin atoms ($\\Delta'$ - $\\bar {\\tau'}$ bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo ...

  5. Chaos suppression through asymmetric coupling

    Science.gov (United States)

    Bragard, J.; Vidal, G.; Mancini, H.; Mendoza, C.; Boccaletti, S.

    2007-12-01

    We study pairs of identical coupled chaotic oscillators. In particular, we have used Roessler (in the funnel and no funnel regimes), Lorenz, and four-dimensional chaotic Lotka-Volterra models. In all four of these cases, a pair of identical oscillators is asymmetrically coupled. The main result of the numerical simulations is that in all cases, specific values of coupling strength and asymmetry exist that render the two oscillators periodic and synchronized. The values of the coupling strength for which this phenomenon occurs is well below the previously known value for complete synchronization. We have found that this behavior exists for all the chaotic oscillators that we have used in the analysis. We postulate that this behavior is presumably generic to all chaotic oscillators. In order to complete the study, we have tested the robustness of this phenomenon of chaos suppression versus the addition of some Gaussian noise. We found that chaos suppression is robust for the addition of finite noise level. Finally, we propose some extension to this research.

  6. Force on an Asymmetric Capacitor

    CERN Document Server

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

    2002-01-01

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

  7. 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.

  8. Large-scale asymmetric synthesis of a cathepsin S inhibitor.

    Science.gov (United States)

    Lorenz, Jon C; Busacca, Carl A; Feng, XuWu; Grinberg, Nelu; Haddad, Nizar; Johnson, Joe; Kapadia, Suresh; Lee, Heewon; Saha, Anjan; Sarvestani, Max; Spinelli, Earl M; Varsolona, Rich; Wei, Xudong; Zeng, Xingzhong; Senanayake, Chris H

    2010-02-19

    A potent reversible inhibitor of the cysteine protease cathepsin-S was prepared on large scale using a convergent synthetic route, free of chromatography and cryogenics. Late-stage peptide coupling of a chiral urea acid fragment with a functionalized aminonitrile was employed to prepare the target, using 2-hydroxypyridine as a robust, nonexplosive replacement for HOBT. The two key intermediates were prepared using a modified Strecker reaction for the aminonitrile and a phosphonation-olefination-rhodium-catalyzed asymmetric hydrogenation sequence for the urea. A palladium-catalyzed vinyl transfer coupled with a Claisen reaction was used to produce the aldehyde required for the side chain. Key scale up issues, safety calorimetry, and optimization of all steps for multikilogram production are discussed. PMID:20102230

  9. Stochastic modeling of cell growth with symmetric or asymmetric division

    Science.gov (United States)

    Marantan, Andrew; Amir, Ariel

    2016-07-01

    We consider a class of biologically motivated stochastic processes in which a unicellular organism divides its resources (volume or damaged proteins, in particular) symmetrically or asymmetrically between its progeny. Assuming the final amount of the resource is controlled by a growth policy and subject to additive and multiplicative noise, we derive the recursive integral equation describing the evolution of the resource distribution over subsequent generations and use it to study the properties of stable resource distributions. We find conditions under which a unique stable resource distribution exists and calculate its moments for the class of affine linear growth policies. Moreover, we apply an asymptotic analysis to elucidate the conditions under which the stable distribution (when it exists) has a power-law tail. Finally, we use the results of this asymptotic analysis along with the moment equations to draw a stability phase diagram for the system that reveals the counterintuitive result that asymmetry serves to increase stability while at the same time widening the stable distribution. We also briefly discuss how cells can divide damaged proteins asymmetrically between their progeny as a form of damage control. In the appendixes, motivated by the asymmetric division of cell volume in Saccharomyces cerevisiae, we extend our results to the case wherein mother and daughter cells follow different growth policies.

  10. Stochastic modeling of cell growth with symmetric or asymmetric division.

    Science.gov (United States)

    Marantan, Andrew; Amir, Ariel

    2016-07-01

    We consider a class of biologically motivated stochastic processes in which a unicellular organism divides its resources (volume or damaged proteins, in particular) symmetrically or asymmetrically between its progeny. Assuming the final amount of the resource is controlled by a growth policy and subject to additive and multiplicative noise, we derive the recursive integral equation describing the evolution of the resource distribution over subsequent generations and use it to study the properties of stable resource distributions. We find conditions under which a unique stable resource distribution exists and calculate its moments for the class of affine linear growth policies. Moreover, we apply an asymptotic analysis to elucidate the conditions under which the stable distribution (when it exists) has a power-law tail. Finally, we use the results of this asymptotic analysis along with the moment equations to draw a stability phase diagram for the system that reveals the counterintuitive result that asymmetry serves to increase stability while at the same time widening the stable distribution. We also briefly discuss how cells can divide damaged proteins asymmetrically between their progeny as a form of damage control. In the appendixes, motivated by the asymmetric division of cell volume in Saccharomyces cerevisiae, we extend our results to the case wherein mother and daughter cells follow different growth policies. PMID:27575162

  11. 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.

  12. Massless sunset diagrams in finite asymmetric volumes

    CERN Document Server

    Niedermayer, Ferenc

    2016-01-01

    In this paper we present methods to compute massless sunset diagrams in finite asymmetric volumes in the framework of dimensional regularization and lattice regularization. We also consider 1-loop sums in both regularizations.

  13. 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.

  14. 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...... short-circuit current was analyzed in order to compare the results with the allowable DC current component based in the IEC. Finally the normal operating condition for the power plant was modeled....

  15. An asymmetric pericyclic cascade approach to oxindoles

    OpenAIRE

    Richmond, Edward

    2014-01-01

    The research in this thesis describes an asymmetric pericyclic cascade approach to the synthesis of a range of enantioenriched oxindoles using enantiopure oxazolidine derived nitrones and disubstituted ketenes. Chapter 1 aims to place this work in the context of the literature, describing other commonly employed or state-of-the-art asymmetric approaches to oxindoles and related compounds. Examples of where these approaches have been used successfully in the total synthesis of related indol...

  16. Asymmetric Federalism in Russia: Cure or Poison?

    OpenAIRE

    Jorge Martinez-Vazquez

    2003-01-01

    In the early years of its existence, the Russian Federation adopted a system of differential treatment of its regions in order to cope with the great degree of diversity present in them. This paper examines the Russian Federation’s asymmetric federalism by evaluating the system’s role, significance and effects on the Federation’s development. The study incorporates a detailed description of the asymmetric federalism over time along with the benefits and costs incurred by its implementation. I...

