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Sample records for c-c bond formation

  1. Amide-directed photoredox-catalysed C-C bond formation at unactivated sp3 C-H bonds

    Science.gov (United States)

    Chu, John C. K.; Rovis, Tomislav

    2016-11-01

    Carbon-carbon (C-C) bond formation is paramount in the synthesis of biologically relevant molecules, modern synthetic materials and commodity chemicals such as fuels and lubricants. Traditionally, the presence of a functional group is required at the site of C-C bond formation. Strategies that allow C-C bond formation at inert carbon-hydrogen (C-H) bonds enable access to molecules that would otherwise be inaccessible and the development of more efficient syntheses of complex molecules. Here we report a method for the formation of C-C bonds by directed cleavage of traditionally non-reactive C-H bonds and their subsequent coupling with readily available alkenes. Our methodology allows for amide-directed selective C-C bond formation at unactivated sp3 C-H bonds in molecules that contain many such bonds that are seemingly indistinguishable. Selectivity arises through a relayed photoredox-catalysed oxidation of a nitrogen-hydrogen bond. We anticipate that our findings will serve as a starting point for functionalization at inert C-H bonds through a strategy involving hydrogen-atom transfer.

  2. Building Bridges: Biocatalytic C-C-Bond Formation toward Multifunctional Products.

    Science.gov (United States)

    Schmidt, Nina G; Eger, Elisabeth; Kroutil, Wolfgang

    2016-07-01

    Carbon-carbon bond formation is the key reaction for organic synthesis to construct the carbon framework of organic molecules. The review gives a selection of biocatalytic C-C-bond-forming reactions which have been investigated during the last 5 years and which have already been proven to be applicable for organic synthesis. In most cases, the reactions lead to products functionalized at the site of C-C-bond formation (e.g., α-hydroxy ketones, aminoalcohols, diols, 1,4-diketones, etc.) or allow to decorate aromatic and heteroaromatic molecules. Furthermore, examples for cyclization of (non)natural precursors leading to saturated carbocycles are given as well as the stereoselective cyclopropanation of olefins affording cyclopropanes. Although many tools are already available, recent research also makes it clear that nature provides an even broader set of enzymes to perform specific C-C coupling reactions. The possibilities are without limit; however, a big library of variants for different types of reactions is required to have the specific enzyme for a desired specific (stereoselective) reaction at hand.

  3. An erbium-based bifuctional heterogeneous catalyst: a cooperative route towards C-C bond formation.

    Science.gov (United States)

    Oliverio, Manuela; Costanzo, Paola; Macario, Anastasia; De Luca, Giuseppina; Nardi, Monica; Procopio, Antonio

    2014-07-15

    Heterogeneous bifuctional catalysts are multifunctional synthetic catalysts enabling efficient organic transformations by exploiting two opposite functionalities without mutual destruction. In this paper we report the first Er(III)-based metallorganic heterogeneous catalyst, synthesized by post-calcination MW-assisted grafting and modification of the natural aminoacid L-cysteine. The natural acid-base distance between sites was maintained to assure the cooperation. The applicability of this new bifunctional heterogeneous catalyst to C-C bond formation and the supposed mechanisms of action are discussed as well.

  4. An Erbium-Based Bifuctional Heterogeneous Catalyst: A Cooperative Route Towards C-C Bond Formation

    Directory of Open Access Journals (Sweden)

    Manuela Oliverio

    2014-07-01

    Full Text Available Heterogeneous bifuctional catalysts are multifunctional synthetic catalysts enabling efficient organic transformations by exploiting two opposite functionalities without mutual destruction. In this paper we report the first Er(III-based metallorganic heterogeneous catalyst, synthesized by post-calcination MW-assisted grafting and modification of the natural aminoacid L-cysteine. The natural acid–base distance between sites was maintained to assure the cooperation. The applicability of this new bifunctional heterogeneous catalyst to C-C bond formation and the supposed mechanisms of action are discussed as well.

  5. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  6. Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.

    Science.gov (United States)

    Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B

    2010-12-07

    BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions.

  7. Palladium(II)-Catalyzed C-H Bond Activation/C-C and C-O Bond Formation Reaction Cascade: Direct Synthesis of Coumestans.

    Science.gov (United States)

    Neog, Kashmiri; Borah, Ashwini; Gogoi, Pranjal

    2016-12-02

    A palladium catalyzed cascade reaction of 4-hydroxycoumarins and in situ generated arynes has been developed for the direct synthesis of coumestans. This cascade strategy proceeds via C-H bond activation/C-O and C-C bond formations in a single reaction vessel. This methodology affords moderate to good yields of coumestans and is tolerant of a variety of functional groups including halide. The methodology was applied to the synthesis of natural product flemichapparin C.

  8. Identification of Possible Pathways for C-C Bond Formation during Electrochemical Reduction of CO2: New Theoretical Insights from an Improved Electrochemical Model.

    Science.gov (United States)

    Goodpaster, Jason D; Bell, Alexis T; Head-Gordon, Martin

    2016-04-21

    We have carried out a periodic Kohn-Sham density functional theory investigation of the pathways by which carbon-carbon bonds could be formed during the electrochemical reduction of CO2 on Cu(100) using a model that includes the effects of the electrochemical potential, solvent, and electrolyte. The electrochemical potential was set by relating the applied potential to the Fermi energy and then calculating the number of electrons required by the simulation cell for that specific Fermi energy. The solvent was included as a continuum dielectric, and the electrolyte was described using a linearized Poisson-Boltzmann model. The calculated potential of zero charge for a variety of surfaces agrees with experiment to within a mean average error of 0.09 V, thereby validating the assumptions of the model. Analysis of the mechanism for C-C bond formation revealed that at low-applied potential, C-C bond formation occurs through a CO dimer. However, at high applied potentials, a large activation barrier blocks this pathway; therefore, C-C bond formation occurs through reaction of adsorbed CHO and CO. Rate parameters determined from our calculations were used to simulate the kinetics of ethene formation during the electrochemical reduction of CO over a Cu(100) surface. An excellent match was observed between previously reported measurements of the partial current for ethene formation as a function of applied voltage and the variation in the partial current for C-C bond formation predicted by our microkinetic model. The electrochemical model reported here is simple, fairly easy to implement, and involves only a small increase in computational cost over calculations neglecting the effects of the electrolyte and the applied field. Therefore, it can be used to study the effects of applied potential and electrolyte composition on the energetics of surface reactions for a wide variety of electrochemical reactions.

  9. Free-Radical Triggered Ordered Domino Reaction: An Approach to C-C Bond Formation via Selective Functionalization of α-Hydroxyl-(sp(3))C-H in Fluorinated Alcohols.

    Science.gov (United States)

    Xu, Zhengbao; Hang, Zhaojia; Liu, Zhong-Quan

    2016-09-16

    A free-radical mediated highly ordered radical addition/cyclization/(sp(3))C-C(sp(3)) formation domino reaction is developed. Three new C-C bonds are formed one by one in a mixed system. Furthermore, it represents the first example of cascade C-C bond formation via selective functionalization of α-hydroxyl-C(sp(3))-H in fluorinated alcohols.

  10. Alkali metal mediated C-C bond coupling reaction.

    Science.gov (United States)

    Tachikawa, Hiroto

    2015-02-14

    Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2](-) was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.

  11. The new C-C bond formation in the reaction of o-amidophenolate indium(III) complex with alkyl iodides.

    Science.gov (United States)

    Piskunov, Alexandr V; Meshcheryakova, Irina N; Fukin, Georgy K; Shavyrin, Andrei S; Cherkasov, Vladimir K; Abakumov, Gleb A

    2013-08-07

    The reaction of bis(4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-amidophenolato)indium(III) anion with alkyl iodides is reported. This process includes oxidative addition of two RI (R = Me, Et) molecules to the non-transition metal complex and results in an alkyl transfer to ring carbon atoms with the formation of two new C-C bonds. The interaction proceeds at mild conditions and gives new indium(III) derivatives containing iminocyclohexa-1,4-dienolate type ligands.

  12. Unusual C-C bond cleavage in the formation of amine-bis(phenoxy) group 4 benzyl complexes: Mechanism of formation and application to stereospecific polymerization

    KAUST Repository

    Gowda, Ravikumar R.

    2014-08-11

    Group 4 tetrabenzyl compounds MBn4 (M = Zr, Ti), upon protonolysis with an equimolar amount of the tetradentate amine-tris(phenol) ligand N[(2,4-tBu2C6H2(CH 2)OH]3 in toluene from -30 to 25 °C, unexpectedly lead to amine-bis(phenoxy) dibenzyl complexes, BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn2 (M = Zr (1), Ti (2)) in 80% (1) and 75% (2) yields. This reaction involves an apparent cleavage of the >NCH2-ArOH bond (loss of the phenol in the ligand) and formation of the >NCH 2-CH2Bn bond (gain of the benzyl group in the ligand). Structural characterization of 1 by X-ray diffraction analysis confirms that the complex formed is a bis(benzyl) complex of Zr coordinated by a newly derived tridentate amine-bis(phenoxy) ligand arranged in a mer configuration in the solid state. The abstractive activation of 1 and 2 with B(C6F 5)3·THF in CD2Cl2 at room temperature generates the corresponding benzyl cations {BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn(THF)}+[BnB(C6F5) 3]- (M = Zr (3), Ti, (4)). These cationic complexes, along with their analogues derived from (imino)phenoxy tri- and dibenzyl complexes, [(2,6-iPr2C6H3)N=C(3,5- tBu2C6H2)O]ZrBn3 (5) and [2,4-Br2C6H2(O)(6-CH2(NC 5H9))CH2N=CH(2-adamantyl-4-MeC 6H2O)]ZrBn2 (6), have been found to effectively polymerize the biomass-derived renewable β-methyl-α-methylene- γ-butyrolactone (βMMBL) at room temperature into the highly stereoregular polymer PβMMBL with an isotacticity up to 99% mm. A combined experimental and DFT study has yielded a mechanistic pathway for the observed unusual C-C bond cleavage in the present protonolysis reaction between ZrBn4 and N[(2,4-tBu2C 6H2(CH2)OH]3 for the formation of complex 1, which involves the benzyl radical and the Zr(III) species, resulting from thermal and photochemical decomposition of ZrBn4, followed by a series of reaction sequences consisting of protonolysis, tautomerization, H-transfer, oxidation, elimination, and radical coupling. © 2014 American Chemical Society.

  13. A domino palladium-catalyzed C-C and C-O bonds formation via dual O-H bond activation: synthesis of 6,6-dialkyl-6H-benzo[c]chromenes.

    Science.gov (United States)

    Mahendar, Lodi; Krishna, Jonnada; Reddy, Alavala Gopi Krishna; Ramulu, Bokka Venkat; Satyanarayana, Gedu

    2012-01-20

    An efficient Pd-catalyzed domino reaction of α,α-dialkyl-(2-bromoaryl)methanols to 6,6-dialkyl-6H-benzo[c]chromenes is presented. Their formation can be explained via a five membered Pd(II)-cycle that efficiently involves a domino homocoupling with the second molecule, β-carbon cleavage, and finally intramolecular Buchwald-Hartwig cyclization. This domino process effectively involves breaking of five σ-bonds (2C-Br, 2O-H, and a C-C) and formation of two new σ-bonds (C-C and C-O). This mechanistic pathway is unprecedented and further illustrates the power of transition metal catalysis.

  14. Luminescent pincer platinum(II) complexes with emission quantum yields up to almost unity: photophysics, photoreductive C-C bond formation, and materials applications.

    Science.gov (United States)

    Chow, Pui-Keong; Cheng, Gang; Tong, Glenna So Ming; To, Wai-Pong; Kwong, Wai-Lun; Low, Kam-Hung; Kwok, Chi-Chung; Ma, Chensheng; Che, Chi-Ming

    2015-02-09

    Luminescent pincer-type Pt(II)  complexes supported by C-deprotonated π-extended tridentate RC^N^NR' ligands and pentafluorophenylacetylide ligands show emission quantum yields up to almost unity. Femtosecond time-resolved fluorescence measurements and time-dependent DFT calculations together reveal the dependence of excited-state structural distortions of [Pt(RC^N^NR')(CC-C6 F5 )] on the positional isomers of the tridentate ligand. Pt complexes [Pt(R-C^N^NR')(CC-Ar)] are efficient photocatalysts for visible-light-induced reductive CC bond formation. The [Pt(R-C^N^NR')(CC-C6 F5 )] complexes perform strongly as phosphorescent dopants for green- and red-emitting organic light-emitting diodes (OLEDs) with external quantum efficiency values over 22.1 %. These complexes are also applied in two-photon cellular imaging when incorporated into mesoporous silica nanoparticles (MSNs).

  15. Understanding Rotation about a C=C Double Bond

    Science.gov (United States)

    Barrows, Susan E.; Eberlein, Thomas H.

    2005-09-01

    In this article, twisting about the C=C double bond and the consequential pyramidalization of sp 2 carbon atoms in alkenes were examined in a molecular modeling study using trans -2-butene as a model system. According to our trans -2-butene model and other similar work, most of the strength of a π bond is retained upon twisting, even for remarkably large C C=C C dihedral angles (up to 90°). The phenomenon of sp 2 carbon atom pyramidalization and preservation of π bond strength upon twisting a C=C double bond is well established in the literature, but is rarely discussed in introductory textbooks. This absence is noteworthy because profound manifestations of this effect do occur in compounds that are covered in an introductory organic chemistry curriculum. We present a simple method of introducing the concept of a flexible C=C π bond into beginning organic chemistry courses. We report the energetic demands of partial twisting about the C=C bond in 2-butene as calculated using DFT, LMP2, and MCSCF methods. Finally, using the results of these calculations, we assessed the degree of strain introduced by the twisted nature of the C=C bond in trans cycloalkenes.

  16. The Novel Selective Reduction of the C-C Triple Bond

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A novel reduction system is reported here in which the compounds with terminal C-C triple bond and disubstituted C-C triple bond react with NaBH4/Pd(PPh3)4 in a base condition and only terminal C-C triple bond is reduced.

  17. Reactivity of Tp(Me2) -supported yttrium alkyl complexes toward aromatic N-heterocycles: ring-opening or C-C bond formation directed by C-H activation.

    Science.gov (United States)

    Yi, Weiyin; Zhang, Jie; Huang, Shujian; Weng, Linhong; Zhou, Xigeng

    2014-01-13

    Unusual chemical transformations such as three-component combination and ring-opening of N-heterocycles or formation of a carbon-carbon double bond through multiple C-H activation were observed in the reactions of Tp(Me2) -supported yttrium alkyl complexes with aromatic N-heterocycles. The scorpionate-anchored yttrium dialkyl complex [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with 1-methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24-membered rare-earth metallomacrocyclic compound [Tp(Me2) Y(μ-N,C-Im)(η(2) -N,C-Im)]6 (1; Im=1-methylimidazolyl) through two kinds of C-H activations at the C2- and C5-positions of the imidazole ring. However, [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with two equivalents of 1-methylbenzimidazole to afford a C-C coupling/ring-opening/C-C coupling product [Tp(Me2) Y{η(3) -(N,N,N)-N(CH3 )C6 H4 NHCHC(Ph)CN(CH3 )C6 H4 NH}] (2). Further investigations indicated that [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C-C coupling/ring-opening product {(Tp(Me2) )Y[μ-η(2) :η(1) -SC6 H4 N(CHCHPh)](THF)}2 (3). Moreover, the mixed Tp(Me2) /Cp yttrium monoalkyl complex [(Tp(Me2) )CpYCH2 Ph(THF)] reacted with two equivalents of 1-methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [Tp(Me2) CpY(μ-N,C-Im)]3 (5), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [Tp(Me2) Y(Im-Tp(Me2) )] (7; Im-Tp(Me2) =1-methyl-imidazolyl-Tp(Me2) ) and [Cp3 Y(HIm)] (8; HIm=1-methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a CC bond through multiple C-H activations.

  18. Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes.

    Science.gov (United States)

    Zhang, Shaoguang; Li, Haixia; Appel, Aaron M; Hall, Michael B; Bullock, R Morris

    2016-07-04

    Unusual cleavage of P-C and C-H bonds of the P2 N2 ligand, in heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C,P,P-tridentate coordination mode. The structures of both the heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P-C/C-H bond cleavage, which involves C-H bond cleavage, hydride rotation, Ni-C/P-H bond formation, and P-C bond cleavage.

  19. An excursion from normal to inverted C-C bonds shows a clear demarcation between covalent and charge-shift C-C bonds.

    Science.gov (United States)

    Shaik, Sason; Chen, Zhenhua; Wu, Wei; Stanger, Amnon; Danovich, David; Hiberty, Philippe C

    2009-10-19

    What is the nature of the C-C bond? Valence bond and electron density computations of 16 C-C bonds show two families of bonds that flesh out as a phase diagram. One family, involving ethane, cyclopropane and so forth, is typified by covalent C-C bonding wherein covalent spin-pairing accounts for most of the bond energy. The second family includes the inverted bridgehead bonds of small propellanes, where the bond is neither covalent nor ionic, but owes its existence to the resonance stabilization between the respective structures; hence a charge-shift (CS) bond. The dual family also emerges from calculated and experimental electron density properties. Covalent C-C bonds are characterized by negative Laplacians of the density, whereas CS-bonds display small or positive Laplacians. The positive Laplacian defines a region suffering from neighbouring repulsive interactions, which is precisely the case in the inverted bonding region. Such regions are rich in kinetic energy, and indeed the energy-density analysis reveals that CS-bonds are richer in kinetic energy than the covalent C-C bonds. The large covalent-ionic resonance energy is precisely the mechanism that lowers the kinetic energy in the bonding region and restores equilibrium bonding. Thus, different degrees of repulsive strain create two bonding families of the same chemical bond made from a single atomic constituent. It is further shown that the idea of repulsive strain is portable and can predict the properties of propellanes of various sizes and different wing substituents. Experimentally (M. Messerschmidt, S. Scheins, L. Bruberth, M. Patzel, G. Szeimies, C. Paulman, P. Luger, Angew. Chem. 2005, 117, 3993-3997; Angew. Chem. Int. Ed. 2005, 44, 3925-3928), the C-C bond families are beautifully represented in [1.1.1]propellane, where the inverted C-C is a CS-bond, while the wings are made from covalent C-C bonds. What other manifestations can we expect from CS-bonds? Answers from experiment have the potential

  20. Homolytic Bond Dissociation Enthalpies of C C and C-H Bonds in Highly Crowded Alkanes

    Institute of Scientific and Technical Information of China (English)

    ZHU Chen; RUI Lei; FU Yao

    2008-01-01

    The homolytic C-C and C--H bond dissociation enthalpyies (BDE) of highly crowded alkanes were calcu- lated by using an ONIOM-G3B3 method. Geometric parameters such as bond length, bond angle and molecular volume were carefully investigated, as most of the acyclic alkanes in this study were not yet synthesized. These pa-rameters reflect the influence of steric effect on BDE. Good correlations were found between the rapid decrease of BDE and the increase of molecular volumes. The correlations can be applied to the prediction of the possible exis-tence of many highly strained compounds.

  1. Stereochemistry of enzymatic water addition to C=C bonds.

    Science.gov (United States)

    Chen, Bi-Shuang; Otten, Linda G; Hanefeld, Ulf

    2015-01-01

    Water addition to carbon-carbon double bonds using hydratases is attracting great interest in biochemistry. Most of the known hydratases are involved in primary metabolism and to a lesser extent in secondary metabolism. New hydratases have recently been added to the toolbox, both from natural sources or artificial metalloenzymes. In order to comprehensively understand how the hydratases are able to catalyse the water addition to carbon-carbon double bonds, this review will highlight the mechanistic and stereochemical studies of the enzymatic water addition to carbon-carbon double bonds, focusing on the syn/anti-addition and stereochemistry of the reaction.

  2. Activation of Aromatic C-C Bonds of 2,2'-Bipyridine Ligands.

    Science.gov (United States)

    Fombona, Sergio; Espinal-Viguri, Maialen; Huertos, Miguel A; Díaz, Jesús; López, Ramón; Menéndez, M Isabel; Pérez, Julio; Riera, Lucía

    2016-11-21

    4,4'-Disubstituted-2,2'-bipyridine ligands coordinated to Mo(II) and Re(I) cationic fragments become dearomatized by an intramolecular nucleophilic attack from a deprotonated N-alkylimidazole ligand in cis disposition. The subsequent protonation of these neutral complexes takes place on a pyridine carbon atom rather than at nitrogen, weakening an aromatic C-C bond and affording a dihydropyridyl moiety. Computational calculations allowed for the rationalization of the formation of the experimentally obtained products over other plausible alternatives.

  3. Borane-catalyzed cracking of C-C bonds in coal; Boran-katalysierte C-C-Bindungungsspaltung in Steinkohle

    Energy Technology Data Exchange (ETDEWEB)

    Narangerel, J.; Haenel, M.W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-09-01

    Coal, especially coking coal, was reacted with hydrogen at comparatively mild reaction conditions (150-280 degrees centigrade, 20 MPa hydrogen pressure) in the presence of catalysts consisting of borange reagents and certain transition metal halides to obtaine more than 80 percent of pyridine-soluble products. The influence of the degree of coalification, catalyst and temperature on the borane-catalyzed hydrogenolysis of C-C bonds in coal was investigated. (orig.) [Deutsch] Steinkohlen, insbesondere im Inkohlungsbereich der Fettkohlen (Kokskohlen), werden in Gegenwart von Katalysatoren aus Boran-Reagentien und bestimmten Uebergangsmetallhalogeniden mit Wasserstoff bei vergleichsweise milden Reaktionsbedingungen (250-280 C, 20 MPa Wasserstoffdruck) in zu ueber 80% pyridinloesliche Produkte umgewandelt. Der Einfluss von Inkohlungsgrad, Katalysator und Temperatur auf die Boran-katalysierte C-C-Bindungshydrogenolyse in Kohle wurde untersucht. (orig.)

  4. Bite angle effects of diphosphines in C-C and C-X bond forming cross coupling reactions

    NARCIS (Netherlands)

    Birkholz, M.N.; Freixa, Z.; van Leeuwen, P.W.N.M.

    2009-01-01

    Catalytic reactions of C-C and C-X bond formation are discussed in this critical review with particular emphasis on cross coupling reactions catalyzed by palladium and wide bite angle bidentate diphosphine ligands. Especially those studies have been collected that allow comparison of the ligand bite

  5. Photocatalytic C-C Bond Cleavage and Amination of Cycloalkanols by Cerium(III) Chloride Complex.

    Science.gov (United States)

    Guo, Jing-Jing; Hu, Anhua; Chen, Yilin; Sun, Jianfeng; Tang, Haoming; Zuo, Zhiwei

    2016-12-05

    A general strategy for the cleavage and amination of C-C bonds of cycloalkanols has been achieved through visible-light-induced photoredox catalysis utilizing a cerium(III) chloride complex. This operationally simple methodology has been successfully applied to a wide array of unstrained cyclic alcohols, and represents the first example of catalytic C-C bond cleavage and functionalization of unstrained secondary cycloalkanols.

  6. Mathematical Simulation of Graphene With Modified c-c Bond Length and Transfer Energy

    Directory of Open Access Journals (Sweden)

    P.A. Alvi

    2011-01-01

    Full Text Available In nanotechnology research, allotropes of carbon like Graphene, Fullerene (Buckyball and Carbon nanotubes are widely used due to their remarkable properties. Electrical and mechanical properties of those allotropes vary with their molecular geometry. This paper is specially based on modeling and simulation of graphene in order to calculate energy band structure in k space with varying the C-C bond length and C-C transfer energy. Significant changes have been observed in the energy band structure of graphene due to variation in C-C bond length and C-C transfer energy. In particular, this paper focuses over the electronic structure of graphene within the frame work of tight binding approximation. It has been reported that conduction and valence states in graphene only meet at two points in k-space and that dispersion around these special points is conical.

  7. Mathematical Simulation of Graphene With Modified c-c Bond Length and Transfer Energy

    OpenAIRE

    P.A. Alvi; S.Z. Hashmi; S. Dalela; Rahman, F.

    2011-01-01

    In nanotechnology research, allotropes of carbon like Graphene, Fullerene (Buckyball) and Carbon nanotubes are widely used due to their remarkable properties. Electrical and mechanical properties of those allotropes vary with their molecular geometry. This paper is specially based on modeling and simulation of graphene in order to calculate energy band structure in k space with varying the C-C bond length and C-C transfer energy. Significant changes have been observed in the energy band struc...

  8. Exchanging Alkyl Groups through Unstrained C-C Bond Cleavage in the Presence of a Copper Catalyst.

    Science.gov (United States)

    Wada, Masaru; Noda, Yushi; Nishikata, Takashi

    2017-04-05

    Although numerous reports exist on strained C-C bond cleavage reactions in aryl substitutions, the cleavage methodology for unstrained C-C bonds in alkylation reactions has not yet been established. We found that unstrained allylic C-C bonds can be cleaved using α-radicals to form C(sp(3) )-C(sp(3) ) bonds in the presence of a copper catalyst. In this reaction, the property of leaving and loading radicals is very important for radical fragmentations. In this paper, we investigated the effects of these properties in cleavage reactions for unstrained C-C bonds.

  9. Extended reaction scope of thiamine diphosphate dependent cyclohexane-1,2-dione hydrolase: from C-C bond cleavage to C-C bond ligation.

    Science.gov (United States)

    Loschonsky, Sabrina; Wacker, Tobias; Waltzer, Simon; Giovannini, Pier Paolo; McLeish, Michael J; Andrade, Susana L A; Müller, Michael

    2014-12-22

    ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzes the CC bond cleavage of cyclohexane-1,2-dione to 6-oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH-H28A is much less able to catalyze the CC bond formation, while the ability for CC bond cleavage is still intact. The double variant CDH-H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane-1,2-dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54-94 % enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane-2,3-dione are alternative donor substrates for CC bond formation. Thus, the very rare aldehyde-ketone cross-benzoin reaction has been solved by design of an enzyme variant.

  10. Pd-catalyzed autotandem C-C/C-C bond-forming reactions with tosylhydrazones: synthesis of spirocycles with extended π-conjugation.

    Science.gov (United States)

    Barroso, Raquel; Valencia, Rocío A; Cabal, María-Paz; Valdés, Carlos

    2014-04-18

    A new Pd-catalyzed autotandem process is presented by the reaction of tosylhydrazones of cyclic ketones and 2,2'-dibromobiphenyls and related systems. The process involves cross-coupling with tosylhydrazone followed by an intramolecular Heck reaction and gives rise to spirocyclic structures. Noteworthy, two C-CAr bonds are formed on the hydrazonic carbon during the process. Depending on the starting dibromide, an array of spirofluorenes, spirodibenzofluorenes, spiroacridines, and spiroanthracenes have been prepared. Thus, this methodology may be applied for the preparation of interesting structures useful in the development of optoelectronic materials.

  11. Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shaoguang [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Li, Haixia [Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry; Appel, Aaron M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Hall, Michael B. [Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry; Bullock, R. Morris [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-06-07

    Unusual cleavage of P-C and C-H bonds of the P2N2 ligand in heteroleptic [Ni(P2N2)(diphosphine)]2+ complexes results in the formation of an iminium formyl nickelate featuring a C,P,P-tridentate coordination mode.

  12. Binuclear metal carbonyl DAB complexes X. Activation of h2-C=N coordinated DAB ligands towards C-C bond formation with alkynes. The X-ray structure of {2-phenyl-3-(tert-butylamino)-4-(tertbutyl-imino)-1-butene-1-yl}Ru2(CO)5. Application to the catalytic cyclotrimerization of alkynes

    NARCIS (Netherlands)

    Koten, G. van; Staal, L.H.; Vrieze, K.; Santen, B. van; Stam, C.H.

    1981-01-01

    Ru,(CO),(DAB) (DAB = 1,4-diazabutadiene) complexes react with alkynes forming RU,(CO)~(AIB) complexes (AIB = 3-amino-4-imino-1-buten-1-ylI)n. these products the DAB ligand and the alkyne are coupled via a C-C bond. The molecular structure of these complexes has been determined by a single-crystal X-

  13. Observation of Spontaneous C=C Bond Breaking in the Reaction between Atomic Boron and Ethylene in Solid Neon.

    Science.gov (United States)

    Jian, Jiwen; Lin, Hailu; Luo, Mingbiao; Chen, Mohua; Zhou, Mingfei

    2016-07-11

    A ground-state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene-like compound H2 CBCH2 on annealing in solid neon. This compound can further isomerize to the propyne-like HCBCH3 isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C-H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures.

  14. The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.

    Science.gov (United States)

    Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno

    2013-04-28

    The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

  15. Synthesis and systematic evaluation of symmetric sulfonated centrally C-C bonded cyanine near-infrared dyes for protein labelling

    NARCIS (Netherlands)

    Wal, Van Der Steffen; Kuil, Joeri; Valentijn, A.R.P.M.; Leeuwen, Van Fijs W.B.

    2016-01-01

    The most commonly used near-infrared cyanine dyes contain an aryl ether that is not fully stable towards nucleophiles. Replacement of the aryl ether by a more stable carbon-carbon bond can improve the stability. In this work we have synthesized a series of four negatively-charged symmetrical C-C

  16. Chiral Pd aqua complex-catalyzed asymmetric C-C bond-forming reactions: a Brønsted acid-base cooperative system.

    Science.gov (United States)

    Sodeoka, Mikiko; Hamashima, Yoshitaka

    2009-10-21

    Chiral cationic Pd aqua complexes can function as acid-base catalysts, effectively activating active methylene and methine compounds to give chiral Pd enolates. It is noteworthy that such enolate formation occurs with concomitant formation of a strong protic acid. Although the reactivity of the Pd enolate itself is not sufficient for reactions with carbon-based electrophiles, its cooperative action with the protic acid to activate the electrophiles allows the desired C-C bond-forming reactions to proceed smoothly in a highly enantioselective manner. Based on this mechanistic feature, reactions with acetals have been developed; these are difficult to achieve using conventional basic enolate chemistry.

  17. Application of Sol Self-Clean Bonded Al2O3-SiC-C Castable for Iron Runner

    Institute of Scientific and Technical Information of China (English)

    XU Guotao; ZHANG Honglei; CHEN Huasheng; WANG Yue; LI Huaiyuan; XIONG Yafei

    2006-01-01

    The properties and microstructure of sol self-clean bonded Al2O3-SiC-C castable in iron runner were studied, and the relation between the amount of sol selfclean binder and the properties of castable were discussed. It is believed that the addition of sol self-clean binder can improve the compressive strength, but has little effect on the bulk density and the apparent porosity,which enable the castable to be applicable in different conditions.

  18. Transfer Hydrogenation of C= C Double Bonds Catalyzed by Ruthenium Amido-Complexes:Scopes, Limitation and Enantioselectivity

    Institute of Scientific and Technical Information of China (English)

    XUE,Dong; CHENG,Ying-Chun; CUI,Xin; WANG,Qi-Wei; ZHU,Jin; DENG,Jin-Gen

    2004-01-01

    @@ The reduction of C = C double bonds is one of the most fundamental synthetic transformations and plays a key role in the manufacturing of a wide variety of bulk and fine chemicals. Hydrogenation of olefinic substrates can be achieved readily with molecular hydrogen in many cases, but transfer hydrogenation methods using suitable donor molecules such as formic acid or alcohols are receiving increasing attention as possible synthetic alternatives because it requires no special equipment and avoids the handling of potentially hazardous gaseous hydrogen.

  19. Pd/C-mediated dual C-C bond forming reaction in water: synthesis of 2,4-dialkynylquinoline

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, Ellanki A.; Islam, Aminul; Venu, Bolla K. [Dr. Reddy' s Laboratories Limited, Hyderabad, Andhra Pradesh (India); Mukkanti, K. [JNT University, Hyderabad, Andhra Pradesh (India). Inst. of Science and Technology. Chemistry Division; Pal, Manojit, E-mail: manojitpal@rediffmail.co [Matrix Laboratories Ltd., Medak District, Andra Pradesh (India). New Drug Discovery. R and D Center

    2010-07-01

    Pd/C facilitated dual C-C bond forming reaction between 2,4-diiodoquinoline and terminal alkynes in water providing a practical and one-step synthesis of 2,4-dialkynylquinolines. A number of related quinoline derivatives were prepared in good to excellent yields using this water-based methodology. The use of other palladium catalysts and solvents was examined and the mechanism of the reaction has been discussed. (author)

  20. Unique properties of C,C'-linked nido-biscarborane tetraanions. Synthesis, structure and bonding of ruthenium monocarbollide via unprecedented cage carbon extrusion.

    Science.gov (United States)

    Zhao, Da; Zhang, Jiji; Lin, Zhenyang; Xie, Zuowei

    2016-08-21

    Four reaction pathways have been found in the reaction of a C,C'-linked nido-biscarborane tetraanionic salt with [Ru(p-cymene)Cl2]2, leading to the isolation and structural characterization of redox, triple cage B-H oxidative addition, cage expansion and cage carbon extrusion products. Among these, the unprecedented cage carbon extrusion results in the formation of a new 6π-electron carboranyl ligand [C2B10H10](2-). The bonding interactions between this ligand and the Ru(ii) center have also been discussed on the basis of DFT calculations.

  1. Mechanistic Insights on C-O and C-C Bond Activation and Hydrogen Insertion during Acetic Acid Hydrogenation Catalyzed by Ruthenium Clusters in Aqueous Medium

    Energy Technology Data Exchange (ETDEWEB)

    Shangguan, Junnan; Olarte, Mariefel V.; Chin, Ya-Huei [Cathy

    2016-06-07

    Catalytic pathways for acetic acid (CH3COOH) and hydrogen (H2) reactions on dispersed Ru clusters in the aqueous medium and the associated kinetic requirements for C-O and C-C bond cleavages and hydrogen insertion are established from rate and isotopic assessments. CH3COOH reacts with H2 in steps that either retain its carbon backbone and lead to ethanol, ethyl acetate, and ethane (47-95 %, 1-23 %, and 2-17 % carbon selectivities, respectively) or break its C-C bond and form methane (1-43 % carbon selectivities) at moderate temperatures (413-523 K) and H2 pressures (10-60 bar, 298 K). Initial CH3COOH activation is the kinetically relevant step, during which CH3C(O)-OH bond cleaves on a metal site pair at Ru cluster surfaces nearly saturated with adsorbed hydroxyl (OH*) and acetate (CH3COO*) intermediates, forming an adsorbed acetyl (CH3CO*) and hydroxyl (OH*) species. Acetic acid turnover rates increase proportionally with both H2 (10-60 bar) and CH3COOH concentrations at low CH3COOH concentrations (<0.83 M), but decrease from first to zero order as the CH3COOH concentration and the CH3COO* coverages increase and the vacant Ru sites concomitantly decrease. Beyond the initial CH3C(O)-OH bond activation, sequential H-insertions on the surface acetyl species (CH3CO*) lead to C2 products and their derivative (ethanol, ethane, and ethyl acetate) and the competitive C-C bond cleavage of CH3CO* causes the eventual methane formation. The instantaneous carbon selectivities towards C2 species (ethanol, ethane, and ethyl acetate) increase linearly with the concentration of proton-type Hδ+ (derived from carboxylic acid dissociation) and chemisorbed H*. The selectivities towards C2 products decrease with increasing temperature, because of higher observed barriers for C-C bond cleavage than H-insertion. This study offers an interpretation of mechanism and energetics and provides kinetic evidence of carboxylic acid assisted proton-type hydrogen (Hδ+) shuffling during H

  2. 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.

  3. Mesophase formation of coal-tar pitches used for impregnant of C/C composites

    Institute of Scientific and Technical Information of China (English)

    巩前明; 黄启忠; 黄伯云; 张福勤; 陈腾飞

    2001-01-01

    By a polarized light optical microscopy with a hot stage, liquid-phase nuclear magnetic resonance 13 C-NMR and 1 H-NMR, X-ray diffractometry and scanning electron microscopy (SEM), the factors that affect the formation of mesophase in C/C composites, such as pressure, quinoline insolubles (QI) and heterocylic compounds, were analyzed. Further, the graphitizability of the resultant carbon was discussed. The results indicate that to some degree, QI contents accelerate the formation of mesophase at atmospheric pressure; while at high pressure, the coalescence and growth of mesophase spherules are impeded and the resultant coke produced from higher QI content pitch is harder to be graphitized. This is in agreement with the transfer of microstructure from domain anisotropy to fine-grained mosaics.

  4. General and Efficient C-C Bond Forming Photoredox Catalysis with Semiconductor Quantum Dots.

    Science.gov (United States)

    Caputo, Jill A; Frenette, Leah C; Zhao, Norman; Sowers, Kelly L; Krauss, Todd D; Weix, Daniel J

    2017-03-29

    Photoredox catalysis has become an essential tool in organic synthesis because it enables new routes to important molecules. However, the best available molecular catalysts suffer from high catalyst loadings and rely on precious metals. Here we show that colloidal nanocrystal quantum dots (QDs) can serve as efficient and robust, precious-metal free, photoassisted redox catalysts. A single-sized CdSe quantum dot (3.0 ± 0.2 nm) can replace several different dye catalysts needed for five different photoredox reactions (β-alkylation, β-aminoalkylation, dehalogenation, amine arylation, and decarboxylative radical formation). Even without optimization of the QDs or the reaction conditions, efficiencies rivaling those of the best available metal dyes were obtained.

  5. Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant.

    Science.gov (United States)

    Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K

    2017-03-17

    A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1).

  6. Microstructure characteristic and formation mechanism of crackfree TaC coating on C/C composite

    Institute of Scientific and Technical Information of China (English)

    LI Guo-dong; XIONG Xiang; HUANG Bai-yun

    2005-01-01

    The microstructure characteristic and formation mechanism of the crackfree and ablation-resistant TaC coating deposited on the C/C composite by Chemical Vapour Deposition(CVD) were investigated, using the reaction system of TaCl5-C3H6-H2-Ar. The results show that the nanosized pore structure formed in the TaC coating interior during CVD process is the main factor to reduce the hardness, elastic modulus, linear expansibility and inner thermal stress. Then crackfree coatings can be prepared and their thermal shock resistance can be enhanced. To obtain the dense and homogeneous matrix surface is necessary for the crackfree and low stress coating. The TaC coating structure that distributes from the dense matrix towards loose coating surface will result in the thick crackfree coating with good thermal shock resistance.

  7. First principles study of the electronic and magnetic structures and bonding properties of UCoC2 ternary, characteristic of C-C units

    Science.gov (United States)

    Matar, Samir F.

    2013-03-01

    The electronic structure of UCoC2, a di-carbide with the C-C units is examined from ab initio with an assessment of the properties of chemical bonding. The energy-volume equation of state shows large anisotropy effects due to C-C alignment along tetragonal c-axis leading to high linear incompressibility. Relevant features of selective bonding of uranium and cobalt with carbon at two different Wyckoff sites and strong C-C interactions are remarkable. The vibrational frequencies for C⋯C stretching modes indicate closer behavior to aliphatic C-C rather than Cdbnd C double bond. A ferromagnetic ground state is proposed from the calculations.

  8. Selective scission of C-O and C-C bonds in ethanol using bimetal catalysts for the preferential growth of semiconducting SWNT arrays.

    Science.gov (United States)

    Zhang, Shuchen; Hu, Yue; Wu, Juanxia; Liu, Dan; Kang, Lixing; Zhao, Qiuchen; Zhang, Jin

    2015-01-28

    For the application of single-walled carbon nanotubes (SWNTs) to electronic and optoelectronic devices, techniques to obtain semiconducting SWNT (s-SWNT) arrays are still in their infancy. We have developed herein a rational approach for the preferential growth of horizontally aligned s-SWNT arrays on a ST-cut quartz surface through the selective scission of C-O and C-C bonds of ethanol using bimetal catalysts, such as Cu/Ru, Cu/Pd, and Au/Pd. For a common carbon source, ethanol, a reforming reaction occurs on Cu or Au upon C-C bond breakage and produces C(ads) and CO, while a deoxygenating reaction occurs on Ru or Pd through C-O bond breaking resulting in the production of O(ads) and C2H4. The produced C2H4 by Ru or Pd can weaken the oxidative environment through decomposition and the neutralization of O(ads). When the bimetal catalysts with an appropriate ratio were used, the produced C(ads) and C2H4 can be used as carbon source for SWNT growth, and O(ads) promotes a suitable and durable oxidative environment to inhibit the formation of metallic SWNTs (m-SWNTs). Finally, we successfully obtained horizontally aligned SWNTs on a ST-cut quartz surface with a density of 4-8 tubes/μm and an s-SWNT ratio of about 93% using an Au/Pd (1:1) catalyst. The synergistic effects in bimetallic catalysts provide a new mechanism to control the growth of s-SWNTs.

  9. Metal-catalyzed C-C bond cleavage in alkanes: effects of methyl substitution on transition-state structures and stability.

    Science.gov (United States)

    Flaherty, David W; Hibbitts, David D; Iglesia, Enrique

    2014-07-01

    Methyl substituents at C-C bonds influence hydrogenolysis rates and selectivities of acyclic and cyclic C2-C8 alkanes on Ir, Rh, Ru, and Pt catalysts. C-C cleavage transition states form via equilibrated dehydrogenation steps that replace several C-H bonds with C-metal bonds, desorb H atoms (H*) from saturated surfaces, and form λ H2(g) molecules. Activation enthalpies (ΔH(‡)) and entropies (ΔS(‡)) and λ values for (3)C-(x)C cleavage are larger than for (2)C-(2)C or (2)C-(1)C bonds, irrespective of the composition of metal clusters or the cyclic/acyclic structure of the reactants. (3)C-(x)C bonds cleave through α,β,γ- or α,β,γ,δ-bound transition states, as indicated by the agreement between measured activation entropies and those estimated for such structures using statistical mechanics. In contrast, less substituted C-C bonds involve α,β-bound species with each C atom bound to several surface atoms. These α,β configurations weaken C-C bonds through back-donation to antibonding orbitals, but such configurations cannot form with (3)C atoms, which have one C-H bond and thus can form only one C-M bond. (3)C-(x)C cleavage involves attachment of other C atoms, which requires endothermic C-H activation and H* desorption steps that lead to larger ΔH(‡) values but also larger ΔS(‡) values (by forming more H2(g)) than for (2)C-(2)C and (2)C-(1)C bonds, irrespective of alkane size (C2-C8) or cyclic/acyclic structure. These data and their mechanistic interpretation indicate that low temperatures and high H2 pressures favor cleavage of less substituted C-C bonds and form more highly branched products from cyclic and acyclic alkanes. Such interpretations and catalytic consequences of substitution seem also relevant to C-X cleavage (X = S, N, O) in desulfurization, denitrogenation, and deoxygenation reactions.