  17. Asymmetric septal hypertrophy and hypothyroidism in children.

    OpenAIRE

    Altman, D I; Murray, J.; Milner, S.; Dansky, R; Levin, S. E.

    1985-01-01

    Any echocardiographic study of two children with hypothyroidism demonstrated the presence of asymmetric septal hypertrophy. One child died aged 11 months, and pronounced thickening of the interventricular septum was confirmed at necropsy. There was also hypertrophy of the left ventricular free wall. Histological examination showed only slight muscle fibre disarray, but there was striking vacuolation and hypertrophy of muscle fibres. In the second case, a child aged five years, the asymmetric ...

  18. 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.

  19. The Determinants of the Asymmetric Power Effects in the context of Public-Private Partnership negotiation (PPP): theoretical Analysis and basic assumptions.

    OpenAIRE

    FAKHRI, ISSAOUI; TORKIA, BOUSSIF

    2016-01-01

    The principal aim of this paper is to present the problematic of the asymmetric power effect on public-private partnership. To do this we have mixed the works on PPP and those focusing on asymmetric power on commercial negotiation. This methodology allows us to determine the theoretical variables (in the form of hypothesis) which can be linked to the asymmetric power effect, on PPP negotiation.

  20. Aldol Condensation Products and Polyacetals in Organic Films Formed from Reactions of Propanal in Sulfuric Acid at Upper Troposphere/Lower Stratosphere (UT/LS) Aerosol Acidities

    Science.gov (United States)

    Bui, J. V. H.; Perez-Montano, S.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.; Van Wyngarden, A. L.

    2015-12-01

    Aerosols in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt. %) which is highly reflective towards UV and visible radiation. However, airborne measurements have shown that these particles may also contain a significant amount of organic material. Experiments combining organics (propanal, glyoxal and/or methylglyoxal) with sulfuric acid at concentrations typical of UT/LS aerosols produced highly colored surface films (and solutions) that have the potential to impact chemical, optical and/or cloud-forming properties of aerosols. In order to assess the potential for such films to impact aerosol chemistry or climate properties, experiments were performed to identify the chemical processes responsible for film formation. Surface films were analyzed via Attenuated Total Reflectance-FTIR and Nuclear Magnetic Resonance spectroscopies and are shown to consist primarily of aldol condensation products and cyclic and linear polyacetals, the latter of which are likely responsible for separation from the aqueous phase.

  1. Influence of anode pore forming additives on the densification of supported BaCe0.7Ta0.1Y0.2O3−δ electrolyte membranes based on a solid state reaction

    NARCIS (Netherlands)

    Bi, Lei; Fang, Shumin; Tao, Zetian; Zhang, Shangquan; Peng, Ranran; Liu, Wei

    2009-01-01

    We describe a solid state reaction for the preparation of both NiO–BaCe0.7Ta0.1Y0.2O3−δ anode substrates and BaCe0.7Ta0.1Y0.2O3−δ (BCTY10) electrolyte membranes on porous NiO–BCTY10 anode substrates. The amounts of the pore forming additive in the substrates showed a significant influence on the den

  2. Chemical transport reactions

    CERN Document Server

    Schäfer, Harald

    2013-01-01

    Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

  3. Asymmetric plasmonic induced ionic noise in metallic nanopores

    Science.gov (United States)

    Li, Yi; Chen, Chang; Willems, Kherim; Lagae, Liesbet; Groeseneken, Guido; Stakenborg, Tim; van Dorpe, Pol

    2016-06-01

    We present distinct asymmetric plasmon-induced noise properties of ionic transport observed through gold coated nanopores. We thoroughly investigated the effects of bias voltage and laser illumination. We show that the potential drop across top-coated silicon nanocavity pores can give rise to a large noise asymmetry (~2-3 orders of magnitude). Varying the bias voltage has an appreciable effect on the noise density spectra, typically in the Lorentzian components. The laser power is found to strongly affect the ionic noise level as well as the voltage threshold for light-induced noise generation. The asymmetric noise phenomenon is attributed to plasmon-induced interfacial reactions which promote light-induced charge fluctuation in the ion flow and allow voltage modulation of photo-induced carriers surmounting over such Schottky junctions. We further compare the ionic noise performances of gold nanocavities containing different material stacks, among which thermal oxide passivation of the silicon successfully mitigates the light-induced noise and is also fully CMOS-compatible. The understanding of the described noise characteristics will help to foster multiple applications using related structures including plasmonic-based sensing or plasmon-induced catalysis such as water splitting or solar energy conversion devices.We present distinct asymmetric plasmon-induced noise properties of ionic transport observed through gold coated nanopores. We thoroughly investigated the effects of bias voltage and laser illumination. We show that the potential drop across top-coated silicon nanocavity pores can give rise to a large noise asymmetry (~2-3 orders of magnitude). Varying the bias voltage has an appreciable effect on the noise density spectra, typically in the Lorentzian components. The laser power is found to strongly affect the ionic noise level as well as the voltage threshold for light-induced noise generation. The asymmetric noise phenomenon is attributed to plasmon

  4. Teaching Form as Form

    DEFF Research Database (Denmark)

    Keiding, Tina Bering

    2012-01-01

    means that form serves both as the connective value and as the concept for reflection. In other words, form is observed as form, not anything else. The didactical challenge of teaching form as form is accentuated by students’ everyday-based pre-orientation towards function at the expense of form...... reveal highly-structured courses, which alternates systematically between steering and free experimental activities. Consistent with a strong focus on content and the student’s interaction with content, the contributions hardly address the role of the teacher or the interplay between teachers...... and students. This is not to say that teachers do not engage in teaching. They clearly do and obviously play a major role in the progression in course structure and reflection on the student’s learning. My point is that, by neglecting the role of the teacher and the interplay between the teacher and students...

  5. A full-dimensional model of ozone forming reaction: the absolute value of the recombination rate coefficient, its pressure and temperature dependencies.