  10. FeCl2-promoted cleavage of the unactivated C-C bond of alkylarenes and polystyrene: direct synthesis of arylamines.

    Science.gov (United States)

    Qin, Chong; Shen, Tao; Tang, Conghui; Jiao, Ning

    2012-07-09

    Ironing it out: an efficient and convenient nitrogenation strategy involving C-C bond cleavage for the straightforward synthesis of versatile arylamines is presented. Various alkyl azides and alkylarenes, including the common industrial by-product cumene, react using this protocol. Moreover, this method provides a potential strategy for the degradation of polystyrene.

  11. Direct C-C Coupling of CO2 and the Methyl Group from CH4 Activation through Facile Insertion of CO2 into Zn-CH3 σ-Bond.

    Science.gov (United States)

    Zhao, Yuntao; Cui, Chaonan; Han, Jinyu; Wang, Hua; Zhu, Xinli; Ge, Qingfeng

    2016-08-17

    Conversion of CO2 and CH4 to value-added products will contribute to alleviating the green-house gas effect but is a challenge both scientifically and practically. Stabilization of the methyl group through CH4 activation and facile CO2 insertion ensure the realization of C-C coupling. In the present study, we demonstrate the ready C-C coupling reaction on a Zn-doped ceria catalyst. The detailed mechanism of this direct C-C coupling reaction was examined based on the results from density functional theory calculations. The results show that the Zn dopant stabilizes the methyl group by forming a Zn-C bond, thus hindering subsequent dehydrogenation of CH4. CO2 can be inserted into the Zn-C bond in an activated bent configuration, with the transition state in the form of a three-centered Zn-C-C moiety and an activation barrier of 0.51 eV. The C-C coupling reaction resulted in the acetate species, which could desorb as acetic acid by combining with a surface proton. The formation of acetic acid from CO2 and CH4 is a reaction with 100% atom economy, and the implementation of the reaction on a heterogeneous catalyst is of great importance to the utilization of the greenhouse gases. We tested other possible dopants including Al, Ga, Cd, In, and Ni and found a positive correlation between the activation barrier of C-C coupling and the electronegativity of the dopant, although C-H bond activation is likely the dominant reaction on the Ni-doped ceria catalyst.

  12. Di([5]trovacenyl)ethyne, di([5]trovacenyl)butadiyne, and di-1,4-([5]trovacenylethynyl)benzene: electrocommunication and magnetocommunication mediated by --C triple bond C--, --C triple bond C--C triple bond C-- and --C triple bond C--C6H4--C triple bond C-- spacers.

    Science.gov (United States)

    Elschenbroich, Christoph; Plackmeyer, Jörn; Nowotny, Mathias; Harms, Klaus; Pebler, Jürgen; Burghaus, Olaf

    2005-02-21

    The synthesis of dinuclear derivatives of trovacene (eta7-C7H7)V(eta5-C5H5) (1.) is reported, in which ethynyl (6..), butadiynyl (7..), and 1,4-di(ethynyl)phenyl (8..) groups serve as spacers between paramagnetic (S = 1/2) [5]trovacenyl units. The mononuclear precursors [5]trovacenylcarbaldehyde (2.) and [5]trovacenylacetylene (4.) are also described. Structural characterization by X-ray diffraction has been performed for 4., 6.., 7.., and 8.. Electronic communication as gleaned from cyclic voltammetry only manifests itself in the reduction processes where redox splitting deltaE1/2(0/ 1-, 1-/2-) is resolved for 6.. (deltaE1/2 = 150 mV) and indicated for 7.. (deltaE1/2 < or approximately 80 mV). Magnetocommunication leads to exchange coupling of the two electron spins which reside in vanadium centered orbitals. The values JEPR(6..) = (-)0.92, JEPR(7..) = (-)0.56, and JEPR(8..) = (-)0.005 cm(-1) are derived from the 51V hyperfine patterns. Accordingly, attenuation of exchange interaction by oligoalkyne spacers is weak, corresponding to a factor of 0.6 only per added --C triple bond C-- unit. In the determination of very weak long distance exchange interactions, EPR excels because of the range 5 x 10(-4) < or approximately J < or approximately 1.5 cm(-1) accessible in the case of 51V as a reporting magnetic nucleus and because competing intermolecular exchange is quenched in dilute fluid solution. This is demonstrated by the value Jchi(7..) = -3.84 cm(-1) obtained from a magnetic susceptibility study, which exceeds JEPR(7..) by a factor of 7. The small magnitude of spin exchange interaction between trovacene units reflects the fact that the spin bearing V3dz2 orbital is virtually orthogonal to the pi-perimeter ligand orbitals and weakly overlapping only with the a1g(sigma) ring orbitals, creating two bottlenecks for spin-exchange in the spacer-containing ditrovacenes.

  13. Diversification of ortho-Fused Cycloocta-2,5-dien-1-one Cores and Eight- to Six-Ring Conversion by σ Bond C-C Cleavage.

    Science.gov (United States)

    Eccleshare, Lee; Lozada-Rodríguez, Leticia; Cooper, Phillippa; Burroughs, Laurence; Ritchie, John; Lewis, William; Woodward, Simon

    2016-08-22

    Sequential treatment of 2-C6 H4 Br(CHO) with LiC≡CR(1) (R(1) =SiMe3 , tBu), nBuLi, CuBr⋅SMe2 and HC≡CCHClR(2) [R(2) =Ph, 4-CF3 Ph, 3-CNPh, 4-(MeO2 C)Ph] at -50 °C leads to formation of an intermediate carbanion (Z)-1,2-C6 H4 {CA (=O)C≡CB R(1) }{CH=CH(CH(-) )R(2) } (4). Low temperatures (-50 °C) favour attack at CB leading to kinetic formation of 6,8-bicycles containing non-classical C-carbanion enolates (5). Higher temperatures (-10 °C to ambient) and electron-deficient R(2) favour retro σ-bond C-C cleavage regenerating 4, which subsequently closes on CA providing 6,6-bicyclic alkoxides (6). Computational modelling (CBS-QB3) indicated that both pathways are viable and of similar energies. Reaction of 6 with H(+) gave 1,2-dihydronaphthalen-1-ols, or under dehydrating conditions, 2-aryl-1-alkynylnaphthlenes. Enolates 5 react in situ with: H2 O, D2 O, I2 , allylbromide, S2 Me2 , CO2 and lead to the expected C-E derivatives (E=H, D, I, allyl, SMe, CO2 H) in 49-64 % yield directly from intermediate 5. The parents (E=H; R(1) =SiMe3 , tBu; R(2) =Ph) are versatile starting materials for NaBH4 and Grignard C=O additions, desilylation (when R(1) =SiMe) and oxime formation. The latter allows formation of 6,9-bicyclics via Beckmann rearrangement. The 6,8-ring iodides are suitable Suzuki precursors for Pd-catalysed C-C coupling (81-87 %), whereas the carboxylic acids readily form amides under T3P® conditions (71-95 %).

  14. Intramolecular hydroalkoxylation of non-activated C=C bonds catalysed by zeolites: an experimental and theoretical study.

    Science.gov (United States)

    Pérez-Mayoral, Elena; Matos, Ines; Nachtigall, Petr; Položij, Miroslav; Fonseca, Isabel; Vitvarová-Procházková, Dana; Čejka, Jiří

    2013-06-01

    The high activity and selectivity of zeolites in the cyclisation of unsaturated alcohols is reported for the first time; the details of a reaction mechanism based on quantum chemical calculations are also provided. The high efficiency of zeolites MFI, BEA and FAU in the cyclisation of unsaturated alcohols (cis-decen-1-ol, 6-methylhept-5-en-2-ol and 2-allylphenol) to afford oxygen-containing heterocyclic rings is demonstrated. The best catalytic performance is found for zeolites with the optimum concentration of Brønsted acid sites (ca. 0.2 mmol g(-1)) and the minimum number of Lewis acid sites. It is proposed that the efficiency of the catalysts is reduced by the existence of the so-called dual site, at which a molecule of unsaturated alcohol can simultaneously interact with two acid sites (an OH group with one and the double bond with the other Brønsted site), which increases the interaction strength. The formation of such adsorption complexes leads to a decrease in the catalyst activity because of (i) an increase in the reaction barrier, (ii) an unfavourable conformation and (iii) diffusion limitations. A new procedure for the preparation of tetrahydrofurans and pyrans over zeolite catalysts provides important oxygen-containing heterocycles with numerous applications.

  15. Raman spectroscopic determination of the length, strength, compressibility, Debye temperature, elasticity, and force constant of the C-C bond in graphene.

    Science.gov (United States)

    Yang, X X; Li, J W; Zhou, Z F; Wang, Y; Yang, L W; Zheng, W T; Sun, Chang Q

    2012-01-21

    From the perspective of bond relaxation and bond vibration, we have formulated the Raman phonon relaxation of graphene, under the stimuli of the number-of-layers, the uni-axial strain, the pressure, and the temperature, in terms of the response of the length and strength of the representative bond of the entire specimen to the applied stimuli. Theoretical unification of the measurements clarifies that: (i) the opposite trends of the Raman shifts, which are due to the number-of-layers reduction, of the G-peak shift and arises from the vibration of a pair of atoms, while the D- and the 2D-peak shifts involve the z-neighbor of a specific atom; (ii) the tensile strain-induced phonon softening and phonon-band splitting arise from the asymmetric response of the C(3v) bond geometry to the C(2v) uni-axial bond elongation; (iii) the thermal softening of the phonons originates from bond expansion and weakening; and (iv) the pressure stiffening of the phonons results from bond compression and work hardening. Reproduction of the measurements has led to quantitative information about the referential frequencies from which the Raman frequencies shift as well as the length, energy, force constant, Debye temperature, compressibility and elastic modulus of the C-C bond in graphene, which is of instrumental importance in the understanding of the unusual behavior of graphene.

  16. Highly stable organic monolayers for reacting silicon with further functionalities: the effect of the C-C bond nearest the silicon surface.

    Science.gov (United States)

    Puniredd, Sreenivasa Reddy; Assad, Ossama; Haick, Hossam

    2008-10-15

    Crystalline Si(111) surfaces have been alkylated in a two-step chlorination/alkylation process using various organic molecules having similar backbones but differing in their C-C bond closest to the silicon surface (i.e., C-C vs C=C vs C[triple bond]C bonds). X-ray photoelectron spectroscopic (XPS) data show that functionalization of silicon surfaces with propenyl magnesium bromide (CH3-CH=CH-MgBr) organic molecules gives nearly full coverage of the silicon atop sites, as on methyl- and propynyl-terminated silicon surfaces. Propenyl-terminated silicon surface shows less surface oxidation and is more robust against solvent attacks when compared to methyl- and propynyl-terminated silicon surfaces. We also show a secondary functionalization process of propenyl-terminated silicon surface with 4'-[3-Trifluoromethyl-3H-diazirin-3-yl]-benzoic acid N-hydroxysuccinimide ester [TDBA-OSu] cross-linker. The Si-CH=CH-CH3 surfaces thus offer a means of attaching a variety of chemical moieties to a silicon surface through a short linking group, enabling applications in molecular electronics, energy conversion, catalysis, and sensing.

  17. A Substrate-Assisted Mechanism of Nucleophile Activation in a Ser-His-Asp Containing C-C Bond Hydrolase

    Energy Technology Data Exchange (ETDEWEB)

    Ruzzini, Antonio C.; Bhowmik, Shiva; Ghosh, Subhangi; Yam, Katherine C.; Bolin, Jeffrey T.; Eltis, Lindsay D. [Purdue; (UBC)

    2013-11-12

    The meta-cleavage product (MCP) hydrolases utilize a Ser–His–Asp triad to hydrolyze a carbon–carbon bond. Hydrolysis of the MCP substrate has been proposed to proceed via an enol-to-keto tautomerization followed by a nucleophilic mechanism of catalysis. Ketonization involves an intermediate, ESred, which possesses a remarkable bathochromically shifted absorption spectrum. We investigated the catalytic mechanism of the MCP hydrolases using DxnB2 from Sphingomonas wittichii RW1. Pre-steady-state kinetic and LC ESI/MS evaluation of the DxnB2-mediated hydrolysis of 2-hydroxy-6-oxo-6-phenylhexa-2,4-dienoic acid to 2-hydroxy-2,4-pentadienoic acid and benzoate support a nucleophilic mechanism catalysis. In DxnB2, the rate of ESred decay and product formation showed a solvent kinetic isotope effect of 2.5, indicating that a proton transfer reaction, assigned here to substrate ketonization, limits the rate of acylation. For a series of substituted MCPs, this rate was linearly dependent on MCP pKa2nuc ~ 1). Structural characterization of DxnB2 S105A:MCP complexes revealed that the catalytic histidine is displaced upon substrate-binding. The results provide evidence for enzyme-catalyzed ketonization in which the catalytic His–Asp pair does not play an essential role. The data further suggest that ESred represents a dianionic intermediate that acts as a general base to activate the serine nucleophile. This substrate-assisted mechanism of nucleophilic catalysis distinguishes MCP hydrolases from other serine hydrolases.

  18. Bonding and Integration of C-C Composite to Cu-Clad-Molybdenum for Thermal Management Applications

    Science.gov (United States)

    Asthana, R.; Singh, M.; Shpargel, T.P.

    2008-01-01

    Two- and three-dimensional carbon-carbon composites with either resin-derived matrix or CVI matrix were joined to Cu-clad-Mo using active Ag-Cu braze alloys for thermal management applications. The joint microstructure and composition were examined using Field-Emission Scanning Electron Microscopy and Energy-Dispersive Spectroscopy, and the joint hardness was characterized using the Knoop microhardness testing. Observations on the infiltration of the composite with molten braze, dissolution of metal substrate, and solute segregation at the C-C surface have been discussed. The thermal response of the integrated assembly is also briefly discussed.

  19. Palladium complexes containing diphosphine and sulfonated phosphine ligands for c-c bond forming reactions. catalytic and mechanistic studies

    OpenAIRE

    García Suárez, Eduardo José

    2007-01-01

    El uso de compuestos de paladio(II) para catalizar reacciones de copolimerización de monóxido de carbono y olefinas así como otros tipos de reacciones de formación de enlaces C-C muestra un creciente interés, prueba de ello es el importante numero de publicaciones realizadas en estos últimos años.En catálisis una de las mayores causas de baja productividad es la degradación del catalizador a especies menos activas. Por este motivo se dedican constantemente esfuerzos al diseño de ligandos capa...

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

    KAUST Repository

    Yang, Wenguo

    2012-02-08

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

  1. Redox noninnocence of carbene ligands: carbene radicals in (catalytic) C-C bond formation

    NARCIS (Netherlands)

    Dzik, W.I.; Zhang, X.P.; de Bruin, B.

    2011-01-01

    In this Forum contribution, we highlight the radical-type reactivities of one-electron-reduced Fischer-type carbenes. Carbene complexes of group 6 transition metals (Cr, Mo, and W) can be relatively easily reduced by an external reducing agent, leading to one-electron reduction of the carbene ligand

  2. Heme carbonyls: environmental effects on nu(C-O) and Fe-C/C-O bond length correlations.

    Science.gov (United States)

    Silvernail, Nathan J; Roth, Arne; Schulz, Charles E; Noll, Bruce C; Scheidt, W Robert

    2005-10-19

    The synthesis and characterization of four low-spin (carbonyl)iron(II) tetraphenylporphyrinates, [Fe(TPP)(CO)(L)], where L = 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole (unsolvated), and 1,2-dimethylimidazole (toluene solvate) are reported. The complexes show nearly the same value of nu(C-O) in toluene solution (1969-72 cm(-1)) but a large range of CO stretching frequencies in the solid-state (1926-1968 cm(-1)). The large solid-state variation results from CO interactions in the solid state, as shown by an examination of the crystal structures of the four complexes. The high precision of the four structures obtained allows us to make a number of structural and spectroscopic correlations that describe the Fe-C-O and N(Im)-Fe-CO units. The values of nu(C-O) and the Fe-C and C-O bond distances are strongly correlated and provide a structural, as well as a spectroscopic, correlation of the pi back-bonding model. The interactions of CO described are closely related to the large range of CO stretching frequencies observed in heme proteins and specific interactions observed in carbonylmyoglobin (MbCO).

  3. Robust C-C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas.

    Science.gov (United States)

    Thirion, Damien; Lee, Joo S; Özdemir, Ercan; Yavuz, Cafer T

    2016-01-01

    Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon-carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile-aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m(2)/g) and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C.

  4. New Concept of the Biosynthesis of 4-Alkyl-L-proline Precursors of Lincomycin, Hormaomycin and Pyrrolobenzodiazepines: Could a γ-Glutamyltransferase Cleave the C-C Bond?

    Directory of Open Access Journals (Sweden)

    Petra eJiraskova

    2016-03-01

    Full Text Available Structurally different and functionally diverse natural compounds – antitumour agents pyrrolo[1,4]benzodiazepines, bacterial hormone hormaomycin and lincosamide antibiotic lincomycin – share a common building unit, 4-alkyl-L-proline derivative (APD. APDs arise from L-tyrosine through a special biosynthetic pathway. Its generally accepted scheme, however, did not comply with current state of knowledge. Based on gene inactivation experiments and in vitro functional tests with recombinant enzymes, we designed a new APD biosynthetic scheme for the model of lincomycin biosynthesis. In the new scheme at least one characteristic in each of five final biosynthetic steps has been changed: the order of reactions, assignment of enzymes and/or reaction mechanisms. First, we demonstrate that LmbW methylates a different substrate than previously assumed. Second, we propose a unique reaction mechanism for the next step, in which a putative γ-glutamyltransferase LmbA indirectly cleaves off the oxalyl residue by transient attachment of glutamate to LmbW product. This unprecedented mechanism would represent the first example of the C-C bond cleavage catalyzed by a γ-glutamyltransferase, i.e., an enzyme that appears unsuitable for such activity. Finally, the inactivation experiments show that LmbX is an isomerase indicating that it transforms its substrate into a compound suitable for reduction by LmbY, thereby facilitating its subsequent complete conversion to APD 4-propyl-L-proline. Elucidation of the APD biosynthesis has long time resisted mainly due to the apparent absence of relevant C-C bond cleaving enzymatic activity. Our proposal aims to unblock this situation not only for lincomycin biosynthesis, but generally for all above mentioned groups of bioactive natural products with biotechnological potential.

  5. Lewis acid promoted dual bond formation: facile synthesis of dihydrocoumarins and spiro-tetracyclic dihydrocoumarins.

    Science.gov (United States)

    Niharika, Pedireddi; Ramulu, Bokka Venkat; Satyanarayana, Gedu

    2014-07-07

    Lewis acid (FeCl3) mediated dual bond (C-C and C-O) formation for synthesis of 3,4-dihydrocoumarins is presented. This method has successfully delivered a number of dihydrocoumarins containing dense functionalities on the aromatic ring. Significantly, the present method enabled achieving dihydrocoumarins with tertiary as well as quaternary carbon atoms at the benzylic position. Gratifyingly, the novel spiro-tetracyclic lactones have also been dextrously prepared using this process.

  6. Solid-state Photochemical [2+2] Cycloaddition Reaction of Hydrogen-Bonded Zn(II) Metal Complex Containing Several Parallel C=C Bonds

    Indian Academy of Sciences (India)

    ABDUL MALIK P PEEDIKAKKAL

    2017-02-01

    A 2D hydrogen-bonded dinuclear Zn(II) complex, [{Zn(H₂O) ₃ (bpe) ₂} ₂ (bpe)](NO₃) ₄・3bpe・14H₂O,1 (bpe = 4,4_-bipyridylethylene) containing coordination complex cations, [{Zn(H₂O) ₃ (bpe) ₂} ₂ (μ-bpe)] ⁴⁺and free bpe and lattice water molecules shows face-to-face, π ・ ・ ・ π stacking of two of the four free bpemolecules with coordinated bpe ligands. Out of eight bpe molecules, six are aligned in parallel fashion withshort C・ ・ ・ C distances of 3.663–3.814Å and they undergo photochemical [2+2] cycloaddition reaction. The photoreaction conducted on ground sample of 1 in the solid-state affords rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) product in 75% yield. The molecular movement of free bpe molecules was tested by conducting thephotoreaction in ground sample and heated sample of single crystals. The photoreactivity study of 1 indicates that the free bpe molecules are locked between the cationic [{Zn(H₂O) ₃ (bpe) ₂} ₂ (bpe)] ⁴⁺ layers.

  7. An iron-catalysed C-C bond-forming spirocyclization cascade providing sustainable access to new 3D heterocyclic frameworks

    Science.gov (United States)

    Adams, Kirsty; Ball, Anthony K.; Birkett, James; Brown, Lee; Chappell, Ben; Gill, Duncan M.; Lo, P. K. Tony; Patmore, Nathan J.; Rice, Craig. R.; Ryan, James; Raubo, Piotr; Sweeney, Joseph B.

    2016-12-01

    Heterocyclic architectures offer powerful creative possibilities to a range of chemistry end-users. This is particularly true of heterocycles containing a high proportion of sp3-carbon atoms, which confer precise spatial definition upon chemical probes, drug substances, chiral monomers and the like. Nonetheless, simple catalytic routes to new heterocyclic cores are infrequently reported, and methods making use of biomass-accessible starting materials are also rare. Here, we demonstrate a new method allowing rapid entry to spirocyclic bis-heterocycles, in which inexpensive iron(III) catalysts mediate a highly stereoselective C-C bond-forming cyclization cascade reaction using (2-halo)aryl ethers and amines constructed using feedstock chemicals readily available from plant sources. Fe(acac)3 mediates the deiodinative cyclization of (2-halo)aryloxy furfuranyl ethers, followed by capture of the intermediate metal species by Grignard reagents, to deliver spirocycles containing two asymmetric centres. The reactions offer potential entry to key structural motifs present in bioactive natural products.

  8. The nature of solid-state N-H triplebondO/O-H triplebond N tautomeric competition in resonant systems. Intramolecular proton transfer in low-barrier hydrogen bonds formed by the triplebond O=C-C=N-NH triple bond --> <-- triplebond HO-C=C-N=N triplebond Ketohydrazone-Azoenol system. A variable-temperature X-ray crystallographic and DFT computational study.

    Science.gov (United States)

    Gilli, Paola; Bertolasi, Valerio; Pretto, Loretta; Lycka, Antonín; Gilli, Gastone

    2002-11-13

    The tautomeric.O=C-C=N-NH triplebond --> competition in these compounds is studied here through variable-temperature (100, 150, 200, and 295 K) crystal-structure determination of pF = 1-(4-F-phenylazo)2-naphthol and oF = 1-(2-F-phenylazo)2-naphthol, two molecules that, on the ground of previous studies (Gilli, P; Bertolasi, V.; Ferretti, V.; Gilli, G. J. Am. Chem. Soc. 2000, 122, 10405), were expected to represent an almost perfect balance of the two tautomers. According to predictions, the two molecules form remarkably strong bonds (d(N triplebond O) = 2.53-2.55 A) of double-minimum or LBHB type with dynamic N-H triplebond O/ O-H triplebond N exchange in the solid state. The enthalpy differences between the two minima, as measured by van't Hoff methods from the X-ray-determined proton populations, are very small and amount to DeltaH degrees = -0.120 and DeltaH degrees = -0.156 kcal mol(-)(1) in favor of the N-H triplebond O form for pF and oF, respectively. Successive emulation of pF by DFT methods at the B3LYP/6-31+G(d,p)//B3LYP/6-31+G(d,p) level has shown that both energetic and geometric experimental aspects can be almost perfectly reproduced. Generalization of these results was sought by performing DFT calculations at the same level of theory along the complete proton-transfer (PT) pathway for five test molecules designed in such a way that the RAHB formed changes smoothly from weak N-H triplebond O to strong O-H.N through very strong N-H triplebond O/O-H triplebond N bond of LBHB type. A systematic correlation analysis of H-bond energies, H-bond and pi-conjugated fragment geometries, and H-bond Bader's AIM topological properties performed along the PT-pathways leads to the following conclusions: (a) any X-H triplebond Y H-bonded system is fully characterized by its intrinsic PT-barrier, that is, the symmetric barrier occurring when the proton affinities of X and Y are identical; (b) the intrinsic X-H triplebond Y bond associated with the symmetric barrier is

  9. Shedding light on disulfide bond formation

    DEFF Research Database (Denmark)

    Ostergaard, H; Henriksen, A; Hansen, F G;

    2001-01-01

    in the intrinsic fluorescence. Inter conversion between the two redox states could thus be followed in vitro as well as in vivo by non-invasive fluorimetric measurements. The 1.5 A crystal structure of the oxidized protein revealed a disulfide bond-induced distortion of the beta-barrel, as well as a structural...

  10. Disulphide bond formation in food protein aggregation and gelation

    NARCIS (Netherlands)

    Visschers, R.W.; Jongh, de H.H.J.

    2005-01-01

    In this short review we discuss the role of cysteine residues and cystine bridges for the functional aggregation of food proteins. We evaluate how formation and cleavage of disulphide bonds proceeds at a molecular level, and how inter- and intramolecular disulfide bonds can be detected and modified.

  11. Preparation of phosphines through C–P bond formation

    Directory of Open Access Journals (Sweden)

    Iris Wauters

    2014-05-01

    Full Text Available Phosphines are an important class of ligands in the field of metal-catalysis. This has spurred the development of new routes toward functionalized phosphines. Some of the most important C–P bond formation strategies were reviewed and organized according to the hybridization of carbon in the newly formed C–P bond.

  12. Formation of Embedded Microstructures by Thermal Activated Solvent Bonding

    CERN Document Server

    Ng, S H; Wang, Z F; Lu, A C W; Rodriguez, I; De Rooij, N

    2008-01-01

    We present a thermal activated solvent bonding technique for the formation of embedded microstrucutres in polymer. It is based on the temperature dependent solubility of polymer in a liquid that is not a solvent at room temperature. With thermal activation, the liquid is transformed into a solvent of the polymer, creating a bonding capability through segmental or chain interdiffusion at the bonding interface. The technique has advantages over the more commonly used thermal bonding due to its much lower operation temperature (30 degrees C lower than the material's Tg), lower load, as well as shorter time. Lap shear test indicated bonding shear strength of up to 2.9 MPa. Leak test based on the bubble emission technique showed that the bonded microfluidic device can withstand at least 6 bars (87 psi) of internal pressure (gauge) in the microchannel. This technique can be applied to other systems of polymer and solvent.

  13. Formation of Au-Silane Bonds

    Directory of Open Access Journals (Sweden)

    Shira Yochelis

    2012-01-01

    Full Text Available Many intriguing aspects of molecular electronics are attributed to organic-inorganic interactions, yet charge transfer through such junctions still requires fundamental study. Recently, there is a growing interest in anchoring groups, which considered dominating the charge transport. With this respect, we choose to investigate self-assembly of disilane molecules sandwiched between gold surface and gold nanoparticles. These assemblies are found to exhibit covalent bonds not only between the anchoring Si groups and the gold surfaces but also in plane crosslinks that increase the monolayer stability. Finally, using scanning tunneling spectroscopy we demonstrate that the disilane molecules provide strong electrical coupling between the Au nanoparticles and a superconductor substrate.

  14. Interface formation and strength of Be/DSCu diffusion bonding

    Science.gov (United States)

    Makino, T.; Iwadachi, T.

    1998-10-01

    Beryllium has been proposed to be used as a plasma facing material of the first wall for ITER, and will be bonded by HIP process to Dispersion Strengthened Copper (DSCu). Be/DSCu diffusion bonding tests in the range of temperature from 600°C to 850°C by hot pressing techniques have been conducted to identify the effect of bonding temperature and time on interface formation and joint strength. The bonded Be/DSCu joints were evaluated by microstructural analysis of the interface and shear strength tests at room temperature. The diffusion layer of directly bonded Be/DSCu joints and the joints with Be-Cu interlayer consisted of Be 2Cu( δ) phase on the Be side and Cu + BeCu( γ) phase on the DSCu side. Cu + BeCu( γ) phase generated remarkably fast at 800-850°C. The thickness of the diffusion layer was linear to a square root of bonding time. Shear strength of the joints bonded at 650-750°C are all around 200 MPa. Shear strength is dominated by the formation of the layer of Be 2Cu( δ) phase on the Be side.

  15. Disulfide bond formation in prokaryotes: history, diversity and design.

    Science.gov (United States)

    Hatahet, Feras; Boyd, Dana; Beckwith, Jon

    2014-08-01

    The formation of structural disulfide bonds is essential for the function and stability of a great number of proteins, particularly those that are secreted. There exists a variety of dedicated cellular catalysts and pathways from archaea to humans that ensure the formation of native disulfide bonds. In this review we describe the initial discoveries of these pathways and report progress in recent years in our understanding of the diversity of these pathways in prokaryotes, including those newly discovered in some archaea. We will also discuss the various successful efforts to achieve laboratory-based evolution and design of synthetic disulfide bond formation machineries in the bacterium Escherichia coli. These latter studies have also led to new more general insights into the redox environment of the cytoplasm and bacterial cell envelope. This article is part of a Special Issue entitled: Thiol-Based Redox Processes.

  16. Hydrophobic interactions and hydrogen bonds in \\beta-sheet formation

    CERN Document Server

    Narayanan, Chitra

    2013-01-01

    In this study, we investigate interactions of extended conformations of homodimeric peptides made of small (glycine or alanine) and large hydrophobic (valine or leucine) sidechains using all-atom molecular dynamics simulations to decipher driving forces for \\beta-sheet formation. We make use of a periodic boundary condition setup in which individual peptides are infinitely long and stretched. Dimers adopt \\beta-sheet conformations at short interpeptide distances (\\xi ~ 0.5 nm) and at intermediate distances (~ 0.8 nm), valine and leucine homodimers assume cross-\\beta-like conformations with side chains interpenetrating each other. These two states are identified as minima in the Potential of Mean Force (PMF). While the number of interpeptide hydrogen bonds increases with decreasing interpeptide distance, the total hydrogen bond number in the system does not change significantly, suggesting that formation of \\beta-sheet structures from extended conformations is not driven by hydrogen bonds. This is supported by...

  17. Investigations of Reactive Carbohydrates in Glycosidic Bond Formation and Degradation

    DEFF Research Database (Denmark)

    Heuckendorff, Mads

    The overall objective of the research described in this thesis was to explore the field of glycosidic bond formation and degradation. In more detail, the objective was to do further research in the field of highly reactive glycosyl donors. New ways of making highly reactive donors were explored...

  18. Asymmetric C-C Bond-Formation Reaction with Pd: How to Favor Heterogeneous or Homogeneous Catalysis?

    DEFF Research Database (Denmark)

    Reimann, S.; Grunwaldt, Jan-Dierk; Mallat, T.

    2010-01-01

    The enantioselective allylic alkylation of (E)-1,3-diphenylallyl acetate was studied to clarify the heterogeneous or homogeneous character of the Pd/Al2O3-(R)-BINAP catalyst system. A combined approach was applied: the catalytic tests were completed with in situ XANES measurements to follow...

  19. Reversible Sigma C-C Bond Formation Between Phenanthroline Ligands Activated by (C5Me5)2Yb

    Energy Technology Data Exchange (ETDEWEB)

    Nocton, Gr& #233; gory; Lukens, Wayne W.; Booth, Corwin H.; Rozenel, Sergio S.; Medling, Scott A.; Maron, Laurent; Andersen, Richard A.

    2014-06-26

    The electronic structure and associated magnetic properties of the 1,10-phenanthroline adducts of Cp*2Yb are dramatically different from those of the 2,2?-bipyridine adducts. The monomeric phenanthroline adducts are ground state triplets that are based upon trivalent Yb(III), f13, and (phen ) that are only weakly exchange coupled, which is in contrast to the bipyridine adducts whose ground states are multiconfigurational, open-shell singlets in which ytterbium is intermediate valent ( J. Am. Chem. Soc 2009, 131, 6480; J. Am. Chem. Soc 2010, 132, 17537). The origin of these different physical properties is traced to the number and symmetry of the LUMO and LUMO+1 of the heterocyclic diimine ligands. The bipy has only one 1 orbital of b1 symmetry of accessible energy, but phen has two orbitals of b1 and a2 symmetry that are energetically accessible. The carbon p-orbitals have different nodal properties and coefficients and their energies, and therefore their populations change depending on the position and number of methyl substitutions on the ring. A chemical ramification of the change in electronic structure is that Cp 2Yb(phen) is a dimer when crystallized from toluene solution, but a monomer when sublimed at 180190 C. When 3,8-Me2phenanthroline is used, the adduct Cp*2Yb(3,8-Me2phen) exists in the solution in a dimer monomer equilibrium in which G is near zero. The adducts with 3-Me, 4-Me, 5-Me, 3,8-Me2, and 5,6-Me2-phenanthroline are isolated and characterized by solid state X-ray crystallography, magnetic susceptibility and LIII-edge XANES spectroscopy as a function of temperature and variable-temperature 1H NMR spectroscopy.

  20. Sulfur(IV)-mediated carbon-carbon bond formation

    OpenAIRE

    Dean, William Michael

    2016-01-01

    This thesis details the development of methods for and application of the synthesis of carbon carbon bonds using organic sulfur(IV) chemistry. More specifically, the formation of C(sp2) C(sp3) and C(sp3) C(sp3) bonds is explored in detail. The necessity for this research stems from a correlation between a high proportion of sp3 centres in drug candidates, and their success in clinical trials. By facilitating the synthesis of drug candidates with higher fractions of sp3 hybridised carbon atoms...

  1. CYP96T1 of Narcissus sp. aff. pseudonarcissus Catalyzes Formation of the Para-Para' C-C Phenol Couple in the Amaryllidaceae Alkaloids

    Science.gov (United States)

    Kilgore, Matthew B.; Augustin, Megan M.; May, Gregory D.; Crow, John A.; Kutchan, Toni M.

    2016-01-01

    The Amaryllidaceae alkaloids are a family of amino acid derived alkaloids with many biological activities; examples include haemanthamine, haemanthidine, galanthamine, lycorine, and maritidine. Central to the biosynthesis of the majority of these alkaloids is a C-C phenol-coupling reaction that can have para-para', para-ortho', or ortho-para' regiospecificity. Through comparative transcriptomics of Narcissus sp. aff. pseudonarcissus, Galanthus sp., and Galanthus elwesii we have identified a para-para' C-C phenol coupling cytochrome P450, CYP96T1, capable of forming the products (10bR,4aS)-noroxomaritidine and (10bS,4aR)-noroxomaritidine from 4′-O-methylnorbelladine. CYP96T1 was also shown to catalyzed formation of the para-ortho' phenol coupled product, N-demethylnarwedine, as less than 1% of the total product. CYP96T1 co-expresses with the previously characterized norbelladine 4′-O-methyltransferase. The discovery of CYP96T1 is of special interest because it catalyzes the first major branch in Amaryllidaceae alkaloid biosynthesis. CYP96T1 is also the first phenol-coupling enzyme characterized from a monocot. PMID:26941773

  2. CYP96T1 of Narcissus sp. aff. pseudonarcissus Catalyzes Formation of the Para-Para’ C-C Phenol Couple in the Amaryllidaceae Alkaloids

    Directory of Open Access Journals (Sweden)

    Matthew eKilgore

    2016-02-01

    Full Text Available The Amaryllidaceae alkaloids are a family of amino acid derived alkaloids with many biological activities; examples include haemanthamine, haemanthidine, galanthamine, lycorine, and maritidine. Central to the biosynthesis of the majority of these alkaloids is a C-C phenol-coupling reaction that can have para-para’, para-ortho’, or ortho-para’ regiospecificity. Through comparative transcriptomics of Narcissus sp. aff. pseudonarcissus, Galanthus sp., and Galanthus elwesii we have identified a para-para’ C-C phenol coupling cytochrome P450, CYP96T1, capable of forming the products (10bR,4aS-noroxomaritidine and (10bS,4aR-noroxomaritidine from 4’-O-methylnorbelladine. CYP96T1 was also shown to catalyzed formation of the para-ortho’ phenol coupled product, N-demethylnarwedine, as less than 1 % of the total product. CYP96T1 co-expresses with the previously characterized norbelladine 4’-O-methyltransferase. The discovery of CYP96T1 is of special interest because it catalyzes the first major branch in Amaryllidaceae alkaloid biosynthesis. CYP96T1 is also the first phenol-coupling enzyme characterized from a monocot.

  3. Effect of Electronic Factor in Ru-phosphine-diamine Complexes on Selective Hydrogenation of C=C and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yu; Yu,Xiaojun; YU,Changbin; XIA,Yuqing; LI,Ruixiang; CHEN,Hua; LI,Xianjun

    2009-01-01

    A series of ruthenium complexes bearing different phosphines and diamines were synthesized and their compo-nents and structures were characterized by NMR spectra and elemental analyses. The catalytic properties of these complexes for the hydrogenation of benzylideneacetone and the mixture of acetophenone and styrene were investi-gated. The results showed that the basicity increase of phosphine or diamine dramatically facilitates the hydrogena-tion activity and selectivity to C=O double bond. On the contrary, the basicity decrease of phosphine or diamine not only slows down the catalytic activity, but also significantly suppresses the hydrogenation selectivity to C=O double bond. Based on the effect of electron factors of these complexes on the hydrogenation activity and selectiv-ity of benzylideneacetone and the mixture of styrene and acetophenone, the activation mechanism of dihydrogen in ruthenium-phosphine-diamine system was proposed.

  4. Irregular Characteristics of Bond Interface Formation in Ultrasonic Wire Wedge Bonding

    Institute of Scientific and Technical Information of China (English)

    Mingyu LI; Hongjun JI; Chunqing WANG; Au Tai KUNG; Han Sur BANG; Hee Seon BANG

    2006-01-01

    The mechanism of ultrasonic wire wedge bonding, one of the die/chip interconnection methods, was investigated based on the characteristics of the ultrasonic wire bonding joints. The Al-1%Si wire of 25 μm in diameter was bonded on Au/Ni/Cu pad and the joint cross-section was analyzed by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The results indicated that it is irregular for the ultrasonic bond formation, non-welded at the centre but joining well at the periphery, especially at the heel and toe of the joint. Furthermore, the diffusion and/or reaction at the cross-section interface are not clear at C-zone, while there exists a strip layer microstructure at P-zone, and the composition is 78.96 at. pct Al and 14.88 at. pct Ni, close to the Al3Ni intermetallic compound. All these observations are tentatively ascribed to the plastic flow enhanced by ultrasonic vibration and repeated cold deformation driving interdiffusion between Al and Ni at bond interface.

  5. Selective reduction of C=C double bonds in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of microcystins.

    Science.gov (United States)

    Deleuze, Christelle; De Pauw, Edwin; Quinton, Loic

    2010-01-01

    Cyanobacteria are photosynthetic bacteria encountered in various aquatic environments. Some of them are able to produce powerful toxins called cyanotoxins. Among cyanotoxins, microcystins (MCs) constitute a group of closely related cyclic heptapeptides. Their sequences are made up of classical amino acids as well as post- translational modified ones. Interestingly, in vivo metabolism of microcystins seems to be greatly dependent on various minor structural differences and particularly those of the seventh amino acid, which can be either dehydroalanine (or a derivative), dehydroaminobutyric acid (or a derivative), serine or alanine. As a consequence, microcystins have been classified on the basis of the nature of this singular amino acid. A major difficulty in the classification of such toxins is that some of them share the same molecular masses and the same molecular formulas. Consequently, a simple mass measurement is not sufficient to determine the structure and the class of a toxin of interest. Heavy and expensive techniques are used to classify them, such as multi-dimensional nuclear magnetic resonance and amino acid analysis. In this work, a new matrix-assisted laser desorption/ionization time-of-flight method leading to an easy classification of MCs is proposed. The methodology relies on the reductive properties of the matrix 1,5-diaminonaphtalene (1,5-DAN) which appears to be able to selectively reduce the double carbon-carbon bond belonging to the seventh amino acid. Moreover, the yield of reduction seems to be influenced by the degree of substitution of this double bond, allowing a discrimination between dehydroalanine and dehydroaminobutyric acid. This selective reduction was confirmed by the study of three synthetic peptides by mass spectrometry and tandem mass spectrometry. According to these results, the use of reductive matrices seems to be promising in the study of microcystins and in their classification. More generally, 1,5-DAN allows the selective

  6. Alkynyl functionalized Al/P-based frustrated Lewis pairs - aluminium alkynide elimination and evidence for the formation of 3H-phosphaallenes [R-P=C=C(H)-(t)Bu].

    Science.gov (United States)

    Klöcker, Hans; Roters, Steffi; Hepp, Alexander; Uhl, Werner

    2015-07-28

    Hydroalumination of dialkynylphosphines, aryl-P(C≡C-(t)Bu)2 (aryl = 2,4,6-Me3C6H2 (1), Ph (2)), with the bulky dialkylaluminium hydride H-Al[CH(SiMe3)2]2 afforded mixed alkenyl-alkynyl phosphines (3 and 4) with aluminium atoms in geminal positions to phosphorus. These compounds contain coordinatively unsaturated aluminium and phosphorus atoms and may be applicable as alkynyl functionalised frustrated Lewis pairs. Their unique constitution with dialkylaluminium and alkynyl groups in close proximity favours unusual secondary reactions with the elimination of an aluminium alkynide and formation of reactive 3H-phosphaallenes, aryl-P=C=C(H)-(t)Bu (5 and 6), which depending on the steric shielding by the aryl groups, oligomerize at room temperature over days or weeks. The mesityl derivative 5 is formed in a very selective reaction, but the relatively unstable phenyl compound 6 was only detected in a mixture of several components. One of these (7) was isolated as orange-red crystals and identified as a heterocyclic zwitterionic compound with a central AlC2P2 ring. One of its phosphorus atoms is bonded to a terminal alkynyl group.

  7. Primary photodissociation pathways of epichlorohydrin and analysis of the C-C bond fission channels from an O((3)P)+allyl radical intermediate.

    Science.gov (United States)

    Fitzpatrick, Benjamin L; Alligood, Bridget W; Butler, Laurie J; Lee, Shih-Huang; Lin, Jim Jr-Min

    2010-09-01

    This study initially characterizes the primary photodissociation processes of epichlorohydrin, c-(H(2)COCH)CH(2)Cl. The three dominant photoproduct channels analyzed are c-(H(2)COCH)CH(2)+Cl, c-(H(2)COCH)+CH(2)Cl, and C(3)H(4)O+HCl. In the second channel, the c-(H(2)COCH) photofission product is a higher energy intermediate on C(2)H(3)O global potential energy surface and has a small isomerization barrier to vinoxy. The resulting highly vibrationally excited vinoxy radicals likely dissociate to give the observed signal at the mass corresponding to ketene, H(2)CCO. The final primary photodissociation pathway HCl+C(3)H(4)O evidences a recoil kinetic energy distribution similar to that of four-center HCl elimination in chlorinated alkenes, so is assigned to production of c-(H(2)COC)=CH(2); the epoxide product is formed with enough vibrational energy to isomerize to acrolein and dissociate. The paper then analyzes the dynamics of the C(3)H(5)O radical produced from C-Cl bond photofission. When the epoxide radical photoproduct undergoes facile ring opening, it is the radical intermediate formed in the O((3)P)+allyl bimolecular reaction when the O atom adds to an end C atom. We focus on the HCO+C(2)H(4) and H(2)CO+C(2)H(3) product channels from this radical intermediate in this report. Analysis of the velocity distribution of the momentum-matched signals from the HCO+C(2)H(4) products at m/e=29 and 28 shows that the dissociation of the radical intermediate imparts a high relative kinetic energy, peaking near 20 kcal/mol, between the products. Similarly, the energy imparted to relative kinetic energy in the H(2)CO+C(2)H(3) product channel of the O((3)P)+allyl radical intermediate also peaks at high-recoil kinetic energies, near 18 kcal/mol. The strongly forward-backward peaked angular distributions and the high kinetic energy release result from tangential recoil during the dissociation of highly rotationally excited nascent radicals formed photolytically in this

  8. Understanding the Formation of Limited Interlamellar Bonding in Plasma Sprayed Ceramic Coatings Based on the Concept of Intrinsic Bonding Temperature

    Science.gov (United States)

    Yao, Shu-Wei; Tian, Jia-Jia; Li, Chang-Jiu; Yang, Guan-Jun; Li, Cheng-Xin

    2016-12-01

    Interlamellar bonding is an important factor controlling the mechanical, thermal and electrical properties of plasma sprayed ceramic coatings. In order to understand the formation of limited interlamellar bonding, a theoretical model is proposed based on the concept of the intrinsic bonding temperature. The numerical simulation of the interface temperature between a molten splat and underlying splats was performed for splats with uniform and non-uniform thickness, in order to reveal the conditions for the interlamellar bonding formation. The interlamellar bonding ratio was theoretically estimated based on the bonding forming conditions. The features of interlamellar bonding revealed by the simulation agree well with the experimental observations. The bonding ratio of plasma sprayed coatings is significantly influenced by the distribution of splat thickness. According to the distribution of Al2O3 splat thickness in the coating, the theoretical estimation of bonding ratio yielded a value of 0.41 for the plasma sprayed Al2O3 coating at the ambient atmosphere conditions, which is reasonably consistent with the observation value. Therefore, the limited interlamellar bonding can be reasonably explained based on the sufficient condition that the maximum interface temperature between a molten splat and underlying splats is larger than the intrinsic bonding temperature.

  9. Surface Reconstruction-Induced Coincidence Lattice Formation Between Two-Dimensionally Bonded Materials and a Three-Dimensionally Bonded Substrate

    NARCIS (Netherlands)

    Boschker, Jos E.; Momand, Jamo; Bragaglia, Valeria; Wang, Ruining; Perumal, Karthick; Giussani, Alessandro; Kooi, Bart J.; Riechert, Henning; Calarco, Raffaella

    2014-01-01

    Sb2Te3 films are used for studying the epitaxial registry between two-dimensionally bonded (2D) materials and three-dimensional bonded (3D) substrates. In contrast to the growth of 3D materials, it is found that the formation of coincidence lattices between Sb2Te3 and Si(111) depends on the geometry

  10. Carbon-Carbon Bond Formation in a Weak Ligand Field: Leveraging Open Shell First Row Transition Metal Catalysts.

    Science.gov (United States)

    Chirik, Paul James

    2017-01-12

    Unique features of Earth abundant transition metal catalysts are reviewed in the context of catalytic carbon-carbon bond forming reactions. Aryl-substituted bis(imino)pyridine iron and cobalt dihalide compounds, when activated with alkyl aluminum reagents, form highly active catalysts for the polymerization of ethylene. Open shell iron and cobalt alkyl complexes have been synthesized that serve as single component olefin polymerization catalysts. Reduced bis(imino)pyridine iron- and cobalt dinitrogen compounds have also been discovered that promote the unique [2+2] cycloaddition of unactivated terminal alkenes. Electronic structure studies support open shell intermediates, a deviation from traditional strong field organometallic compounds that promote catalytic C-C bond formation.

  11. Addition of Carbon–Fluorine Bonds to a Mg(I)–Mg(I) Bond: An Equivalent of Grignard Formation in Solution

    Science.gov (United States)

    2016-01-01

    Addition of the carbon–fluorine bond of a series of perfluorinated and polyfluorinated arenes across the Mg–Mg bond of a simple coordination complex proceeds rapidly in solution. The reaction results in the formation of a new carbon–magnesium bond and a new fluorine–magnesium bond and is analogous to Grignard formation in homogeneous solution. PMID:27636244

  12. Shedding light on disulfide bond formation: engineering a redox switch in green fluorescent protein

    DEFF Research Database (Denmark)

    Østergaard, H.; Henriksen, A.; Hansen, Flemming G.

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease in the i......To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...

  13. Asymmetric and symmetric bolaform supra-amphiphiles: formation of imine bond influenced by aggregation.

    Science.gov (United States)

    Wang, Guangtong; Wu, Guanglu; Wang, Zhiqiang; Zhang, Xi

    2014-02-18

    A series of bolaform supra-amphilphiles with different symmetries were fabricated through dynamic benzoic imine bond formation. The pH dependence of imine formations of these supra-amphiphiles were characterazied. We found that the extent of the imine formation of these supra-amphiphies were different. The supra-amphiphiles with a poorer symmetry always exhibited a lower imine formation at a given pH. Therefore, the varied extent of imine bond formation indicate the different aggregations of these supra-amphilphiles, which are controlled by the molecular symmetry of the supra-amphiphiles.

  14. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A

    2009-08-10

    Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride

  15. Evidence for chemical bond formation at rubber-brass interface: Photoelectron spectroscopy study of bonding interaction between copper sulfide and model molecules of natural rubber

    Science.gov (United States)

    Ozawa, Kenichi; Mase, Kazuhiko

    2016-12-01

    Strong adhesion between rubber and brass has been considered to arise mainly from the mechanical interaction, which is characterized by dendritic interlocking at the interface. In order to examine a possible contribution of the chemical interaction, chemical state analysis was carried out for model molecules of natural rubber (2-methyl-2-butene and isoprene) adsorbed on Cu2S, a key chemical species for adhesion, by means of photoelectron spectroscopy (PES). Absence of a C 1s PES component associated with C=C bonds and the appearance of adsorption-induced components in the S 2p region indicate that the molecules interact with the Cu2S surface via the C=C bond to form C-S covalent bonds. This proves that the chemical interaction certainly plays a role in rubber-brass adhesion along with the mechanical interaction.

  16. Formation of amide bonds without a condensation agent and implications for origin of life.

    Science.gov (United States)

    Keller, M; Blöchl, E; Wächtershäuser, G; Stetter, K O

    1994-04-28

    Amide bonds are of central importance for biochemistry; in the guise of peptide bonds, they form the backbone of proteins. The formation of amide bonds without the assistance of enzymes poses a major challenge for theories of the origin of life. Enzyme-free formation of amide bonds between amino acids has been demonstrated in the presence of condensing agents such as cyanamide. Here we report the formation of amide bonds in aqueous solution in the absence of any condensing agent. We find that the formation of pyrite (FeS2) from FeS and H2S can provide the driving force for reductive acetylation of amino acids with mercaptoacetic acid (HSCH2COOH). The redox energy of pyrite formation permits the activation of the carboxylic acid group, which is converted to a species that reacts readily with amines. This process provides support for the chemo-autotrophic theory for the origin of life, in which pyrite formation supplies the energy source for the first autocatalytic reproduction cycle.

  17. Maturation of Pseudomonas aeruginosa elastase - Formation of the disulfide bonds

    NARCIS (Netherlands)

    Braun, P; Ockhuijsen, C; Eppens, E; Koster, M; Bitter, W; Tommassen, J

    2001-01-01

    Elastase of Pseudomonas aeruginosa is synthesized as a preproenzyme. After propeptide-mediated folding in the periplasm, the proenzyme is autoproteolytically processed, prior to translocation of both the mature enzyme and the propeptide across the outer membrane. The formation of the two disulfide b

  18. Drinking alcohol has sex-dependent effects on pair bond formation in prairie voles.

    Science.gov (United States)

    Anacker, Allison M J; Ahern, Todd H; Hostetler, Caroline M; Dufour, Brett D; Smith, Monique L; Cocking, Davelle L; Li, Ju; Young, Larry J; Loftis, Jennifer M; Ryabinin, Andrey E

    2014-04-22

    Alcohol use and abuse profoundly influences a variety of behaviors, including social interactions. In some cases, it erodes social relationships; in others, it facilitates sociality. Here, we show that voluntary alcohol consumption can inhibit male partner preference (PP) formation (a laboratory proxy for pair bonding) in socially monogamous prairie voles (Microtus ochrogaster). Conversely, female PP is not inhibited, and may be facilitated by alcohol. Behavior and neurochemical analysis suggests that the effects of alcohol on social bonding are mediated by neural mechanisms regulating pair bond formation and not alcohol's effects on mating, locomotor, or aggressive behaviors. Several neuropeptide systems involved in the regulation of social behavior (especially neuropeptide Y and corticotropin-releasing factor) are modulated by alcohol drinking during cohabitation. These findings provide the first evidence to our knowledge that alcohol has a direct impact on the neural systems involved in social bonding in a sex-specific manner, providing an opportunity to explore the mechanisms by which alcohol affects social relationships.

  19. Carenium—Calkyl Bond Making and Breaking: Key Process in the Platinum-Mediated Caryl—Calkyl Bond Formation. Analogies to Organic Electrophilic Aromatic Substitution

    NARCIS (Netherlands)

    Koten, G. van; Albrecht, M.A.; Spek, A.L.

    2001-01-01

    The reaction of cationic platinum aqua complexes 2 [Pt(C6H2{CH2NMe2}2-E-4)(OH2)](X') (X' = SO3CF3, BF4) with alkyl halides RX gave various air-stable arenium complexes 3-5 containing a new C-C bond (R = Me, 3; Et, 4; Bn, 5). Electron-releasing oxo-substituents on the aromatic ligand (E = e.g., OH, b

  20. Preventing disulfide bond formation weakens non-covalent forces among lysozyme aggregates.

    Directory of Open Access Journals (Sweden)

    Vijay Kumar Ravi

    Full Text Available Nonnative disulfide bonds have been observed among protein aggregates in several diseases like amyotrophic lateral sclerosis, cataract and so on. The molecular mechanism by which formation of such bonds promotes protein aggregation is poorly understood. Here in this work we employ previously well characterized aggregation of hen eggwhite lysozyme (HEWL at alkaline pH to dissect the molecular role of nonnative disulfide bonds on growth of HEWL aggregates. We employed time-resolved fluorescence anisotropy, atomic force microscopy and single-molecule force spectroscopy to quantify the size, morphology and non-covalent interaction forces among the aggregates, respectively. These measurements were performed under conditions when disulfide bond formation was allowed (control and alternatively when it was prevented by alkylation of free thiols using iodoacetamide. Blocking disulfide bond formation affected growth but not growth kinetics of aggregates which were ∼50% reduced in volume, flatter in vertical dimension and non-fibrillar in comparison to control. Interestingly, single-molecule force spectroscopy data revealed that preventing disulfide bond formation weakened the non-covalent interaction forces among monomers in the aggregate by at least ten fold, thereby stalling their growth and yielding smaller aggregates in comparison to control. We conclude that while constrained protein chain dynamics in correctly disulfide bonded amyloidogenic proteins may protect them from venturing into partial folded conformations that can trigger entry into aggregation pathways, aberrant disulfide bonds in non-amyloidogenic proteins (like HEWL on the other hand, may strengthen non-covalent intermolecular forces among monomers and promote their aggregation.

  1. FeF(3) catalyzed cascade C-C and C-N bond formation: synthesis of differentially substituted triheterocyclic benzothiazole functionalities under solvent-free condition.

    Science.gov (United States)

    Atar, Amol B; Jeong, Yeon Tae

    2014-05-01

    A series of diverse polyfunctionalized triheterocyclic benzothiazoles were easily prepared in excellent yields via the Biginelli reaction of 2-aminobenzothiazole with substituted benzaldehydes and α-methylene ketones using FeF(3) as an expeditious catalyst under solvent-free conditions. The protocol provides a practical and straightforward approach toward highly functionalized triheterocyclic benzothiazole derivatives in excellent yields. The reaction was conveniently promoted by FeF(3) and the catalyst could be recovered easily after the reaction and reused without any loss of its catalytic activity. The advantageous features of this methodology are high atom economy, operational simplicity, shorter reaction time, convergence, and facile automation.

  2. Formation of RNA phosphodiester bond by histidine-containing dipeptides

    DEFF Research Database (Denmark)

    Wieczorek, Rafal; Dörr, Mark; Chotera, Agata;

    2013-01-01

    A new scenario for prebiotic formation of nucleic acid oligomers is presented. Peptide catalysis is applied to achieve condensation of activated RNA monomers into short RNA chains. As catalysts, L-dipeptides containing a histidine residue, primarily Ser-His, were used. Reactions were carried out....... Details of the mechanism and kinetics, which were elucidated with a set of control experiments, further establish that the imidazole side chain of a histidine at the carboxyl end of the dipeptide plays a crucial role in the catalysis. These results suggest that this oligomerisation catalysis occurs...

  3. Vascular Stem/Progenitor Cell Migration Induced by Smooth Muscle Cell-Derived Chemokine (C-C Motif) Ligand 2 and Chemokine (C-X-C motif) Ligand 1 Contributes to Neointima Formation.

    Science.gov (United States)

    Yu, Baoqi; Wong, Mei Mei; Potter, Claire M F; Simpson, Russell M L; Karamariti, Eirini; Zhang, Zhongyi; Zeng, Lingfang; Warren, Derek; Hu, Yanhua; Wang, Wen; Xu, Qingbo

    2016-09-01

    Recent studies have shown that Sca-1(+) (stem cell antigen-1) stem/progenitor cells within blood vessel walls may contribute to neointima formation, but the mechanism behind their recruitment has not been explored. In this work Sca-1(+) progenitor cells were cultivated from mouse vein graft tissue and found to exhibit increased migration when cocultured with smooth muscle cells (SMCs) or when treated with SMC-derived conditioned medium. This migration was associated with elevated levels of chemokines, CCL2 (chemokine (C-C motif) ligand 2) and CXCL1 (chemokine (C-X-C motif) ligand 1), and their corresponding receptors on Sca-1(+) progenitors, CCR2 (chemokine (C-C motif) receptor 2) and CXCR2 (chemokine (C-X-C motif) receptor 2), which were also upregulated following SMC conditioned medium treatment. Knockdown of either receptor in Sca-1(+) progenitors significantly inhibited cell migration. The GTPases Cdc42 and Rac1 were activated by both CCL2 and CXCL1 stimulation and p38 phosphorylation was increased. However, only Rac1 inhibition significantly reduced migration and p38 phosphorylation. After Sca-1(+) progenitors labeled with green fluorescent protein (GFP) were applied to the adventitial side of wire-injured mouse femoral arteries, a large proportion of GFP-Sca-1(+) -cells were observed in neointimal lesions, and a marked increase in neointimal lesion formation was seen 1 week post-operation. Interestingly, Sca-1(+) progenitor migration from the adventitia to the neointima was abrogated and neointima formation diminished in a wire injury model using CCL2(-/-) mice. These findings suggest vascular stem/progenitor cell migration from the adventitia to the neointima can be induced by SMC release of chemokines which act via CCR2/Rac1/p38 and CXCR2/Rac1/p38 signaling pathways. Stem Cells 2016;34:2368-2380.

  4. How do halogen bonds (S-O⋯I, N-O⋯I and C-O⋯I) and halogen-halogen contacts (C-I⋯I-C, C-F⋯F-C) subsist in crystal structures? A quantum chemical insight.

    Science.gov (United States)

    Pandiyan, B Vijaya; Deepa, P; Kolandaivel, P

    2017-01-01

    Thirteen X-ray crystal structures containing various non-covalent interactions such as halogen bonds, halogen-halogen contacts and hydrogen bonds (I⋯N, I⋯F, I⋯I, F⋯F, I⋯H and F⋯H) were considered and investigated using the DFT-D3 method (B97D/def2-QZVP). The interaction energies were calculated at MO62X/def2-QZVP and MP2/aug-cc-pvDZ level of theories. The higher interaction and dispersion energies (2nd crystal) of -9.58 kcal mol(-1) and -7.10 kcal mol(-1) observed for 1,4-di-iodotetrafluorobenzene bis [bis (2-phenylethyl) sulfoxide] structure indicates the most stable geometrical arrangement in the crystal packing. The electrostatic potential values calculated for all crystal structures have a positive σ-hole, which aids understanding of the nature of σ-hole bonds. The significance of the existence of halogen bonds in crystal packing environments was authenticated by replacing iodine atoms by bromine and chlorine atoms. Nucleus independent chemical shift analysis reported on the resonance contribution to the interaction energies of halogen bonds and halogen-halogen contacts. Hirshfeld surface analysis and topological analysis (atoms in molecules) were carried out to analyze the occurrence and strength of all non-covalent interactions. These analyses revealed that halogen bond interactions were more dominant than hydrogen bonding interactions in these crystal structures. Graphical Abstract Molecluar structure of 1,4-Di-iodotetrafluorobenzene bis(thianthrene 5-oxide) moelcule and its corresponding molecular electrostatic potential map for the view of σ-hole.

  5. Enhanced van der Waals epitaxy via electron transfer-enabled interfacial dative bond formation

    CERN Document Server

    Xie, Weiyu; Wang, Gwo-Ching; Bhat, Ishwara; Zhang, Shengbai

    2016-01-01

    Enhanced van der Waals (vdW) epitaxy of semiconductors on layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe2 is a vdW layered material, first-principles calculations reveal that the bond strength at CdTe-NbSe2 interface is five times as large as that of vdW interaction at CdTe-graphene interface. The unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at CdTe surface to metallic non-bonding NbSe2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

  6. Anomalous absorption in c-C_3H and c-C_3D radicals

    Science.gov (United States)

    Chandra, S.; Shinde, S. V.; Kegel, W. H.; Sedlmayr, E.

    Yamamoto et al. (1987) reported the first detection of the c-C_3H radical in TMC-1 through its transition 2_1 2 rightarrow 1_1 1 at 91.5 GHz. The column density of c-C_3H in TMC-1 was estimated to be 6 times 10^12 cm^-2, which is about one order of magnitude lower than that of the c-C_3H_2 which is ubiquitous in galactic objects. Mangum & Wootten (1990) detected c-C_3H through the transition 1_1 0 rightarrow 1_1 1 at 14.8 GHz in 12 additional galactic objects. The most probable production mechanism of both the c-C_3H and c-C_3H_2 in dark clouds is a common dissociation reaction of the C_3H_3^+ ion (Adams & Smith 1987). Although the c-C_3H is 0.8 eV less stable than its isomer l-C_3H, finding of comparable column densities of both the isomers in TMC-1 suggests that the formation rate for both, c-C_3H and l-C_3H, are of about the same order in the cosmic objects. The existence of a metastable isomer under interstellar conditions is a well known phenomenon in astronomy. The aim of this investigation is a quantitative estimate of relative line intensities under NLTE conditions. For wide ranges of physical parameters, where these molecules may be found, we have solved a set of statistical equilibrium equations coupled with the equations of radiative transfer in an on-the-spot approximation. For c-C_3H, we accounted for 51 energy levels connected by 207 radiative transitions and for c-C_3D, we accounted for 51 energy levels connected by 205 radiative transitions. Our results show that the 3_3 1 rightarrow 3_3 0 transition of c-C_3H and c-C_3D may be found in absorption against the cosmic microwave background (CMB). Furthermore, we found population inversion for the 1_1 0 rightarrow 1_1 1 transition. These findings may be useful in identifying these molecules in other cosmic objects, as well as for the determination of physical parameters in these objects.

  7. Disulfide bond formation network in the three biological kingdoms, bacteria, fungi and mammals.

    Science.gov (United States)

    Sato, Yoshimi; Inaba, Kenji

    2012-07-01

    Almost all organisms, from bacteria to humans, possess catalytic systems that promote disulfide bond formation-coupled protein folding, i.e. oxidative protein folding. These systems are necessary for the biosynthesis of many secretory and membrane proteins, such as antibodies, major histocompatibility complex molecules, growth factors, and insulin. Over the last decade, structural studies have made striking progress in this field of research, identifying how oxidative systems operate in a specific and regulated manner to maintain redox and protein homeostasis within cells. Interestingly, more and more novel catalysts that promote disulfide bond formation have been discovered in mammals, suggesting that the oxidative protein folding network is even more complicated in higher eukaryotes than previously thought. This review highlights the physiological roles and molecular bases of the disulfide bond formation pathways that have evolved in the bacterial periplasm and the endoplasmic reticulum of fungi and mammals. Accumulating knowledge about disulfide bond formation networks widely distributed throughout the biological kingdom has significantly advanced our understanding of the cellular mechanisms dedicated to protein quality control.

  8. Ring-opening of cyclic ethers with carbon–carbon bond formation by Grignard reagents

    DEFF Research Database (Denmark)

    Christensen, Stig Holden; Holm, Torkil; Madsen, Robert

    2014-01-01

    The ring-opening of cyclic ethers with concomitant C–C bond formation was studied with a number of Grignard reagents. The transformation was performed in a sealed vial by heating to ∼160 °C in an aluminum block or at 180 °C in a microwave oven. Good yields of the product alcohols were obtained wi...

  9. Formation of metal-F bonds during frictional sliding : Influence of water and applied load

    NARCIS (Netherlands)

    Shen, J. T.; Pei, Y. T.; De Hosson, J. Th. M.

    2016-01-01

    Effects of water lubrication and applied load on the formation of PTFE transfer films and metal-F bonds during sliding when PTFE filled composites sliding against steel and Al2O3 are investigated. In water lubricated conditions, XPS analysis reveals that a thin layer of water molecules at the slidin

  10. Identification of disulfide bond formation between MitoNEET and glutamate dehydrogenase 1.

    Science.gov (United States)

    Roberts, Morgan E; Crail, Jacquelyn P; Laffoon, Megan M; Fernandez, William G; Menze, Michael A; Konkle, Mary E

    2013-12-17

    MitoNEET is a protein that was identified as a drug target for diabetes, but its cellular function as well as its role in diabetes remains elusive. Protein pull-down experiments identified glutamate dehydrogenase 1 (GDH1) as a potential binding partner. GDH1 is a key metabolic enzyme with emerging roles in insulin regulation. MitoNEET forms a covalent complex with GDH1 through disulfide bond formation and acts as an activator. Proteomic analysis identified the specific cysteine residues that participate in the disulfide bond. This is the first report that effectively links mitoNEET to activation of the insulin regulator GDH1.

  11. Behavior of intermetallics formation and evolution in Ag–8Au–3Pd alloy wire bonds

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Rui [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai (China); Hang, Tao, E-mail: hangtao@sjtu.edu.cn [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai (China); Mao, Dali [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai (China); Li, Ming, E-mail: mingli90@sjtu.edu.cn [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai (China); Qian, Kaiyou; Lv, Zhong; Chiu, Hope [Packaging RnD and Advanced MFG Engineering, SanDisk Semiconductor (Shanghai) Co., Ltd., Shanghai (China)

    2014-03-05

    Highlights: • Two IMC layers formed between Ag–8Au–3Pd alloy wire and Al pad were identified. • IMCs growth during annealing was discussed by diffusion kinetics. • Ag diffusion controls voids filling at bonding interface during thermal aging. -- Abstract: Ag–8Au–3Pd alloy wire has shown promise as an economical substitute for gold wire interconnects from integrated circuits to substrates. This work is undertaken to gain a better understanding on the intermetallic compounds (IMC) formation and evolution at the interface between Ag–8Au–3Pd wire and Al metallization pad. Longitudinal cross-section of bond interface was prepared by dual-beam focused ion beam (FIB) micro-machining for transmission electron microscopy (TEM) analysis. Two intermetallic regions formed at interface were crystallochemically identified as AuAl{sub 2} + (Au, Ag){sub 4}Al and Ag{sub 2}Al respectively. Interface evolution tracking by back scattered electron (BSE) imaging showed that IMC initially formed at periphery of bonding area. After short-term annealing treatment (175 °C for 24 h), the voids in the center of the bonding interface shrank and vanished, due to the Ag diffusion played dominant part in IMC growing. The mechanism of IMC formation and evolution at interface was finally elaborated on the basis of thermodynamics and diffusion kinetics respectively.

  12. Cytosolic disulfide bond formation in cells infected with large nucleocytoplasmic DNA viruses.

    Science.gov (United States)

    Hakim, Motti; Fass, Deborah

    2010-10-01

    Proteins that have evolved to contain stabilizing disulfide bonds generally fold in a membrane-delimited compartment in the cell [i.e., the endoplasmic reticulum (ER) or the mitochondrial intermembrane space (IMS)]. These compartments contain sulfhydryl oxidase enzymes that catalyze the pairing and oxidation of cysteine residues. In contrast, most proteins in a healthy cytosol are maintained in reduced form through surveillance by NADPH-dependent reductases and the lack of sulfhydryl oxidases. Nevertheless, one of the core functionalities that unify the broad and diverse set of nucleocytoplasmic large DNA viruses (NCLDVs) is the ability to catalyze disulfide formation in the cytosol. The substrates of this activity are proteins that contribute to the assembly, structure, and infectivity of the virions. If the last common ancestor of NCLDVs was present during eukaryogenesis as has been proposed, it is interesting to speculate that viral disulfide bond formation pathways may have predated oxidative protein folding in intracellular organelles.

  13. Nickel-catalyzed Csp2-Csp3 bond formation by carbon-fluorine activation.

    Science.gov (United States)

    Sun, Alex D; Leung, Kaylyn; Restivo, Anita D; LaBerge, Nicole A; Takasaki, Harumi; Love, Jennifer A

    2014-03-10

    We report herein a general catalytic method for Csp(2)-Csp(3) bond formation through C-F activation. The process uses an inexpensive nickel complex with either diorganozinc or alkylzinc halide reagents, including those with β-hydrogen atoms. A variety of fluorine substitution patterns and functional groups can be readily incorporated. Sequential reactions involving different precatalysts and coupling partners permit the synthesis of densely functionalized fluorinated building blocks.

  14. Peptide bond formation of alanine on silica and alumina surfaces as a catalyst

    Science.gov (United States)

    Sánchez Arenillas, M.; Mateo-Martí, E.

    2012-09-01

    Polymerization of amino acids has been important for the origin of life because the peptides may have been the first self-replicating systems. The amino acid concentrations in the oceans may have been too diluted in the early phases of the Earth. The formation of the biopolymers could have been due to the catalytic action of various minerals (such as silica or alumina). Our work is based on the comparison between alumina and silica minerals with and without prior activation of their silanol groups for the formation of peptide bonds using alanina like amino acid which it is the simplest quiral amino acid.

  15. C/C喉衬炭沉积形成机理及抑制方法研究%Experimental investigation on formation mechanism of carbon deposition of C/C throat-insert

    Institute of Scientific and Technical Information of China (English)

    徐开民; 李江; 王磊; 陈莎

    2011-01-01

    C/C喉衬在烧蚀后其内表面会出现炭沉积层,沉积层的出现阻碍了喉衬材料微观烧蚀形貌的分析.针对该问题,采用烧蚀实验发动机,在发动机工作末期喷注氮气和减小喷管喉径2种实验方法展开研究,明确了炭沉积层形成机理以及提出抑制该沉积层的方法.通过实验研究证明,炭沉积层成型于发动机工作末期,沉积是由于氧化性燃气中的烃烷类分子在一定的温度和流速条件下分解形成;工作末期喷注氮气起到了抑制沉积的效果,但是骤然冷却,热应力和剪切力使表面部分微观纤维形貌被破坏;由于减少了喉衬处于沉积温度范围内的时间,减小喷管喉径可很好地抑制炭沉积层出现进行微观烧蚀形貌的研究.%The carbon deposition layer appears on inner surface of C/C throat-insert, which hinders the micro-morphology analysis of materials. A kind of small-size solid rocket motor was used for experimental investigation, and two experimental method were adopted, I. e. injecting nitrogen into nozzle during late working process and reducing nozzle throat diameter. The result clarifies the formation mechanism of carbon deposits and presents method for inhibiting the deposition layer. Experimental investigations prove that the carbon deposits form at the end of working process for the hydrocarbon under certain temperature and flow rate. Injecting nitrogen inhibits deposition effect obviously, but the micro-morphology of surfaces was damaged by heat stress and shear stress. Because throat insert station time in deposition temperature range is decreased, reducing the nozzle throat diameter may inhibit carbon deposition. The results can be used for microscopic morphology research of C/C nozzle.

  16. {alpha}-Man monolayer formation via Si-C bond formation and protein recognition

    Energy Technology Data Exchange (ETDEWEB)

    Funato, Koji [School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan); Shirahata, Naoto [National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Miura, Yoshiko, E-mail: miuray@jaist.ac.j [School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan)

    2009-11-30

    An acetylenyl-terminated saccharide was synthesized and the thin layer formation on the hydrogen-terminated silicon was investigated. The acetylenyl-terminated saccharide was synthesized by the condensation reaction of hexynoic acid and p-aminophenyl saccharide. This was reacted with hydrogen-terminated silicon (Si-H) by a photochemical reaction. The resulting saccharide modified substrate was analyzed by ellipsometry and X-ray photoelectron spectroscopy, which showed the formation of a uniform monolayer. The surface's ability to recognize proteins was analyzed by fluorescent microscopy, and showed specific interactions with sugar recognition proteins.

  17. Building Bridges: Biocatalytic C–C-Bond Formation toward Multifunctional Products

    Science.gov (United States)

    2016-01-01

    Carbon–carbon bond formation is the key reaction for organic synthesis to construct the carbon framework of organic molecules. The review gives a selection of biocatalytic C–C-bond-forming reactions which have been investigated during the last 5 years and which have already been proven to be applicable for organic synthesis. In most cases, the reactions lead to products functionalized at the site of C–C-bond formation (e.g., α-hydroxy ketones, aminoalcohols, diols, 1,4-diketones, etc.) or allow to decorate aromatic and heteroaromatic molecules. Furthermore, examples for cyclization of (non)natural precursors leading to saturated carbocycles are given as well as the stereoselective cyclopropanation of olefins affording cyclopropanes. Although many tools are already available, recent research also makes it clear that nature provides an even broader set of enzymes to perform specific C–C coupling reactions. The possibilities are without limit; however, a big library of variants for different types of reactions is required to have the specific enzyme for a desired specific (stereoselective) reaction at hand. PMID:27398261

  18. Understanding the effect of substitution on the formation of S. . .F chalcogen bond

    Indian Academy of Sciences (India)

    RAHUL SHUKLA; DEEPAK CHOPRA

    2016-10-01

    In this study, we have investigated the effect of substitution on the formation of S. . .F non-covalent interactions in XHS. . .FCH₃ complexes (X= −H, −F, −Cl, −OH, −OCH₃, −NH₂, −NHCH₃, −NO₂, −CN) at MP2/aug-cc-pVDZ level of theory. The formation of S. . .F chalcogen bonds was observed in all the cases, except for X = −H. The binding energy of the S. . .F non-covalent interactions is strongly dependent on the nature of the substituent groups. The energy decomposition analysis revealed that electrostatic and exchangeenergy component are the dominant contributors towards the stability of these interactions. The topological analysis established the presence of the S. . .F chalcogen bond due to the presence of a bond critical point exclusively between sulphur and fluorine atoms representing a closed-shell interaction. The natural bondorbital analysis shows that the stability of the interaction comes from a charge transfer from F(lp) to σ* (S-X) orbital transition.

  19. Radical carbon-carbon bond formations enabled by visible light active photocatalysts.

    Science.gov (United States)

    Wallentin, Carl-Johan; Nguyen, John D; Stephenson, Corey R J

    2012-01-01

    This mini-review highlights the Stephenson group's contribution to the field of photoredox catalysis with emphasis on carbon-carbon bond formation. The realization of photoredox mediated reductive dehalogenation initiated investigations toward both intra- and intermolecular coupling reactions. These reactions commenced via visible light-mediated reduction of activated halogens to give carbon-centered radicals that were subsequently involved in carbon-carbon bond forming transformations. The developed protocols using Ru and Ir based polypyridyl complexes as photoredox catalysts were further tuned to efficiently catalyze overall redox neutral atom transfer radical addition reactions. Most recently, a simplistic flow reactor technique has been utilized to affect a broad scope of photocatalytic transformations with significant enhancement in reaction efficiency.

  20. Hydrophilicity of dentin bonding systems influences in vitro Streptococcus mutans biofilm formation

    Science.gov (United States)

    Brambilla, Eugenio; Ionescu, Andrei; Mazzoni, Annalisa; Cadenaro, Milena; Gagliani, Massimo; Ferraroni, Monica; Tay, Franklin; Pashley, David; Breschi, Lorenzo

    2014-01-01

    Objectives To evaluate in vitro Streptococcus mutans (S. mutans) biofilm formation on the surface of five light-curing experimental dental bonding systems (DBS) with increasing hydrophilicity. The null hypothesis tested was that resin chemical composition and hydrophilicity does not affect S. mutans biofilm formation. Methods Five light-curing versions of experimental resin blends with increasing hydrophilicity were investigated (R1, R2, R3, R4 and R5). R1 and R2 contained ethoxylated BisGMA/TEGDMA or BisGMA/TEGDMA, respectively, and were very hydrophobic, were representative of pit-and-fissure bonding agents. R3 was representative of a typical two-step etch- and-rinse adhesive, while R4 and R5 were very hydrophilic resins analogous to self-etching adhesives. Twenty-eight disks were prepared for each resin blend. After a 24 h-incubation at 37 °C, a multilayer monospecific biofilm of S. mutans was obtained on the surface of each disk. The adherent biomass was determined using the MTT assay and evaluated morphologically with confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). Results R2 and R3 surfaces showed the highest biofilm formation while R1 and R4 showed a similar intermediate biofilm formation. R5 was more hydrophilic and acidic and was significantly less colonized than all the other resins. A significant quadratic relationship between biofilm formation and hydrophilicity of the resin blends was found. CLSM and SEM evaluation confirmed MTT assay results. Conclusions The null hypothesis was rejected since S. mutans biofilm formation was influenced by hydrophilicity, surface acidity and chemical composition of the experimental resins. Further studies using a bioreactor are needed to confirm the results and clarify the role of the single factors. PMID:24954666

  1. Thermodynamic Strategies for C-O Bond Formation and Cleavage via Tandem Catalysis.

    Science.gov (United States)

    Lohr, Tracy L; Li, Zhi; Marks, Tobin J

    2016-05-17

    To reduce global reliance on fossil fuels, new renewable sources of energy that can be used with the current infrastructure are required. Biomass represents a major source of renewable carbon based fuel; however, the high oxygen content (∼40%) limits its use as a conventional fuel. To utilize biomass as an energy source, not only with current infrastructure, but for maximum energy return, the oxygen content must be reduced. One method to achieve this is to develop selective catalytic methods to cleave C-O bonds commonly found in biomass (aliphatic and aromatic ethers and esters) for the eventual removal of oxygen in the form of volatile H2O or carboxylic acids. Once selective methods of C-O cleavage are understood and perfected, application to processing real biomass feedstocks such as lignin can be undertaken. This Laboratory previously reported that recyclable "green" lanthanide triflates are excellent catalysts for C-O bond-forming hydroalkoxylation reactions. Based on the virtues of microscopic reversibility, the same lanthanide triflate catalyst should catalyze the reverse C-O cleavage process, retrohydroalkoxylation, to yield an alcohol and an alkene. However, ether C-O bond-forming (retrohydroalkoxylation) to form an alcohol and alkene is endothermic. Guided by quantum chemical analysis, our strategy is to couple endothermic, in tandem, ether C-O bond cleavage with exothermic alkene hydrogenation, thereby leveraging the combined catalytic cycles thermodynamically to form an overall energetically favorable C-O cleavage reaction. This Account reviews recent developments on thermodynamically leveraged tandem catalysis for ether and more recently, ester C-O bond cleavage undertaken at Northwestern University. First, the fundamentals of lanthanide-catalyzed hydroelementation are reviewed, with particular focus on ether C-O bond formation (hydroalkoxylation). Next, the reverse C-O cleavage/retrohydroalkoxylation processes enabled by tandem catalysis are

  2. A Synthesis of 1H-Indazoles via a Cu(OAc)2-Catalyzed N-N Bond Formation.

    Science.gov (United States)

    Chen, Cheng-yi; Tang, Guangrong; He, Fengxian; Wang, Zhaobin; Jing, Hailin; Faessler, Roger

    2016-04-01

    A facile synthesis of 1H-indazoles featuring a Cu(OAc)2-catalyzed N-N bond formation using oxygen as the terminal oxidant is described. The reaction of readily available 2-aminobenzonitriles with various organometallic reagents led to o-aminoaryl N-H ketimine species. The subsequent Cu(OAc)2-catalyzed N-N bond formation in DMSO under oxygen afforded a wide variety of 1H-indazoles in good to excellent yields.

  3. Bridging and bonding interactions in higher education: social capital and students' academic and professional identity formation.

    Science.gov (United States)

    Jensen, Dorthe H; Jetten, Jolanda

    2015-01-01

    It is increasingly recognized that graduates' achievements depend in important ways on their opportunities to develop an academic and a professional identity during their studies. Previous research has shown that students' socio-economic status (SES) and social capital prior to entering university affects their ability to obtain these identities in higher education. However, what is less well understood is whether social capital that is built during university studies shapes identity development, and if so, whether the social capital gained during university years impacts on academic and professional identity differently. In a qualitative study, we interviewed 26 Danish and 11 Australian university students about their social interaction experiences, their opportunities to develop bonding capital as well as bridging capital, and their academic and professional identity. Findings show that while bonding social capital with co-students facilitated academic identity formation, such social capital does not lead to professional identity development. We also found that the development of bridging social capital with educators facilitated students' professional identity formation. However, bonding social capital among students stood in the way of participating in bridging interaction with educators, thereby further hindering professional identity formation. Finally, while students' parental background did not affect the perceived difficulty of forming professional identity, there was a tendency for students from lower SES backgrounds to be more likely to make internal attributions while those from higher SES backgrounds were more likely to make external attributions for the failure to develop professional identity. Results point to the importance of creating opportunities for social interaction with educators at university because this facilitates the generation of bridging social capital, which, in turn, is essential for students' professional identity development.

  4. Electrochemically informed synthesis and characterization of salts of the [Pt2(mu-kappaAs,kappaC-C6H3-5-Me-2-AsPh2)4]+ lantern complex containing a Pt-Pt bond of order 1/2.

    Science.gov (United States)

    Bennett, Martin A; Bhargava, Suresh K; Boas, John F; Boeré, René T; Bond, Alan M; Edwards, Alison J; Guo, Si-Xuan; Hammerl, Anton; Pilbrow, John R; Privér, Steven H; Schwerdtfeger, Peter

    2005-04-01

    Detailed electrochemical studies in dichloromethane (0.1 M Bu4NPF6) on the oxidation of the half-lantern [Pt2(kappa2As,C-C6H3-5-Me-2-AsPh2)2(mu-kappaAs,kappaC-C6H3-5-Me-2-AsPh2)2] (1) and full-lantern [Pt2(mu-kappaAs,kappaC-C6H3-5-Me-2-AsPh2)4] (2) complexes reveal the presence of an exceptionally stable dinuclear Pt cation 2+. Thus, oxidation of 1 occurs on the voltammetric time scale via a ladder-square scheme to give 2+, whereas 2 is directly converted to 2+. Electrochemically informed chemical synthesis enabled the isolation of solid [2+][BF4-] to be achieved. Single-crystal X-ray structural analysis showed that 2+ also has a lantern structure but with a shorter separation between the Pt centers [2.7069(3) A (2+), 2.8955(4) A (2)]. EPR spectra of 2+ provide unequivocal evidence for axial symmetry of the complex and are noteworthy because of an exceptionally large, nearly isotropic hyperfine coupling constant of about 0.1 cm(-1). Spectroscopic data support the conclusion that the unpaired electron in the 2+ cation is distributed equally between the two Pt nuclei and imply that oxidation of 2 to 2+ leads to the establishment of the metal-to-metal hemibond. Results of extended Huckel molecular orbital and density functional calculations on 2 and 2+ lead to the conclusions that s, p, dz2 mixing of orbitals contributes to the large EPR Pt hyperfine coupling and also that the structural adjustments that occur upon removal of an electron from 2 are driven by the metal-metal bonding character present in 2+.