    Science.gov (United States)

    Teplukhin, Alexander; Babikov, Dmitri

    2016-07-28

    Rigorous calculations of scattering resonances in ozone are carried out for a broad range of rotational excitations. The accurate potential energy surface of Dawes is adopted, and a new efficient method for calculations of ro-vibrational energies, wave functions and resonance lifetimes is employed (which uses hyper-spherical coordinates, the sequential diagonalization/truncation approach, grid optimization and complex absorbing potential). A detailed analysis is carried out to characterize distributions of resonance energies and lifetimes, their rotational/vibrational content and their positions with respect to the centrifugal barrier. Emphasis is on the contribution of these resonances to the recombination process that forms ozone. It is found that major contributions come from localized resonances at energies near the top of the barrier. Delocalized resonances at higher energies should also be taken into account, while very narrow resonances at low energies (trapped far behind the centrifugal barrier) should be treated as bound states. The absolute value of the recombination rate coefficient, its pressure and temperature dependencies are obtained using the energy-transfer model developed in the earlier work. Good agreement with experimental data is obtained if one follows the suggestion of Troe, who argued that the energy transfer mechanism of recombination is responsible only for 55% of the recombination rate (with the remaining 45% coming from the competing chaperon mechanism). PMID:27364351

  6. Asymmetric Receptor Contact is Required for Tyrosine Autophosphorylation of Fibroblast Growth Factor Receptor in Living Cells

    Energy Technology Data Exchange (ETDEWEB)

    Bae, J.; Boggon, T; Tomé, F; Mandiyan, V; Lax, I; Schlessinge, J

    2010-01-01

    Tyrosine autophosphorylation of receptor tyrosine kinases plays a critical role in regulation of kinase activity and in recruitment and activation of intracellular signaling pathways. Autophosphorylation is mediated by a sequential and precisely ordered intermolecular (trans) reaction. In this report we present structural and biochemical experiments demonstrating that formation of an asymmetric dimer between activated FGFR1 kinase domains is required for transphosphorylation of FGFR1 in FGF-stimulated cells. Transphosphorylation is mediated by specific asymmetric contacts between the N-lobe of one kinase molecule, which serves as an active enzyme, and specific docking sites on the C-lobe of a second kinase molecule, which serves a substrate. Pathological loss-of-function mutations or oncogenic activating mutations in this interface may hinder or facilitate asymmetric dimer formation and transphosphorylation, respectively. The experiments presented in this report provide the molecular basis underlying the control of transphosphorylation of FGF receptors and other receptor tyrosine kinases.

  7. 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

  8. Constraining Asymmetric Dark Matter through observations of compact stars

    DEFF Research Database (Denmark)

    Kouvaris, Christoforos; Tinyakov, Peter

    2011-01-01

    We put constraints on asymmetric dark matter candidates with spin-dependent interactions based on the simple existence of white dwarfs and neutron stars in globular clusters. For a wide range of the parameters (WIMP mass and WIMP-nucleon cross section), WIMPs can be trapped in progenitors in large...... numbers and once the original star collapses to a white dwarf or a neutron star, these WIMPs might self-gravitate and eventually collapse forming a mini-black hole that eventually destroys the star. We impose constraints competitive to direct dark matter search experiments, for WIMPs with masses down...

  9. Asymmetrical Modulation for Uplink Communication in Cooperative Networks

    DEFF Research Database (Denmark)

    Zhang, Qi; Fitzek, Frank H.P.; Iversen, Villy Bæk

    2008-01-01

    In this paper a spectrum efficient uplink communication method for cooperative wireless networks is presented. In cellular controlled peer to peer (CCP2P) cooperative wireless networks the mobile device is logically connected over cellular links with the base station and simultaneously over short......-range links with neighboring mobile devices to form cooperative clusters. So far the physical communication over cellular links and over short-range links are separated in time or in frequency. Beyond this state of the art, we exploit a method, referred to as asymmetrical modulation, where a mobile device...

  10. Inhomogeneous Generalization of a Multispecies Totally Asymmetric Zero Range Process

    Science.gov (United States)

    Kuniba, Atsuo; Maruyama, Shouya; Okado, Masato

    2016-06-01

    The n-species totally asymmetric zero range process (n-TAZRP) on a one-dimensional periodic chain studied recently by the authors is a continuous time Markov process where arbitrary number of particles can occupy the same sites and hop to the adjacent sites only in one direction with a priority constraint according to their species. In this paper we introduce an n-parameter generalization of the n-TAZRP having inhomogeneous transition rate. The steady state probability is obtained in a matrix product form and also by an algorithm related to combinatorial R.

  11. Decentralization Policies for Supply Chain Investments under Asymmetric Information

    DEFF Research Database (Denmark)

    Agrell, Per J.; Bogetoft, Peter

    2016-01-01

    Supply chains need specific investments for improved performance in terms of lead-time, cost, and quality. We study the contractual choice of a coordinator to either centralize or delegate the investment decision in a three-stage chain. The analysis derives closed-form results for the economic...... performance of three decentralized contracting schemes under asymmetric information on investment cost, as well as the optimal full revelation results. The results show that the observed practice of tier-1 delegated investments leads to relatively poor performance because of underinvestment. We illustrate...

  12. Open bottom mesons in hot asymmetric hadronic medium

    OpenAIRE

    Pathak, Divakar; Mishra, Amruta

    2014-01-01

    The in-medium masses and optical potentials of $B$ and ${\\bar B}$ mesons are studied in an isospin asymmetric, strange, hot and dense hadronic environment using a chiral effective model. The chiral $SU(3)$ model originally designed for the light quark sector, is generalized to include the heavy quark sector ($c$ and $b$) to derive the interactions of the $B$ and ${\\bar B}$ mesons with the light hadrons. Due to large mass of bottom quark, we use only the empirical form of these interactions fo...

  13. Organocatalytic asymmetric epoxidation and tandem epoxidation/Passerini reaction under eco-friendly reaction conditions.

    Science.gov (United States)

    Deobald, Anna Maria; Corrêa, Arlene G; Rivera, Daniel G; Paixão, Márcio Weber

    2012-10-14

    An eco-friendly synthesis of highly functionalized epoxides and their incorporation into an organocatalytic multicomponent approach are reported. For this, a modified class of diarylprolinol silyl ethers was designed to enable high catalytic activity in an environmentally benign solvent system. The one-pot procedure showed great efficiency in promoting stereoselective multicomponent transformations in a tandem, 'green' fashion. Because of its non-residual, efficient and selective character, this synthetic design shows promise for large-scale applications in both diversity and target-oriented syntheses. PMID:22918441

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

    Energy Technology Data Exchange (ETDEWEB)

    J Bae; J Schlessinger

    2011-12-31

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

  15. Highly Efficient C--N Bond Forming Reactions in Water Catalyzed by Copper(I) Iodide with Calix[4]arene Supported Amino Acid Ionic Liquid%Highly Efficient C--N Bond Forming Reactions in Water Catalyzed by Copper(I) Iodide with Calix[4]arene Supported Amino Acid Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    黄利; 金灿; 苏为科

    2012-01-01

    A novel and effective protocol has been developed for the Ullmann-type C--N coupling reaction catalyzed by calix[4]arene supported amino acid ionic liquid and copper(I) iodide in water under microwave irradiation condition The protocol uses ealix[4]arene supported amino acid ionic liquid as double function of the ligand and phase-transfer catalyst, and shows good tolerance in good to excellent yields.