  5. C/C-PAA与C/C-FA弯曲性能对比%Comparison of Flexural Properties Between C/C-PAA and C/C-FA

    Institute of Scientific and Technical Information of China (English)

    张万强; 赵英民; 王涛; 詹万初

    2014-01-01

    通过PIP工艺制备了C/C-PAA、C/C-FA复合材料,对PAA、FA裂解碳的XRD、浸渍效果以及C/C-PAA和C/C-FA的弯曲强度进行了分析.结果表明:PAA裂解碳的炭质量、浸渍效果较好,C/C-PAA弯曲强度比C/C-FA弯曲强度高34.9%,弯曲模量对比不明显.

  6. Dissecting the role of disulfide bonds on the amyloid formation of insulin

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yang; Gong, Hao [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Sun, Yue [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Yan, Juan; Cheng, Biao; Zhang, Xin [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Huang, Jing [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Yu, Mengying; Guo, Yu [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Zheng, Ling, E-mail: lzheng217@hotmail.com [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Huang, Kun, E-mail: kunhuang2008@hotmail.com [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Centre for Biomedicine Research, Wuhan Institutes of Biotechnology, Wuhan 430070 (China)

    2012-06-29

    Highlights: Black-Right-Pointing-Pointer We dissect how individual disulfide bond affects the amyloidogenicity of insulin. Black-Right-Pointing-Pointer A controlled reduction system for insulin is established in this study. Black-Right-Pointing-Pointer Disulfide breakage is associated with unfolding and increased amyloidogenicity. Black-Right-Pointing-Pointer Breakage of A6-A11 is associated with significantly increased cytotoxicity. Black-Right-Pointing-Pointer Analogs without A6-A11 have a higher potency to form high order toxic oligomers. -- Abstract: Disulfide bonds play a critical role in the stability and folding of proteins. Here, we used insulin as a model system, to investigate the role of its individual disulfide bond during the amyloid formation of insulin. Tris(2-carboxyethyl)phosphine (TCEP) was applied to reduce two of the three disulfide bonds in porcine insulin and the reduced disulfide bonds were then alkylated by iodoacetamide. Three disulfide bond-modified insulin analogs, INS-2 (lack of A6-A11), INS-3 (lack of A7-B7) and INS-6 (lack of both A6-A11 and A7-B7), were obtained. Far-UV circular dichroism (CD) spectroscopy results indicated that the secondary structure of INS-2 was the closest to insulin under neutral conditions, followed by INS-3 and INS-6, whereas in an acidic solution all analogs were essentially unfolded. To test how these modifications affect the amyloidogenicity of insulin, thioflavin-T (ThT) fluorescence and transmission electronic microscopy (TEM) were performed. Our results showed that all analogs were more prone to aggregation than insulin, with the order of aggregation rates being INS-6 > INS-3 > INS-2. Cross-linking of unmodified proteins (PICUP) assay results showed that analogs without A6-A11 (INS-2 and INS-6) have a higher potential for oligomerization than insulin and INS-3, which is accompanied with a higher cytotoxicity as the hemolytic assays of human erythrocytes suggested. The results indicated that breakage of A7

  7. Optimized Reaction Conditions for Amide Bond Formation in DNA-Encoded Combinatorial Libraries.

    Science.gov (United States)

    Li, Yizhou; Gabriele, Elena; Samain, Florent; Favalli, Nicholas; Sladojevich, Filippo; Scheuermann, Jörg; Neri, Dario

    2016-08-08

    DNA-encoded combinatorial libraries are increasingly being used as tools for the discovery of small organic binding molecules to proteins of biological or pharmaceutical interest. In the majority of cases, synthetic procedures for the formation of DNA-encoded combinatorial libraries incorporate at least one step of amide bond formation between amino-modified DNA and a carboxylic acid. We investigated reaction conditions and established a methodology by using 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide, 1-hydroxy-7-azabenzotriazole and N,N'-diisopropylethylamine (EDC/HOAt/DIPEA) in combination, which provided conversions greater than 75% for 423/543 (78%) of the carboxylic acids tested. These reaction conditions were efficient with a variety of primary and secondary amines, as well as with various types of amino-modified oligonucleotides. The reaction conditions, which also worked efficiently over a broad range of DNA concentrations and reaction scales, should facilitate the synthesis of novel DNA-encoded combinatorial libraries.

  8. Bimetallic bonding and mixed oxide formation in the Ga-Pd-CeO2 system

    Science.gov (United States)

    Skála, Tomáš; Tsud, Nataliya; Prince, Kevin C.; Matolín, Vladimír

    2011-08-01

    The interaction of gallium and palladium with 2 nm CeO2(111) layers grown on Cu(111) was studied by core level photoelectron spectroscopy and resonant valence band spectroscopy. Palladium alone interacted weakly with ceria layers. Gallium deposited on cerium dioxide formed a mixed Ga2O3-Ce2O3 oxide of 1:1 stoichiometry (cerium gallate CeGaO3), with both metals in the M3+ oxidation state. Increasing Ga coverages led to the formation of lower oxidation states, i.e., Ga1+ in Ga2O oxide and metallic Ga0. Palladium deposited onto this complex system interacted with gallium leading to a breakage of Ga-ceria bonds, a decrease of the oxidation state of gallium, and formation of a Ga-Pd intermetallic alloy in which all components (CeO2, CeGaO3, Ga2O, Ga-Pd, and Pd) are in equilibrium.

  9. Evaluation of the Role of Water in the H2 Bond Formation by Ni(II)-Based Electrocatalysts.

    Science.gov (United States)

    Ho, Ming-Hsun; Raugei, Simone; Rousseau, Roger; Dupuis, Michel; Bullock, R Morris

    2013-08-13

    We investigate the role of water in the H-H bond formation by a family of nickel molecular catalysts that exhibit high rates for H2 production in acetonitrile solvent. A key feature leading to the high reactivity is the Lewis acidity of the Ni(II) center and pendant amines in the diphosphine ligand that function as Lewis bases, facilitating H-H bond formation or cleavage. Significant increases in the rate of H2 production have been reported in the presence of added water. Our calculations show that molecular water can displace an acetonitrile solvent molecule in the first solvation shell of the metal. One or two water molecules can also participate in shuttling a proton that can combine with a metal hydride to form the H-H bond. However the participation of the water molecules does not lower the barrier to H-H bond formation. Thus these calculations suggest that the rate increase due to water in these electrocatalysts is not associated with the elementary step of H-H bond formation or cleavage but rather with the proton delivery steps. We attribute the higher barrier in the H-H bond formation in the presence of water to a decrease in direct interaction between the protic and hydridic hydrogen atoms forced by the water molecules.

  10. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    Science.gov (United States)

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2015-01-01

    Succinimide formation from aspartic acid (Asp) residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe) as a model compound, we propose the possibility that acetic acid (AA), which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition) to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds) occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism. PMID:25588215

  11. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi

    2015-01-01

    Full Text Available Succinimide formation from aspartic acid (Asp residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe as a model compound, we propose the possibility that acetic acid (AA, which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism.

  12. In vivo biofilm formation on stainless steel bonded retainers during different oral health-care regimens

    Institute of Scientific and Technical Information of China (English)

    Marije A Jongsma; Henny C van der Mei; Jelly Atema-Smit; Henk J Busscher; Yijin Ren

    2015-01-01

    Retention wires permanently bonded to the anterior teeth are used after orthodontic treatment to prevent the teeth from relapsing to pre-treatment positions. A disadvantage of bonded retainers is biofilm accumulation on the wires, which produces a higher incidence of gingival recession, increased pocket depth and bleeding on probing. This study compares in vivo biofilm formation on single-strand and multi-strand retention wires with different oral health-care regimens. Two-centimetre wires were placed in brackets that were bonded to the buccal side of the first molars and second premolars in the upper arches of 22 volunteers. Volunteers used a selected toothpaste with or without the additional use of a mouthrinse containing essential oils. Brushing was performed manually. Regimens were maintained for 1 week, after which the wires were removed and the oral biofilm was collected to quantify the number of organisms and their viability, determine the microbial composition and visualize the bacteria by electron microscopy. A 6-week washout period was employed between regimens. Biofilm formation was reduced on single-strand wires compared with multi-strand wires;bacteria were observed to adhere between the strands. The use of antibacterial toothpastes marginally reduced the amount of biofilm on both wire types, but significantly reduced the viability of the biofilm organisms. Additional use of the mouthrinse did not result in significant changes in biofilm amount or viability. However, major shifts in biofilm composition were induced by combining a stannous fluoride-or triclosan-containing toothpaste with the mouthrinse. These shifts can be tentatively attributed to small changes in bacterial cell surface hydrophobicity after the adsorption of the toothpaste components, which stimulate bacterial adhesion to the hydrophobic oil, as illustrated for a Streptococcus mutans strain.

  13. Ruthenium(II)-Catalyzed C-C Arylations and Alkylations: Decarbamoylative C-C Functionalizations.

    Science.gov (United States)

    Moselage, Marc; Li, Jie; Kramm, Frederik; Ackermann, Lutz

    2017-04-05

    Ruthenium(II)biscarboxylate catalysis enabled selective C-C functionalizations by means of decarbamoylative C-C arylations. The versatility of the ruthenium(II) catalysis was reflected by widely applicable C-C arylations and C-C alkylations of aryl amides, as well as acids with modifiable pyrazoles, through facile organometallic C-C activation.

  14. Disruption of reducing pathways is not essential for efficient disulfide bond formation in the cytoplasm of E. coli

    Directory of Open Access Journals (Sweden)

    Hatahet Feras

    2010-09-01

    Full Text Available Abstract Background The formation of native disulfide bonds is a complex and essential post-translational modification for many proteins. The large scale production of these proteins can be difficult and depends on targeting the protein to a compartment in which disulfide bond formation naturally occurs, usually the endoplasmic reticulum of eukaryotes or the periplasm of prokaryotes. It is currently thought to be impossible to produce large amounts of disulfide bond containing protein in the cytoplasm of wild-type bacteria such as E. coli due to the presence of multiple pathways for their reduction. Results Here we show that the introduction of Erv1p, a sulfhydryl oxidase and FAD-dependent catalyst of disulfide bond formation found in the inter membrane space of mitochondria, allows the efficient formation of native disulfide bonds in heterologously expressed proteins in the cytoplasm of E. coli even without the disruption of genes involved in disulfide bond reduction, for example trxB and/or gor. Indeed yields of active disulfide bonded proteins were higher in BL21 (DE3 pLysSRARE, an E. coli strain with the reducing pathways intact, than in the commercial Δgor ΔtrxB strain rosetta-gami upon co-expression of Erv1p. Conclusions Our results refute the current paradigm in the field that disruption of at least one of the reducing pathways is essential for the efficient production of disulfide bond containing proteins in the cytoplasm of E. coli and open up new possibilities for the use of E. coli as a microbial cell factory.

  15. A Rough Energy Landscape to Describe Surface-Linked Antibody and Antigen Bond Formation

    Science.gov (United States)

    Limozin, Laurent; Bongrand, Pierre; Robert, Philippe

    2016-01-01

    Antibodies and B cell receptors often bind their antigen at cell-cell interface while both molecular species are surface-bound, which impacts bond kinetics and function. Despite the description of complex energy landscapes for dissociation kinetics which may also result in significantly different association kinetics, surface-bound molecule (2D) association kinetics usually remain described by an on-rate due to crossing of a single free energy barrier, and few experimental works have measured association kinetics under conditions implying force and two-dimensional relative ligand-receptor motion. We use a new laminar flow chamber to measure 2D bond formation with systematic variation of the distribution of encounter durations between antigen and antibody, in a range from 0.1 to 10 ms. Under physiologically relevant forces, 2D association is 100-fold slower than 3D association as studied by surface plasmon resonance assays. Supported by brownian dynamics simulations, our results show that a minimal encounter duration is required for 2D association; an energy landscape featuring a rough initial part might be a reasonable way of accounting for this. By systematically varying the temperature of our experiments, we evaluate roughness at 2kBT, in the range of previously proposed rough parts of landscapes models during dissociation. PMID:27731375

  16. Anatomy of bond formation. Bond length dependence of the extent of electron sharing in chemical bonds from the analysis of domain-averaged Fermi holes.

    Science.gov (United States)

    Ponec, Robert; Cooper, David L

    2007-01-01

    We demonstrate that domain-average Fermi hole (DAFH) analysis, which has previously been used at the Hartree-Fock level, remains useful after the proper introduction of electron correlation. We perform a systematic investigation of the variation of the picture of bonding with increasing bond length in simple diatomic molecules such as N2 and LiH. Alongside values of a shared-electron distribution index (SEDI), this analysis provides further insight into the geometry dependence of the extent of electron sharing in polar and non-polar systems. We also use DAFH analysis, with correlated wave functions, to evaluate the (potential) multicentre bonding in the electron-deficient and electron-rich molecules CH2Li2 and CH2N2, respectively.

  17. Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR)

    Energy Technology Data Exchange (ETDEWEB)

    Roth, Justine P. [Johns Hopkins Univ., Baltimore, MD (United States)

    2015-03-03

    Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR) Research during the project period focused primarily on mechanisms of water oxidation by structurally defined transition metal complexes. Competitive oxygen isotope fractionation of water, mediated by oxidized precursors or reduced catalysts together with ceric, Ce(IV), ammonium nitrate in aqueous media, afforded oxygen-18 kinetic isotope effects (O-18 KIEs). Measurement, calculation, and interpretation of O-18 KIEs, described in the accompanying report has important ramifications for the production of electricity and solar hydrogen (as fuel). The catalysis division of BES has acknowledged that understanding mechanisms of transition metal catalyzed water oxidation has major ramifications, potentially leading to transformation of the global economy and natural environment in years to come. Yet, because of program restructuring and decreased availability of funds, it was recommended that the Solar Photochemistry sub-division of BES would be a more appropriate parent program for support of continued research.

  18. DsbL and DsbI contribute to periplasmic disulfide bond formation in Salmonella enterica serovar Typhimurium

    OpenAIRE

    Lin, Dongxia; Kim, Byoungkwan; Slauch, James M.

    2009-01-01

    Disulfide bond formation in periplasmic proteins is catalysed by the DsbA/DsbB system in most Gram-negative bacteria. Salmonella enterica serovar Typhimurium also encodes a paralogous pair of proteins to DsbA and DsbB, DsbL and DsbI, respectively, downstream of a periplasmic arylsulfate sulfotransferase (ASST). We show that DsbL and DsbI function as a redox pair contributing to periplasmic disulfide bond formation and, as such, affect transcription of the Salmonella pathogenicity island 1 (SP...

  19. Heterolytic OO bond cleavage: Functional role of Glu113 during bis-Fe(IV) formation in MauG.

    Science.gov (United States)

    Geng, Jiafeng; Huo, Lu; Liu, Aimin

    2017-02-01

    The diheme enzyme MauG utilizes H2O2 to perform oxidative posttranslational modification on a protein substrate. A bis-Fe(IV) species of MauG was previously identified as a key intermediate in this reaction. Heterolytic cleavage of the OO bond of H2O2 drives the formation of the bis-Fe(IV) intermediate. In this work, we tested a hypothesis that a glutamate residue, Glu113 in the distal pocket of the pentacoordinate heme of MauG, facilitates heterolytic OO bond cleavage, thereby leading to bis-Fe(IV) formation. This hypothesis was proposed based on sequence alignment and structural comparison with other H2O2-utilizing hemoenzymes, especially those from the diheme enzyme superfamily that MauG belongs to. Electron paramagnetic resonance (EPR) characterization of the reaction between MauG and H2O2 revealed that mutation of Glu113 inhibited heterolytic OO bond cleavage, in agreement with our hypothesis. This result was further confirmed by the HPLC study in which an analog of H2O2, cumene hydroperoxide, was used to probe the pattern of OO bond cleavage. Together, our data suggest that Glu113 functions as an acid-base catalyst to assist heterolytic OO bond cleavage during the early stage of the catalytic reaction. This work advances our mechanistic understanding of the H2O2-activation process during bis-Fe(IV) formation in MauG.

  20. Bond formation effects on the metal-insulator transition in the half-filled kagome Hubbard model

    Science.gov (United States)

    Higa, Ryota; Asano, Kenichi

    2016-06-01

    We study the metal-insulator transition in the half-filled Hubbard model on a Kagome lattice using the variational cluster approximation. The strong coupling limit of the model corresponds to the S =1 /2 Kagome Heisenberg antiferromagnet, which is known to have a singlet ground state, although its detail is still debated. As the results of the cluster methods generally depend much on the choice of the unit cluster, we have chosen the clusters that are compatible with these singlet ground states in the strong coupling case found so far, which basically consist of even number of sites. It is found that the correlated electrons on the Kagome lattice have a strong tendency to form valence-bond structures, which are the resonation of electrons on a single bond or several bonds forming loops. The zero-temperature metal-insulator transition at some interaction strength is possibly driven by the formation of such short range valence bonds and shows a second order character, which is distinctive from the Brinkman-Rice scenario. The electrons on these valence bonds further localizes onto each site as the interaction increases, and the valence bonds of electrons finally turn into magnetic singlet bonds between localized S =1 /2 spins, which are consistent with the ground states of the Kagome antiferromagnet.

  1. A class of luminescent cyclometalated alkynylgold(III) complexes: synthesis, characterization, and electrochemical, photophysical, and computational studies of [Au(C=N=C)(C triple bond C-R)] (C=N=C = kappa(3)C,N,C bis-cyclometalated 2,6-diphenylpyridyl).

    Science.gov (United States)

    Wong, Keith Man-Chung; Hung, Ling-Ling; Lam, Wai Han; Zhu, Nianyong; Yam, Vivian Wing-Wah

    2007-04-11

    A new class of luminescent cyclometalated alkynylgold(III) complexes, [Au(RC=N(R')=CR)(CCR' ')], i.e., [Au(C=N=C)(C triple bond CR'')] (HC=N=CH = 2,6-diphenylpyridine) R' ' = C6H5 1, C6H4-Cl-p 2, C6H4-NO2-p 3, C6H4-OCH3-p 4, C6H4-NH2-p 5, C6H4-C6H13-p 6, C6H13 7, [Au(tBuC=N=CtBu)(C triple bond CC6H5)] 8 (HtBuC=N=CtBuH = 2,6-bis(4-tert-butylphenyl)pyridine), and [Au(C=NTol=C)(CCC6H4-C6H13-p)] 9 (HC=NTol=CH = 2,6-diphenyl-4-p-tolylpyridine), have been synthesized and characterized. The X-ray crystal structures of most of the complexes have also been determined. Electrochemical studies show that, in general, the first oxidation wave is an alkynyl ligand-centered oxidation, while the first reduction couple is ascribed to a ligand-centered reduction of the cyclometalated ligand with the exception of 3 in which the first reduction couple is assigned as an alkynyl ligand-centered reduction. Their electronic absorption and luminescence behaviors have also been investigated. In dichloromethane solution at room temperature, the low-energy absorption bands are assigned as the pi-pi* intraligand (IL) transition of the cyclometalated RC=N(R')=CR ligand with some mixing of a [pi(C triple bond CR'') --> pi*(RC=N(R')=CR)] ligand-to-ligand charge transfer (LLCT) character. The low-energy emission bands of all the complexes, with the exception of 5, are ascribed to origins mainly derived from the pi-pi* IL transition of the cyclometalated RC=N(R')=CR ligand. In the case of 5 that contains an electron-rich amino substituent on the alkynyl ligand, the low-energy emission band was found to show an obvious shift to the red. A change in the origin of emission is evident, and the emission of 5 is tentatively ascribed to a [pi(CCC6H4NH2) --> pi*(C=N=C)] LLCT excited-state origin. DFT and TDDFT computational studies have been performed to verify and elucidate the results of the electrochemical and photophysical studies.

  2. Paleobotany and palynology of the Bristol Hill Coal Member (Bond Formation) and Friendsville Coal Member (Mattoon Formation) of the Illinois Basin (Upper Pennsylvania)

    Energy Technology Data Exchange (ETDEWEB)

    Willard, D.A.; Phillips, T.L. [US Geological Survey, Reston, VA (United States)

    1993-12-01

    Late Pennsylvanian coal swamps of the Illinois Basin were dominated by Psaronius tree ferns with a spatially heterogeneous distribution of medullosan pteridosperms (subdominant), calamites, sigillarian lycopsids, and cordaites. Miospore and coal-ball plant assemblages from the Missourian-age Bristol Hill Coal Member (Bond Formation) and Friendsville Coal Member (Mattoon Formation) of southeastern Illinois were quantified to analyze vegetational patterns in Late Pennsylvanian peat swamps and to compare vegetational composition of the coals.

  3. MICROWAVE-ASSISTED CHEMISTRY: SYNTHESIS OF AMINES AND HETEROCYCLES VIA CARBON-NITROGEN BOND FORMATION IN AQUEOUS MEDIA

    Science.gov (United States)

    Improved C-N bond formation under MW influence is demonstrated by a) solventless three-component coupling reaction to generate propargyl amines that uses only Cu (I); b) aqueous N-alkylation of amines by alkyl halides that proceeds expeditiously in the presence of NaOH to deliver...

  4. Imbalance of heterologous protein folding and disulfide bond formation rates yields runaway oxidative stress

    Directory of Open Access Journals (Sweden)

    Tyo Keith EJ

    2012-03-01

    Full Text Available Abstract Background The protein secretory pathway must process a wide assortment of native proteins for eukaryotic cells to function. As well, recombinant protein secretion is used extensively to produce many biologics and industrial enzymes. Therefore, secretory pathway dysfunction can be highly detrimental to the cell and can drastically inhibit product titers in biochemical production. Because the secretory pathway is a highly-integrated, multi-organelle system, dysfunction can happen at many levels and dissecting the root cause can be challenging. In this study, we apply a systems biology approach to analyze secretory pathway dysfunctions resulting from heterologous production of a small protein (insulin precursor or a larger protein (α-amylase. Results HAC1-dependent and independent dysfunctions and cellular responses were apparent across multiple datasets. In particular, processes involving (a degradation of protein/recycling amino acids, (b overall transcription/translation repression, and (c oxidative stress were broadly associated with secretory stress. Conclusions Apparent runaway oxidative stress due to radical production observed here and elsewhere can be explained by a futile cycle of disulfide formation and breaking that consumes reduced glutathione and produces reactive oxygen species. The futile cycle is dominating when protein folding rates are low relative to disulfide bond formation rates. While not strictly conclusive with the present data, this insight does provide a molecular interpretation to an, until now, largely empirical understanding of optimizing heterologous protein secretion. This molecular insight has direct implications on engineering a broad range of recombinant proteins for secretion and provides potential hypotheses for the root causes of several secretory-associated diseases.

  5. Ions colliding with clusters of fullerenes-Decay pathways and covalent bond formations

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, F.; Zettergren, H.; Chen, T.; Gatchell, M.; Alexander, J. D.; Stockett, M. H.; Schmidt, H. T.; Cederquist, H. [Department of Physics, Stockholm University, S-106 91 Stockholm (Sweden); Rousseau, P.; Chesnel, J. Y.; Capron, M.; Poully, J. C.; Mery, A.; Maclot, S.; Adoui, L. [CIMAP, UMR 6252, CEA/CNRS/ENSICAEN/Universite de Caen Basse-Normandie, bd Henri Becquerel, BP 5133, F-14070 Caen cedex 05 (France); Universite de Caen Basse-Normandie, Esplanade de la Paix, F-14032 Caen (France); Wang, Y.; Martin, F. [Departamento de Quimica, Modulo 13, Universidad Autonoma de Madrid, 28049 Madrid (Spain); Instituto Madrileno de Estudios Avanzados en Nanociencia (IMDEA-Nano), Cantoblanco, 28049 Madrid (Spain); Rangama, J.; Domaracka, A.; Vizcaino, V. [CIMAP, UMR 6252, CEA/CNRS/ENSICAEN/Universite de Caen Basse-Normandie, bd Henri Becquerel, BP 5133, F-14070 Caen cedex 05 (France); and others

    2013-07-21

    We report experimental results for the ionization and fragmentation of weakly bound van der Waals clusters of n C{sub 60} molecules following collisions with Ar{sup 2+}, He{sup 2+}, and Xe{sup 20+} at laboratory kinetic energies of 13 keV, 22.5 keV, and 300 keV, respectively. Intact singly charged C{sub 60} monomers are the dominant reaction products in all three cases and this is accounted for by means of Monte Carlo calculations of energy transfer processes and a simple Arrhenius-type [C{sub 60}]{sub n}{sup +}{yields}C{sub 60}{sup +}+(n-1)C{sub 60} evaporation model. Excitation energies in the range of only {approx}0.7 eV per C{sub 60} molecule in a [C{sub 60}]{sub 13}{sup +} cluster are sufficient for complete evaporation and such low energies correspond to ion trajectories far outside the clusters. Still we observe singly and even doubly charged intact cluster ions which stem from even more distant collisions. For penetrating collisions the clusters become multiply charged and some of the individual molecules may be promptly fragmented in direct knock-out processes leading to efficient formations of new covalent systems. For Ar{sup 2+} and He{sup 2+} collisions, we observe very efficient C{sub 119}{sup +} and C{sub 118}{sup +} formation and molecular dynamics simulations suggest that they are covalent dumb-bell systems due to bonding between C{sub 59}{sup +} or C{sub 58}{sup +} and C{sub 60} during cluster fragmentation. In the Ar{sup 2+} case, it is possible to form even smaller C{sub 120-2m}{sup +} molecules (m= 2-7), while no molecular fusion reactions are observed for the present Xe{sup 20+} collisions.

  6. A conserved cysteine residue is involved in disulfide bond formation between plant plasma membrane aquaporin monomers.

    Science.gov (United States)

    Bienert, Gerd P; Cavez, Damien; Besserer, Arnaud; Berny, Marie C; Gilis, Dimitri; Rooman, Marianne; Chaumont, François

    2012-07-01

    AQPs (aquaporins) are conserved in all kingdoms of life and facilitate the rapid diffusion of water and/or other small solutes across cell membranes. Among the different plant AQPs, PIPs (plasma membrane intrinsic proteins), which fall into two phylogenetic groups, PIP1 and PIP2, play key roles in plant water transport processes. PIPs form tetramers in which each monomer acts as a functional channel. The intermolecular interactions that stabilize PIP oligomer complexes and are responsible for the resistance of PIP dimers to denaturating conditions are not well characterized. In the present study, we identified a highly conserved cysteine residue in loop A of PIP1 and PIP2 proteins and demonstrated by mutagenesis that it is involved in the formation of a disulfide bond between two monomers. Although this cysteine seems not to be involved in regulation of trafficking to the plasma membrane, activity, substrate selectivity or oxidative gating of ZmPIP1s (Zm is Zea mays), ZmPIP2s and hetero-oligomers, it increases oligomer stability under denaturating conditions. In addition, when PIP1 and PIP2 are co-expressed, the loop A cysteine of ZmPIP1;2, but not that of ZmPIP2;5, is involved in the mercury sensitivity of the channels.

  7. Molecular dynamics simulation of the formation of sp3 hybridized bonds in hydrogenated diamondlike carbon deposition processes.

    Science.gov (United States)

    Murakami, Yasuo; Horiguchi, Seishi; Hamaguchi, Satoshi

    2010-04-01

    The formation process of sp3 hybridized carbon networks (i.e., diamondlike structures) in hydrogenated diamondlike carbon (DLC) films has been studied with the use of molecular-dynamics simulations. The processes simulated in this study are injections of hydrocarbon (CH3 and CH) beams into amorphous carbon (a-C) substrates. It has been shown that diamondlike sp3 structures are formed predominantly at a subsurface level when the beam energy is relatively high, as in the "subplantation" process for hydrogen-free DLC deposition. However, for hydrogenated DLC deposition, the presence of abundant hydrogen at subsurface levels, together with thermal spikes caused by energetic ion injections, substantially enhances the formation of carbon-to-carbon sp3 bonds. Therefore, the sp3 bond formation process for hydrogenated DLC films essentially differs from that for hydrogen-free DLC films.

  8. Legionella pneumophila utilizes a single-player disulfide-bond oxidoreductase system to manage disulfide bond formation and isomerization.

    Science.gov (United States)

    Kpadeh, Zegbeh Z; Day, Shandra R; Mills, Brandy W; Hoffman, Paul S

    2015-03-01

    Legionella pneumophila uses a single homodimeric disulfide bond (DSB) oxidoreductase DsbA2 to catalyze extracytoplasmic protein folding and to correct DSB errors through protein-disulfide isomerase (PDI) activity. In Escherichia coli, these functions are separated to avoid futile cycling. In L. pneumophila, DsbA2 is maintained as a mixture of disulfides (S-S) and free thiols (SH), but when expressed in E. coli, only the SH form is observed. We provide evidence to suggest that structural differences in DsbB oxidases (LpDsbB1 and LpDsbB2) and DsbD reductases (LpDsbD1 and LpDsbD2) (compared with E. coli) permit bifunctional activities without creating a futile cycle. LpdsbB1 and LpdsbB2 partially complemented an EcdsbB mutant while neither LpdsbD1 nor LpdsbD2 complemented an EcdsbD mutant unless DsbA2 was also expressed. When the dsb genes of E. coli were replaced with those of L. pneumophila, motility was restored and DsbA2 was present as a mixture of redox forms. A dominant-negative approach to interfere with DsbA2 function in L. pneumophila determined that DSB oxidase activity was necessary for intracellular multiplication and assembly/function of the Dot/Icm Type IVb secretion system. Our studies show that a single-player system may escape the futile cycle trap by limiting transfer of reducing equivalents from LpDsbDs to DsbA2.

  9. Biofilm formation on stainless steel and gold wires for bonded retainers in vitro and in vivo and their susceptibility to oral antimicrobials

    NARCIS (Netherlands)

    Jongsma, Marije A.; Pelser, Floris D. H.; van der Mei, Henny C.; Atema-Smit, Jelly; van de Belt-Gritter, Betsy; Busscher, Henk J.; Ren, Yijin

    2013-01-01

    OBJECTIVE: Bonded retainers are used in orthodontics to maintain treatment result. Retention wires are prone to biofilm formation and cause gingival recession, bleeding on probing and increased pocket depths near bonded retainers. In this study, we compare in vitro and in vivo biofilm formation on d

  10. Iron-Catalyzed C-C Cross-Couplings Using Organometallics.

    Science.gov (United States)

    Guérinot, Amandine; Cossy, Janine

    2016-08-01

    Over the last decades, iron-catalyzed cross-couplings have emerged as an important tool for the formation of C-C bonds. A wide variety of alkenyl, aryl, and alkyl (pseudo)halides have been coupled to organometallic reagents, the most currently used being Grignard reagents. Particular attention has been devoted to the development of iron catalysts for the functionalization of alkyl halides that are generally challenging substrates in classical cross-couplings. The high functional group tolerance of iron-catalyzed cross-couplings has encouraged organic chemists to use them in the synthesis of bioactive compounds. Even if some points remain obscure, numerous studies have been carried out to investigate the mechanism of iron-catalyzed cross-coupling and several hypotheses have been proposed.

  11. In vivo biofilm formation on stainless steel bonded retainers during different oral health-care regimens

    NARCIS (Netherlands)

    Jongsma, Marije A.; van der Mei, Henny C.; Atema-Smit, Jelly; Busscher, Henk I.; Ren, Yijin

    2015-01-01

    Retention wires permanently bonded to the anterior teeth are used after orthodontic treatment to prevent the teeth from relapsing to pre-treatment positions. A disadvantage of bonded retainers is biofilm accumulation on the wires, which produces a higher incidence of gingival recession, increased po

  12. Ultraclean Si/Si interface formation by surface preparation and direct bonding in ultrahigh vacuum

    DEFF Research Database (Denmark)

    Hermansson, Karin; Grey, Francois; Bengtsson, Stefan;

    1998-01-01

    Silicon surfaces have been cleaned and bonded in ultrahigh vacuum, at a pressure in the 10(-10) Torr range. The bonded interfaces show extremely low contamination levels as measured by secondary ion mass spectroscopy. Nevertheless, a potential barrier could be detected at the interface by spreading...

  13. Bridge-bonded formate: active intermediate or spectator species in formic acid oxidation on a Pt film electrode?

    Science.gov (United States)

    Chen, Y-X; Heinen, M; Jusys, Z; Behm, R J

    2006-12-01

    We present and discuss the results of an in situ IR study on the mechanism and kinetics of formic acid oxidation on a Pt film/Si electrode, performed in an attenuated total reflection (ATR) flow cell configuration under controlled mass transport conditions, which specifically aimed at elucidating the role of the adsorbed bridge-bonded formates in this reaction. Potentiodynamic measurements show a complex interplay between formation and desorption/oxidation of COad and formate species and the total Faradaic current. The notably faster increase of the Faradaic current compared to the coverage of bridge-bonded formate in transient measurements at constant potential, but with different formic acid concentrations, reveals that adsorbed formate decomposition is not rate-limiting in the dominant reaction pathway. If being reactive intermediate at all, the contribution of formate adsorption/decomposition to the reaction current decreases with increasing formic acid concentration, accounting for at most 15% for 0.2 M DCOOH at 0.7 VRHE. The rapid build-up/removal of the formate adlayer and its similarity with acetate or (bi-)sulfate adsorption/desorption indicate that the formate adlayer coverage is dominated by a fast dynamic adsorption-desorption equilibrium with the electrolyte, and that formate desorption is much faster than its decomposition. The results corroborate the proposal of a triple pathway reaction mechanism including an indirect pathway, a formate pathway, and a dominant direct pathway, as presented previously (Chen, Y. X.; et al. Angew. Chem. Int. Ed. 2006, 45, 981), in which adsorbed formates act as a site-blocking spectator in the dominant pathway rather than as an active intermediate.

  14. Formation process,microstructure and mechanical property of transient liquid phase bonded aluminium-based metal matrix composite joint

    Institute of Scientific and Technical Information of China (English)

    孙大谦; 刘卫红; 贾树盛; 邱小明

    2004-01-01

    The formation process, microstructure and mechanical properties of transient liquid phase (TLP) bonded aluminium-based metal matrix composite (MMC) joint with copper interlayer were investigated. The formation process of the TLP joint comprises a number of stages: plastic deformation and solid diffusion (stage 1), dissolution of interlayer and base metal (stage 2), isothermal solidification (stage 3) and homogenization (stage 4). The microstructure of the joint depends on the joint formation process (distinct stages). The plastic deformation and solid diffusion in stage 1 favoure the intimate contact at interfaces and liquid layer formation. The microstructure of joint consists of aluminium solid solution, alumina particle, Al2Cu and MgAl2O4 compounds in stage 2. The most pronounced feature of joint microstructure in stage 3 is the alumina particle segregation in the center of the joint. The increase of joint shear strength with increasing bonding temperature is mainly attributed to improving the fluidity and wettability of liquid phase and decreasing the amount of Al2Cu brittle phase in the joint. The principal reason of higher bonding temperature (>600 ℃) resulting in lowering obviously the joint shear strength is the widening of alumina particle segregation region that acts as a preferential site for failure. The increase of joint shear strength with increasing holding time is mainly associated with decreasing the amount of Al2 Cu brittle phase and promoting homogenization of joint.

  15. Slow peptide bond formation by proline and other N-alkylamino acids in translation

    Science.gov (United States)

    Pavlov, Michael Y.; Watts, Richard E.; Tan, Zhongping; Cornish, Virginia W.; Ehrenberg, Måns; Forster, Anthony C.

    2009-01-01

    Proteins are made from 19 aa and, curiously, one N-alkylamino acid (“imino acid”), proline (Pro). Pro is thought to be incorporated by the translation apparatus at the same rate as the 19 aa, even though the alkyl group in Pro resides directly on the nitrogen nucleophile involved in peptide bond formation. Here, by combining quench-flow kinetics and charging of tRNAs with cognate and noncognate amino acids, we find that Pro incorporates in translation significantly more slowly than Phe or Ala and that other N-alkylamino acids incorporate much more slowly. Our results show that the slowest step in incorporation of N-alkylamino acids is accommodation/peptidyl transfer after GTP hydrolysis on EF-Tu. The relative incorporation rates correlate with expectations from organic chemistry, suggesting that amino acid sterics and basicities affect translation rates at the peptidyl transfer step. Cognate isoacceptor tRNAs speed Pro incorporation to rates compatible with in vivo, although still 3–6 times slower than Phe incorporation from Phe-tRNAPhe depending on the Pro codon. Results suggest that Pro is the only N-alkylamino acid in the genetic code because it has a privileged cyclic structure that is more reactive than other N-alkylamino acids. Our data on the variation of the rate of incorporation of Pro from native Pro-tRNAPro isoacceptors at 4 different Pro codons help explain codon bias not accounted for by the “tRNA abundance” hypothesis. PMID:19104062

  16. Modification of the catalytic function of human hydroxysteroid sulfotransferase hSULT2A1 by formation of disulfide bonds.

    Science.gov (United States)

    Qin, Xiaoyan; Teesch, Lynn M; Duffel, Michael W

    2013-05-01

    The human cytosolic sulfotransferase hSULT2A1 catalyzes the sulfation of a broad range of xenobiotics, as well as endogenous hydroxysteroids and bile acids. Reversible modulation of the catalytic activity of this enzyme could play important roles in its physiologic functions. Whereas other mammalian sulfotransferases are known to be reversibly altered by changes in their redox environment, this has not been previously shown for hSULT2A1. We have examined the hypothesis that the formation of disulfide bonds in hSULT2A1 can reversibly regulate the catalytic function of the enzyme. Three thiol oxidants were used as model compounds to investigate their effects on homogeneous preparations of hSULT2A1: glutathione disulfide, 5,5'-dithiobis(2-nitrobenzoic acid), and 1,1'-azobis(N,N-dimethylformamide) (diamide). Examination of the effects of disulfide bond formation with these agents indicated that the activity of the enzyme is reversibly altered. Studies on the kinetics of the hSULT2A1-catalyzed sulfation of dehydroepiandrosterone (DHEA) showed the effects of disulfide bond formation on the substrate inhibition characteristics of the enzyme. The effects of these agents on the binding of substrates and products, liquid chromatography-mass spectrometry identification of the disulfides formed, and structural modeling of the modified enzyme were examined. Our results indicate that conformational changes at cysteines near the nucleotide binding site affect the binding of both the nucleotide and DHEA to the enzyme, with the specific effects dependent on the structure of the resulting disulfide. Thus, the formation of disulfide bonds in hSULT2A1 is a potentially important reversible mechanism for alterations in the rates of sulfation of both endogenous and xenobiotic substrates.

  17. Regioselective carbon–carbon bond formation of 5,5,5-trifluoro-1-phenylpent-3-en-1-yne

    Directory of Open Access Journals (Sweden)

    Motoki Naka

    2013-10-01

    Full Text Available The regioselective carbon–carbon bond formation was studied using 5,5,5-trifluoro-1-phenylpent-3-en-1-yne as a model substrate, and predominant acceptance of electrophiles β to a CF3 group as well as a deuterium trap experiment of the lithiated species led to the conclusion that the obtained regioselectivity is kinetically determined for the reactions with electrophiles, under equilibration of the possible two anionic species.

  18. Surveying approaches to the formation of carbon-carbon bonds between a pyran and an adjacent ring

    OpenAIRE

    Frein, Jeffrey D.; Rovis, Tomislav

    2006-01-01

    We have examined several methods for the stereoselective formation of carbon-carbon bonds between contiguous rings where a stereogenic center is already present. The approaches investigated were a [1,3] oxygen to carbon rearrangement of cyclic vinyl acetals, an intermolecular enolsilane addition into an in situ generated oxocarbenium ion, an intramolecular conjugate addition of tethered alkoxy enones, and epimerization of several α-pyranyl cycloalkanones. These routes have been found to be co...

  19. Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

    Science.gov (United States)

    2013-01-01

    Summary Organophosphorus compounds are important in organic chemistry. This review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis. This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides. PMID:23843922

  20. Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

    Directory of Open Access Journals (Sweden)

    Hideki Yorimitsu

    2013-06-01

    Full Text Available Organophosphorus compounds are important in organic chemistry. This review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis. This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides.

  1. Functional-Group-Tolerant, Silver-Catalyzed N-N Bond Formation by Nitrene Transfer to Amines.

    Science.gov (United States)

    Maestre, Lourdes; Dorel, Ruth; Pablo, Óscar; Escofet, Imma; Sameera, W M C; Álvarez, Eleuterio; Maseras, Feliu; Díaz-Requejo, M Mar; Echavarren, Antonio M; Pérez, Pedro J

    2017-02-15

    Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhI═NTs. Remarkably, this transformation proceeds in a selective manner in the presence of olefins and other functional groups without formation of the commonly observed aziridines or C-H insertion products. The methodology can be applied not only to rather simple tertiary amines but also to complex natural molecules such as brucine or quinine, where the products derived from N-N bond formation were exclusively formed. Theoretical mechanistic studies have shown that this selective N-amidation reaction proceeds through triplet silver nitrenes.

  2. Phosphoric acid-etching promotes bond strength and formation of acid-base resistant zone on enamel.

    Science.gov (United States)

    Li, N; Nikaido, T; Alireza, S; Takagaki, T; Chen, J-H; Tagami, J

    2013-01-01

    This study examined the effect of phosphoric acid (PA) etching on the bond strength and acid-base resistant zone (ABRZ) formation of a two-step self-etching adhesive (SEA) system to enamel. An etch-and-rinse adhesive (EAR) system Single Bond (SB) and a two-step SEA system Clearfil SE Bond (SE) were used. Human teeth were randomly divided into four groups according to different adhesive treatments: 1) SB; 2) SE; 3) 35% PA etching→SE primer→SE adhesive (PA/SEp+a); (4) 35% PA etching→SE adhesive (PA/SEa). Microshear bond strength to enamel was measured and then statistically analyzed using one-way analysis of variance and the Tukey honestly significant difference test. The failure mode was recorded and analyzed by χ( 2 ) test. The etching pattern of the enamel surface was observed with scanning electron microscope (SEM). The bonded interface was exposed to a demineralizing solution (pH=4.5) for 4.5 hours and then 5% sodium hypochlorite with ultrasonication for 30 minutes. After argon-ion etching, the interfacial ultrastructure was observed using SEM. The microshear bond strength to enamel of the SE group was significantly lower (p<0.05) than that of the three PA-etched groups, although the latter three were not significantly different from one another. The ABRZ was detected in all the groups. In morphological observation, the ABRZ in the three PA-etched groups were obviously thicker compared with the SE group with an irregular wave-shaped edge.

  3. Rh(III)/Cu(II)-cocatalyzed synthesis of 1H-indazoles through C-H amidation and N-N bond formation.

    Science.gov (United States)

    Yu, Da-Gang; Suri, Mamta; Glorius, Frank

    2013-06-19

    Substituted 1H-indazoles can be formed from readily available arylimidates and organo azides by Rh(III)-catalyzed C-H activation/C-N bond formation and Cu-catalyzed N-N bond formation. For the first time the N-H-imidates are demonstrated to be good directing groups in C-H activation, also capable of undergoing intramolecular N-N bond formation. The process is scalable and green, with O2 as the terminal oxidant and N2 and H2O formed as byproducts. Moreover, the products could be transformed to diverse important derivatives.

  4. Diacetoxyiodobenzene assisted C-O bond formation via sequential acylation and deacylation process: synthesis of benzoxazole amides and their mechanistic study by DFT.

    Science.gov (United States)

    Nahakpam, Lokendrajit; Chipem, Francis A S; Chingakham, Brajakishor S; Laitonjam, Warjeet S

    2016-08-10

    An efficient method for the transformation of N-substituted-N'-benzoylthioureas to substituted N-benzoxazol-2-yl-amides using diacetoxyiodobenzene (DIB) is described in this work. The transformation follows the C-O bond formation leading to the benzoxazole derivative, due to oxidative dehydrogenation by DIB, instead of the expected C-S bond formation of the benzothiazole moiety. The C-O bond formation leading to benzoxazole is due to consecutive acylation and deacylation in conjunction with the reduction of two moles of DIB. A plausible mechanism was proposed for the reaction and density functional calculations were also performed to study the reaction mechanism.

  5. Effect of ZnO on the interfacial bonding between Na 2O-B 2O 3-SiO 2 vitrified bond and diamond

    Science.gov (United States)

    Wang, P. F.; Li, Zh. H.; Li, J.; Zhu, Y. M.

    2009-08-01

    Diamond composites were prepared by sintering diamond grains with low melting Na 2O-B 2O 3-SiO 2 vitrified bonds in air. The influence of ZnO on the wettability and flowing ability of Na 2O-B 2O 3-SiO 2 vitrified bonds was characterized by wetting angle, the interfacial bonding states between diamond grains and the vitrified bonds were observed by scanning electron microscope (SEM), and the micro-scale bonding mechanism in the interfaces was investigated by means of energy-dispersive spectrometer (EDS), Fourier transform infrared (FTIR) spectrometer and X-ray photoelectron spectroscopy (XPS). The experimental results showed that ZnO facilitated the dissociation of boron/silicon-oxygen polyhedra and the formation of larger amount of non-bridging oxygen in the glass network, which resulted in the increase of the vitrified bonds' wettability and the formation of -C dbnd O, -O-H and -C-H bonds on the surface of diamond grains. B and Si diffused from the vitrified bonds to the interface, and C-C, C-O, C dbnd O and C-B bond formed on the surface of sintered diamond grains during sintering process, by which the interfacial bonding between diamond grains and the vitrified bonds was strengthened.

  6. Synthesis of Oxygen Heterocycles via Aromatic C-O Bond Formation Using Arynes.

    Science.gov (United States)

    Miyabe, Hideto

    2015-07-09

    Most of the synthetic approaches to the benzo-fused heterocycles containing an oxygen atom have involved the use of phenol derivatives as a starting material. This review highlights the new synthetic approaches involving the aromatic C-O bond-forming process using arynes. The insertion of arynes into the C=O bond gives the unstable intermediates, [2 + 2] cycloaddition-type adducts, which can be easily converted into a variety of oxygen atom-containing heterocycles in a single operation. In this review, the syntheses of oxygen heterocycles, such as coumarin, chromene, xanthene, dihydrobenzofuran and benzofuran derivatives, via the insertion of arynes into the C=O bond of aldehydes or formamides are summarized.

  7. Synthesis of Oxygen Heterocycles via Aromatic C-O Bond Formation Using Arynes

    Directory of Open Access Journals (Sweden)

    Hideto Miyabe

    2015-07-01

    Full Text Available Most of the synthetic approaches to the benzo-fused heterocycles containing an oxygen atom have involved the use of phenol derivatives as a starting material. This review highlights the new synthetic approaches involving the aromatic C-O bond-forming process using arynes. The insertion of arynes into the C=O bond gives the unstable intermediates, [2 + 2] cycloaddition-type adducts, which can be easily converted into a variety of oxygen atom-containing heterocycles in a single operation. In this review, the syntheses of oxygen heterocycles, such as coumarin, chromene, xanthene, dihydrobenzofuran and benzofuran derivatives, via the insertion of arynes into the C=O bond of aldehydes or formamides are summarized.

  8. Sequential C-Si Bond Formations from Diphenylsilane: Application to Silanediol Peptide Isostere Precursors

    DEFF Research Database (Denmark)

    Nielsen, Lone; Skrydstrup, Troels

    2008-01-01

    and the first new carbon-silicon bond. The next step is the reduction of this hydridosilane with lithium metal providing a silyl lithium reagent, which undergoes a highly diastereoselective addition to an optically active tert-butanesulfinimine, thus generating the second C-Si bond. This method allows......-step assembly of the carbon-silicon backbone of a silane-containing dipeptide fragment. The synthetic scheme is comprised of an alkene hydrosilylation step with the simple precursor, diphenylsilane, using either a radical initiator or RhCl(PPh3)3, Wilkinson's catalyst, for the creation of a hydridosilane...

  9. Formation of Me–O–Si covalent bonds at the interface between polysilazane and stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Amouzou, Dodji, E-mail: adodji@gmail.com [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, 5000 Namur (Belgium); Fourdrinier, Lionel; Maseri, Fabrizio [CRM-Group, Boulevard de Colonster, B 57, 4000 Liège (Belgium); Sporken, Robert [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, 5000 Namur (Belgium)

    2014-11-30

    Highlights: • Natural metal-oxides, hydroxides are detected on the top surface of steel substrates we tested. • Polysilazane reacts with hydroxide functional groups on steel substrates to form Cr–O–Si and Fe–O–Si covalent bonds. • Covalent bonding between steel and polysilazane at the interface was probed using spectroscopic techniques. - Abstract: In earlier works, we demonstrated the potential of polysilazane (PSZ) coatings for a use as insulating layers in Cu(In,Ga)Se{sub 2} (CIGS) solar cells prepared on steels substrates and showed a good adhesion between PSZ coatings and both AISI316 and AISI430 steels. In the present paper, spectroscopic techniques are used to elucidate the reason of such adhesion. X-ray Photoelectron Spectroscopy (XPS) was used to investigate surfaces for the two steel substrates and showed the presence of metal oxides and metal hydroxides at the top surface. XPS has been also used to probe interfaces between substrates and PSZ, and metallosiloxane (Me–O–Si) covalent bonds have been detected. These results were confirmed by Infra-Red Reflection Absorption Spectroscopy (IRRAS) analyses since vibrations related to Cr–O–Si and Fe–O–Si compounds were detected. Thus, the good adhesion between steel substrates and PSZ coatings was explained by covalent bonding through chemical reactions between PSZ precursors and hydroxide functional groups present on top surface of the two types of steel. Based on these results, an adhesion mechanism between steel substrates and PSZ coatings is proposed.

  10. Reusable ionic liquid-catalyzed oxidative coupling of azoles and benzylic compounds via sp(3) C-N bond formation under metal-free conditions.

    Science.gov (United States)

    Liu, Wenbo; Liu, Chenjiang; Zhang, Yonghong; Sun, Yadong; Abdukadera, Ablimit; Wang, Bin; Li, He; Ma, Xuecheng; Zhang, Zengpeng

    2015-07-14

    The heterocyclic ionic liquid-catalyzed direct oxidative amination of benzylic sp(3) C-H bonds via intermolecular sp(3) C-N bond formation for the synthesis of N-alkylated azoles under metal-free conditions is reported for the first time. The catalyst 1-butylpyridinium iodide can be recycled and reused with similar efficacies for at least eight cycles.

  11. Effect of hydrogen bonding and hydrophobic interaction on the formation of supramolecular hydrogels formed by L-phenylalanine derivative hydrogelator

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A new hydrogelator, pyridinium bromide salt of N-6-bromohexanoyl-L-phenylamino octadecane, was synthesized. Supramolecular hydrogels can be formed through the self-assembly of this hydrogelator in water. In this work, D2O was used instead of H2O as solvent for FT-IR measurement due to the fact that it is impossible to obtain useful FT-IR information on the hydrogen bonding in water. The investigation of FT-IR and steady-state fluorescence indicated that the driving forces for the self-assembly were mainly hydrogen bonding and hydrophobic interaction. Based on the data of XRD and molecular modeling, the possible mechanism of the formation of hydrogelator aggregates was proposed.

  12. Computational assessment of electron density in metallo-organic nickel pincer complexes for formation of PC bonds.

    Science.gov (United States)

    Eller, Joshua J; Downey, Karen

    2015-10-05

    Hydrophosphination is an atomically efficient method for introducing new carbon-phosphorous bonds in organic synthesis. New late-transition metal catalytic complexes are proposed to facilitate this process. These nickel-based complexes are analyzed using semiempirical (SE), Hartree-Fock (H-F), and density functional theory (DFT) models. H-F proves to be ineffective, while the SE approach has limited, qualitative use. DFT shows electron density at the metal center suitable for catalyzing bond formation in the proposed, reductive hydrophosphination mechanism. It also shows that the pincer complexes under investigation are relatively insensitive to solvent dielectric constant and to the chemical character of the monodentate ligand, both in terms of electron distribution and in terms of molecular orbital energies.

  13. The large 1 1Ag - 2 1Ag C=C stretching vibronic interaction in all-trans polyenes

    NARCIS (Netherlands)

    Buma, W.J.; Zerbetto, F.

    1998-01-01

    An ab initio theoretical approach at several levels of theory is employed to calculate the 11Ag--21Ag- (non)adiabatic vibronic couplings induced by the completely in-phase C=C and C-C bond stretching vibrations of five all-trans polyenes (from butadiene to dodecahexaene). The nonadiabatic couplings

  14. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    Science.gov (United States)

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao

    2016-08-03

    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling.

  15. Size effects in tin-based lead-free solder joints: Kinetics of bond formation and mechanical characteristics

    Science.gov (United States)

    Abdelhadi, Ousama Mohamed Omer

    Continuous miniaturization of microelectronic interconnects demands smaller joints with comparable microstructural and structural sizes. As the size of joints become smaller, the volume of intermetallics (IMCs) becomes comparable with the joint size. As a result, the kinetics of bond formation changes and the types and thicknesses of IMC phases that form within the constrained region of the bond varies. This dissertation focuses on investigating combination effects of process parameters and size on kinetics of bond formation, resulting microstructure and the mechanical properties of joints that are formed under structurally constrained conditions. An experiment is designed where several process parameters such as time of bonding, temperature, and pressure, and bond thickness as structural chracteristic, are varied at multiple levels. The experiment is then implemented on the process. Scanning electron microscope (SEM) is then utilized to determine the bond thickness, IMC phases and their thicknesses, and morphology of the bonds. Electron backscatter diffraction (EBSD) is used to determine the grain size in different regions, including the bulk solder, and different IMC phases. Physics-based analytical models have been developed for growth kinetics of IMC compounds and are verified using the experimental results. Nanoindentation is used to determine the mechanical behavior of IMC phases in joints in different scales. Four-point bending notched multilayer specimen and four-point bending technique were used to determine fracture toughness of the bonds containing IMCs. Analytical modeling of peeling and shear stresses and fracture toughness in tri-layer four-point bend specimen containing intermetallic layer was developed and was verified and validated using finite element simulation and experimental results. The experiment is used in conjunction with the model to calculate and verify the fracture toughness of Cu6Sn5 IMC materials. As expected two different IMC phases

  16. Effects of Cluster Size on Platinum-Oxygen Bonds Formation in Small Platinum Clusters

    Science.gov (United States)

    Oemry, Ferensa; Padama, Allan Abraham B.; Kishi, Hirofumi; Kunikata, Shinichi; Nakanishi, Hiroshi; Kasai, Hideaki; Maekawa, Hiroyoshi; Osumi, Kazuo; Sato, Kaoru

    2012-03-01

    We present the results of density functional theory calculation in oxygen dissociative adsorption process on two types of isolated platinum (Pt) clusters: Pt4 and Pt10, by taking into account the effect of cluster reconstruction. The strength of Pt-Pt bonds in the clusters is mainly defined by d-d hybridization and interstitial bonding orbitals (IBO). Oxygen that adsorbed on the clusters is weakening the IBO and thus inducing geometry reconstruction as occurred in Pt10 cluster. However, cluster that could undergo structural deformation is found to promote oxygen dissociation with no energy barrier. The details show that maintaining well-balanced of attractive and repulsive (Hellmann-Feynman) forces between atoms is considered to be the main key to avoid any considerable rise of energy barrier. Furthermore, a modest energy barrier that gained in Pt4 cluster is presumed to be originate from inequality of intramolecular forces between atoms.

  17. Disulfide bond formation and folding of plant peroxidases expressed as inclusion body protein in Escherichia coli thioredoxin reductase negative strains

    DEFF Research Database (Denmark)

    Teilum, K; Ostergaard, L; Welinder, K G

    1999-01-01

    , two Ca2+ ions, and a heme group. We have studied the expression yield and folding efficiency of (i) a novel Arabidopsis thaliana peroxidase, ATP N; and (ii) barley grain peroxidase, BP 1. The expression yield ranges from 0 to 60 microgram/ml of cell culture depending on the peroxidase gene...... and the vector/host combination. The choice of E. coli strain in particular affects the yield of active peroxidase obtained in the folding step. Thus, the yield of active ATP N peroxidase can be increased 50-fold by using thioredoxin reductase negative strains, which facilitate the formation of disulfide bonds...

  18. Assessment of covalent bond formation between coupling agents and wood by FTIR spectroscopy and pull strength tests

    DEFF Research Database (Denmark)

    Rasmussen, Jonas Stensgaard; Barsberg, Søren Talbro; Venås, Thomas Mark

    2014-01-01

    In the focus was the question whether metal alkoxide coupling agents – titanium, silane, and zirconium – form covalent bonds to wood and how they improve coating adhesion. In a previous work, a downshift of the lignin infrared (IR) band ∼1600 cm-1 was shown to be consistent with the formation...... of ether linkages between lignin and titanium coupling agent. In the present work, changes were found in the attenuated total reflectance-Fourier transform IR (ATR-FTIR) spectra of lignin and wood mixed with silane, and titanium coupling agents, and to a lesser extent for a zirconium coupling agent...

  19. Total synthesis of feglymycin based on a linear/convergent hybrid approach using micro-flow amide bond formation

    Science.gov (United States)

    Fuse, Shinichiro; Mifune, Yuto; Nakamura, Hiroyuki; Tanaka, Hiroshi

    2016-11-01

    Feglymycin is a naturally occurring, anti-HIV and antimicrobial 13-mer peptide that includes highly racemizable 3,5-dihydroxyphenylglycines (Dpgs). Here we describe the total synthesis of feglymycin based on a linear/convergent hybrid approach. Our originally developed micro-flow amide bond formation enabled highly racemizable peptide chain elongation based on a linear approach that was previously considered impossible. Our developed approach will enable the practical preparation of biologically active oligopeptides that contain highly racemizable amino acids, which are attractive drug candidates.

  20. A quantum-chemical validation about the formation of hydrogen bonds and secondary interactions in intermolecular heterocyclic systems

    Directory of Open Access Journals (Sweden)

    Boaz Galdino Oliveira

    2009-08-01

    Full Text Available We have performed a detailed theoretical study in order to understand the charge density topology of the C2H4O···C2H2 and C2H4S···C2H2 heterocyclic hydrogen-bonded complexes. Through the calculations derived from Quantum Theory of Atoms in Molecules (QTAIM, it was observed the formation of hydrogen bonds and secondary interactions. Such analysis was performed through the determination of optimized geometries at B3LYP/6-31G(d,p level of theory, by which is that QTAIM topological operators were computed, such as the electronic density ρ(r, Laplacian Ñ2ρ(r, and ellipticity ε. The examination of the hydrogen bonds has been performed through the measurement of ρ(r, Ñ2ρ(r and ε between (O···H—C and (S···H—C, whereas the secondary interaction between axial hydrogen atoms Hα and carbon of acetylene. In this insight, it was verified the existence of secondary interaction only in C2H4S···C2H2 complex because its structure is propitious to form multiple interactions.

  1. Synthesis of 1,2,4-Triazoles via Oxidative Heterocyclization: Selective C-N Bond Over C-S Bond Formation.

    Science.gov (United States)

    Gogoi, Anupal; Guin, Srimanta; Rajamanickam, Suresh; Rout, Saroj Kumar; Patel, Bhisma K

    2015-09-18

    The higher propensity of C-N over C-S bond forming ability was demonstrated, through formal C-H functionalization during the construction of 4,5-disubstituted 1,2,4-triazole-3-thiones from arylidenearylthiosemicarbazides catalyzed by Cu(II). However, steric factors imparted by the o-disubstituted substrates tend to change the reaction path giving thiodiazole as the major or an exclusive product. Upon prolonging the reaction time, the in situ generated thiones are transformed to 4,5-disubstituted 1,2,4-triazoles via a desulfurization process. Two classes of heterocycles viz. 4,5-disubstituted 1,2,4-triazole-3-thiones and 4,5-disubstituted 1,2,4-triazoles can be synthesized from arylidenearylthiosemicarbazides by simply adjusting the reaction time. Desulfurization of 1,2,4-triazole-3-thiones is assisted by thiophilic Cu to provide 1,2,4-triazoles with concomitant formation of CuS and polynuclear sulfur anions as confirmed from scanning electron microscope and energy dispersive X-ray spectroscopy measurements. A one-pot synthesis of an antimicrobial compound has been successfully achieved following this strategy.

  2. Photoinduced C-C Cross-Coupling of Aryl Chlorides and Inert Arenes

    Directory of Open Access Journals (Sweden)

    Lele Wang

    2016-01-01

    Full Text Available Here we report a facile, efficient, and catalyst-free method to realize C-C cross-coupling of aryl chlorides and inert arenes under UV light irradiation. The aryl radical upon homolytic cleavage of C-Cl bond initiated the nucleophilic substitution reaction with inert arenes to give biaryl products. This mild reaction mode can also be applied to other synthetic reactions, such as the construction of C-N bonds and trifluoromethylated compounds.

  3. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Ji, Pengfei; McIsaac, Alexandra R.; Lin, Zekai; Abney, Carter W.; Lin, Wenbin [UC

    2016-02-01

    We have designed the first chiral diene-based metal–organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

  4. Mirrors fabricated with slightly oxidized C/C composites

    Science.gov (United States)

    Wang, Yongjie; Xu, Liang; Ding, Jiaoteng; Xie, Yongjie; Ma, Zhen

    2016-10-01

    Up to now, traditional materials, such as glass, metal and SiC ceramic, gradually begin to be unsatisfied development of the future mirrors. Designable carbon fiber reinforced composites became optimized material for large aperture lightweight mirrors. Carbon/carbon composites exhibit low thermal expansion and no moisture-absorption expansion problem, therefore, they get particular attention in the space reflector field. Ni was always employed as optical layer in the mirror, however, the coating behaved poor bond with substrate and often peeled off during optical processing. In order to solve this problem, slight oxidation was carried on the C/C composites before Ni plated. The Ni coating exhibited stronger coherence and better finish performance. Finally, a 100mm diameter plane mirror was successful fabricated.

  5. Bile salt-induced intermolecular disulfide bond formation activates Vibrio cholerae virulence.

    Science.gov (United States)

    Yang, Menghua; Liu, Zhi; Hughes, Chambers; Stern, Andrew M; Wang, Hui; Zhong, Zengtao; Kan, Biao; Fenical, William; Zhu, Jun

    2013-02-01

    To be successful pathogens, bacteria must often restrict the expression of virulence genes to host environments. This requires a physical or chemical marker of the host environment as well as a cognate bacterial system for sensing the presence of a host to appropriately time the activation of virulence. However, there have been remarkably few such signal-sensor pairs identified, and the molecular mechanisms for host-sensing are virtually unknown. By directly applying a reporter strain of Vibrio cholerae, the causative agent of cholera, to a thin layer chromatography (TLC) plate containing mouse intestinal extracts, we found two host signals that activate virulence gene transcription. One of these was revealed to be the bile salt taurocholate. We then show that a set of bile salts cause dimerization of the transmembrane transcription factor TcpP by inducing intermolecular disulfide bonds between cysteine (C)-207 residues in its periplasmic domain. Various genetic and biochemical analyses led us to propose a model in which the other cysteine in the periplasmic domain, C218, forms an inhibitory intramolecular disulfide bond with C207 that must be isomerized to form the active C207-C207 intermolecular bond. We then found bile salt-dependent effects of these cysteine mutations on survival in vivo, correlating to our in vitro model. Our results are a demonstration of a mechanism for direct activation of the V. cholerae virulence cascade by a host signal molecule. They further provide a paradigm for recognition of the host environment in pathogenic bacteria through periplasmic cysteine oxidation.

  6. Regio-selectivity of the Oxidative C-S Bond Formation in Ergothioneine and Ovothiol Biosyntheses

    Science.gov (United States)

    Song, Heng; Leninger, Maureen; Lee, Norman

    2014-01-01

    Ergothioneine (5) and ovothiol (8) are two novel thiol-containing natural products. Their C-S bonds are formed by oxidative coupling reactions catalyzed by EgtB and OvoA enzymes, respectively. In this work, it was discovered that besides catalyzing the oxidative coupling between histidine and cysteine (1 → 6 conversion), OvoA can also catalyze a direct oxidative coupling between hercynine (2) and cysteine (2 → 4 conversion), which can shorten the ergothioneine biosynthetic pathway by two steps. PMID:24016264

  7. Regioselectivity of the oxidative C-S bond formation in ergothioneine and ovothiol biosyntheses.

    Science.gov (United States)

    Song, Heng; Leninger, Maureen; Lee, Norman; Liu, Pinghua

    2013-09-20

    Ergothioneine (5) and ovothiol (8) are two novel thiol-containing natural products. Their C-S bonds are formed by oxidative coupling reactions catalyzed by EgtB and OvoA enzymes, respectively. In this work, it was discovered that in addition to catalyzing the oxidative coupling between histidine and cysteine (1 → 6 conversion), OvoA can also catalyze a direct oxidative coupling between hercynine (2) and cysteine (2 → 4 conversion), which can shorten the ergothioneine biosynthetic pathway by two steps.

  8. Instantaneous carbon-carbon bond formation using a microchannel reactor with a catalytic membrane.

    Science.gov (United States)

    Uozumi, Yasuhiro; Yamada, Yoichi M A; Beppu, Tomohiko; Fukuyama, Naoshi; Ueno, Masaharu; Kitamori, Takehiko

    2006-12-20

    Instantaneous catalytic carbon-carbon bond forming reactions were achieved in a microchannel reactor having a polymeric palladium complex membrane. The catalytic membrane was constructed inside the microchannel via self-assembling complexation at the interface between the organic and aqueous phases flowing laminarly, where non-cross-linked polymer-bound phosphine and ammonium tetrachloropalladate dissolved, respectively. A palladium-catalyzed coupling reaction of aryl halides and arylboronic acids was performed using the microchannel reactor to give quantitative yields of biaryls within 4 s of retention time in the defined channel region.

  9. Formation and densification of SiAlON materials by reaction bonding and silicothermal reduction routes

    Science.gov (United States)

    Rouquié, Yann; Jones, Mark I.

    2011-05-01

    Samples of β and O-sialon with different levels of substitution (i.e. z = 1 and 4 for β-sialon and x = 0.05 and 0.2 for O-sialon) have been synthesized by both reaction bonding and silicothermal reduction techniques in a nitrogen atmosphere. The possibility of obtaining dense sialon materials by these lower cost production methods has been investigated using a statistical design methodology. The influence of different parameters (temperature, gas pressure and additive type) on the densification and decomposition has been studied and will be discussed in this presentation.

  10. Formation and densification of SiAlON materials by reaction bonding and silicothermal reduction routes

    Energy Technology Data Exchange (ETDEWEB)

    Rouquie, Yann; Jones, Mark I, E-mail: yrou002@aucklanduni.ac.nz [Department of Material and Chemicals Engineering, University of Auckland, New Zealand Private bag 92019, Auckland Mail Center, Auckland, 1142 (New Zealand)

    2011-05-15

    Samples of {beta} and O-sialon with different levels of substitution (i.e. z = 1 and 4 for {beta}-sialon and x = 0.05 and 0.2 for O-sialon) have been synthesized by both reaction bonding and silicothermal reduction techniques in a nitrogen atmosphere. The possibility of obtaining dense sialon materials by these lower cost production methods has been investigated using a statistical design methodology. The influence of different parameters (temperature, gas pressure and additive type) on the densification and decomposition has been studied and will be discussed in this presentation.

  11. Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

    Directory of Open Access Journals (Sweden)

    Burkhard Koenig

    2011-01-01

    Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

  12. Emotional experiences of preservice science teachers in online learning: the formation, disruption and maintenance of social bonds

    Science.gov (United States)

    Bellocchi, Alberto; Mills, Kathy A.; Ritchie, Stephen M.

    2016-09-01

    The enactment of learning to become a science teacher in online mode is an emotionally charged experience. We attend to the formation, maintenance and disruption of social bonds experienced by online preservice science teachers as they shared their emotional online learning experiences through blogs, or e-motion diaries, in reaction to videos of face-to-face lessons. A multi-theoretic framework drawing on microsociological perspectives of emotion informed our hermeneutic interpretations of students' first-person accounts reported through an e-motion diary. These accounts were analyzed through our own database of emotion labels constructed from the synthesis of existing literature on emotion across a range of fields of inquiry. Preservice science teachers felt included in the face-to-face group as they watched videos of classroom transactions. The strength of these feelings of social solidarity were dependent on the quality of the video recording. E-motion diaries provided a resource for interactions focused on shared emotional experiences leading to formation of social bonds and the alleviation of feelings of fear, trepidation and anxiety about becoming science teachers. We offer implications to inform practitioners who wish to improve feelings of inclusion amongst their online learners in science education.

  13. Formation of Me-O-Si covalent bonds at the interface between polysilazane and stainless steel

    Science.gov (United States)

    Amouzou, Dodji; Fourdrinier, Lionel; Maseri, Fabrizio; Sporken, Robert

    2014-11-01

    In earlier works, we demonstrated the potential of polysilazane (PSZ) coatings for a use as insulating layers in Cu(In,Ga)Se2 (CIGS) solar cells prepared on steels substrates and showed a good adhesion between PSZ coatings and both AISI316 and AISI430 steels. In the present paper, spectroscopic techniques are used to elucidate the reason of such adhesion. X-ray Photoelectron Spectroscopy (XPS) was used to investigate surfaces for the two steel substrates and showed the presence of metal oxides and metal hydroxides at the top surface. XPS has been also used to probe interfaces between substrates and PSZ, and metallosiloxane (Me-O-Si) covalent bonds have been detected. These results were confirmed by Infra-Red Reflection Absorption Spectroscopy (IRRAS) analyses since vibrations related to Cr-O-Si and Fe-O-Si compounds were detected. Thus, the good adhesion between steel substrates and PSZ coatings was explained by covalent bonding through chemical reactions between PSZ precursors and hydroxide functional groups present on top surface of the two types of steel. Based on these results, an adhesion mechanism between steel substrates and PSZ coatings is proposed.

  14. Oxo-group-14-element bond formation in binuclear uranium(V) Pacman complexes.

    Science.gov (United States)

    Jones, Guy M; Arnold, Polly L; Love, Jason B

    2013-07-29

    Simple and versatile routes to the functionalization of uranyl-derived U(V)-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)3LiOUO}2(L)] and [{(py)3LiOUO}(OUOSiMe3)(L)] were prepared by the direct combination of the uranyl(VI) silylamide "ate" complex [Li(py)2][(OUO)(N")3] (N" = N(SiMe3)2) with the polypyrrolic macrocycle H4L or the mononuclear uranyl (VI) Pacman complex [UO2(py)(H2L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R3Sn)OUO}2(L)] (R = nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr)3] to form U-O-C bonds [{(py)3LiOUO}(OUOiPr)(L)] and [(iPrOUO)2(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements.

  15. ON THE FORMATION AND ISOMER SPECIFIC DETECTION OF PROPENAL (C{sub 2}H{sub 3}CHO) AND CYCLOPROPANONE (c-C{sub 3}H{sub 4}O) IN INTERSTELLAR MODEL ICES—A COMBINED FTIR AND REFLECTRON TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDY

    Energy Technology Data Exchange (ETDEWEB)

    Abplanalp, Matthew J.; Borsuk, Aleca; Jones, Brant M.; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu [W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, Hawaii, HI, 96822 (United States)

    2015-11-20

    The formation routes of two structural isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—were investigated experimentally by exposing ices of astrophysical interest to energetic electrons at 5.5 K thus mimicking the interaction of ionizing radiation with interstellar ices in cold molecular clouds. The radiation-induced processing of these ices was monitored online and in situ via Fourier Transform Infrared spectroscopy and via temperature programmed desorption exploiting highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon ionization in the post irradiation phase. To selectively probe which isomer(s) is/are formed, the photoionization experiments were conducted with 10.49 and 9.60 eV photons. Our studies provided compelling evidence on the formation of both isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—in ethylene (C{sub 2}H{sub 4})—carbon monoxide (CO) ices forming propenal and cyclopropanone at a ratio of (4.5 ± 0.9):1. Based on the extracted reaction pathways, the cyclopropanone molecule can be classified as a tracer of a low temperature non-equilibrium chemistry within interstellar ices involving most likely excited triplet states, whereas propenal can be formed at ultralow temperatures, but also during the annealing phase via non-equilibrium as well as thermal chemistry (radical recombination). Since propenal has been detected in the interstellar medium and our laboratory experiments demonstrate that both isomers originated from identical precursor molecules our study predicts that the hitherto elusive second isomer—cyclopropanone—should also be observable toward those astronomical sources such as Sgr B2(N) in which propenal has been detected.

  16. Structural Phase Transformation (F. C. C. - B. C. C.) in F. C. C. Metals and Their Stability on the Path of Transformation

    Science.gov (United States)

    Öztekýn, Yasemin; Çolakoðlu, Kemal

    1997-08-01

    Because of its importance in Solid-State Physics, Metalurgy, Solid Mechanics and geophysics, theoretical strength calculations are performed to locate the stress-free b.c.c phase on three f.c.c metals (Ca, Pb, Ir). Internal energies correspponding to the unstresed b.c.c. and f.c.c. phase, and the required stress and energy changes for f.c.c.-b.c.c. transformation for these crystals are computed. To determine the range of stability (G stability), the Born criterion is used by calculating the values of deformation connecting the stress-free b.c.c. and stress-free f.c.c. phases of Ca, Pb and Ir. The studied crystals are subjected to unconstrained (100) uniaxial tension in all computations, and E.G.E.P. (Extended generalized exponantial potential) model is used to carry out these calculations.

  17. An Iron-Catalyzed Bond-Making/Bond-Breaking Cascade Merges Cycloisomerization and Cross-Coupling Chemistry.

    Science.gov (United States)

    Echeverria, Pierre-Georges; Fürstner, Alois

    2016-09-05

    Treatment of readily available enynes with alkyl-Grignard reagents in the presence of catalytic amounts of Fe(acac)3 engenders a remarkably facile and efficient reaction cascade that results in the net formation of two new C-C bonds while a C-Z bond in the substrate backbone is broken. Not only does this new manifold lend itself to the extrusion of heteroelements (Z=O, NR), but it can even be used for the cleavage of activated C-C bonds. The reaction likely proceeds via metallacyclic intermediates, the iron center of which gains ate character before reductive elimination occurs. The overall transformation represents a previously unknown merger of cycloisomerization and cross-coupling chemistry. It provides ready access to highly functionalized 1,3-dienes comprising a stereodefined tetrasubstituted alkene unit, which are difficult to make by conventional means.

  18. Catalysis of peptide bond formation by histidyl-histidine in a fluctuating clay environment

    Science.gov (United States)

    White, D. H.; Erickson, J. C.

    1980-01-01

    The condensation of glycine to form oligoglycines during wet-dry fluctuations on clay surfaces was enhanced up to threefold or greater by small amounts of histidyl-histidine. In addition, higher relative yields of the longer oligomers were produced. Other specific dipeptides tested gave no enhancement, and imidazole, histidine, and N-acetylhistidine gave only slight enhancements. Histidyl-histidine apparently acts as a true catalyst (in the sense of repeatedly catalyzing the reaction), since up to 52 nmol of additional glycine were incorporated into oligoglycine for each nmol of catalyst added. This is the first known instance of a peptide or similar molecule demonstrating a catalytic turnover number greater than unity in a prebiotic oligomer synthesis reaction, and suggests that histidyl-histidine is a model for a primitive prebiotic proto-enzyme. Catalysis of peptide bond synthesis by a molecule which is itself a peptide implies that related systems may be capable of exhibiting autocatalytic growth.

  19. Biosynthesis of pyranonaphthoquinone polyketides reveals diverse strategies for enzymatic carbon-carbon bond formation.

    Science.gov (United States)

    Metsä-Ketelä, Mikko; Oja, Terhi; Taguchi, Takaaki; Okamoto, Susumu; Ichinose, Koji

    2013-08-01

    Pyranonaphthoquinones synthesized by Streptomyces bacteria via type II polyketide pathways are aromatic compounds build around a common three-ring structure, which is composed of pyran, quinone and benzene rings. Over the years, actinorhodin in particular has served as a model compound for studying the biosynthesis of aromatic polyketides, while some of the other metabolites such as granaticin, medermycin, frenolicin and alnumycin A have enabled comparative studies that complement our understanding how these complex biological systems function and have evolved. In addition, despite the similarity of the aglycone units, pyranonaphthoquinones in effect display remarkable diversity in tailoring reactions, which include numerous enzymatic carbon-carbon bond forming reactions. This review focuses on the current status of molecular genetic, biochemical and structural investigations on this intriguing family of natural products.

  20. Formation of hydrogen bonds precedes the rate-limiting formation of persistent structure in the folding of ACBP

    DEFF Research Database (Denmark)

    Teilum, K; Kragelund, B B; Knudsen, J;

    2000-01-01

    A burst phase in the early folding of the four-helix two-state folder protein acyl-coenzyme A binding protein (ACBP) has been detected using quenched-flow in combination with site-specific NMR-detected hydrogen exchange. Several of the burst phase structures coincide with a structure consisting...... of eight conserved hydrophobic residues at the interface between the two N and C-terminal helices. Previous mutation studies have shown that the formation of this structure is rate limiting for the final folding of ACBP. The burst phase structures observed in ACBP are different from the previously reported...... collapsed types of burst phase intermediates observed in the folding of other proteins....

  1. Thermoacoustical analysis of solutions of poly(ethylene glycol) 200 through H-bond complex formation

    Energy Technology Data Exchange (ETDEWEB)

    Yasmin, Maimoona, E-mail: myasmin908@gmail.com [Department of Physics, University of Lucknow, Lucknow 226007 (India); Gupta, Manisha, E-mail: guptagm@rediffmail.com [Department of Physics, University of Lucknow, Lucknow 226007 (India)

    2011-05-10

    Research highlights: {yields} The presence of two electronegative elements viz. nitrogen and oxygen in its molecular architecture, ethanolamine has greater extent of interaction with PEG. {yields} Ethanolamine and m-cresol may be involved in a complex type of network of hydrogen bonding. {yields} Ethanolamine has greater extent of interaction with PEG than m-cresol and aniline particularly with least magnitude from aniline, where electron availability is least because of delocalization. {yields} The difference in molar volume between the components of the mixture control the mixture properties. - Abstract: Densities ({rho}) and ultrasonic velocities (u) of binary mixtures of poly(ethylene glycol) 200, PEG, with ethanolamine, m-cresol and aniline have been measured at various concentrations at 293.15, 303.15 and 313.15 K and have been fitted by third order polynomial equations at each temperature. The calculated values of isentropic compressibility (k{sub s}), free volume (V{sub f}), internal pressure ({pi}{sub i}), relaxation time ({tau}) and surface tension ({sigma}) at different mole fractions of PEG have been used to explain the hydrogen bonding and intermolecular interactions present in the mixture. Using these data, excess molar volume (V{sup E}), excess intermolecular free length (L{sub f}{sup E}), excess acoustic impedance (Z{sup E}) and excess pseudo-Grueneisen parameter ({Gamma}{sup E}) have been calculated and the results have been fitted to Redlich-Kister polynomial equation. All the results support each other and help in understanding the interactions in the mixture. Various models and mixing rules have been applied to evaluate the ultrasonic velocity data and have been compared with the experimental results.

  2. Enthalpy of Formation and O-H Bond Dissociation Enthalpy of Phenol: Inconsistency between Theory and Experiment.

    Science.gov (United States)

    Dorofeeva, Olga V; Ryzhova, Oxana N

    2016-04-21

    Gas-phase O–H homolytic bond dissociation enthalpy in phenol, DH298°(C6H5O–H), is still disputed, despite a large number of experimental and computational studies. In estimating this value, the experimental enthalpy of formation of phenol, ΔfH298°(C6H5OH, g) = −96.4 ± 0.6 kJ/mol (Cox, J. D. Pure Appl. Chem. 1961, 2, 125−128), is often used assuming high accuracy of the experimental value. In the present work a substantially less negative value of ΔfH298°(C6H5OH, g) = −91.8 ± 2.5 kJ/mol was calculated combining G4 theory with an isodesmic reaction approach. A benchmark quality of this result was achieved by using a large number of reliable reference species in isodesmic reaction calculations. Among these are the most accurate ΔfH298° values currently available from the Active Thermochemical Tables (ATcT) for 36 species (neutral molecules, radicals, and ions), anisole with recently reassessed enthalpy of formation, and 13 substituted phenols. The internal consistency of the calculated ΔfH298°(C6H5OH, g) value with the experimental enthalpies of formation of more than 50 reference species suggests that the reported experimental enthalpy of formation of phenol is in error. Taking into account that the enthalpy of formation of phenol has not been investigated experimentally since 1961, the new measurements would be extremely valuable. Using the accurate enthalpies of formation of C6H5OH and C6H5O• calculated in the present work, we obtained DH298°(C6H5O–H) = 369.6 ± 4.0 kJ/mol. This value is in satisfactory agreement with that determined from the most precise experimental measurement.

  3. Effects of Hydrogen Ion Implantation on TiC-C Coating of Stainless Steel

    Institute of Scientific and Technical Information of China (English)

    ZHANG Rui-qian; LIU Yao-guang; HUANG Ning-kang

    2008-01-01

    Titanium carbide coatings are widely used as various wear-resistant material.The hydrogen erosion resistance of TiC-C films and the effect of hydrogen participation on TiC-C films were studied.Seventy-five percent TiC-C films are prepared on stainless steel surface by using ion mixing,where TiC-C films are deposited by rf magnetron sputtering followed by argon ion bombardment.The samples are then submitted to hydrogen ion implantation at 1.2×10-3 Pa.Characterization for the 75% TiC-C films was done with SIMS,XRD,AES,and XPS.Secondary ion mass spectroscopy (SIMS) was used to analyze hydrogen concentration variation with depth,X-Ray diffraction (XRD) was used to identify the phases,and Auger electron spectra (AES) as well as X-ray photoelectron spectra (XPS) were used to check the effects of hydrogen on shifts of chemical bonding states of C and Ti in the TiC-C films.It is found that TiC-C films on stainless steel surface can prevent hydrogen from entering stainless steel.

  4. Heat-induced whey protein isolate fibrils: Conversion, hydrolysis, and disulphide bond formation

    NARCIS (Netherlands)

    Bolder, S.G.; Vasbinder, A.; Sagis, L.M.C.; Linden, van der E.

    2007-01-01

    Fibril formation of individual pure whey proteins and whey protein isolate (WPI) was studied. The heat-induced conversion of WPI monomers into fibrils at pH 2 and low ionic strength increased with heating time and protein concentration. Previous studies, using a precipitation method, size-exclusion

  5. A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

    DEFF Research Database (Denmark)

    Due-Hansen, Maria E; Pandey, Sunil K; Christiansen, Elisabeth;

    2016-01-01

    A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed....