  16. Organocatalytic Asymmetric Michael Additions%有机催化不对称Michael加成反应

    Institute of Scientific and Technical Information of China (English)

    李宁; 郗国宏; 吴秋华; 刘伟华; 马晶军; 王春

    2009-01-01

    有机催化的不对称合成反应是目前研究最为活跃的领域之一.不对称Michael加成反应是合成众多重要的手性合成子和药物中间体的有效手段.目前报道的催化Michael加成反应的有机催化剂主要有脯氨酸及其衍生物、手性咪唑啉酮、手性(硫)脲、金鸡纳碱衍生物等.对各类有机催化剂在有机催化不对称Michael加成反应中的应用,以及不对称诱导反应的机理、催化剂分子结构及反应条件对其催化活性和不对称诱导作用的影响进行了评述.%Organocatalytic asymmetric reaction is an increasingly active area in organic synthesis. The asymmetric Michael addition provides a rapid access to versatile important chiral building blocks and intermediates for the synthesis of bioactive agrochemicals and pharmaceutical compounds. The reported organocatalysts for asymmetric Michael additions include proline and its derivatives, chiral imidazolidinone derivatives, chiral (thio) urea, cinchona alkaloids and so on. The applications of various organocatalysts to asymmetric Michael additions are reviewed in this paper. The reaction mechanism, catalytic activity and the asymmetric induction influenced by the structure of organocatalysts and the reaction condition are also discussed.

  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. Renewable resource management under asymmetric information

    DEFF Research Database (Denmark)

    Jensen, Frank; Andersen, Peder; Nielsen, Max

    2013-01-01

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

  19. Dc SQUIDs with asymmetric shunt resistors

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-07-01

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

  20. Synthesis of 3-Substituted BINOL derivatives and application in asymmetric epoxidation reaction%手性3-取代联二萘酚衍生物的合成及在不对称环氧化中的应用

    Institute of Scientific and Technical Information of China (English)

    尤强; 王琳; 宋华; 何玉玲; 牟瑶; 王钦; 王力

    2013-01-01

    目的:研究α,β不饱和酮的不对称环氧化反应。方法:利用手性的3-取代联二萘酚和Fe3+、La3+、Al3+的配和物诱导不对称环氧化反应。结果:成功合成了三个3取代联二萘酚衍生物,并将其运用于不对称环氧化反应。手性La3+配合物催化的环氧化反应,取得88%的产率以及46%对映异构体过量;手性Fe3+和Al3+配合物体系,环氧化产率较高,产物为消旋体。结论:手性的3-羟甲基联二萘酚镧配合物能够催化α,β不饱和酮的不对称环氧化反应并获得较高产率和中等的对映选择性。对该不对称环氧化反应的研究,为合成光活性环氧化物类药物中间体提供了新方法。%Objective: To study the asymmetric epoxidation of α,β-unsaturated ketone with BINOL derivative as catalyst. Method: The chiral 3-substitued-BINOL derivative ligands were first synthesized ,and then coordinated with Fe3+, La3+or Al3+to catalyze the asymmetric epoxidation of chalcone. Results: The 3-substituted BINOL derivatives (4~5) were successfully synthesized and applied in the asymmetric epoxidation of chalcone. The optical active epoxide was obtained in high yield (88%) and moderate ee value (46%) with 3-hydroxyl-methylnaphthol/La3+ as catalyst,while poor enantioselectivity was observed when the 3-hydroxylmethylnaphthol/Fe3+or 3-hydroxylmethylnaphthol/Al3+complex was used. Conclusion: The chiral 3-hydroxylmethylnaphthol/La3+complex is able to catalyze the asymmetric epoxidation of chalcone in high yield and moderate enantioselectivity , which pvovides a new approach to the construction of optical epoxide intermediate in the synthesis of material and medicine.

  1. Asymmetric counter propagation of domain walls

    Science.gov (United States)

    Andrade-Silva, I.; Clerc, M. G.; Odent, V.

    2016-07-01

    Far from equilibrium systems show different states and domain walls between them. These walls, depending on the type of connected equilibria, exhibit a rich spatiotemporal dynamics. Here, we investigate the asymmetrical counter propagation of domain walls in an in-plane-switching cell filled with a nematic liquid crystal. Experimentally, we characterize the shape and speed of the domain walls. Based on the molecular orientation, we infer that the counter propagative walls have different elastic deformations. These deformations are responsible of the asymmetric counter propagating fronts. Theoretically, based on symmetry arguments, we propose a simple bistable model under the influence of a nonlinear gradient, which qualitatively describes the observed dynamics.

  2. Asymmetric acoustic transmission in multiple frequency bands

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-11-23

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

  3. Asymmetric transfer hydrogenation of prochiral ketone catalyzed over Fe-CS/SBA-15 catalyst

    Institute of Scientific and Technical Information of China (English)

    XUE Ping; WU Tao

    2007-01-01

    A heterogeneous chiral catalyst Fe(Ⅲ)-CS (chitosan)complex/mesoporous molecular sieve SBA-15 (Santa Barbara Amorphous) was prepared.The asymmetric transfer hydrogenations of prochiral acetophenone and 4-methyl-2-pentanone to corresponding chiral alcohols were carried out on Fe-CS/SBA-15 at atmosphere pressure using 2-propanol as hydrogen donor.Effects of Fe content in catalyst,reaction temperature,reaction time and promoter KOH concentration on the conversion of substrates and enantioselectivity were investigated.Fe-CS/SBA-15 with 2.2%mass fraction Fe exhibits considerable enantioselectivity and catalytic activity for the asymmetric transfer hydrogenations of aromatic ketone and aliphatic ketone.Under optimal reaction conditions:KOH concentration 0.03 mol/L,reaction temperature 70℃ and reaction time 4 h,enantiomer excess(ee)of (R)-1-phenylethanol and conversion of acetophenone can reach 87.4%and 27.7%,respectively.Under the above KOH concentration and reaction temperature and reaction time of 8 h,the ee of(R)-4-methyl-2-pentanol and conversion 4-methyl-2-pentanone amounted to 50.2%and 25.5%,respectively.

  4. Non-stationary probabilities for the asymmetric exclusion process on a ring

    Indian Academy of Sciences (India)

    V B Priezzhev

    2005-06-01

    A solution of the master equation for a system of interacting particles for finite time and particle density is presented. By using a new form of the Bethe ansatz, the totally asymmetric exclusion process on a ring is solved for arbitrary initial conditions and time intervals.