  6. Assembly of macrocycles by zirconocene-mediated, reversible carbon-carbon bond formation.

    Science.gov (United States)

    Gessner, Viktoria H; Tannaci, John F; Miller, Adam D; Tilley, T Don

    2011-06-21

    Macrocyclic compounds have attracted considerable attention in numerous applications, including host-guest chemistry, chemical sensing, catalysis, and materials science. A major obstacle, however, is the limited number of convenient, versatile, and high-yielding synthetic routes to functionalized macrocycles. Macrocyclic compounds have been typically synthesized by ring-closing or condensation reactions, but many of these procedures produce mixtures of oligomers and cyclic compounds. As a result, macrocycle syntheses are often associated with difficult separations and low yields. Some successful approaches that circumvent these problems are based on "self-assembly" processes utilizing reversible bond-forming reactions, but for many applications, it is essential that the resulting macrocycle be built with a strong covalent bond network. In this Account, we describe how zirconocene-mediated reductive couplings of alkynes can provide reversible carbon-carbon bond-forming reactions well-suited for this purpose. Zirconocene coupling of alkenes and alkynes has been used extensively as a source of novel, versatile pathways to functionalized organic compounds. Here, we describe the development of zirconocene-mediated reductive couplings as a highly efficient method for the preparation of macrocycles and cages with diverse compositions, sizes, and shapes. This methodology is based on the reversible, regioselective coupling of alkynes with bulky substituents. In particular, silyl substituents provide regioselective, reversible couplings that place them into the α-positions of the resulting zirconacyclopentadiene rings. According to density functional theory (DFT) calculations and kinetic studies, the mechanism of this coupling involves a stepwise process, whereby an insertion of the second alkyne influences regiochemistry through both steric and electronic factors. Zirconocene coupling of diynes that incorporate silyl substituents generates predictable macrocyclic products

  7. Proton transfer in hydrogen-bonded network of phenol molecules: intracluster formation of water.

    Science.gov (United States)

    Lengyel, Jozef; Gorejová, Radka; Herman, Zdeněk; Fárník, Michal

    2013-11-07

    Electron ionization and time-of-flight mass spectrometry was used to investigate the phenol clusters (PhOH)n of different size from single molecule to large clusters: in coexpansion with He, the dimers n = 2 are mostly generated; in Ar, large species of n ≥ 10 also occur. Besides [(PhOH)n](+•) cluster ion series, hydrated phenol cluster ions [(PhOH)n·xH2O](+•) with up to x = 3 water molecules and dehydrated phenol clusters [(PhOH)n-H2O](+•) were observed. The hydrated phenol series exhibits minima and maxima that are interpreted as evidence for proton transfer between the hydrogen bonded cluster ions of cyclic structures. The proton transfer leads to a water generation within the clusters, and subsequent elimination of the diphenyl ether molecule(s) from the cluster yields the hydrated phenol cluster ions. Alternatively, a water molecule release yields a series of dehydrated phenols, among which the diphenyl ether ion [PhOPh](+•) (n = 2) constitutes the maximum.

  8. Interface formation of two- and three-dimensionally bonded materials in the case of GeTe-Sb₂Te₃ superlattices.

    Science.gov (United States)

    Momand, Jamo; Wang, Ruining; Boschker, Jos E; Verheijen, Marcel A; Calarco, Raffaella; Kooi, Bart J

    2015-12-07

    GeTe-Sb2Te3 superlattices are nanostructured phase-change materials which are under intense investigation for non-volatile memory applications. They show superior properties compared to their bulk counterparts and significant efforts exist to explain the atomistic nature of their functionality. The present work sheds new light on the interface formation between GeTe and Sb2Te3, contradicting previously proposed models in the literature. For this purpose [GeTe(1 nm)-Sb2Te3(3 nm)]15 superlattices were grown on passivated Si(111) at 230 °C using molecular beam epitaxy and they have been characterized particularly with cross-sectional HAADF scanning transmission electron microscopy. Contrary to the previously proposed models, it is found that the ground state of the film actually consists of van der Waals bonded layers (i.e. a van der Waals heterostructure) of Sb2Te3 and rhombohedral GeSbTe. Moreover, it is shown by annealing the film at 400 °C, which reconfigures the superlattice into bulk rhombohedral GeSbTe, that this van der Waals layer is thermodynamically favored. These results are explained in terms of the bonding dimensionality of GeTe and Sb2Te3 and the strong tendency of these materials to intermix. The findings debate the previously proposed switching mechanisms of superlattice phase-change materials and give new insights in their possible memory application.

  9. Interface structure and formation mechanism of diffusion-bonded joints of TiAl-based alloy to titanium alloy

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Vacuum diffusion bonding of a TiAl-based alloy (TAD) to a titanium alloy (TC2) was carried out at 1 273 K for 15~120 min under a pressure of 25 MPa. The kinds of the reaction products and the interface structures of the joints were investigated by SEM, EPMA and XRD. Based on this, a formation mechanism of the interface structure was elucidated. Experimental and analytical results show that two reaction layers have formed during the diffusion bonding of TAD to TC2. One is Al-rich α(Ti)layer adjacent to TC2,and the other is (Ti3Al+TiAl)layer adjacent to TAD,thus the interface structure of the TAD/TC2 joints is TAD/(Ti3Al+TiAl)/α(Ti)/TC2.This interface structure forms according to a three-stage mechanism,namely(a)the occurrence of a single-phase α(Ti)layer;(b)the occurrence of a duplex-phase(Ti3Al+TiAl)layer;and(c)the growth of the α(Ti)and (Ti3Al+TiAl)layers.

  10. Silicon-Carbon Bond Formation via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Unactivated Secondary and Tertiary Alkyl Electrophiles

    OpenAIRE

    Chu, Crystal K.; Liang, Yufan; Fu, Gregory C.

    2016-01-01

    A wide array of cross-coupling methods for the formation of C–C bonds from unactivated alkyl electrophiles have been described in recent years. In contrast, progress in the development of methods for the construction of C–heteroatom bonds has lagged; for example, there have been no reports of metal-catalyzed cross-couplings of unactivated secondary or tertiary alkyl halides with silicon nucleophiles to form C–Si bonds. In this study, we address this challenge, establishing that a simple, comm...

  11. Synthesis of Reusable Silica Nanosphere-Supported Pt(IV Complex for Formation of Disulfide Bonds in Peptides

    Directory of Open Access Journals (Sweden)

    Xiaonan Hou

    2017-02-01

    Full Text Available Some peptide-based drugs, including oxytocin, vasopressin, ziconotide, pramlintide, nesiritide, and octreotide, contain one intramolecular disulfide bond. A novel and reusable monodispersed silica nanosphere-supported Pt(IV complex (SiO2@TPEA@Pt(IV; TPEA: N-[3-(trimethoxysilylpropyl]ethylenediamine was synthesized via a four-step procedure and was used for the formation of intramolecular disulfide bonds in peptides. Transmission electron microscopy (TEM and chemical mapping results for the Pt(II intermediates and for SiO2@TPEA@Pt(IV show that the silica nanospheres possess a monodisperse spherical structure and contain uniformly-distributed Si, O, C, N, Cl, and Pt. The valence state of Pt on the silica nanospheres was characterized by X-ray photoelectron spectroscopy (XPS. The Pt(IV loaded on SiO2@TPEA@Pt(IV was 0.15 mmol/g, as determined by UV-VIS spectrometry. The formation of intramolecular disulfides in six dithiol-containing peptides of variable lengths by the use of SiO2@TPEA@Pt(IV was investigated, and the relative oxidation yields were determined by high-performance liquid chromatography (HPLC. In addition, peptide 1 (Ac-CPFC-NH2 was utilized to study the reusability of SiO2@TPEA@Pt(IV. No significant decrease in the relative oxidation yield was observed after ten reaction cycles. Moreover, the structure of SiO2@TPEA@Pt(IV after being used for ten cycles was determined to be similar to its initial one, demonstrating the cycling stability of the complex.

  12. Supramolecular Formation via Hydrogen Bonding in Copper and Nickel Complexes with 2-Hydroxynicotinic Acid

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Two complexes, Cu(HnicO)2 1 and Ni(HnicO)2(H2O)2 2 (H2nicO = 2-hydroxy- nicolinic acid), were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in monoclinic, space group P21/n, with a = 8.314(7), b = 6.275(4), c = 11.283(7) (A), β = 98.32(3)°, V = 582.5(7) (A)3, Z = 2, Mr = 339.74, Dc = 1.937 g/cm3, F(000) = 342, μ = 1.908 mm-1, S = 1.097, the final R = 0.0284 and wR = 0.0781 for 1177 observed reflections with I>2σ(I). Complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.438(5), b = 12.22(1), c = 7.537(5) (A), β = 100.07(3)°, V = 674.3(8) (A)3, Z = 2, Mr = 370.95, Dc = 1.827 g/cm3, F(000) = 380, μ = 1.487 mm-1, S = 1.041, the final R = 0.0335 and wR = 0.0779 for 1202 observed reflections with I>2σ(I). There are extended 3D framework structures in complexes 1 and 2 due to the N-H…O and C-H…O hydrogen bonds. The copper atom in 1 has square planar coordination, while the nickel atom in 2 adopts octahedral coordination geometry. The TG curve shows that complex 2 is stable in solid state to 150 ℃.

  13. On the formation and bonding of a surface carbonate on Ni(100)

    Science.gov (United States)

    Behm, R. J.; Brundle, C. R.

    1991-09-01

    The formation, stability, adsorption geometry and electronic structure of a surface carbonate on Ni(100) have been investigated by photoemission (XPS, UPS) and temperature-programmed reaction (TPR). The core level binding energies of 531.2 eV for 0(1s) and 289.0 eV for C(1s) are comparable to those of bulk carbonates. The He(II) spectrum of the carbonate valence levels is not well defined because of the coexisting adsorbed and oxidic oxygen. The angular dependence of the carbonate core level intensities is characteristic of the carbonate being present as an overlayer species rather than a thicker surface phase. The XPS data and isotope labelled TPR experiments indicate the oxygen atoms of the carbonate to be electronically and chemically equivalent, and on this basis we favor a structure in which the carbonate is attached to the metal via all three oxygen atoms. This is supported by comparision with the core level binding energies of HCOO ab and chemisorbed CO 2,ad, which are similarly attached to the surface. From the core level angular behavior, the close similarity of core level binding energies and available vibrational spectroscopic data, a (nearly) planar geometry of the CO 3,ad on Ni(100) is concluded, which is comparable to the planar bulk carbonate anion and the planar carbonate species on Ag(110). The activation barrier for decomposition is estimated from the observed maximum in TPR at 420 K to be 25 ± 2 kcal/mol. CO 2 does not accumulate on the clean or O ad-precovered Ni(100) surface at 130 K. The stabilized, chemisorbed CO 2,ad species often observed on other metal surfaces therefore does not play a critical role for carbonate formation on Ni(100). Also a mechanism involving the disproportionation of a CO 2… CO 2,ad- dimer anion can be ruled out from TPR data. The evidence of the experiments discussed in this paper suggests that the carbonate is predominantly formed by reaction of CO 2,ad with a less stable, defect (disordered) O ad species rather

  14. Evidence that the pathway of disulfide bond formation in Escherichia coli involves interactions between the cysteines of DsbB and DsbA.

    OpenAIRE

    Guilhot, C; Jander, G.; Martin, N L; Beckwith, J

    1995-01-01

    Disulfide bond formation is catalyzed in the periplasm of Escherichia coli. This process involves at least two proteins: DsbA and DsbB. Recent evidence suggests that DsbA, a soluble periplasmic protein directly catalyzes disulfide bond formation in proteins, whereas DsbB, an inner membrane protein, is involved in the reoxidation of DsbA. Here we present direct evidence of an interaction between DsbA and DsbB. (Kishigami et al. [Kishigami, S., Kanaya, E., Kikuchi, M. & Ito, K. (1995) J. Biol. ...

  15. Evaluation by Rocket Combustor of C/C Composite Cooled Structure Using Metallic Cooling Tubes

    Science.gov (United States)

    Takegoshi, Masao; Ono, Fumiei; Ueda, Shuichi; Saito, Toshihito; Hayasaka, Osamu

    In this study, the cooling performance of a C/C composite material structure with metallic cooling tubes fixed by elastic force without chemical bonding was evaluated experimentally using combustion gas in a rocket combustor. The C/C composite chamber was covered by a stainless steel outer shell to maintain its airtightness. Gaseous hydrogen as a fuel and gaseous oxygen as an oxidizer were used for the heating test. The surface of these C/C composites was maintained below 1500 K when the combustion gas temperature was about 2800 K and the heat flux to the combustion chamber wall was about 9 MW/m2. No thermal damage was observed on the stainless steel tubes that were in contact with the C/C composite materials. The results of the heating test showed that such a metallic tube-cooled C/C composite structure is able to control the surface temperature as a cooling structure (also as a heat exchanger) as well as indicated the possibility of reducing the amount of coolant even if the thermal load to the engine is high. Thus, application of this metallic tube-cooled C/C composite structure to reusable engines such as a rocket-ramjet combined-cycle engine is expected.

  16. Mineral catalysis of the formation of the phosphodiester bond in aqueous solution - The possible role of montmorillonite clays

    Science.gov (United States)

    Ferris, James P.; Ertem, Gozen; KAMALUDDIN; Agarwal, Vipin; Hua, Lu Lin

    1989-01-01

    The possible role of montmorillonite clays in the spontaneous formation on the primitive earth of the phosphodiester bond in the presence of water was investigated in experiments measuring the binding of various nucleosides and nucleotides with Na(+)-montmorillonite 22A and the reactions of these compounds with a water-soluble carbodiimide. It was found that, at neutral pH, adenine derivatives bind stronger than the corresponding uracil derivatives, consistent with the protonation of the adenine by the acidic clay surface and a cationic binding of the protonated ring to the anionic clay surface. The reaction of the 5-prime-AMP with carbodiimide resulted in the formation of 2-prime,5-prime-pApA (18.9 percent), 3-prime,5-prime-pApA (11 percent), and AppA (4.8 percent). The yields of these oligomers obtained when poly(U) was used in place of the clay were 15.5 percent, 3.7 percent, and 14.9 percent AppA, respectively.

  17. From Molecules to Surfaces: Radical-Based Mechanisms of Si-S and Si-Se Bond Formation on Silicon.

    Science.gov (United States)

    Buriak, Jillian M; Sikder, Md Delwar H

    2015-08-05

    The derivatization of silicon surfaces can have profound effects on the underlying electronic properties of the semiconductor. In this work, we investigate the radical surface chemistry of silicon with a range of organochalcogenide reagents (comprising S and Se) on a hydride-terminated silicon surface, to cleanly and efficiently produce surface Si-S and Si-Se bonds, at ambient temperature. Using a diazonium-based radical initiator, which induces formation of surface silicon radicals, a group of organochalcogenides were screened for reactivity at room temperature, including di-n-butyl disulfide, diphenyl disulfide, diphenyl diselenide, di-n-butyl sulfide, diphenyl selenide, diphenyl sulfide, 1-octadecanethiol, t-butyl disulfide, and t-butylthiol, which comprises the disulfide, diselenide, thiol, and thioether functionalities. The surface reactions were monitored by transmission mode Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ionization mass spectrometry. Calculation of Si-Hx consumption, a semiquantitative measure of yield of production of surface-bound Si-E bonds (E = S, Se), was carried out via FTIR spectroscopy. Control experiments, sans the BBD diazonium radical initiator, were all negative for any evident incorporation, as determined by FTIR spectroscopy. The functional groups that did react with surface silicon radicals included the dialkyl/diphenyl disulfides, diphenyl diselenide, and 1-octadecanethiol, but not t-butylthiol, diphenyl sulfide/selenide, and di-n-butyl sulfide. Through a comparison with the rich body of literature regarding molecular radicals, and in particular, silyl radicals, reaction mechanisms were proposed for each. Armed with an understanding of the reaction mechanisms, much of the known chemistry within the extensive body of radical-based reactivity has the potential to be harnessed on silicon and could be extended to a range of technologically relevant semiconductor

  18. Thermoelectric properties of porous SiC/C composites

    NARCIS (Netherlands)

    Fujisawa, Masashi; Hata, Toshimitsu; Kitagawa, Hiroyuki; Bronsveld, Paul; Suzuki, Youki; Hasezaki, Kazuhiro; Noda, Yasutoshi; Imamura, Yuji

    2008-01-01

    We developed a porous SiC/C composite by oxidizing a SiC/C composite made from a mixed powder of wood charcoal and SiO2 (32-45 mu m) by pulse current sintering at 1600 and 1800 degrees C under a N-2 atmosphere. The microstructures of the porous SiC/C composites with oxidation and the SiC/C composite

  19. Tracing the Fingerprint of Chemical Bonds within the Electron Densities of Hydrocarbons: A Comparative Analysis of the Optimized and the Promolecule Densities.

    Science.gov (United States)

    Keyvani, Zahra Alimohammadi; Shahbazian, Shant; Zahedi, Mansour

    2016-10-18

    The equivalence of the molecular graphs emerging from the comparative analysis of the optimized and the promolecule electron densities in two hundred and twenty five unsubstituted hydrocarbons was recently demonstrated [Keyvani et al. Chem. Eur. J. 2016, 22, 5003]. Thus, the molecular graph of an optimized molecular electron density is not shaped by the formation of the C-H and C-C bonds. In the present study, to trace the fingerprint of the C-H and C-C bonds in the electron densities of the same set of hydrocarbons, the amount of electron density and its Laplacian at the (3, -1) critical points associated with these bonds are derived from both optimized and promolecule densities, and compared in a newly proposed comparative analysis. The analysis not only conforms to the qualitative picture of the electron density build up between two atoms upon formation of a bond in between, but also quantifies the resulting accumulation of the electron density at the (3, -1) critical points. The comparative analysis also reveals a unified mode of density accumulation in the case of 2318 studied C-H bonds, but various modes of density accumulation are observed in the case of 1509 studied C-C bonds and they are classified into four groups. The four emerging groups do not always conform to the traditional classification based on the bond orders. Furthermore, four C-C bonds described as exotic bonds in previous studies, for example the inverted C-C bond in 1,1,1-propellane, are naturally distinguished from the analysis.

  20. Remarkably efficient synthesis of 2H-indazole 1-oxides and 2H-indazoles via tandem carbon-carbon followed by nitrogen-nitrogen bond formation.

    Science.gov (United States)

    Bouillon, Isabelle; Zajícek, Jaroslav; Pudelová, Nadĕzda; Krchnák, Viktor

    2008-11-21

    Base-catalyzed tandem carbon-carbon followed by nitrogen-nitrogen bond formations quantitatively converted N-alkyl-2-nitro-N-(2-oxo-2-aryl-ethyl)-benzenesulfonamides to 2H-indazoles 1-oxides under mild conditions. Triphenylphosphine or mesyl chloride/triethylamine-mediated deoxygenation afforded 2H-indazoles.

  1. Consecutive condensation, C-N and N-N bond formations: a copper- catalyzed one-pot three-component synthesis of 2H-indazole.

    Science.gov (United States)

    Kumar, Manian Rajesh; Park, Ahbyeol; Park, Namjin; Lee, Sunwoo

    2011-07-01

    2H-Indazoles are synthesized using copper-catalyzed, one-pot, three-component reactions of 2-bromobenzaldehydes, primary amines, and sodium azide. A copper catalyst plays the key role in the formation of C-N and N-N bonds. This method has a broad substrate scope with a high tolerance for a variety of functional groups.

  2. Possible evidence of amide bond formation between sinapinic acid and lysine-containing bacterial proteins by matrix-assisted laser desorption/ionization (MALDI) at 355 nm

    Science.gov (United States)

    We previously reported the apparent formation of matrix adducts of 3,5-dimethoxy-4-hydroxy-cinnamic acid (sinapinic acid or SA) via covalent attachment to disulfide bond-containing proteins (HdeA, HdeB and YbgS) from bacterial cell lysates ionized by matrix-assisted laser desorption/ionization (MALD...

  3. Theoretical studies on N-O or N-N bond formation from aryl azide catalyzed by iron(II) bromide complex.

    Science.gov (United States)

    Li, Juan; Zhang, Qi; Zhou, Lixin

    2012-03-02

    DFT calculations have been carried out to study the reaction mechanism on N-O or N-N bond formation from aryl azide catalyzed by iron(II) bromide complex. A favorable reaction pathway is proposed to account for the construction of the core structure of 2H-indazoles or 2,1-benzisoxazoles.

  4. Characterization of Brazed Joints of C-C Composite to Cu-clad-Molybdenum

    Science.gov (United States)

    Singh, M.; Asthana, R.

    2008-01-01

    Carbon-carbon composites with either pitch+CVI matrix or resin-derived matrix were joined to copper-clad molybdenum using two active braze alloys, Cusil-ABA (1.75% Ti) and Ticusil (4.5% Ti). The brazed joints revealed good interfacial bonding, preferential precipitation of Ti at the composite/braze interface, and a tendency toward de-lamination in resin-derived C-C composite due to its low inter-laminar shear strength. Extensive braze penetration of the inter-fiber channels in the pitch+CVI C-C composites was observed. The relatively low brazing temperatures (Cu-clad-Mo/braze interface and higher hardness in Ticusil (approx.85-250 HK) than in Cusil-ABA (approx.50-150 HK). These C-C/Cu-clad-Mo joints with relatively low thermal resistance may be promising for thermal management applications.

  5. Constructing safe and durable antibacterial textile surfaces using a robust graft-to strategy via covalent bond formation

    Science.gov (United States)

    He, Liang; Li, Sha; Chung, Cordelia T. W.; Gao, Chang; Xin, John H.

    2016-11-01

    Recently zwitterionic materials have been widely applied in the biomedical and bioengineering fields due to their excellent biocompatibility. Inspired by these, this study presents a graft-to strategy via covalent bond formation to fabricate safe and durable antibacterial textile surfaces. A novel zwitterionic sulfobetaine containing triazine reactive group was specifically designed and synthesized. MTT assay showed that it had no obvious cytotoxicity to human skin HaCaT cells as verified by ca. 89.9% relative viability at a rather high concentration of 0.8 mg·mL‑1. In the evaluation for its skin sensitization, the maximum score for symptoms of erythema and edema in all tests were 0 in all observation periods. The sulfobetaine had a hydrophilic nature and the hydrophilicity of the textiles was enhanced by 43.9% when it was covalently grafted onto the textiles. Moreover, the textiles grafted with the reactive sulfobetaine exhibited durable antibacterial activities, which was verified by the fact that they showed antibacterial rates of 97.4% against gram-positive S. aureus and 93.2% against gram-negative E. coli even after they were laundered for 30 times. Therefore, the titled zwitterionic sulfobetaine is safe to human for healthcare and wound dressing and shows a promising prospect on antibacterial textile application.

  6. Chemically fixed p-n heterojunctions for polymer electronics by means of covalent B-F bond formation

    Science.gov (United States)

    Hoven, Corey V.; Wang, Huiping; Elbing, Mark; Garner, Logan; Winkelhaus, Daniel; Bazan, Guillermo C.

    2010-03-01

    Widely used solid-state devices fabricated with inorganic semiconductors, including light-emitting diodes and solar cells, derive much of their function from the p-n junction. Such junctions lead to diode characteristics and are attained when p-doped and n-doped materials come into contact with each other. Achieving bilayer p-n junctions with semiconducting polymers has been hindered by difficulties in the deposition of thin films with independent p-doped and n-doped layers. Here we report on how to achieve permanently fixed organic p-n heterojunctions by using a cationic conjugated polyelectrolyte with fluoride counteranions and an underlayer composed of a neutral conjugated polymer bearing anion-trapping functional groups. Application of a bias leads to charge injection and fluoride migration into the neutral layer, where irreversible covalent bond formation takes place. After the initial charging and doping, one obtains devices with no delay in the turn on of light-emitting electrochemical behaviour and excellent current rectification. Such devices highlight how mobile ions in organic media can open opportunities to realize device structures in ways that do not have analogies in the world of silicon and promise new opportunities for integrating organic materials within technologies now dominated by inorganic semiconductors.

  7. Kinetics of T3-DNA Ligase-Catalyzed Phosphodiester Bond Formation Measured Using the α-Hemolysin Nanopore.

    Science.gov (United States)

    Tan, Cherie S; Riedl, Jan; Fleming, Aaron M; Burrows, Cynthia J; White, Henry S

    2016-12-27

    The latch region of the wild-type α-hemolysin (α-HL) protein channel can be used to distinguish single base modifications in double-stranded DNA (dsDNA) via ion channel measurements upon electrophoretic capture of dsDNA in the vestibule of α-HL. Herein, we investigated the use of the latch region to detect a nick in the phosphodiester DNA backbone. The presence of a nick in the phosphodiester backbone of one strand of the duplex results in a significant increase in both the blockade current and noise level relative to the intact duplex. Differentiation between the nicked and intact duplexes based on blockade current or noise, with near baseline resolution, allows real-time monitoring of the rate of T3-DNA ligase-catalyzed phosphodiester bond formation. Under low ionic strength conditions containing divalent cations and a molecular crowding agent (75 mg mL(-1) PEG), the rate of enzyme-catalyzed reaction in the bulk solution was continuously monitored by electrophoretically capturing reaction substrate or product dsDNA in the α-HL protein channel vestibule. Enzyme kinetic results obtained from the nanopore experiments match those from gel electrophoresis under the same reaction conditions, indicating the α-HL nanopore measurement provides a viable approach for monitoring enzymatic DNA repair activity.

  8. On-Surface Synthesis of Two-Dimensional Covalent Organic Structures versus Halogen-Bonded Self-Assembly: Competing Formation of Organic Nanoarchitectures.

    Science.gov (United States)

    Peyrot, David; Silly, Fabien

    2016-05-24

    The competition between the on-surface synthesis of covalent nanoarchitectures and the self-assembly of star-shaped 1,3,5-Tris(4-iodophenyl)benzene molecules on Au(111) in vacuum is investigated using scanning tunneling microscopy above room temperature. The molecules form covalent polygonal nanoachitectures at the gold surface step edges and at the elbows of the gold reconstruction at low coverage. With coverage increasing two-dimensional halogen-bonded structures appear and grow on the surface terraces. Two different halogen-bonded nanoarchitectures are coexisting on the surface and hybrid covalent-halogen bonded structures are locally observed. At high coverage covalent nanoarchitectures are squeezed at the domain boundary of the halogen-bonded structures. The competitive growth between the covalent and halogen-bonded nanoarchitectures leads to formation of a two-layer film above one monolayer deposition. For this coverage, the covalent nanoarchitectures are propelled on top of the halogen-bonded first layer. These observations open up new opportunities for decoupling covalent nanoarchitectures from catalytically active and metal surfaces in vacuum.

  9. Density functional study of hydrogen bond formation between methanol and organic molecules containing Cl, F, NH2, OH, and COOH functional groups.

    Science.gov (United States)

    Kolev, Stefan K; St Petkov, Petko; Rangelov, Miroslav A; Vayssilov, Georgi N

    2011-12-08

    Various hydrogen-bonded complexes of methanol with different proton accepting and proton donating molecules containing Cl, F, NH(2), OH, OR, and COOH functional groups have been modeled using DFT with hybrid B3LYP and M05-2X functionals. The latter functional was found to provide more accurate estimates of the structural and thermodynamic parameters of the complexes of halides, amines, and alcohols. The characteristics of these complexes are influenced not only by the principle hydrogen bond of the methanol OH with the proton acceptor heteroatom, but also by additional hydrogen bonds of a C-H moiety with methanol oxygen as a proton acceptor. The contribution of the former hydrogen bond in the total binding enthalpy increases in the order chlorides contribution of the second type of hydrogen bond increases in the reverse order. A general correlation was found between the binding enthalpy of the complex and the electrostatic potential at the hydrogen center participating in the formation of the hydrogen bond. The calculated binding enthalpies of different complexes were used to clarify which functional groups can potentially form a hydrogen bond to the 2'-OH hydroxyl group in ribose, which is strong enough to block it from participation in the intramolecular catalytic activation of the peptide bond synthesis. Such blocking could result in inhibition of the protein biosynthesis in the living cell if the corresponding group is delivered as a part of a drug molecule in the vicinity of the active site in the ribosome. According to our results, such activity can be accomplished by secondary or tertiary amines, alkoxy groups, deprotonated carboxyl groups, and aliphatic fluorides, but not by the other modeled functional groups.

  10. Hypertriglyceridemia associated with the c.553G>T APOA5 SNP results from aberrant hetero-disulfide bond formation

    Science.gov (United States)

    Sharma, Vineeta; Witkowski, Andrzej; Witkowska, H. Ewa; Dykstra, Andrew; Simonsen, Jens B.; Nelbach, Lisa; Beckstead, Jennifer A.; Pullinger, Clive R.; Kane, John P.; Malloy, Mary J.; Watson, Gordon; Forte, Trudy M.; Ryan, Robert O.

    2014-01-01

    Objective Apolipoprotein (apo) A-V is a low abundance plasma protein that modulates triacylglycerol (TG) homeostasis. Gene transfer studies were undertaken in apoa5 (−/−) mice to define the mechanism underlying the correlation between the single nucleotide polymorphism (SNP) c.553G>T in APOA5 and hypertriglyceridemia (HTG). Approach and Results Adeno-associated virus (AAV) 2/8 mediated gene transfer of wild type (WT) apoA-V induced a dramatic lowering of plasma TG in apoa5 (−/−) mice while AAV2/8-Gly162Cys apoA-V (corresponding to the c.553G>T SNP: rs2075291) had a modest effect. Characterization studies revealed that plasma levels of WT- and G162C apoA-V in transduced mice were similar and within the physiological range. Fractionation of plasma from mice transduced with AAV2/8-G162C apoA-V indicated that, unlike WT apoA-V, >50% of G162C apoA-V was recovered in the lipoprotein-free fraction. Non-reducing SDS-PAGE immunoblot analysis provided evidence that G162C apoA-V present in the lipoprotein-free fraction, but not that portion associated with lipoproteins, displayed altered electrophoretic mobility consistent with disulfide-linked hetero-dimer formation. Immunoprecipitation followed by liquid chromatography/mass spectrometry of human plasma from subjects homozygous for WT APOA5 and c.553G>T APOA5 revealed that G162C apoA-V forms adducts with extraneous plasma proteins including fibronectin, kininogen-1 and others. Conclusion Substitution of Cys for Gly at position 162 of mature apoA-V introduces a free cysteine that forms disulfide bonds with plasma proteins such that its lipoprotein binding and TG modulation functions are compromised. PMID:25127531

  11. Femtosecond X-ray solution scattering reveals that bond formation mechanism of a gold trimer complex is independent of excitation wavelength

    Directory of Open Access Journals (Sweden)

    Kyung Hwan Kim

    2016-07-01

    Full Text Available The [Au(CN2−]3 trimer in water experiences a strong van der Waals interaction between the d10 gold atoms due to large relativistic effect and can serve as an excellent model system to study the bond formation process in real time. The trimer in the ground state (S0 exists as a bent structure without the covalent bond between the gold atoms, and upon the laser excitation, one electron in the antibonding orbital goes to the bonding orbital, thereby inducing the formation of a covalent bond between gold atoms. This process has been studied by various time-resolved techniques, and most of the interpretation on the structure and dynamics converge except that the structure of the first intermediate (S1 has been debated due to different interpretations between femtosecond optical spectroscopy and femtosecond X-ray solution scattering. Recently, the excitation wavelength of 267 nm employed in our previous scattering experiment was suggested as the culprit for misinterpretation. Here, we revisited this issue by performing femtosecond X-ray solution scattering with 310 nm excitation and compared the results with our previous study employing 267 nm excitation. The data show that a linear S1 structure is formed within 500 fs regardless of excitation wavelength and the structural dynamics observed at both excitation wavelengths are identical to each other within experimental errors.

  12. Evidence of covalent bond formation at the silane-metal interface during plasma polymerization of bis-1,2-(triethoxysilyl)ethane (BTSE) on aluminium

    Science.gov (United States)

    Batan, A.; Mine, N.; Douhard, B.; Brusciotti, F.; De Graeve, I.; Vereecken, J.; Wenkin, M.; Piens, M.; Terryn, H.; Pireaux, J. J.; Reniers, F.

    2010-06-01

    Silane and silane-like films were deposited from bis-1,2-(triethoxysilyl)ethane by vacuum and atmospheric plasma onto aluminium. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used for probing the aluminium/plasma polymer film interface. An AlOSi + fragment was identified at nominal mass m/ z = 70.9539 amu, indicating a strong chemical interaction (formation of a covalent bond) at the substrate/film interface. Until now, this strong silane-aluminium interaction has never been observed in plasma polymer BTSE films. Ageing tests in an ultrasonic water bath combined with X-ray photoelectron spectroscopy measurements allowed to indirectly confirm good adhesion, and therefore the formation of a chemical bond at the interface.

  13. Transition metal-promoted synthesis of 2-aryl/heteroaryl-thioquinazoline: C-S Bond formation by “Chan-Lam Cross-Coupling” Reaction

    Indian Academy of Sciences (India)

    SATYA KARUNA PULAKHANDAM; NARESH KUMAR KATARI; RAVI PRAKASH REDDY MANDA

    2017-02-01

    An efficient method for the synthesis of S-aryl/heteroaryl-quinazoline has been developed through the cross-coupling of 1,4-dihydroquinazoline with a variety of aryl and heteroaryl boronic acids assisted by [Cu(OAc)₂] as the catalyst for the formation of carbon-sulfur bonds. This newly developed method demonstratesthat the conditions of the traditional copper-catalyzed Chan-Lam reaction can be improved. Optimized reaction involves base, solvent and catalyst.

  14. Formation of unsaturated hydrocarbons in interstellar ice analogs by cosmic rays

    OpenAIRE

    Pilling, S.; Andrade, D. P. P.; Da Silveira, E.F.; Rothard, H.; Domaracka, A.; Boduch, P.

    2012-01-01

    The formation of double and triple C-C bonds from the processing of pure c-C6H12 (cyclohexane) and mixed H2O:NH3:c-C6H12 (1:0.3:0.7) ices by highly-charged, and energetic ions (219 MeV O^{7+} and 632 MeV Ni^{24+}) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ices analogs. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accel\\'erat\\'eur National d'Ions Lourds) ...

  15. Uniform Free-Energy Profiles of the P-O Bond Formation and Cleavage Reactions Catalyzed by DNA Polymerases β and λ.

    Science.gov (United States)

    Klvaňa, Martin; Bren, Urban; Florián, Jan

    2016-12-29

    Human X-family DNA polymerases β (Polβ) and λ (Polλ) catalyze the nucleotidyl-transfer reaction in the base excision repair pathway of the cellular DNA damage response. Using empirical valence bond and free-energy perturbation simulations, we explore the feasibility of various mechanisms for the deprotonation of the 3'-OH group of the primer DNA strand, and the subsequent formation and cleavage of P-O bonds in four Polβ, two truncated Polλ (tPolλ), and two tPolλ Loop1 mutant (tPolλΔL1) systems differing in the initial X-ray crystal structure and nascent base pair. The average calculated activation free energies of 14, 18, and 22 kcal mol(-1) for Polβ, tPolλ, and tPolλΔL1, respectively, reproduce the trend in the observed catalytic rate constants. The most feasible reaction pathway consists of two successive steps: specific base (SB) proton transfer followed by rate-limiting concerted formation and cleavage of the P-O bonds. We identify linear free-energy relationships (LFERs) which show that the differences in the overall activation and reaction free energies among the eight studied systems are determined by the reaction free energy of the SB proton transfer. We discuss the implications of the LFERs and suggest pKa of the 3'-OH group as a predictor of the catalytic rate of X-family DNA polymerases.

  16. Un-catalyzed peptide bond formation between two monomers of glycine, alanine, serine, threonine, and aspartic acid in gas phase: a density functional theory study

    Science.gov (United States)

    Bhunia, Snehasis; Singh, Ajeet; Ojha, Animesh K.

    2016-05-01

    In the present report, un-catalyzed peptide bond formation between two monomers of glycine (Gly), alanine (Ala), serine (Ser), threonine (Thr), and aspartic acid (Asp) has been investigated in gas phase via two steps reaction mechanism and concerted mechanism at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. The peptide bond is formed through a nucleophilic reaction via transition states, TS1 and TS2 in stepwise mechanism. The TS1 reveals formation of a new C-N bond while TS2 illustrate the formation of C=O bond. In case of concerted mechanism, C-N bond is formed by a single four-centre transition state (TS3). The energy barrier is used to explain the involvement of energy at each step of the reaction. The energy barrier (20-48 kcal/mol) is required for the transformation of reactant state R1 to TS1 state and intermediate state I1 to TS2 state. The large value of energy barrier is explained in terms of distortion and interaction energies for stepwise mechanism. The energy barrier of TS3 in concerted mechanism is very close to the energy barrier of the first transition state (TS1) of the stepwise mechanism for the formation of Gly-Gly and Ala-Ala di- peptide. However, in case of Ser-Ser, Thr-Thr and Asp-Asp di-peptide, the energy barrier of TS3 is relatively high than that of the energy barrier of TS1 calculated at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. In both the mechanisms, the value of energy barrier calculated at B3LYP/6-31G(d,p) level of theory is greater than that of the value calculated at M062X/6-31G(d,p) level of theory.

  17. Molecular chirality and chiral capsule-type dimer formation of cyclic triamides via hydrogen-bonding interactions.

    Science.gov (United States)

    Fujimoto, Noriko; Matsumura, Mio; Azumaya, Isao; Nishiyama, Shizuka; Masu, Hyuma; Kagechika, Hiroyuki; Tanatani, Aya

    2012-05-18

    Chiral properties of bowl-shaped cyclic triamides bearing functional groups with hydrogen-bonding ability were examined. Chiral induction of cyclic triamide 3a was observed by addition of chiral amine in solution, and chiral separation was achieved by simple crystallization to afford chiral capsule-type dimer structure of 4a.

  18. Experimental and theoretical evaluation of the reactions leading to formation of internal double bonds in suspension PVC

    NARCIS (Netherlands)

    Purmova, Jindra; Pauwels, Kim F. D.; Agostini, Michela; Bruinsma, Maarten; Vorenkamp, Eltio J.; Schouten, Arend J.; Coote, Michelle L.

    2008-01-01

    The number of internal double bonds in poly(vinyl chloride) (PVC) samples was studied as a function of molecular weight at various monomer conversions. These defect structures were found to exhibit end-group-like characteristics: their concentration per chain was largely constant as a function of mo

  19. Formation and reshuffling of disulfide bonds in bovine serum albumin demonstrated using tandem mass spectrometry with collision-induced and electron-transfer dissociation.

    Science.gov (United States)

    Rombouts, Ine; Lagrain, Bert; Scherf, Katharina A; Lambrecht, Marlies A; Koehler, Peter; Delcour, Jan A

    2015-07-20

    Thermolysin hydrolyzates of freshly isolated, extensively stored (6 years, 6 °C, dry) and heated (60 min, 90 °C, in excess water) bovine serum albumin (BSA) samples were analyzed with liquid chromatography (LC) electrospray ionization (ESI) tandem mass spectrometry (MS/MS) using alternating electron-transfer dissociation (ETD) and collision-induced dissociation (CID). The positions of disulfide bonds and free thiol groups in the different samples were compared to those deduced from the crystal structure of native BSA. Results revealed non-enzymatic posttranslational modifications of cysteine during isolation, extensive dry storage, and heating. Heat-induced extractability loss of BSA was linked to the impact of protein unfolding on the involvement of specific cysteine residues in intermolecular and intramolecular thiol-disulfide interchange and thiol oxidation reactions. The here developed approach holds promise for exploring disulfide bond formation and reshuffling in various proteins under conditions relevant for chemical, biochemical, pharmaceutical and food processing.

  20. Formación de enlaces C-C, C-N y N-N con catalizadores de óxido de cerio y de oro/óxido de cerio.

    OpenAIRE

    Cómbita Merchán, Diego Fernando

    2016-01-01

    [EN] Heterogeneous catalysis is one of the most important tools in the advancement of green chemistry, understood it as one that efficiently uses (preferably renewable) raw materials, eliminate waste and avoids the use of toxic and/or dangerous reagents and solvents in chemicals production and application. In this thesis we have investigated the reaction mechanisms and the nature of the active centers in C-C, C-N and N-N bond forming reactions over cerium oxide and over gold nanoparticles...

  1. Testing of DLR C/C-SiC and C/C for HIFiRE 8 Scramjet Combustor

    Science.gov (United States)

    Glass, David E.; Capriotti, Diego P.; Reimer, Thomas; Kutemeyer, Marius; Smart, Michael K.

    2014-01-01

    Ceramic Matrix Composites (CMCs) have been proposed for use as lightweight hot structures in scramjet combustors. Previous studies have calculated significant weight savings by utilizing CMCs (active and passive) versus actively cooled metallic scramjet structures. Both a carbon/carbon (C/C) and a carbon/carbon-silicon carbide (C/C-SiC) material fabricated by DLR (Stuttgart, Germany) are being considered for use in a passively cooled combustor design for Hypersonic International Flight Research Experimentation (HIFiRE) 8, a joint Australia / Air Force Research Laboratory hypersonic flight program, expected to fly at Mach 7 for approximately 30 sec, at a dynamic pressure of 55 kilopascals. Flat panels of the DLR C/C and C/C-SiC materials were installed downstream of a hydrogen-fueled, dual-mode scramjet combustor and tested for several minutes at conditions simulating flight at Mach 5 and Mach 6. Gaseous hydrogen fuel was used to fuel the scramjet combustor. The test panels were instrumented with embedded Type K and Type S thermocouples. Zirconia felt insulation was used during some of the tests to reduce heat loss from the back surface and thus increase the heated surface temperature of the C/C-SiC panel approximately 177 C (350 F). The final C/C-SiC panel was tested for three cycles totaling over 135 sec at Mach 6 enthalpy. Slightly more erosion was observed on the C/C panel than the C/C-SiC panels, but both material systems demonstrated acceptable recession performance for the HIFiRE 8 flight.

  2. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Brymora, Katarzyna [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France); Fouineau, Jonathan; Eddarir, Asma; Chau, François [Université Paris Diderot, Sorbonne Paris Cité, ITODYS CNRS UMR 7086 (France); Yaacoub, Nader; Grenèche, Jean-Marc [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France); Pinson, Jean; Ammar, Souad [Université Paris Diderot, Sorbonne Paris Cité, ITODYS CNRS UMR 7086 (France); Calvayrac, Florent, E-mail: florent.calvayrac@univ-lemans.fr [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France)

    2015-11-15

    Combining ab initio modeling and {sup 57}Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal–oxygen–carbon bonding and not a metal–carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces.

  3. Oxaloacetate hydrolase, the C-C bond lyase of oxalate secreting fungi

    NARCIS (Netherlands)

    Han, Y.; Joosten, H.J.; Niu, W.; Zhao, Z.; Mariano, P.S.; McCalman, M.; Kan, van J.; Schaap, P.J.; Dunaway-Mariano, D.

    2007-01-01

    Oxalate secretion by fungi is known to be associated with fungal pathogenesis. In addition, oxalate toxicity is a concern for the commercial application of fungi in the food and drug industries. Although oxalate is generated through several different biochemical pathways, oxaloacetate acetylhydrolas

  4. Catalytic C-C Bond Cleavage for the Production of Chemicals from Lignin

    NARCIS (Netherlands)

    Jastrzebski, R.

    2016-01-01

    Lignin is a major component of lignocellulosic biomass and could be an important renewable feedstock in industry for the production of (aromatic) bulk and fine chemicals. To this end, the development of new catalytic processes is required; both to depolymerise the biopolymer into small aromatic buil

  5. In Pursuit of an Ideal C-C Bond-Forming Reaction

    Science.gov (United States)

    RajanBabu, T. V.

    2009-01-01

    Attempts to introduce the highly versatile vinyl group into other organic molecules in a chemo-, regio- and stereoselective fashion via catalytic activation of ethylene provided challenging opportunities to explore new ligand and salt effects in homogeneous catalysis. This review provides a personal account of the development of enantioselective reactions involving ethylene. PMID:19606231

  6. A Facile Method to Prepare Double-Layer Isoporous Hollow Fiber Membrane by In Situ Hydrogen Bond Formation in the Spinning Line.

    Science.gov (United States)

    Noor, Nazia; Koll, Joachim; Radjabian, Maryam; Abetz, Clarissa; Abetz, Volker

    2016-03-01

    A double-layer hollow fiber is fabricated where an isoporous surface of polystyrene-block-poly(4-vinylpyridine) is fixed on a support layer by co-extrusion. Due to the sulfonation of the support layer material, delamination of the two layers is suppressed without increasing the number of subsequent processing steps for isoporous composite membrane formation. Electron microscope-energy-dispersive X-ray spectroscopy images unveil the existence of a high sulfur concentration in the interfacial region by which in-process H-bond formation between the layers is evidenced. For the very first time, our study reports a facile method to fabricate a sturdy isoporous double-layer hollow fiber.

  7. Assessment of covalent bond formation between coupling agents and wood by FTIR spectroscopy and pull strength tests

    DEFF Research Database (Denmark)

    Rasmussen, Jonas Stensgaard; Barsberg, Søren Talbro; Venås, Thomas Mark;

    2014-01-01

    . This was seen as evidence for covalent bonds between lignin phenolics and the coupling agents. No spectral changes were observed when the coupling agents were mixed with the wood constituents cellulose and hemicellulose. For verification of the results, a modified EN 311 wet adhesion pull strength test...... was performed with softwood panels painted with a solvent-borne alkyd/acrylic coating. The results revealed an improved adhesion for all tested coupling agents compared to the untreated reference. The spectroscopic and pull test results underline that the presence of the lignin moiety in wood is of central...

  8. Efficient C/C++ programming smaller, faster, better

    CERN Document Server

    Heller, Steve

    1994-01-01

    Efficient C/C++ Programming describes a practical, real-world approach to efficient C/C++ programming. Topics covered range from how to save storage using a restricted character set and how to speed up access to records by employing hash coding and caching. A selective mailing list system is used to illustrate rapid access to and rearrangement of information selected by criteria specified at runtime.Comprised of eight chapters, this book begins by discussing factors to consider when deciding whether a program needs optimization. In the next chapter, a supermarket price lookup system is used to

  9. Deformation microstructure and orientation of F.C.C. crystals

    DEFF Research Database (Denmark)

    Liu, Q.; Hansen, N.

    1995-01-01

    The effect of crystallographic orientation on the microstructural evolution in f.c.c. metals with medium to high stacking fault energy is analyzed. This analysis is based on a literature review of the behaviour of single crystals and polycrystals supplemented with an experimental study of cold...

  10. Oxidative electrochemical aryl C-C coupling of spiropyrans

    NARCIS (Netherlands)

    Ivashenko, Oleksii; van Herpt, Jochem T.; Rudolf, Petra; Feringa, Ben L.; Browne, Wesley R.

    2013-01-01

    The isolation and definitive assignment of the species formed upon electrochemical oxidation of nitro-spiropyran (SP) is reported. The oxidative aryl C-C coupling at the indoline moiety of the SP radical cation to form covalent dimers of the ring-closed SP form is demonstrated. The coupling is block

  11. Get more control over your C/C++ service

    CERN Document Server

    CERN. Geneva

    2015-01-01

    Are you looking for a way to better diagnose or monitor your C/C++ programs? Find out more about CMX - a neat, lightweight library (<32Kb) which targets this need. It allows to expose information from inside a process through a simple API, enabling pre-failure detection in combination with your favourite monitoring system.

  12. Interstellar detection of c-C3D2

    CERN Document Server

    Spezzano, S; Schilke, P; Caselli, P; Menten, K M; McCarthy, M C; Bizzocchi, L; Trevino-Morales, S P; Aikawa, Y; Schlemmer, S

    2013-01-01

    We report the first interstellar detection of c-C3D2. The doubly deuterated cyclopropenylidene, a carbene, has been detected toward the starless cores TMC- 1C and L1544 using the IRAM 30m telescope. The J(Ka,Kc) = 3(0,3)-2(1,2), 3(1,3)-2(0,2), and 2(2,1)-1(1,0) transitions of this species have been observed at 3 mm in both sources. The expected 1:2 intensity ratio has been found in the 3(0,3)-2(1,2) and 3(1,3)-2(0,2) lines, belonging to the para and ortho species respectively. We also observed lines of the main species, c-C3H2, the singly deuterated c-C3HD, and the species with one 13C off of the principal axis of the molecule, c-H13CC2H. The lines of c-C3D2 have been observed with high signal to noise ratio, better than 7.5 sigma in TMC-1C and 9 sigma in L1544. The abundance of doubly deuterated cyclopropenylidene with respect to the normal species is found to be (0.4 - 0.8)% in TMC-1C and (1.2 - 2.1)% in L1544. The deuteration of this small hydrocarbon ring is analysed with a comprehensive gas-grain model, ...

  13. Effect of intrachain hydrogen bond on the formation of L amino acids along α helix of peptide

    Institute of Scientific and Technical Information of China (English)

    梅镇岳

    1995-01-01

    The model of right-handed α helix of peptide,in which the intrachain hydrogen bonds be-tween amino acid residues are in the direction of the axis of the helix,is used to compute the energy differ-ences between D-and L-form residues.The dominant intramolecular interactions involved are the Coulombinteraction for the residues with charged and polarized R group and van der Waals interaction for thehydrophobic residues respectively.The results obtained show that the energy states of L-forms are lower thanthose of the corresponding D-forms.Therefore,L-form states are more stable.The racemization of the aminoacid after the residue has been dislocated from the peptide chain is interpreted as the consequence of the pari-ty conservation of the electromagnetic interaction.

  14. Carbon-carbon bond activation of cyclobutenones enabled by the addition of chiral organocatalyst to ketone.

    Science.gov (United States)

    Li, Bao-Sheng; Wang, Yuhuang; Jin, Zhichao; Zheng, Pengcheng; Ganguly, Rakesh; Chi, Yonggui Robin

    2015-02-05

    The activation of carbon-carbon (C-C) bonds is an effective strategy in building functional molecules. The C-C bond activation is typically accomplished via metal catalysis, with which high levels of enantioselectivity are difficult to achieve due to high reactivity of metal catalysts and the metal-bound intermediates. It remains largely unexplored to use organocatalysis for C-C bond activation. Here we describe an organocatalytic activation of C-C bonds through the addition of an NHC to a ketone moiety that initiates a C-C single bond cleavage as a key step to generate an NHC-bound intermediate for chemo- and stereo-selective reactions. This reaction constitutes an asymmetric functionalization of cyclobutenones using organocatalysts via a C-C bond activation process. Structurally diverse and multicyclic compounds could be obtained with high optical purities via an atom and redox economic process.

  15. Peptide bond formation through gas-phase reactions in the interstellar medium: formamide and acetamide as prototypes

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es [Computational Chemistry Group, Departamento de Química Física, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2014-09-20

    A theoretical study of the reactions of NH{sub 4}{sup +} with formaldehyde and CH{sub 5}{sup +} with formamide is carried out. The viability of these gas-phase ion-molecule reactions as possible sources of formamide and acetamide under the conditions of interstellar medium is evaluated. We report a theoretical estimation of the reaction enthalpies and an analysis of their potential energy surfaces. Formation of protonated formamide from the reaction between ammonium cation and formaldehyde is an exothermic process, but all the channels located on the potential energy surface leading to this product present net activation energies. For the reaction between methanium and formamide, different products are possible from a thermodynamic point of view. An analysis of its potential energy surface showed that formation of protonated acetamide and amino acetaldehyde takes place through barrier-free paths. Therefore, this reaction could be a feasible source of acetamide and amino acetaldehyde in space.

  16. How covalent heme to protein bonds influence the formation and reactivity of redox intermediates of a bacterial peroxidase.

    Science.gov (United States)

    Auer, Markus; Nicolussi, Andrea; Schütz, Georg; Furtmüller, Paul G; Obinger, Christian

    2014-11-07

    The most striking feature of mammalian peroxidases, including myeloperoxidase and lactoperoxidase (LPO) is the existence of covalent bonds between the prosthetic group and the protein, which has a strong impact on their (electronic) structure and biophysical and chemical properties. Recently, a novel bacterial heme peroxidase with high structural and functional similarities to LPO was described. Being released from Escherichia coli, it contains mainly heme b, which can be autocatalytically modified and covalently bound to the protein by incubation with hydrogen peroxide. In the present study, we investigated the reactivity of these two forms in their ferric, compound I and compound II state in a multi-mixing stopped-flow study. Upon heme modification, the reactions between the ferric proteins with cyanide or H2O2 were accelerated. Moreover, apparent bimolecular rate constants of the reaction of compound I with iodide, thiocyanate, bromide, and tyrosine increased significantly and became similar to LPO. Kinetic data are discussed and compared with known structure-function relationships of the mammalian peroxidases LPO and myeloperoxidase.

  17. In-line near infrared spectroscopy during freeze-drying as a tool to measure efficiency of hydrogen bond formation between protein and sugar, predictive of protein storage stability

    OpenAIRE

    Mensink, Maarten A.; Van Bockstal, Pieter-Jan; Pieters, S; De Meyer, Laurens; Frijlink, Henderik W.; van der Voort Maarschalk, Kees; Hinrichs, Wouter L.J.; De Beer, Thomas

    2015-01-01

    Sugars are often used as stabilizers of protein formulations during freeze-drying. However, not all sugars are equally suitable for this purpose. Using in-line near-infrared spectroscopy during freeze-drying, it is shown here that hydrogen bond formation during freeze-drying, under secondary drying conditions in particular, can be related to the preservation of the functionality and structure of proteins during storage. The disaccharide trehalose was best capable of forming hydrogen bonds wit...

  18. Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure, phosphate activation and montmorillonite composition on phosphodiester bond formation

    Science.gov (United States)

    Ferris, James P.; KAMALUDDIN; Ertem, Gozen

    1990-01-01

    The 2(prime)-d-5(prime)-GMP and 2(prime)-d-5(prime)-AMP bind 2 times more strongly to montmorillonite 22A than do 2(prime)-d-5(prime)-CMP and 5(prime)-TMP. The dinucleotide d(pG)2 forms in 9.2 percent yield and the cyclic dinucleotide c(dpG)2 in 5.4 percent yield in the reaction of 2(prime)-d-5(prime)-GMP with EDAC in the presence of montmorillonite 22A. The yield of dimers which contain the phosphodiester bond decreases as the reaction medium is changed from 0.2 M NaCl to a mixture of 0.2 M NaCl and 0.075 M MgCl2. A low yield of d(pA)2 was observed in the condensation reaction of 5(prime)-ImdpA on montmorillonite 22A. The yield of d(pA)2 obtained when EDAC is used as the condensing agent increases with increasing iron content of the Na(+)-montmorillonite used as catalyst. Evidence is presented which shows that the acidity of the Na(+)-montmorillonite is a necessary but not sufficient factor for the montmorillonite catalysis of phosphodiester bond formation.

  19. Roles of Intramolecular and Intermolecular Hydrogen Bonding in a Three-Water-Assisted Mechanism of Succinimide Formation from Aspartic Acid Residues

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi

    2014-08-01

    Full Text Available Aspartic acid (Asp residues in peptides and proteins are prone to isomerization to the β-form and racemization via a five-membered succinimide intermediate. These nonenzymatic reactions have relevance to aging and age-related diseases. In this paper, we report a three water molecule-assisted, six-step mechanism for the formation of succinimide from Asp residues found by density functional theory calculations. The first two steps constitute a stepwise iminolization of the C-terminal amide group. This iminolization involves a quintuple proton transfer along intramolecular and intermolecular hydrogen bonds formed by the C-terminal amide group, the side-chain carboxyl group, and the three water molecules. After a conformational change (which breaks the intramolecular hydrogen bond involving the iminol nitrogen and a reorganization of water molecules, the iminol nitrogen nucleophilically attacks the carboxyl carbon of the Asp side chain to form a five-membered ring. This cyclization is accompanied by a triple proton transfer involving two water molecules, so that a gem-diol tetrahedral intermediate is formed. The last step is dehydration of the gem-diol group catalyzed by one water molecule, and this is the rate-determining step. The calculated overall activation barrier (26.7 kcal mol−1 agrees well with an experimental activation energy.

  20. Formation of intersubunit disulfide bonds and properties of the single histidine and cysteine residues in each subunit relative to the decameric structure of cyanase.

    Science.gov (United States)

    Anderson, P M; Korte, J J; Holcomb, T A; Cho, Y G; Son, C M; Sung, Y C

    1994-05-27

    Reaction of the single cysteine residue in each subunit of cyanase with certain SH reagents gives an active decameric derivative that dissociates reversibly to an inactive dimer derivative (Anderson, P. M., Johnson, W. V., Korte, J. J., Xiong, X., Sung, Y.-c., and Fuchs, J. A. (1988) J. Biol. Chem. 263, 5674-5680). Reaction of mixed disulfide dimer derivatives of cyanase with dithiothreitol at 0 degree C results in formation of a disulfide bond between the subunits in the dimer. The disulfide dimer was inactive and did not associate to a decamer; the intersubunit disulfide bond could not be formed when the dimers were associated as a decamer. The two SH groups apparently are in close proximity to each other in the dissociated dimer but not when the dimer is associated to a decamer. Substitution of glycine for the cysteine residue or of tyrosine, asparagine, glycine, valine, or leucine for the single histidine residue in each subunit gave mutant enzymes that were active. However, H113N, H113Y, and C83G were unstable at low temperature and/or ionic strength, dissociating reversibly to an inactive dimer. Efficient reassociation required the presence of bicarbonate or cyanate analog. The results are consistent with a proposed single site per subunit model explaining apparent half-site binding of substrates and the requirement of decameric structure for activity.

  1. Hydrogen Bonding-Mediated Microphase Separation during the Formation of Mesoporous Novolac-Type Phenolic Resin Templated by the Triblock Copolymer, PEO-b-PPO-b-PEO

    Directory of Open Access Journals (Sweden)

    Wei-Cheng Chu

    2013-11-01

    Full Text Available After blending the triblock copolymer, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide (PEO-b-PPO-b-PEO with novolac-type phenolic resin, Fourier transform infrared spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen bond acceptors for the OH groups of phenolic resin than were the ether groups of the PPO block. Thermal curing with hexamethylenetetramine as the curing agent resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. Mild pyrolysis conditions led to the removal of the PEO-b-PPO-b-PEO triblock copolymer and formation of mesoporous phenolic resin. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-centered-cubic spherical and disorder micelles. The regular mesoporous novolac-type phenolic resin was formed only at a phenolic content of 40–60 wt %, the result of an intriguing balance of hydrogen bonding interactions among the phenolic resin and the PEO and PPO segments of the triblock copolymer.

  2. Synthesis of Bioactive 2-(Arylaminothiazolo[5,4-f]-quinazolin-9-ones via the Hügershoff Reaction or Cu- Catalyzed Intramolecular C-S Bond Formation

    Directory of Open Access Journals (Sweden)

    Damien Hédou

    2016-06-01

    Full Text Available A library of thirty eight novel thiazolo[5,4-f]quinazolin-9(8H-one derivatives (series 8, 10, 14 and 17 was prepared via the Hügershoff reaction and a Cu catalyzed intramolecular C-S bond formation, helped by microwave-assisted technology when required. The efficient multistep synthesis of the key 6-amino-3-cyclopropylquinazolin-4(3H-one (3 has been reinvestigated and performed on a multigram scale from the starting 5-nitroanthranilic acid. The inhibitory potency of the final products was evaluated against five kinases involved in Alzheimer’s disease and showed that some molecules of the 17 series described in this paper are particularly promising for the development of novel multi-target inhibitors of kinases.

  3. Efficient export of human growth hormone, interferon α2b and antibody fragments to the periplasm by the Escherichia coli Tat pathway in the absence of prior disulfide bond formation.

    Science.gov (United States)

    Alanen, Heli I; Walker, Kelly L; Lourdes Velez Suberbie, M; Matos, Cristina F R O; Bönisch, Sarah; Freedman, Robert B; Keshavarz-Moore, Eli; Ruddock, Lloyd W; Robinson, Colin

    2015-03-01

    Numerous therapeutic proteins are expressed in Escherichia coli and targeted to the periplasm in order to facilitate purification and enable disulfide bond formation. Export is normally achieved by the Sec pathway, which transports proteins through the plasma membrane in a reduced, unfolded state. The Tat pathway is a promising alternative means of export, because it preferentially exports correctly folded proteins; however, the reducing cytoplasm of standard strains has been predicted to preclude export by Tat of proteins that contain disulfide bonds in the native state because, in the reduced state, they are sensed as misfolded and rejected. Here, we have tested a series of disulfide-bond containing biopharmaceuticals for export by the Tat pathway in CyDisCo strains that do enable disulfide bond formation in the cytoplasm. We show that interferon α2b, human growth hormone (hGH) and two antibody fragments are exported with high efficiency; surprisingly, however, they are efficiently exported even in the absence of cytoplasmic disulfide formation. The exported proteins acquire disulfide bonds in the periplasm, indicating that the normal disulfide oxidation machinery is able to act on the proteins. Tat-dependent export of hGH proceeds even when the disulfide bonds are removed by substitution of the Cys residues involved, suggesting that these substrates adopt tertiary structures that are accepted as fully-folded by the Tat machinery.

  4. Mutational analysis of bacteriophage T4 RNA ligase 1. Different functional groups are required for the nucleotidyl transfer and phosphodiester bond formation steps of the ligation reaction.

    Science.gov (United States)

    Wang, Li Kai; Ho, C Kiong; Pei, Yi; Shuman, Stewart

    2003-08-08

    T4 RNA ligase 1 (Rnl1) exemplifies an ATP-dependent RNA ligase family that includes fungal tRNA ligase (Trl1) and a putative baculovirus RNA ligase. Rnl1 acts via a covalent enzyme-AMP intermediate generated by attack of Lys-99 N zeta on the alpha phosphorus of ATP. Mutation of Lys-99 abolishes ligase activity. Here we tested the effects of alanine mutations at 19 conserved positions in Rnl1 and thereby identified 9 new residues essential for ligase activity: Arg-54, Lys-75, Phe-77, Gly-102, Lys-119, Glu-227, Gly-228, Lys-240, and Lys-242. Seven of the essential residues are located within counterparts of conserved nucleotidyltransferase motifs I (99KEDG102), Ia (118SK119), IV (227EGYVA231), and V (238HFKIK242) that comprise the active sites of DNA ligases, RNA capping enzymes, and T4 RNA ligase 2. Three other essential residues, Arg-54, Lys-75 and Phe-77, are located upstream of the AMP attachment site within a conserved domain unique to the Rnl1-like ligase family. We infer a shared evolutionary history and active site architecture in Rnl1 (a tRNA repair enzyme) and Trl1 (a tRNA splicing enzyme). We determined structure-activity relationships via conservative substitutions and examined mutational effects on the isolated steps of Rnl1 adenylylation (step 1) and phosphodiester bond formation (step 3). Lys-75, Lys-240, and Lys-242 were found to be essential for step 1 and overall ligation of 5'-phosphorylated RNA but not for phosphodiester bond formation. These results suggest that the composition of the Rnl1 active site is different during steps 1 and 3. Mutations at Arg-54 and Lys-119 abolished the overall RNA ligation reaction without affecting steps 1 and 3. Arg-54 and Lys-119 are thereby implicated as specific catalysts of the RNA adenylation reaction (step 2) of the ligation pathway.

  5. Dynamic analysis of C/C composite finger seal

    Institute of Scientific and Technical Information of China (English)

    Chen Guoding; Wang Li’na; Yu Qiangpeng; Su Hua

    2014-01-01

    A seal device as an important component of aeroengines has decisive influence on per-formance, reliability, and working life of aeroengines. With the development of aeroengines, demands on the performance characteristics of seal devices are made strictly. Finger seal as a novel kind of sealing device, recently attracts more and more attentions in academic circles and engineer-ing fields at home and abroad. Research on finger seals has been extensively developed, especially on leakage and wear performances under dynamic conditions. However, it is a pity that the work on finger seals has been limited with a single approach that is improving the performance by structural optimization;in addition, the technology of dynamic analysis on finger seals is weak. Aiming at the problems mentioned above, a distributed mass equivalent dynamic model of finger seals considering the coupling effect of overlaid laminates is established in the present paper, the dynamic perfor-mance of 2.5 dimension C/C composite finger seal is analyzed with the model, and then the effects of fiber bundle density and fiber bundle preparation direction on finger seal’s dynamic performance are discussed, as well as compared with those of Co-based alloy finger seal. The current work is about dynamic analysis of finger seals and application of C/C composite in this paper may have much academic significance and many engineering values for improving research level of finger seal dynamics and exploring feasibility of C/C composite being used for finger seals.

  6. [Study on spectral emissivity of C/C composites].

    Science.gov (United States)

    Zhu, Bo; Cao, Wei-Wei; Jing, Min; Dong, Xing-Guang; Wang, Cheng-Guo

    2009-11-01

    Different types of C/C composites were prepared by conventional molding, and the changes in normal spectral emissivity of samples were tested. The testing results show that spectral emissivity of C/C composite reinforced by short cut carbon fibers is generally higher than the sample reinforced by carbon cloth in the entire 2500-13000nm wavelength region. The structure of short cut carbon fibers is relatively loose and the number of material particles is less than other samples in unit volume, which increases the penetration depth of electromagnetic waves. This is the reason for higher normal spectral emissivity and better heat radiation property. Meanwhile, the test results of normal spectral emissivity for fiber perform and C/C composite samples show that the spectral emissivity of resin carbon is better than fiber carbon because of the difference in microstructure for the two kinds of carbon materials. Laser Raman spectroscopy was employed to analyze the microstructures of different carbon materials, and the results show that because sp3 and sp2 hybrid states of carbon atoms in resin carbon produced more vibration modes, the resin carbon also has higher normal spectral emissivity and better characteristics of heat radiation.

  7. Microstructure of C/C Composites with Different Matrix Carbon

    Directory of Open Access Journals (Sweden)

    LIU Hao

    2016-07-01

    Full Text Available The microstructure of carbon/carbon(C/C composites with different matrix carbon was studied by polarized light microscopy (PLM, scanning electron microscopy (SEM, transmission electron microscopy (TEM and XRD techniques respectively. PLM results indicate that the different matrix carbon exhibits different optical reactivity, and the average optical reactivity is gradually enhanced from normal pitch carbon, smooth laminar of pyrocarbon, rough laminar of pyrocarbon to mesophase pitch carbon; SEM results show that the normal pitch carbon is mainly of grapy structure, the pyrocarbon exhibits like-crinkle lamellar structure, while the mesophase pitch carbon exhibits lamellar banded structure with different shapes. Under HRTEM, the lattice fringes of the mesophase pitch carbon are arranged regularly, is a long range ordered crystal structure, and the preferred orientation is high. The degree of the graphite and the interlayer spacing of the material B (mesophase pitch-based C/C composites are better than that of the material D (pyrocarbon-based C/C composites.

  8. Dynamic analysis of C/C composite finger seal

    Directory of Open Access Journals (Sweden)

    Chen Guoding

    2014-06-01

    Full Text Available A seal device as an important component of aeroengines has decisive influence on performance, reliability, and working life of aeroengines. With the development of aeroengines, demands on the performance characteristics of seal devices are made strictly. Finger seal as a novel kind of sealing device, recently attracts more and more attentions in academic circles and engineering fields at home and abroad. Research on finger seals has been extensively developed, especially on leakage and wear performances under dynamic conditions. However, it is a pity that the work on finger seals has been limited with a single approach that is improving the performance by structural optimization; in addition, the technology of dynamic analysis on finger seals is weak. Aiming at the problems mentioned above, a distributed mass equivalent dynamic model of finger seals considering the coupling effect of overlaid laminates is established in the present paper, the dynamic performance of 2.5 dimension C/C composite finger seal is analyzed with the model, and then the effects of fiber bundle density and fiber bundle preparation direction on finger seal’s dynamic performance are discussed, as well as compared with those of Co-based alloy finger seal. The current work is about dynamic analysis of finger seals and application of C/C composite in this paper may have much academic significance and many engineering values for improving research level of finger seal dynamics and exploring feasibility of C/C composite being used for finger seals.

  9. Toward Design Principles for Diffusionless Transformations: The Frustrated Formation of Co–Co Bonds in a Low-Temperature Polymorph of GdCoSi 2

    Energy Technology Data Exchange (ETDEWEB)

    Vinokur, Anastasiya I.; Fredrickson, Daniel C.

    2016-06-20

    Diffusionless (or displacive) phase transitions allow inorganic materials to show exquisite responsiveness to external stimuli, as is illustrated vividly by the superelasticity, shape memory, and magnetocaloric effects exhibited by martensitic materials. In this Article, we present a new diffusionless transition in the compound GdCoSi2, whose origin in frustrated bonding points toward generalizable design principles for these transformations. We first describe the synthesis of GdCoSi2 and the determination of its structure using single crystal X-ray diffraction. While previous studies based on powder X-ray diffraction assigned this compound to the simple CeNi1–xSi2 structure type (space group Cmcm), our structure solution reveals a superstructure variant (space group Pbcm) in which the Co sublattice is distorted to create zigzag chains of Co atoms. DFT-calibrated Hückel calculations, coupled with a reversed approximation Molecular Orbital (raMO) analysis, trace this superstructure to the use of Co–Co isolobal bonds to complete filled 18 electron configurations on the Co atoms, in accordance with the 18–n rule. The formation of these Co–Co bonds is partially impeded, however, by a small degree of electron transfer from Si-based electronic states to those with Co–Co σ* character. The incomplete success of Co–Co bond creation suggests that these interactions are relatively weak, opening the possibility of them being overcome by thermal energy at elevated temperatures. In fact, high-temperature powder and single crystal X-ray diffraction data, as well as differential scanning calorimetry, indicate that a reversible Pbcm to Cmcm transition occurs at about 380 K. This transition is diffusionless, and the available data point toward it being first-order. We expect that similar cases of frustrated interactions could be staged in other rare earth–transition metal–main group phases, providing a potentially rich

  10. Synthesis of the proteinase inhibitor LEKTI domain 6 by the fragment condensation method and regioselective disulfide bond formation.

    Science.gov (United States)

    Vasileiou, Zoe; Barlos, Kostas K; Gatos, Dimitrios; Adermann, Knut; Deraison, Celine; Barlos, Kleomenis

    2010-01-01

    Proteinase inhibitors are of high pharmaceutical interest and are drug candidates for a variety of indications. Specific kallikrein inhibitors are important for their antitumor activity and their potential application to the treatment of skin diseases. In this study we describe the synthesis of domain 6 of the kallikrein inhibitor Lympho-Epithilial Kazal-Type Inhibitor (LEKTI) by the fragment condensation method and site-directed cystine bridge formation. To obtain the linear LEKTI precursor, the condensation was best performed in solution, coupling the protected fragment 1-22 to 23-68. This method yielded LEKTI domain 6 of high purity and equipotent to the recombinantly produced peptide.

  11. Hydrogen bond and halogen bond inside the carbon nanotube

    Science.gov (United States)

    Wang, Weizhou; Wang, Donglai; Zhang, Yu; Ji, Baoming; Tian, Anmin

    2011-02-01

    The hydrogen bond and halogen bond inside the open-ended single-walled carbon nanotubes have been investigated theoretically employing the newly developed density functional M06 with the suitable basis set and the natural bond orbital analysis. Comparing with the hydrogen or halogen bond in the gas phase, we find that the strength of the hydrogen or halogen bond inside the carbon nanotube will become weaker if there is a larger intramolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom donor to the antibonding orbital of the X-H or X-Hal bond involved in the formation of the hydrogen or halogen bond and will become stronger if there is a larger intermolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom acceptor to the antibonding orbital of the X-H or X-Hal bond. According to the analysis of the molecular electrostatic potential of the carbon nanotube, the driving force for the electron-density transfer is found to be the negative electric field formed in the carbon nanotube inner phase. Our results also show that the X-H bond involved in the formation of the hydrogen bond and the X-Hal bond involved in the formation of the halogen bond are all elongated when encapsulating the hydrogen bond and halogen bond within the carbon nanotube, so the carbon nanotube confinement may change the blue-shifting hydrogen bond and the blue-shifting halogen bond into the red-shifting hydrogen bond and the red-shifting halogen bond. The possibility to replace the all electron nanotube-confined calculation by the simple polarizable continuum model is also evaluated.

  12. Active Brazing of C/C Composite to Copper by AgCuTi Filler Metal

    Science.gov (United States)

    Zhang, Kexiang; Xia, Lihong; Zhang, Fuqin; He, Lianlong

    2016-05-01

    Brazing between the carbon-fiber-reinforced carbon composite (C/C composite) and copper has gained increasing interest because of its important application in thermal management systems in nuclear fusion reactors and in the aerospace industry. In order to examine the "interfacial shape effect" on the mechanical properties of the joint, straight and conical interfacial configurations were designed and machined on the surface of C/C composites before joining to copper using an Ag-68.8Cu-4.5Ti (wt pct) alloy. The microstructure and interfacial microchemistry of C/C composite/AgCuTi/Cu brazed joints were comprehensively investigated by using high-resolution transmission electron microscopy. The results indicate that the joint region of both straight and conical joints can be described as a bilayer. Reaction products of Cu3Ti3O and γ-TiO were formed near the copper side in a conical interface joint, while no reaction products were found in the straight case. The effect of Ag on the interfacial reaction was discussed, and the formation mechanism of the joints during brazing was proposed. On the basis of the detailed microstructure presented, the mechanical performance of the brazed joints was discussed in terms of reaction and morphology across the joint.

  13. Morphological effects of single-layer graphene oxide in the formation of covalently bonded polypyrrole composites using intermediate diisocyanate chemistry

    Science.gov (United States)

    Whitby, Raymond L. D.; Korobeinyk, Alina; Mikhalovsky, Sergey V.; Fukuda, Takahiro; Maekawa, Toru

    2011-10-01

    Single-layer graphene oxide (SLGO) possesses carboxylic and hydroxyl groups suitable for reactions with aliphatic or aromatic diisocyanate molecules. TEM analysis reveals that aliphatic diisocyanate molecules caused SLGO to scroll into star-like formations, whereas aromatic diisocyanate molecules retained SGLO in a flat-sheet morphology. TGA confirms the stabilisation of the formed urea and urethane groups on SLGO, but the onset of sheet pyrolysis occurs at a lower temperature due to isocyanate reactions with anhydride and epoxide groups embedded in the sheet. Pendant isocyanate groups act as bridging units to facilitate the attachment of pyrrole molecules, which are then used as anchor sites for the covalent polymerisation of pyrrole to polypyrrole (PPy). The use of FeCl3 as the polymerisation catalyst generated both covalent and free PPy, but also iron hydroxide nanoparticles were observed decorating the SLGO surface. When using ammonium persulfate as a catalyst and dodecylbenzenesulfonate as a dopant, free PPy could be removed under treatment with solvents to leave a purely covalent system. Discrete regions of SLGO were observed decorated with nanoparticles of PPy along the edge or across the surface of individual sheets. It was found that the flexibility of the SLGO sheet and the type of diisocyanate used directly affected the electrical resistance of the final composite.

  14. Interface formation of two- and three-dimensionally bonded materials in the case of GeTe-Sb2Te3 superlattices

    Science.gov (United States)

    Momand, Jamo; Wang, Ruining; Boschker, Jos E.; Verheijen, Marcel A.; Calarco, Raffaella; Kooi, Bart J.

    2015-11-01

    GeTe-Sb2Te3 superlattices are nanostructured phase-change materials which are under intense investigation for non-volatile memory applications. They show superior properties compared to their bulk counterparts and significant efforts exist to explain the atomistic nature of their functionality. The present work sheds new light on the interface formation between GeTe and Sb2Te3, contradicting previously proposed models in the literature. For this purpose [GeTe(1 nm)-Sb2Te3(3 nm)]15 superlattices were grown on passivated Si(111) at 230 °C using molecular beam epitaxy and they have been characterized particularly with cross-sectional HAADF scanning transmission electron microscopy. Contrary to the previously proposed models, it is found that the ground state of the film actually consists of van der Waals bonded layers (i.e. a van der Waals heterostructure) of Sb2Te3 and rhombohedral GeSbTe. Moreover, it is shown by annealing the film at 400 °C, which reconfigures the superlattice into bulk rhombohedral GeSbTe, that this van der Waals layer is thermodynamically favored. These results are explained in terms of the bonding dimensionality of GeTe and Sb2Te3 and the strong tendency of these materials to intermix. The findings debate the previously proposed switching mechanisms of superlattice phase-change materials and give new insights in their possible memory application.GeTe-Sb2Te3 superlattices are nanostructured phase-change materials which are under intense investigation for non-volatile memory applications. They show superior properties compared to their bulk counterparts and significant efforts exist to explain the atomistic nature of their functionality. The present work sheds new light on the interface formation between GeTe and Sb2Te3, contradicting previously proposed models in the literature. For this purpose [GeTe(1 nm)-Sb2Te3(3 nm)]15 superlattices were grown on passivated Si(111) at 230 °C using molecular beam epitaxy and they have been characterized

  15. Hydrogen Implantation in Silicates: The role of solar wind in OH bond formation on the lunar surface

    Science.gov (United States)

    Schaible, Micah J; Baragiola, Raul

    2014-06-01

    Airless bodies in space such as the Moon, asteroids and interplanetary dust particles are subject to bombardment from energetic electrons and ions, ultraviolet photons, micrometeorites and cosmic rays. These bombarding particles modify optical, chemical and physical characteristics of the ices and minerals that make up these bodies in a process known as space weathering. In particular, solar wind protons implanted in silicate materials can participate in hydroxylation reactions with the oxygen to form OH. This mechanism has been suggested to explain a reported 3-14% absorption signal identified as OH on the surface of lunar soil grains and present in decreasing magnitude from polar to equatorial latitudes. With the goal of determining a precise OH formation rate due to H+ implantation in silicates, a series of experiments were carried out on terrestrial minerals as analogs to lunar and interstellar material.Experiments were carried out under UHV pressures (OH in thermally grown silicon oxide and San Carlos olivine, before and after irradiated with 1 - 5 keV H+ ions. The increase in Si-OH content due to irradiation was determined by subtracting the unirradiated spectra from the irradiated spectra. The implanted protons induced OH stretch absorptions in the mid-infrared peaked at 3673 cm-1 for SiO2 and 3570 cm-1 for olivine. The initial yield (OH formed per incident ion) was ~90% and the OH absorption band was found to saturate at implantation fluences of ~2x1017 H/cm2. Irradiation also modified the Si-O stretch band at ~1090 cm-1 (9.2 μm) causing an exponential decrease in the peak height with increasing fluence and the appearance of a silanol structure peaking at ~1030 cm-1. These measurements allow constraints to be placed on stellar wind contribution to observational and theoretical models of water on the lunar surface and on interstellar dust grains.

  16. Surface chemistry in the process of coating mesoporous SiO2 onto carbon nanotubes driven by the formation of Si-O-C bonds.

    Science.gov (United States)

    Paula, Amauri J; Stéfani, Diego; Souza Filho, Antonio G; Kim, Yoong Ahm; Endo, Morinobu; Alves, Oswaldo L

    2011-03-07

    The deposition of mesoporous silica (SiO(2)) on carbon nanotubes (CNTs) has opened up a wide range of assembling possibilities by exploiting the sidewall of CNTs and organosilane chemistry. The resulting systems may be suitable for applications in catalysis, energy conversion, environmental chemistry, and nanomedicine. However, to promote the condensation of silicon monomers on the nanotube without producing segregated particles, (OR)(4-x)SiO(x)(x-) units must undergo nucleophilic substitution by groups localized on the CNT sidewall during the transesterification reaction. In order to achieve this preferential attachment, we have deposited silica on oxidized carbon nanotubes (single-walled and multiwalled) in a sol-gel process that also involved the use of a soft template (cetyltrimethylammonium bromide, CTAB). In contrast to the simple approach normally used to describe the attachment of inorganic compounds on CNTs, SiO(2) nucleation on the tube is a result of nucleophilic attack mainly by hydroxyl radicals, localized in a very complex surface chemical environment, where various oxygenated groups are covalently bonded to the sidewall and carboxylated carbonaceous fragments (CCFs) are adsorbed on the tubes. Si-O-C covalent bond formation in the SiO(2)-CNT hybrids was observed even after removal of the CCFs with sodium hydroxide. By adding CTAB, and increasing the temperature, time, and initial amount of the catalyst (NH(4)OH) in the synthesis, the SiO(2) coating morphology could be changed from one of nanoparticles to mesoporous shells. Concomitantly, pore ordering was achieved by increasing the amount of CTAB. Furthermore, preferential attachment on the sidewall results mostly in CNTs with uncapped ends, having sites (carboxylic acids) that can be used for further localized reactions.

  17. Progress in the Formation of Carbon-Hetero Bond Based on 2(5H)-Furanones%基于2(5H)-呋喃酮的碳-杂成键反应研究进展

    Institute of Scientific and Technical Information of China (English)

    谭越河; 李建晓; 洪文坤; 汪朝阳

    2011-01-01

    2(5H)-呋喃酮结构单元广泛存在于天然产物中,同时许多2(5H)-呋喃酮类化合物也是重要的有机合成中间体.因此,基于常见2(5H)-呋喃酮(1)的有机合成研究近年来引起了人们的关注.根据在有机合成反应中成键方式的不同,综述了在2(5H)-呋喃酮(1)环上形成C-O,C-N,C-S,C-P,C-Se,C-Si等碳-杂键的反应研究进展.%Recently, the organic synthesis based on 2(5H)-furanones (1) has attracted much attention owing to the unique carbon skeleton of 2(5H)-furanone which is widely present in a variety of natural products and their utility as valuable synthetic intermediates.Classified as different bond kinds, the progress in the formation reactions of carbon-oxygen bond, carbon-nitrogen bond, carbon-sulfur bond, carbon-phosphorus bond, carbon-selenium bond and carbon-silicon bond on 2(5H)-furanone ring is reviewed.

  18. In-line near infrared spectroscopy during freeze-drying as a tool to measure efficiency of hydrogen bond formation between protein and sugar, predictive of protein storage stability.

    Science.gov (United States)

    Mensink, Maarten A; Van Bockstal, Pieter-Jan; Pieters, Sigrid; De Meyer, Laurens; Frijlink, Henderik W; van der Voort Maarschalk, Kees; Hinrichs, Wouter L J; De Beer, Thomas

    2015-12-30

    Sugars are often used as stabilizers of protein formulations during freeze-drying. However, not all sugars are equally suitable for this purpose. Using in-line near-infrared spectroscopy during freeze-drying, it is shown here that hydrogen bond formation during freeze-drying, under secondary drying conditions in particular, can be related to the preservation of the functionality and structure of proteins during storage. The disaccharide trehalose was best capable of forming hydrogen bonds with the model protein, lactate dehydrogenase, thereby stabilizing it, followed by the molecularly flexible oligosaccharide inulin 4kDa. The molecularly rigid oligo- and polysaccharides dextran 5kDa and 70kDa, respectively, formed the least amount of hydrogen bonds and provided least stabilization of the protein. It is concluded that smaller and molecularly more flexible sugars are less affected by steric hindrance, allowing them to form more hydrogen bonds with the protein, thereby stabilizing it better.