  5. An asymmetric trihydrido-bridged arene ruthenium complex

    OpenAIRE

    Vieille-Petit, Ludovic; Therrien, Bruno; Süss-Fink, Georg

    2009-01-01

    Reaction of [Ru(η6-indane)(H2O)3]2+ and [Ru(η6-C6Me6)(H2O)3]2+ with NaBH4 in water gives a mixture of three triple hydrido-bridged arene ruthenium cations [(η6-arene)Ru(μ-H)3Ru(η6-arene′)]+ (arene=indane and hexamethylbenzene; arene′=indane and hexamethylbenzene). After treatment with NaBF4, the three complexes are separated by column chromatography and the asymmetrical [(η6-indane)Ru(μ-H)3Ru(η6-C6Me6)][BF4] (cation 1a) can be isolated in moderate yield. 1a decomposes in solution to give the ...

  6. Asymmetric Dielectric Elastomer Composite Material

    Science.gov (United States)

    Stewart, Brian K. (Inventor)

    2014-01-01

    Embodiments of the invention provide a dielectric elastomer composite material comprising a plurality of elastomer-coated electrodes arranged in an assembly. Embodiments of the invention provide improved force output over prior DEs by producing thinner spacing between electrode surfaces. This is accomplished by coating electrodes directly with uncured elastomer in liquid form and then assembling a finished component (which may be termed an actuator) from coated electrode components.

  7. Asymmetric catalysis: An enabling science

    OpenAIRE

    Trost, Barry M.

    2004-01-01

    Chirality of organic molecules plays an enormous role in areas ranging from medicine to material science, yet the synthesis of such entities in one enantiomeric form is one of the most difficult challenges. The advances being made stem from the convergence of a broader understanding of theory and how structure begets function, the developments in the interface between organic and inorganic chemistry and, most notably, the organic chemistry of the transition metals, and the continuing advancem...

  8. Chemoepitaxial guiding underlayers for density asymmetric and energetically asymmetric diblock copolymers

    Science.gov (United States)

    Nation, Benjamin D.; Ludovice, Peter J.; Henderson, Clifford L.

    2016-04-01

    Block copolymers, polymers composed of two or more homopolymers covalently bonded together, are currently being investigated as a method to extend optical lithography due to their ability to microphase separate on small size scales. In order to drive down the size that these BCPs phase separate, the BCPs with larger Flory-Huggin's χparameter needs to be found. Typically these BCPs are composed of more dissimilar homopolymers. However, changing these interactions also changes how BCPs interact with their guiding underlayers. In this paper, several block copolymers are simulated annealing on chemoepitaxial guiding underlayers using a coarse-grained molecular dynamics model in order to explore the effect that either energetic asymmetry or density asymmetry in the BCP have on the pattern registration. It is found that energetic asymmetry in BCPs causes one of the blocks to desire to skin, which shifts the composition of the background region that leads to well aligned vertical lamellae formation. It is hypothesized that moderate footing and undercutting at the underlayer or slight skinning at the free surface can increase the kinetics of defect annihilation by decreasing the distance that bridges must form. The density asymmetric BCPs simulated in this paper have different mechanical properties which lead to straighter sidewalls in the BCP film and potentially lead to better pattern registration. It is hypothesized that altering the compressibility of the blocks can alter equilibrium defectivity.

  9. Formation of the reduced form of furaneol® (2,5-dimethyl-4-hydroxy-tetrahydrofuran-3-one) during the Maillard reaction through catalysis of amino acid metal salts.

    Science.gov (United States)

    Nashalian, Ossanna; Wang, Xi; Yaylayan, Varoujan A

    2016-11-01

    Under pyrolytic conditions the acidity/basicity of Maillard reaction mixtures can be controlled through the use of hydrochloride or sodium salts of amino acids to generate a diversity of products. When the degradation of glucose was studied under pyrolytic conditions using excess sodium glycinate the reaction was found to generate a major unknown peak having a molecular ion at m/z 130. Subsequent in-depth isotope labelling studies indicated that acetol was an important precursor of this compound under pyrolytic and aqueous heating conditions. The dimerisation and cyclisation of acetol into 2,5-dimethyl-4-hydroxy-tetrahydrofuran-3-one was found to be catalysed by amino acid metal salts. Also, ESI/qTOF/MS studies indicated that the unknown peak has expected molecular formula of C6H10O3. Finally, a peak having the same retention time and mass spectrum was also generated pyrolytically when furaneol® was reduced with NaBH4 confirming the initial hypothesis regarding the unknown peak to be the reduced form of furaneol®. PMID:27211618

  10. Feasibility studies for the measurement of the time-like electromagnetic form factors of the proton in reactions of anti pp → μ{sup +}μ{sup -} at the PANDA-experiment at FAIR

    Energy Technology Data Exchange (ETDEWEB)

    Zimmermann, Iris; Dbeyssi, Alaa; Khaneft, Dmitry; Maas, Frank; Zambrana, Manuel; Mora Espi, Maria Carmen; Morales Morales, Cristina; Lin, Dexu; Froehlich, Bertold; Capozza, Luigi; Noll, Oliver; Deiseroth, Malte; Ahmed, Samer; Ahmadi, Heybat; Valente, Roserio; Rodriguez Pineiro, David [Helmholtz-Institut Mainz (Germany); GSI Darmstadt (Germany); Collaboration: PANDA-Collaboration

    2015-07-01

    The measurement of the time-like electromagnetic form factors (TL em FF), G{sub E} and G{sub M}, using reactions of anti pp → l{sup +}l{sup -} (l=e,μ) gives access to the structure of the proton. It will be the first time measurement of TL em FF of the proton accessing the muons in the final state. One advantage of using this channel is that radiative corrections due to final state radiation are suppressed by the heavy mass of the muon. Measuring anti pp → μ{sup +}μ{sup -} will also serve as a consistency check of the TL em FF data from anti pp → e{sup +}e{sup -}. Feasibility studies for the individual extraction of G{sub E} and G{sub M} out of the measured angular distribution are in progress for the muonic channel using the software package PANDARoot. Due to the strong hadronic background, mainly reactions of anti pp → π{sup +}π{sup -}, a very good signal-to-background separation is needed. For the analysis of both signal and background channel different multivariate classification methods are used. The current status of the studies is presented.

  11. Measurements of the Electric Form Factor of the Neutron up to Q2=3.4 GeV2 using the Reaction He3(e,e'n)pp

    CERN Document Server

    Riordan, S; Craver, B; Kelleher, A; Kolarkar, A; Miller, J; Cates, G D; Liyanage, N; Wojtsekhowski, B; Acha, A; Allada, K; Anderson, B; Aniol, K A; Annand, J R M; Arrington, J; Averett, T; Beck, A; Bellis, M; Boeglin, W; Breuer, H; Calarco, J R; Camsonne, A; Chen, J P; Chudakov, E; Coman, L; Crowe, B; Cusanno, F; Day, D; Degtyarenko, P; Dolph, P A M; Dutta, C; Ferdi, C; Fernandez-Ramirez, C; Feuerbach, R; Fraile, L M; Franklin, G; Frullani, S; Fuchs, S; Garibaldi, F; Gevorgyan, N; Gilman, R; Glamazdin, A; Gomez, J; Grimm, K; Hansen, J O; Herraiz, J L; Higinbotham, D W; Holmes, R; Holmstrom, T; Howell, D; deJager, C W; Jiang, X; Jones, M K; Katich, J; Kaufman, L J; Khandaker, M; Kelly, J J; Kiselev, D; Korsch, W; LeRose, J; Lindgren, R; Markowitz, P; Margaziotis, D J; Beck, S May-Tal; Mayilyan, S; McCormick, K; Meziani, Z E; Michaels, R; Moffit, B; Nanda, S; Nelyubin, V; Ngo, T; Nikolenko, D M; Norum, B; Pentchev, L; Perdrisat, C F; Piasetzky, E; Pomatsalyuk, R; Protopopescu, D; Puckett, A J R; Punjabi, V A; Qian, X; Qiang, Y; Quinn, B; Rachek, I; Ransome, R D; Reimer, P E; Reitz, B; Roche, J; Ron, G; Rondon, O; Rosner, G; Saha, A; Sargsian, M; Sawatzky, B; Segal, J; Shabestari, M; Shahinyan, A; Shestakov, Yu; Singh, J; Sirca, S; Souder, P; Stepanyan, S; Stibunov, V; Sulkosky, V; Tajima, S; Tobias, W A; Udias, J M; Urciuoli, G M; Vlahovic, B; Voskanyan, H; Wang, K; Wesselmann, F R; Vignote, J R; Wood, S A; Wright, J; Yao, H; Zhu, X

    2010-01-01

    The electric form factor of the neutron was determined from studies of the reaction He3(e,e'n)pp in quasi-elastic kinematics in Hall A at Jefferson Lab. Longitudinally polarized electrons were scattered off a polarized target in which the nuclear polarization was oriented perpendicular to the momentum transfer. The scattered electrons were detected in a magnetic spectrometer in coincidence with neutrons that were registered in a large-solid-angle detector. More than doubling the Q2-range over which it is known, we find GEn = 0.0225 +/- 0.0017 (stat) +/- 0.0024 (syst), 0.0200 +/- 0.0023 +/- 0.0018, and 0.0142 +/- 0.0019 +/- 0.0013 for Q2 = 1.72, 2.48, and 3.41 GeV2, respectively.

  12. Measurements of the Electric Form Factor of the Neutron up to Q2=3.4GeV2 Using the Reaction 3He→(e→,e'n)pp

    Science.gov (United States)

    Riordan, S.; Abrahamyan, S.; Craver, B.; Kelleher, A.; Kolarkar, A.; Miller, J.; Cates, G. D.; Liyanage, N.; Wojtsekhowski, B.; Acha, A.; Allada, K.; Anderson, B.; Aniol, K. A.; Annand, J. R. M.; Arrington, J.; Averett, T.; Beck, A.; Bellis, M.; Boeglin, W.; Breuer, H.; Calarco, J. R.; Camsonne, A.; Chen, J. P.; Chudakov, E.; Coman, L.; Crowe, B.; Cusanno, F.; Day, D.; Degtyarenko, P.; Dolph, P. A. M.; Dutta, C.; Ferdi, C.; Fernández-Ramírez, C.; Feuerbach, R.; Fraile, L. M.; Franklin, G.; Frullani, S.; Fuchs, S.; Garibaldi, F.; Gevorgyan, N.; Gilman, R.; Glamazdin, A.; Gomez, J.; Grimm, K.; Hansen, J.-O.; Herraiz, J. L.; Higinbotham, D. W.; Holmes, R.; Holmstrom, T.; Howell, D.; de Jager, C. W.; Jiang, X.; Jones, M. K.; Katich, J.; Kaufman, L. J.; Khandaker, M.; Kelly, J. J.; Kiselev, D.; Korsch, W.; Lerose, J.; Lindgren, R.; Markowitz, P.; Margaziotis, D. J.; Beck, S. May-Tal; Mayilyan, S.; McCormick, K.; Meziani, Z.-E.; Michaels, R.; Moffit, B.; Nanda, S.; Nelyubin, V.; Ngo, T.; Nikolenko, D. M.; Norum, B.; Pentchev, L.; Perdrisat, C. F.; Piasetzky, E.; Pomatsalyuk, R.; Protopopescu, D.; Puckett, A. J. R.; Punjabi, V. A.; Qian, X.; Qiang, Y.; Quinn, B.; Rachek, I.; Ransome, R. D.; Reimer, P. E.; Reitz, B.; Roche, J.; Ron, G.; Rondon, O.; Rosner, G.; Saha, A.; Sargsian, M. M.; Sawatzky, B.; Segal, J.; Shabestari, M.; Shahinyan, A.; Shestakov, Yu.; Singh, J.; Širca, S.; Souder, P.; Stepanyan, S.; Stibunov, V.; Sulkosky, V.; Tajima, S.; Tobias, W. A.; Udias, J. M.; Urciuoli, G. M.; Vlahovic, B.; Voskanyan, H.; Wang, K.; Wesselmann, F. R.; Vignote, J. R.; Wood, S. A.; Wright, J.; Yao, H.; Zhu, X.

    2010-12-01

    The electric form factor of the neutron was determined from studies of the reaction 3He→(e→,e'n)pp in quasielastic kinematics in Hall A at Jefferson Lab. Longitudinally polarized electrons were scattered off a polarized target in which the nuclear polarization was oriented perpendicular to the momentum transfer. The scattered electrons were detected in a magnetic spectrometer in coincidence with neutrons that were registered in a large-solid-angle detector. More than doubling the Q2 range over which it is known, we find GEn=0.0236±0.0017(stat)±0.0026(syst), 0.0208±0.0024±0.0019, and 0.0147±0.0020±0.0014 for Q2=1.72, 2.48, and 3.41GeV2, respectively.

  13. Measurements of the electric form factor of the neutron up to Q2=3.4 GeV2 using the reaction 3He(e,e'n)pp.

    Science.gov (United States)

    Riordan, S; Abrahamyan, S; Craver, B; Kelleher, A; Kolarkar, A; Miller, J; Cates, G D; Liyanage, N; Wojtsekhowski, B; Acha, A; Allada, K; Anderson, B; Aniol, K A; Annand, J R M; Arrington, J; Averett, T; Beck, A; Bellis, M; Boeglin, W; Breuer, H; Calarco, J R; Camsonne, A; Chen, J P; Chudakov, E; Coman, L; Crowe, B; Cusanno, F; Day, D; Degtyarenko, P; Dolph, P A M; Dutta, C; Ferdi, C; Fernández-Ramírez, C; Feuerbach, R; Fraile, L M; Franklin, G; Frullani, S; Fuchs, S; Garibaldi, F; Gevorgyan, N; Gilman, R; Glamazdin, A; Gomez, J; Grimm, K; Hansen, J-O; Herraiz, J L; Higinbotham, D W; Holmes, R; Holmstrom, T; Howell, D; de Jager, C W; Jiang, X; Jones, M K; Katich, J; Kaufman, L J; Khandaker, M; Kelly, J J; Kiselev, D; Korsch, W; LeRose, J; Lindgren, R; Markowitz, P; Margaziotis, D J; Beck, S May-Tal; Mayilyan, S; McCormick, K; Meziani, Z-E; Michaels, R; Moffit, B; Nanda, S; Nelyubin, V; Ngo, T; Nikolenko, D M; Norum, B; Pentchev, L; Perdrisat, C F; Piasetzky, E; Pomatsalyuk, R; Protopopescu, D; Puckett, A J R; Punjabi, V A; Qian, X; Qiang, Y; Quinn, B; Rachek, I; Ransome, R D; Reimer, P E; Reitz, B; Roche, J; Ron, G; Rondon, O; Rosner, G; Saha, A; Sargsian, M M; Sawatzky, B; Segal, J; Shabestari, M; Shahinyan, A; Shestakov, Yu; Singh, J; Sirca, S; Souder, P; Stepanyan, S; Stibunov, V; Sulkosky, V; Tajima, S; Tobias, W A; Udias, J M; Urciuoli, G M; Vlahovic, B; Voskanyan, H; Wang, K; Wesselmann, F R; Vignote, J R; Wood, S A; Wright, J; Yao, H; Zhu, X

    2010-12-31

    The electric form factor of the neutron was determined from studies of the reaction 3He(e,e'n)pp in quasielastic kinematics in Hall A at Jefferson Lab. Longitudinally polarized electrons were scattered off a polarized target in which the nuclear polarization was oriented perpendicular to the momentum transfer. The scattered electrons were detected in a magnetic spectrometer in coincidence with neutrons that were registered in a large-solid-angle detector. More than doubling the Q2 range over which it is known, we find G(E)(n)=0.0236±0.0017(stat)±0.0026(syst), 0.0208±0.0024±0.0019, and 0.0147±0.0020±0.0014 for Q(2)=1.72, 2.48, and 3.41 GeV2, respectively.

  14. Measurements of the Electric Form Factor of the Neutron up to Q2 = 3.4 GeV2 using the Reaction He-3(e,e'n)pp

    Energy Technology Data Exchange (ETDEWEB)

    Riordan, Seamus; Craver, Brandon; Kelleher, Aidan; Kolarkar, Ameya; Miller, Jonathan; Cates, Gordon; Liyanage, Nilanga; Wojtsekhowski, Bogdan; Quimper, Armando Acha; Allada, Kalyan; Anderson, Byron; Aniol, Konrad; Annand, John; Arrington, John; Averett, Todd; Beck, Arie; Bellis, Matthew; Boeglin, Werner; Breuer, Herbert; Calarco, John; Chen, Jian-Ping; Chudakov, Eugene; Coman, Luminita; Crowe, Benjamin; Cusanno, Francesco; Day, Donal; Degtiarenko, Pavel; Dolph, P.A.M.; Dutta, Chiranjib; Ferdi, Catherine; Fernandez-Ramirez, Cezar; Feuerbach, Robert; Fraile Prieto, Luis; Franklin, Gregg; Frullani, Salvatore; Fuchs, Sabine; Garibaldi, Franco; Gevorgyan, Nerses; Gilman, Ronald; Glazmazdin, Oleksandr; Gomez, Javier; Grimm, Klaus; Hansen, Jens-Ole; Herraiz, Joaquin Lopez; Higinbotham, Douglas; Holmes, Richard; Holmstrom, Timothy; Howell, David; De Jager, Cornelis; Jiang, Xiaodong; Jones, Mark; Katich, Joseph; Kaufman, Lisa; Khandaker, Mahbubul; Kelly, James; Kiselev, Daniela; Korsch, Wolfgang; LeRose, John; Markowitz, Pete; Margaziotis, Demetrius; May-Tal Beck, Sharon; Mayilyan, Samvel; McCormick, Kathy; Meziani, Zein-Eddine; Michaels, Robert; Moffit, Bryan; Nanda, Sirish; Nelyubin, Vladimir; Ngo, Tim; Nikolenko, Dmitri; Norum, Blaine; Pentchev, Lubomir; Perdrisat, Charles; Piasetzky, Eliazer; Pomatsalyuk, Roman; Protopoescu, Dan; Puckett, Andrew; Punjabi, Vina; Qian, XIn; Qiang, Yi; Quinn, Brian; Rachek, Igor; Ransome, Ronald; Reimer, Paul; Reitz, Bodo; Roche, Julie; Ron, Guy; Rondon-Aramayo, Oscar; Rosner, Guenther; Saha, Arunava; Sargsian, Misak; Sawatzky, Bradley; Segal, John; Shabestari, Mitra Hashemi; Shahinyan, Albert; Singh, Jaideep; Sirca, Simon; Souder, Paul; Stepanyan, Samuel; Stibunov, Victor; Sulkosky, Vince; Sulkosky, Vincent; Tajima, Shigeyuki; Tobias, William; Moinelo, Jose Udias; Urciuoli, Guido; Vlahovic, Branislav; Voskanyan, Hakob; Wang, Kebin; Wesselmann, Frank; Vignote, Javier Rodriguez; Wood, Stephen; Wright, Justin; Yao, Huan; Zhu, Zianfang

    2010-12-01

    The electric form factor of the neutron was determined from studies of the reaction \\rea{} in quasi-elastic kinematics in Hall A at Jefferson Lab. Longitudinally polarized electrons were scattered off a polarized target in which the nuclear polarization was oriented perpendicular to the momentum transfer. The scattered electrons were detected in a magnetic spectrometer in coincidence with neutrons that were registered in a large-solid-angle detector. More than doubling the $Q^2$-range over which it is known, we find \\GEn{}$ = 0.0225 \\pm 0.0017 (stat) \\pm 0.0024 (syst)$, $0.0200 \\pm 0.0023 \\pm 0.0018$, and $0.0142 \\pm 0.0019 \\pm 0.0013$ for $Q^2$ = 1.72, 2.48, and 3.41~\\gevsq, respectively.

  15. Measurement of the neutron electric to magnetic form factor ratio at Q2 = 1.58 GeV2 using the reaction 3He(e,e'n)pp

    CERN Document Server

    Schlimme, B S; Gayoso, C A Ayerbe; Bernauer, J C; Böhm, R; Bosnar, D; Challand, Th; Distler, M O; Doria, L; Fellenberger, F; Fonvieille, H; Rodríguez, M Gómez; Grabmayr, P; Hehl, T; Heil, W; Kiselev, D; Krimmer, J; Makek, M; Merkel, H; Middleton, D G; Müller, U; Nungesser, L; Ott, B A; Pochodzalla, J; Potokar, M; Majos, S Sánchez; Sargsian, M M; Sick, I; Širca, S; Weinriefer, M; Wendel, M; Yoon, C J

    2013-01-01

    A measurement of beam helicity asymmetries in the reaction 3He(e,e'n)pp has been performed at the Mainz Microtron in quasielastic kinematics in order to determine the electric to magnetic form factor ratio of the neutron, GEn/GMn, at a four momentum transfer Q2 = 1.58 GeV2. Longitudinally polarized electrons were scattered on a highly polarized 3He gas target. The scattered electrons were detected with a high-resolution magnetic spectrometer, and the ejected neutrons with a dedicated neutron detector composed of scintillator bars. To reduce systematic errors data were taken for four different target polarization orientations allowing the determination of GEn/GMn from a double ratio. We find mu_n GEn/GMn = 0.250 +/- 0.058(stat.) +/- 0.017 (sys.).

  16. Measurement of the neutron electric to magnetic form factor ratio at Q2=1.58  GeV2 using the reaction 3He[over →](e[over →],e'n)pp.

    Science.gov (United States)

    Schlimme, B S; Achenbach, P; Ayerbe Gayoso, C A; Bernauer, J C; Böhm, R; Bosnar, D; Challand, Th; Distler, M O; Doria, L; Fellenberger, F; Fonvieille, H; Gómez Rodríguez, M; Grabmayr, P; Hehl, T; Heil, W; Kiselev, D; Krimmer, J; Makek, M; Merkel, H; Middleton, D G; Müller, U; Nungesser, L; Ott, B A; Pochodzalla, J; Potokar, M; Sánchez Majos, S; Sargsian, M M; Sick, I; Sirca, S; Weinriefer, M; Wendel, M; Yoon, C J

    2013-09-27

    A measurement of beam helicity asymmetries in the reaction 3He[over →](e[over →],e'n)pp is performed at the Mainz Microtron in quasielastic kinematics to determine the electric to magnetic form factor ratio of the neutron GEn/GMn at a four-momentum transfer Q2=1.58  GeV2. Longitudinally polarized electrons are scattered on a highly polarized 3He gas target. The scattered electrons are detected with a high-resolution magnetic spectrometer, and the ejected neutrons are detected with a dedicated neutron detector composed of scintillator bars. To reduce systematic errors, data are taken for four different target polarization orientations allowing the determination of GEn/GMn from a double ratio. We find μnGEn/GMn=0.250±0.058(stat)±0.017(syst). PMID:24116774

  17. Pricing and collecting decisions in a closed-loop supply chain with symmetric and asymmetric information

    DEFF Research Database (Denmark)

    Wei, Jie; Govindan, Kannan; Li, Yongjian;

    2015-01-01

    The optimal decision problem of a closed-loop supply chain with symmetric and asymmetric information structures is considered using game theory in this paper. The paper aims to explore how the manufacturer and the retailer make their own decisions about wholesale price, retail price, and collection....... The optimal strategies in closed form are given under the decision scenarios with symmetric information; moreover, the first order conditions that the optimal retail price, optimal wholesale price, and optimal collection rate satisfy are given under the decision scenarios with asymmetric information...

  18. Behavior of asymmetric Bessel beam in focal plane of high numerical aperture objective

    Science.gov (United States)

    Stafeev, Sergey S.; Kotlyar, Victor V.; Porfirev, Alexey P.

    2016-04-01

    Tight focusing of a linearly-polarized asymmetric Bessel beam, which has a crescent profile, was investigated numerically and experimentally. FDTD calculations show that a binary zone plate of numerical aperture NA = 0.995 forms a crescent in the focal plane, which is rotated clockwise around the optical axis, moving away from the focal plane. Using the Debye formulae it was shown that a direction of polarization of incident light has a significant influence on intensity distribution in focal plane. The crescent in the focal plane was also observed experimentally by focusing of the asymmetric Bessel beam using an immersive objective (NA = 1.25).

  19. THE REACTION BETWEEN ZnO AND MOLTEN NA2S2O7 OR K2S2O7 FORMING NA2Zn(SO4)2 OR K2Zn(SO4)2, STUDIED BY RAMAN SPECTROSCOPY AND X-RAY DIFFRACTION

    DEFF Research Database (Denmark)

    Berg, Rolf W.; Thorup, Niels

    2005-01-01

    Reactions between solid ZnO and molten Na2S2O7 or K2S2O7 at 500 are shown by Raman spectroscopy to be 1:1 reactions leading to solns. By lowering the temp. of the soln. melts, colorless crystals form. Raman spectra of the crystals are given and tentatively assigned. Crystal structures of the mon...

  20. The Chiral Pool in the Pictet-Spengler Reaction for the Synthesis of β-Carbolines.

    Science.gov (United States)

    Dalpozzo, Renato

    2016-01-01

    The Pictet-Spengler reaction (PSR) is the reaction of a β-arylethylamine with an aldehyde or ketone, followed by ring closure to give an aza-heterocycle. When the β-arylethylamine is tryptamine, the product is a β-carboline, a widespread skeleton in natural alkaloids. In the natural occurrence, these compounds are generally enantiopure, thus the asymmetric synthesis of these compounds have been attracting the interest of organic chemists. This review aims to give an overview of the asymmetric PSR, in which the chirality arises from optically pure amines or carbonyl compounds both from natural sources and from asymmetric syntheses to assemble the reaction partners. PMID:27240334