  19. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  20. In-line near infrared spectroscopy during freeze-drying as a tool to measure efficiency of hydrogen bond formation between protein and sugar, predictive of protein storage stability

    NARCIS (Netherlands)

    Mensink, Maarten A; Van Bockstal, Pieter-Jan; Pieters, Sigrid; De Meyer, Laurens; Frijlink, Henderik W; van der Voort Maarschalk, Kees; Hinrichs, Wouter L J; De Beer, Thomas

    2015-01-01

    Sugars are often used as stabilizers of protein formulations during freeze-drying. However, not all sugars are equally suitable for this purpose. Using in-line near-infrared spectroscopy during freeze-drying, it is shown here that hydrogen bond formation during freeze-drying, under secondary drying

  1. Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC3.

    Science.gov (United States)

    Molpeceres, Germán; Rayón, Víctor M; Barrientos, Carmen; Largo, Antonio

    2016-04-14

    The most relevant species of plutonium tricarbide were characterized using theoretical methods. The global minimum is predicted to be a fan structure where the plutonium atom is bonded to a quasi-linear C3 unit. A rhombic isomer, shown to be a bicyclic species with transannular C-C bonding, lies about 39 kJ/mol above the fan isomer. A linear PuCCC isomer and a three-membered ring CPuC2 isomer were found to be higher in energy (150 and 195 kJ/mol, respectively, above the predicted global minimum). The possible processes for the formation of these species are discussed, and the IR spectra were predicted to help in possible experimental detection. The nature of the Pu-C interaction has been analyzed in terms of a topological analysis of the electronic density, showing that Pu-C bonding is essentially ionic with a certain degree of covalent character.

  2. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  3. Measurements of $\\psi(3686) \\to K^{-} \\Lambda \\bar{\\Xi}^{+} +c.c.$ and $\\psi(3686) \\to \\gamma K^{-} \\Lambda \\bar{\\Xi}^{+} +c.c$

    CERN Document Server

    Ablikim, M; Ai, X C; Albayrak, O; Albrecht, M; Ambrose, D J; Amoroso, A; An, F F; An, Q; Bai, J Z; Ferroli, R Baldini; Ban, Y; Bennett, D W; Bennett, J V; Bertani, M; Bettoni, D; Bian, J M; Bianchi, F; Boger, E; Bondarenko, O; Boyko, I; Briere, R A; Cai, H; Cai, X; Cakir, O; Calcaterra, A; Cao, G F; Cetin, S A; Chang, J F; Chelkov, G; Chen, G; Chen, H S; Chen, H Y; Chen, J C; Chen, M L; Chen, S J; Chen, X; Chen, X R; Chen, Y B; Cheng, H P; Chu, X K; Cibinetto, G; Cronin-Hennessy, D; Dai, H L; Dai, J P; Dbeyssi, A; Dedovich, D; Deng, Z Y; Denig, A; Denysenko, I; Destefanis, M; DeMori, F; Ding, Y; Dong, C; Dong, J; Dong, L Y; Dong, M Y; Du, S X; Duan, P F; Fan, J Z; Fang, J; Fang, S S; Fang, X; Fang, Y; Fava, L; Feldbauer, F; Felici, G; Feng, C Q; Fioravanti, E; Fritsch, M; Fu, C D; Gao, Q; Gao, X Y; Gao, Y; Gao, Z; Garzia, I; Geng, C; Goetzen, K; Gong, W X; Gradl, W; Greco, M; Gu, M H; Gu, Y T; Guan, Y H; Guo, A Q; Guo, L B; Guo, Y; Guo, Y P; Haddadi, Z; Hafner, A; Han, S; Han, Y L; Hao, X Q; Harris, F A; He, K L; He, Z Y; Held, T; Heng, Y K; Hou, Z L; Hu, C; Hu, H M; Hu, J F; Hu, T; Hu, Y; Huang, G M; Huang, G S; Huang, H P; Huang, J S; Huang, X T; Huang, Y; Hussain, T; Ji, Q; Ji, Q P; Ji, X B; Ji, X L; Jiang, L L; Jiang, L W; Jiang, X S; Jiao, J B; Jiao, Z; Jin, D P; Jin, S; Johansson, T; Julin, A; Kalantar-Nayestanaki, N; Kang, X L; Kang, X S; Kavatsyuk, M; Ke, B C; Kliemt, R; Kloss, B; Kolcu, O B; Kopf, B; Kornicer, M; Kühn, W; Kupsc, A; Lai, W; Lange, J S; Lara, M; Larin, P; Leng, C; Li, C H; Li, Cheng; Li, D M; Li, F; Li, G; Li, H B; Li, J C; Li, Jin; Li, K; Li, Lei; Li, P R; Li, T; Li, W D; Li, W G; Li, X L; Li, X M; Li, X N; Li, X Q; Li, Z B; Liang, H; Liang, Y F; Liang, Y T; Liao, G R; Lin, D X; Liu, B J; Liu, C X; Liu, F H; Liu, Fang; Liu, Feng; Liu, H B; Liu, H H; Liu, H M; Liu, J; Liu, J P; Liu, J Y; Liu, K; Liu, K Y; Liu, L D; Liu, P L; Liu, Q; Liu, S B; Liu, X; Liu, X X; Liu, Y B; Liu, Z A; Liu, Zhiqiang; Liu, Zhiqing; Loehner, H; Lou, X C; Lu, H J; Lu, J G; Lu, R Q; Lu, Y; Lu, Y P; Luo, C L; Luo, M X; Luo, T; Luo, X L; Lv, M; Lyu, X R; Ma, F C; Ma, H L; Ma, L L; Ma, Q M; Ma, S; Ma, T; Ma, X N; Ma, X Y; Maas, F E; Maggiora, M; Malik, Q A; Mao, Y J; Mao, Z P; Marcello, S; Messchendorp, J G; Min, J; Min, T J; Mitchell, R E; Mo, X H; Mo, Y J; Morales, C Morales; Moriya, K; Muchnoi, N Yu; Muramatsu, H; Nefedov, Y; Nerling, F; Nikolaev, I B; Ning, Z; Nisar, S; Niu, S L; Niu, X Y; Olsen, S L; Ouyang, Q; Pacetti, S; Patteri, P; Pelizaeus, M; Peng, H P; Peters, K; Pettersson, J; Ping, J L; Ping, R G; Poling, R; Pu, Y N; Qi, M; Qian, S; Qiao, C F; Qin, L Q; Qin, N; Qin, X S; Qin, Y; Qin, Z H; Qiu, J F; Rashid, K H; Redmer, C F; Ren, H L; Ripka, M; Rong, G; Ruan, X D; Santoro, V; Sarantsev, A; Savrié, M; Schoenning, K; Schumann, S; Shan, W; Shao, M; Shen, C P; Shen, P X; Shen, X Y; Sheng, H Y; Song, W M; Song, X Y; Sosio, S; Spataro, S; Sun, G X; Sun, J F; Sun, S S; Sun, Y J; Sun, Y Z; Sun, Z J; Sun, Z T; Tang, C J; Tang, X; Tapan, I; Thorndike, E H; Tiemens, M; Toth, D; Ullrich, M; Uman, I; Varner, G S; Wang, B; Wang, B L; Wang, D; Wang, D Y; Wang, K; Wang, L L; Wang, L S; Wang, M; Wang, P; Wang, P L; Wang, Q J; Wang, S G; Wang, W; Wang, X F; Wang, Y D; Wang, Y F; Wang, Y Q; Wang, Z; Wang, Z G; Wang, Z H; Wang, Z Y; Weber, T; Wei, D H; Wei, J B; Weidenkaff, P; Wen, S P; Wiedner, U; Wolke, M; Wu, L H; Wu, Z; Xia, L G; Xia, Y; Xiao, D; Xiao, Z J; Xie, Y G; Xiu, Q L; Xu, G F; Xu, L; Xu, Q J; Xu, Q N; Xu, X P; Yan, L; Yan, W B; Yan, W C; Yan, Y H; Yang, H X; Yang, L; Yang, Y; Yang, Y X; Ye, H; Ye, M; Ye, M H; Yin, J H; Yu, B X; Yu, C X; Yu, H W; Yu, J S; Yuan, C Z; Yuan, W L; Yuan, Y; Yuncu, A; Zafar, A A; Zallo, A; Zeng, Y; Zhang, B X; Zhang, B Y; Zhang, C; Zhang, C C; Zhang, D H; Zhang, H H; Zhang, H Y; Zhang, J J; Zhang, J L; Zhang, J Q; Zhang, J W; Zhang, J Y; Zhang, J Z; Zhang, K; Zhang, L; Zhang, S H; Zhang, X Y; Zhang, Y; Zhang, Y H; Zhang, Y T; Zhang, Z H; Zhang, Z P; Zhang, Z Y; Zhao, G; Zhao, J W; Zhao, J Y; Zhao, J Z; Zhao, Lei; Zhao, Ling; Zhao, M G; Zhao, Q; Zhao, Q W; Zhao, S J; Zhao, T C; Zhao, Y B; Zhao, Z G; Zhemchugov, A; Zheng, B; Zheng, J P; Zheng, W J; Zheng, Y H; Zhong, B; Zhou, L; Zhou, Li; Zhou, X; Zhou, X K; Zhou, X R; Zhou, X Y; Zhu, K; Zhu, K J; Zhu, S; Zhu, X L; Zhu, Y C; Zhu, Y S; Zhu, Z A; Zhuang, J; Zotti, L; Zou, B S; Zou, J H

    2015-01-01

    Using a sample of $1.06\\times10^8\\ \\psip$ events produced in $e^+e^-$ collisions at $\\sqrt{s}$ = 3.686 GeV and collected with the BESIII detector at the BEPCII collider, we present studies of the decays $\\klx+c.c.$ and $\\gklx+c.c.$. We observe two hyperons, $\\Xi(1690)^-$ and $\\Xi(1820)^-$, in the $K^-\\Lambda$ invariant mass distribution in the decay $\\klx+c.c.$ with significances of $4.9 \\sigma$ and $6.2 \\sigma$, respectively. The branching fractions of $\\klx+c.c.$, $\\ksx+c.c.$, $\\psip\\to\\gamma \\chi_{cJ}\\to \\gamma K^- \\Lambda \\bar{\\Xi}^+ +c.c.$ $(J=0,\\ 1,\\ 2)$, and $\\psip\\to \\Xi(1690/1820)^{-} \\bar{\\Xi}^++c.c$ with subsequent decay $\\Xi(1690/1820)^-\\to K^-\\Lambda$ are measured for the first time.

  4. Tribological properties of C/C-SiC composites for brake discs

    Science.gov (United States)

    Jang, G. H.; Cho, K. H.; Park, S. B.; Lee, W. G.; Hong, U. S.; Jang, H.

    2010-02-01

    This study examines the friction and wear of ceramic matrix composites designed for use in automotive brake discs. The composites are produced by reinforcing a SiC matrix with carbon fibers using a liquid silicon infiltration method. C/C-SiC composites with two different compositions are fabricated to examine the compositional effect on the tribological properties. The tribological properties are evaluated using a scale dynamometer with a low-steel type friction material. The results show that the coefficient of friction is determined by the composition of the composite, which affects the propensity of friction film formation on the disc surface. A stable friction film on the disc surface also improves the wear resistance by diminishing the abrasive action of the disc. On the other hand, the friction film formation on the disc is affected by the applied pressure, and stable films are obtained at high pressures. This trend is prominent with discs with high Si content. However, both C/C/-SiC composites show superior performance in terms of the friction force oscillation, which is closely related to brake-induced vibration.

  5. Calorimetric and computational study of thiacyclohexane 1-oxide and thiacyclohexane 1,1-dioxide (thiane sulfoxide and thiane sulfone). Enthalpies of formation and the energy of the S=O bond.

    Science.gov (United States)

    Roux, María Victoria; Temprado, Manuel; Jiménez, Pilar; Dávalos, Juan Zenón; Notario, Rafael; Guzmán-Mejía, Ramón; Juaristi, Eusebio

    2003-03-01

    A rotating-bomb combustion calorimeter specifically designed for the study of sulfur-containing compounds [J. Chem. Thermodyn. 1999, 31, 635] has been used for the determination of the enthalpy of formation of thiane sulfone, 4, Delta(f)H(o) m(g) = -394.8 +/- 1.5 kJ x mol(-1). This value stands in stark contrast with the enthalpy of formation reported for thiane itself, Delta(f)H(o) m(g) = -63.5 +/- 1.0 kJ x mol(-1), and gives evidence of the increased electronegativity of the sulfur atom in the sulfonyl group, which leads to significantly stronger C-SO2 bonds. Given the known enthalpy of formation of atomic oxygen in the gas phase, Delta(f)H(o) m(O,g) = +249.18 kJ x mol(-1), and the reported bond dissociation energy for the S=O bond in alkyl sulfones, BDE(S=O) = +470.0 kJ x mol(-1), it was possible to estimate the enthalpy of formation of thiane sulfoxide, 5, a hygroscopic compound not easy to use in experimental calorimetric measurements, Delta(f)H(o) m(5) = -174.0 kJ x mol(-1). The experimental enthalpy of formation of both 4 and 5 were closely reproduced by theoretical calculations at the G2(MP2)+ level, Delta(f)H(o) m(4) = -395.0 kJ x mol(-1) and Delta(f)H(o) m(5) = -178.0 kJ x mol(-1). Finally, calculated G2(MP2)+ values for the bond dissociation energy of the S=O bond in cyclic sulfoxide 5 and sulfone 4 are +363.7 and +466.2 kJ x mol(-1), respectively.

  6. Hydrogen atom abstraction reactions from tertiary amines by benzyloxyl and cumyloxyl radicals: influence of structure on the rate-determining formation of a hydrogen-bonded prereaction complex.

    Science.gov (United States)

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

    2011-08-05

    A time-resolved kinetic study on the hydrogen atom abstraction reactions from a series of tertiary amines by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out. With the sterically hindered triisobutylamine, comparable hydrogen atom abstraction rate constants (k(H)) were measured for the two radicals (k(H)(BnO(•))/k(H)(CumO(•)) = 2.8), and the reactions were described as direct hydrogen atom abstractions. With the other amines, increases in k(H)(BnO(•))/k(H)(CumO(•)) ratios of 13 to 2027 times were observed. k(H) approaches the diffusion limit in the reactions between BnO(•) and unhindered cyclic and bicyiclic amines, whereas a decrease in reactivity is observed with acyclic amines and with the hindered cyclic amine 1,2,2,6,6-pentamethylpiperidine. These results provide additional support to our hypothesis that the reaction proceeds through the rate-determining formation of a C-H/N hydrogen-bonded prereaction complex between the benzyloxyl α-C-H and the nitrogen lone pair wherein hydrogen atom abstraction occurs, and demonstrate the important role of amine structure on the overall reaction mechanism. Additional mechanistic information in support of this picture is obtained from the study of the reactions of the amines with a deuterated benzyloxyl radical (PhCD(2)O(•), BnO(•)-d(2)) and the 3,5-di-tert-butylbenzyloxyl radical.

  7. The importance of oxygen-containing defects on carbon nanotubes for the detection of polar and non-polar vapours through hydrogen bond formation

    Energy Technology Data Exchange (ETDEWEB)

    Watts, Paul C P; Mureau, Natacha; Tang, Zhenni; Miyajima, Yoji; Carey, J David; Silva, S Ravi P [Nano-Electronics Centre, Advanced Technology Institute, University of Surrey, Guildford, Surrey GU2 7XH (United Kingdom)

    2007-05-02

    We report the electrical responses of water vapour and O{sub 2} adsorption onto macroscopic multi-walled carbon nanotube (MWCNT) ropes, and compare the results with mats of acid-treated MWCNTs on SiO{sub 2} substrates in order to investigate the importance of oxygen-containing defects on CNTs. In the outgassed state both carbon nanotube (CNT) materials exhibit rapid changes in electrical resistance when exposed to dry air, humid air or water vapour at standard temperature and pressure (STP). The measured electrical responses are highly reversible at STP when cycled between humid air, vacuum and dry air. We report a decrease in resistance for the CNT materials in dry air, attributed to O{sub 2} p-type doping of the CNTs, whereas there is an increase in resistance when exposed to a humid environment. This latter effect is attributed to the formation of hydrogen bonding from the polar water molecules with the oxygen-containing defects on the CNTs. Our observations indicate that the increase in electrical resistance upon water absorption affects a reduction of the electron-withdrawing power of the oxygen-containing defect groups, thus leading to a reduced hole carrier concentration in the p-type nanotubes.

  8. Phylogeny of the Vitamin K 2,3-Epoxide Reductase (VKOR) Family and Evolutionary Relationship to the Disulfide Bond Formation Protein B (DsbB) Family.

    Science.gov (United States)

    Bevans, Carville G; Krettler, Christoph; Reinhart, Christoph; Watzka, Matthias; Oldenburg, Johannes

    2015-07-29

    In humans and other vertebrate animals, vitamin K 2,3-epoxide reductase (VKOR) family enzymes are the gatekeepers between nutritionally acquired K vitamins and the vitamin K cycle responsible for posttranslational modifications that confer biological activity upon vitamin K-dependent proteins with crucial roles in hemostasis, bone development and homeostasis, hormonal carbohydrate regulation and fertility. We report a phylogenetic analysis of the VKOR family that identifies five major clades. Combined phylogenetic and site-specific conservation analyses point to clade-specific similarities and differences in structure and function. We discovered a single-site determinant uniquely identifying VKOR homologs belonging to human pathogenic, obligate intracellular prokaryotes and protists. Building on previous work by Sevier et al. (Protein Science 14:1630), we analyzed structural data from both VKOR and prokaryotic disulfide bond formation protein B (DsbB) families and hypothesize an ancient evolutionary relationship between the two families where one family arose from the other through a gene duplication/deletion event. This has resulted in circular permutation of primary sequence threading through the four-helical bundle protein folds of both families. This is the first report of circular permutation relating distant a-helical membrane protein sequences and folds. In conclusion, we suggest a chronology for the evolution of the five extant VKOR clades.

  9. Phylogeny of the Vitamin K 2,3-Epoxide Reductase (VKOR Family and Evolutionary Relationship to the Disulfide Bond Formation Protein B (DsbB Family

    Directory of Open Access Journals (Sweden)

    Carville G. Bevans

    2015-07-01

    Full Text Available In humans and other vertebrate animals, vitamin K 2,3-epoxide reductase (VKOR family enzymes are the gatekeepers between nutritionally acquired K vitamins and the vitamin K cycle responsible for posttranslational modifications that confer biological activity upon vitamin K-dependent proteins with crucial roles in hemostasis, bone development and homeostasis, hormonal carbohydrate regulation and fertility. We report a phylogenetic analysis of the VKOR family that identifies five major clades. Combined phylogenetic and site-specific conservation analyses point to clade-specific similarities and differences in structure and function. We discovered a single-site determinant uniquely identifying VKOR homologs belonging to human pathogenic, obligate intracellular prokaryotes and protists. Building on previous work by Sevier et al. (Protein Science 14:1630, we analyzed structural data from both VKOR and prokaryotic disulfide bond formation protein B (DsbB families and hypothesize an ancient evolutionary relationship between the two families where one family arose from the other through a gene duplication/deletion event. This has resulted in circular permutation of primary sequence threading through the four-helical bundle protein folds of both families. This is the first report of circular permutation relating distant a-helical membrane protein sequences and folds. In conclusion, we suggest a chronology for the evolution of the five extant VKOR clades.

  10. Formation of cationic [RP5Cl](+)-cages via insertion of [RPCl](+)-cations into a P-P bond of the P4 tetrahedron.

    Science.gov (United States)

    Holthausen, Michael H; Feldmann, Kai-Oliver; Schulz, Stephen; Hepp, Alexander; Weigand, Jan J

    2012-03-19

    Fluorobenzene solutions of RPCl(2) and a Lewis acid such as ECl(3) (E = Al, Ga) in a 1:1 ratio are used as reactive sources of chlorophosphenium cations [RPCl](+), which insert into P-P bonds of dissolved P(4). This general protocol represents a powerful strategy for the synthesis of new cationic chloro-substituted organophosphorus [RP(5)Cl](+)-cages as illustrated by the isolation of several monocations (21a-g(+)) in good to excellent yields. For singular reaction two possible reaction mechanisms are proposed on the basis of quantum chemical calculations. The intriguing NMR spectra and structures of the obtained cationic [RP(5)Cl](+)-cages are discussed. Furthermore, the reactions of dichlorophosphanes and the Lewis acid GaCl(3) in various stoichiometries are investigated to obtain a deeper understanding of the species involved in these reactions. The formation of intermediates such as RPCl(2)·GaCl(3) (14) adducts, dichlorophosphanylchlorophosphonium cations [RPCl(2)-RPCl](+) (16(+)) and [RPCl(2)-RPCl-GaCl(3)](+) (17(+)) in reaction mixtures of RPCl(2) and GaCl(3) in fluorobenzene strongly depends on the basicity of the dichlorophosphane RPCl(2) (R = tBu, Cy, iPr, Et, Me, Ph, C(6)F(5)) and the reaction stoichiometry.

  11. Formation of reversible disulfide bonds with the protein matrix of the endoplasmic reticulum correlates with the retention of unassembled Ig light chains.

    Science.gov (United States)

    Reddy, P; Sparvoli, A; Fagioli, C; Fassina, G; Sitia, R

    1996-01-01

    Exposed thiols act as intracellular retention elements for unassembled secretory molecules. Yet, some free Ig lambda light chains are secreted despite the presence of an unpaired cysteine (Cys214). This is due largely to the presence of a flanking acidic residue: substitution of Asp213 for Gly or Lys increases pre-Golgi retention and degradation of free lambda. Secretion is restored by exogenous reducing agents or by assembly with heavy chains. In the endoplasmic reticulum (ER), lambda chains form covalent complexes with many proteins through Cys214. These complexes are absent from the Golgi. They are more abundant in transfectants expressing the lambdaGly2I3 and lambdaLys213 mutants that are poorly secreted. Radioactive N-ethylmaleimide labels some monomeric lambda chains isolated from the ER, but not from the Golgi or from the medium, indicating that the Cys214 thiol is masked during ER-Golgi transport. Mass spectrometry reveals the presence of a free cysteine residue disulfide-linked to Cys214. We suggest that thiol-mediated retention involves the formation of reversible disulfide bonds with the protein matrix of the ER. The presence of an acidic residue next to the critical cysteine may allow the masking of the thiol and transport to the Golgi. Images PMID:8641273

  12. Formation of diphenylphosphanylbutadienyl complexes by insertion of two P-coordinated alkynylphosphanes into a PtbondC6F5 bond: detection of intermediate and reaction products.

    Science.gov (United States)

    Ara, Irene; Forniés, Juan; García, Ana; Gómez, Julio; Lalinde, Elena; Moreno, M Teresa

    2002-08-16

    The reactions between cis-[M(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (M=Pt, Pd; R=Ph, tBu, Tol 2, 3) or cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu)] (R=Ph 4, Tol 5) and cis-[Pt(C(6)F(5))(2)(thf)(2)] 1 have been investigated. Whereas [M](PPh(2)CtriplebondCtBu)(2) ([M]=cis-M(C(6)F(5))(2)) is inert towards 1, the analogous reactions starting from [M](PPh(2)CtriplebondCR)(2) or [Pt](PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu) (R=Ph, Tol) afford unusual binuclear species [Pt(C(6)F(5))(S)mu-[C(R')dbondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]M(C(6)F(5))(2)] (R=R'=Ph, Tol, M=Pt 6 a,c, M=Pd 7 a,c; M=Pt, R'=tBu, R=Ph 8, Tol 9) containing a bis(diphenylphosphanyl)butadienyl bridging ligand formed by an unprecedented sequential insertion reaction of two P-coordinated PPh(2)CtriplebondCR ligands into a PtbondC(6)F(5) bond. Although in solution the presence of coordinated solvent S (S=(thf)(x)(H(2)O)(y)) in 6, 7 is suggested by NMR spectroscopy, X-ray diffraction analyses of different crystals of the mixed complex [Pt(C(6)F(5))mu-[C(tBu)doublebondC(PPh(2))C(PPh(2))doublebondC(Tol)(C(6)F(5))]Pt(C(6)F(5))(2)] 9 unequivocally establish that in the solid state the steric crowding of the new diphenylbutadienyl ligand formed stabilizes an unusual coordinatively unsaturated T-shaped 3-coordinated platinum(II) center. Structure determinations of the mononuclear precursors cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (R=Ph, tBu, Tol) have been carried out to evaluate the factors affecting the insertion processes. The reactions of the platinum complexes 6 towards neutral ligands (L=CO, py, PPh(2)H, CNtBu) in a 1:1 molar ratio afford related diplatinum derivatives 10-13, whereas treatment with CNtBu (1:2 molar ratio) or 2,2'-bipy (1:1 molar ratio) results in the opening of the chelating ring to give cis,cis-[Pt(C(6)F(5))(L)(2)mu-[1-kappaC(1):2-kappaPP'-C(R)doublebondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]Pt(C(6)F(5))(2)] (14, 15). The unsaturated or solvento

  13. LAMMPS Framework for Directional Dynamic Bonding

    DEFF Research Database (Denmark)

    2012-01-01

    and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework.......We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled...... to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  14. Neural Regulation of Pair Bond Formation in a Monogamous Rodent Species%单配制啮齿动物Pair Bond形成的神经调节机制

    Institute of Scientific and Technical Information of China (English)

    Brandon J.Aragona; J.Thomas Curtis; 刘彦; 汪作新

    2004-01-01

    单配制啮齿动物社会结构的神经生物学原理可以通过实验室研究Social bonding而获得.在本文中,我们探讨了如何利用单配制的草原田鼠(Microtus ochrogaster)作为研究模型揭示pair bond形成的神经调控机制.我们进而探讨了单配制与多配制田鼠之间神经解剖学的差异以及神经化学物质的调节是怎样影响pair bond的.本篇综述还讨论了与pair bond形成有关的神经化学系统之间的相互影响以及pair bond形成过程中的两性差异.最后,我们预测了这一研究领域的未来研究方向以及研究social bonding的神经调控对人类健康的重要性.%The neurobiology of monogamous social organization can be studied by laboratory examination of social bonding. In this review, we discuss how the monogamous prairie vole (Microtus ochrogaster) has been used as a model system to provide tremendous insight into the neural regulation of pair bond formation. Neuroanatomical differences between monogamous and non-monogamous voles, as well as how neurochemical manipulations affect pair bond formation are reviewed. In addition, interactions among neurochemical systems that regulate pair bond formation and the extent of sexual dimorphism associated with pair bonding are discussed. Finally, we propose future directions for this line of research and explain why understanding the neural regulation of social bonding is important for human health.

  15. Rapid formation of Ni3Sn4 joints for die attachment of SiC-based high temperature power devices using ultrasound-induced transient liquid phase bonding process.

    Science.gov (United States)

    Li, Z L; Dong, H J; Song, X G; Zhao, H Y; Feng, J C; Liu, J H; Tian, H; Wang, S J

    2017-05-01

    High melting point Ni3Sn4 joints for the die attachment of SiC-based high temperature power devices was successfully achieved using an ultrasound-induced transient liquid phase (TLP) bonding process within a remarkably short bonding time of 8s. The formed intermetallic joints, which are completely composed of the refined equiaxial Ni3Sn4 grains with the average diameter of 2μm, perform the average shear strength of 26.7MPa. The sonochemical effects of ultrasonic waves dominate the mechanism and kinetics of the rapid formation of Ni3Sn4 joints.

  16. Mechanistic information on the reductive elimination from cationic trimethylplatinum(IV) complexes to form carbon-carbon bonds.

    Science.gov (United States)

    Procelewska, Joanna; Zahl, Achim; Liehr, Günter; van Eldik, Rudi; Smythe, Nicole A; Williams, B Scott; Goldberg, Karen I

    2005-10-31

    Cationic complexes of the type fac-[(L(2))Pt(IV)Me(3)(pyr-X)][OTf] (pyr-X = 4-substituted pyridines; L(2) = diphosphine, viz., dppe = bis(diphenylphosphino)ethane and dppbz = o-bis(diphenylphosphino)benzene; OTf = trifluoromethanesulfonate) undergo C-C reductive elimination reactions to form [L(2)Pt(II)Me(pyr-X)][OTf] and ethane. Detailed studies indicate that these reactions proceed by a two-step pathway, viz., initial reversible dissociation of the pyridine ligand from the cationic complex to generate a five-coordinate Pt(IV) intermediate, followed by irreversible concerted C-C bond formation. The reaction is inhibited by pyridine. The highly positive values for DeltaS()(obs) = +180 +/- 30 J K(-1) mol(-1), DeltaH(obs) = 160 +/- 10 kJ mol(-1), and DeltaV()(obs) = +16 +/- 1 cm(3) mol(-1) can be accounted for in terms of significant bond cleavage and/or partial reduction from Pt(IV) to Pt(II) in going from the ground to the transition state. These cationic complexes have provided the first opportunity to carry out detailed studies of C-C reductive elimination from cationic Pt(IV) complexes in a variety of solvents. The absence of a significant solvent effect for this reaction provides strong evidence that the C-C reductive coupling occurs from an unsaturated five-coordinate Pt(IV) intermediate rather than from a six-coordinate Pt(IV) solvento species.

  17. Formats

    Directory of Open Access Journals (Sweden)

    Gehmann, Ulrich

    2012-03-01

    Full Text Available In the following, a new conceptual framework for investigating nowadays’ “technical” phenomena shall be introduced, that of formats. The thesis is that processes of formatting account for our recent conditions of life, and will do so in the very next future. It are processes whose foundations have been laid in modernity and which will further unfold for the time being. These processes are embedded in the format of the value chain, a circumstance making them resilient to change. In addition, they are resilient in themselves since forming interconnected systems of reciprocal causal circuits.Which leads to an overall situation that our entire “Lebenswelt” became formatted to an extent we don’t fully realize, even influencing our very percep-tion of it.

  18. Bond Growth under Temperature Gradient.

    Directory of Open Access Journals (Sweden)

    P.K. Satyawali

    1999-12-01

    Full Text Available Grain and bond growth for dry snow are determined by the distribution of temperature andtemperature gradient in the snow matrix. From the standpoint of particle approach and based oncubic packing structure, a bond growth model has been developed for TG metamorphism. The paper.highlights the importance of bond formation and its effect on snow viscosity and finally on the rateof settlement. This is very important for developing a numerical snow pack model if microstructureis considered to be a basic parameter. A few experiments have been carried out to validate bond formation under temperature gradient.

  19. Formation of a dinuclear copper(II) complex through the cleavage of CBond' name='Single-Bond' value='Single-Bond'/>N bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    Energy Technology Data Exchange (ETDEWEB)

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor (Malaysia); Kassim, Mohammad B. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor, Malaysia and Fuel Cell Institute, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor (Malaysia)

    2014-09-03

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-(3-(pyridin-2-yl)-pyrazolato) and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the C{sub benzoyl}Bond' name='Single-Bond' value='Single-Bond'/>N bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the (3-(pyridin-2-yl)-pyrazolato)(3-(pyridin-2-yl)-1H-pyrazole)Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ε = 116 dm{sup 3} mol{sup −1} cm{sup −1}) supports the presence of Cu(II) centres.

  20. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  1. Transition metal chemistry of cyclodiphosphanes containing phosphine and amide-phosphine functionalities: formation of a stable dipalladium(II) complex containing a Pd-P σ-bond.

    Science.gov (United States)

    Balakrishna, Maravanji S; Venkateswaran, Ramalingam; Mague, Joel T

    2010-12-14

    Cyclodiphosphazanes containing phosphine or phosphine plus amide functionalities {((t)BuNP(OC(6)H(4)PPh(2)-o)}(2) (3), {(t)BuNP(OCH(2)CH(2)PPh(2))}(2) (4), {(t)BuHN((t)BuNP)(2)OC(6)H(4)PPh(2)-o} (5), and {(t)BuHN((t)BuNP)(2)OCH(2)CH(2)PPh(2)} (6) were synthesized by reacting cis-{(t)BuNPCl}(2) (1) and cis-[(t)BuHN((t)BuNP)(2)Cl] (2) with corresponding phosphine substituted nucleophiles. The reactions of 3 and 5 with excess of elemental sulfur or selenium produce the corresponding tetra and trichalcogenides, {((t)BuNP(E)(OC(6)H(4)P(E)Ph(2)-o)}(2) (7, E = S; 8, E = Se) and {(t)BuHN((t)BuNP)(2)OC(6)H(4)P(E)Ph(2)-o} (9, E = S; 10, E = Se), respectively, in quantitative yields. The reactions between 3 and [Rh(COD)Cl](2) or [M(COD)Cl](2) (M = Pd or Pt) afford bischelated complexes [Rh(CO)Cl{(t)BuNP(OC(6)H(4)PPh(2)-o)}](2) (11), and [MCl(2){(t)BuNP(OC(6)H(4)PPh(2)-o)}](2) (12, M = Pd; 13, M = Pt) in good yield. The 1 : 2 reaction between 3 and [PdCl(η(3)-C(3)H(5))](2) in dichloromethane resulted initially in the formation of a tripalladium complex of the type [Pd(3)Cl(4)(η(3)-C(3)H(5))(2){(t)BuNPOC(6)H(4)PPh(2)}(2)] (14a) which readily reacts with moisture to form an interesting binuclear complex, [Cl(2)Pd{μ-(PPh(2)C(6)H(4)OP(μ-(t)BuN)(2)P(O)}(μ-Cl)Pd(OC(6)H(4)PPh(2))] (14b). One of the palladium(II) atoms forms a simple six-membered chelate ring, whereas the other palladium(II) atom facilitates the moisture assisted cleavage of one of the endocyclic P-O bonds followed by the oxidation of P(III) to P(V) thus forming a Pd-P σ-bond. The broken ortho-phosphine substituted phenoxide ion forms a five-membered palladacycle with the same palladium(II) atom. Similar reaction of 5 with [PdCl(η(3)-C(3)H(5))](2) also affords a binuclear complex [{PdCl(η(3)-C(3)H(5))}(t)BuNH{(t)BuNP}(2)OC(6)H(4)PPh(2){PdCl(2)}] (15) containing a PdCl(2) moiety which forms a six-membered chelate ring via ring-phosphorus and PPh(2) moieties on one side and a PdCl(η(3)-C(3)H(5)) fragment

  2. Crystal structure of the 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU–4-nitrophenol (1/2 adduct: the role of anomeric effect in the formation of a second hydrogen-bond interaction

    Directory of Open Access Journals (Sweden)

    Augusto Rivera

    2015-11-01

    Full Text Available In the title ternary co-crystalline adduct, C7H14N4·2C6H5NO3, molecules are linked by two intermolecular O—H...N hydrogen bonds, forming a tricomponent aggregates in the asymmetric unit. The hydrogen-bond formation to one of the N atoms is enough to induce structural stereoelectronic effects in the normal donor→acceptor direction. In the title adduct, the two independent nitrophenol molecules are essentially planar, with maximum deviations of 0.0157 (13 and 0.0039 (13 Å. The dihedral angles between the planes of the nitro group and the attached benzene rings are 4.04 (17 and 5.79 (17°. In the crystal, aggregates are connected by C—H...O hydrogen bonds, forming a supramolecular dimer enclosing an R66(32 ring motif. Additional C—H...O intermolecular hydrogen-bonding interactions form a second supramolecular inversion dimer with an R22(10 motif. These units are linked via C—H...O and C—H...N hydrogen bonds, forming a three-dimensional network.

  3. C/C++预处理分析与改进%Improvement on C/C++ Preprocessor

    Institute of Scientific and Technical Information of China (English)

    饶伟

    2006-01-01

    通常的C/C++预处理器是一个宏处理器,在编译前自动地把源文件转换为编译器可识别的形式.传统的预处理方法基于文本行替换,没有考虑到具体的上下文环境.这种预处理机制在文件包含、宏作用域、头文件关系上存在着一些缺陷;会影响工程项目代码重用,降低程序的可维护性、可扩展性等.通过从分析c预处理器缺陷出发,并利用FOG[1]及其语言可以得到一种基于元变量和元函数的语法替换机制的解决方案.

  4. C-C bond formation and related reactions at the CNC backbone in (smif)FeX (smif = 1,3-di-(2-pyridyl)-2-azaallyl): dimerizations, 3 + 2 cyclization, and nucleophilic attack; transfer hydrogenations and alkyne trimerization (X = N(TMS)2, dpma = (di-(2-pyridyl-methyl)-amide)).

    Science.gov (United States)

    Frazier, Brenda A; Williams, Valerie A; Wolczanski, Peter T; Bart, Suzanne C; Meyer, Karsten; Cundari, Thomas R; Lobkovsky, Emil B

    2013-03-18

    Molecular orbital analysis depicts the CNC(nb) backbone of the smif (1,3-di-(2-pyridyl)-2-azaallyl) ligand as having singlet diradical and/or ionic character where electrophilic or nucleophilic attack is plausible. Reversible dimerization of (smif)Fe{N(SiMe3)2} (1) to [{(Me3Si)2N}Fe]2(μ-κ(3),κ(3)-N,py2-smif,smif) (2) may be construed as diradical coupling. A proton transfer within the backbone-methylated, and o-pyridine-methylated smif of putative ((b)Me2(o)Me2smif)FeN(SiMe3)2 (8) provides a route to [{(Me3Si)2N}Fe]2(μ-κ(4),κ(4)-N,py2,C-((b)Me,(b)CH2,(o)Me2(smif)H))2 (9). A 3 + 2 cyclization of ditolyl-acetylene occurs with 1, leading to the dimer [{2,5-di(pyridin-2-yl)-3,4-di-(p-tolyl-2,5-dihydropyrrol-1-ide)}FeN(SiMe3)2]2 (11), and the collateral discovery of alkyne cyclotrimerization led to a brief study that identified Fe(N(SiMe3)2(THF) as an effective catalyst. Nucleophilic attack by (smif)2Fe (13) on (t)BuNCO and (2,6-(i)Pr2C6H3)NCO afforded (RNHCO-smif)2Fe (14a, R = (t)Bu; 14b, 2,6-(i)PrC6H3). Calculations suggested that (dpma)2Fe (15) would favorably lose dihydrogen to afford (smif)2Fe (13). H2-transfer to alkynes, olefins, imines, PhN═NPh, and ketones was explored, but only stoichiometric reactions were affected. Some physical properties of the compounds were examined, and X-ray structural studies on several dinuclear species were conducted.

  5. Oxidation Behavior of C/C-SiC Gradient Matrix Composites

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Oxidation behavior of C/C-SiC gradient matrix composites and C/C composites were compared in stationary air. The results show that oxidation threshold of C-SiC materials increases with the amount of SiC particles in the codeposition matrix. Oxidation rate of C/C-SiC gradient matrix composites is significantly lower than that of C/C material. The micro-oxidation process was observed by SEM.

  6. Determinación teórica de parámetros estructurales: Estudio de los isómeros [Al,C,C,C] y [Al,C,C,Si

    OpenAIRE

    García Vivas, María Esmeralda

    2015-01-01

    Se ha llevado a cabo un estudio teórico-computacional sobre distintos isómeros [Al,C,C,C] y [Al,C,C,Si]. El estudio se ha realizado dentro del contexto de la Teoría del Funcional de la Densidad (DFT) empleando el funcional B3LYP y la base aug-cc-pVTZ. Para cada uno de los sistemas estudiados hemos caracterizado estructuras lineales (o cuasilineales), cíclicas bien romboidales o de tipo “fan” y estructuras que contienen un anillo de tres miembros. Además se ha llevado a cabo un análisi d...

  7. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

    Science.gov (United States)

    Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

    2016-11-01

    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

  8. Interface structure and formation mechanism of vacuum-free vibration liquid phase diffusion-bonded joints of SiCp/ZL101A composites

    Institute of Scientific and Technical Information of China (English)

    YAN Jiu-chun; XU Hui-bin; XU Zhi-wu; LI Da-cheng; YANG Shi-qin

    2005-01-01

    The vacuum-free vibration liquid phase(VLP) diffusion-bonding of SiCp/ZL101A composites was investigated. The effects of vibration on the interface structure, the phase transformation and the tensile strength of bonded joints were examined. Experimental results show that the oxide film on the surface of the composites is a key factor affecting the tensile strength of boned joints. The distribution of the oxide layers at the interface changes from a continuous line to a discontinuous one during vibration. The tensile strength of the VLP diffusion-bonded joints increases with the vibration time, and is up to the maximum of 172 MPa when the vibration time is 30 s. The phase structure of the bond region changes from the Zn-Al-Cu hyper-eutectic (η+ (β+ η)+(β+η+ε)) phases to Al-rich Al-base solid solution (α-Al) with increasing the vibration time.

  9. Copper-Catalyzed Redox-Triggered Remote C-H Functionalization: Highly Selective Formation of C-CF3 and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    Taotao Li; Peng Yu; Jin-Shun Lin; Yonggang Zhi; Xin-Yuan Liu

    2016-01-01

    A Cu-catalyzed remote sp3 C-H/unactivated alkenes functionalization reaction for the concomitant construction ofC-CF3 and C-O bonds was described.An 1,5-H radical transfer involving an sp3 C-H bond adjacent to a nitrogen atom and an α-CF3-alkyl radical intermediate derived from unactivated alkenes was observed and demonstrated to proceed via the radical process.

  10. A Novel Strategy for Preparation of Si-HA Coatings on C/C Composites by Chemical Liquid Vaporization Deposition/Hydrothermal Treatments.

    Science.gov (United States)

    Xin-Bo, Xiong; Xin-Ye, Ni; Ya-Yun, Li; Cen-Cen, Chu; Ji-Zhao, Zou; Xie-Rong, Zeng

    2016-08-05

    A novel strategy for the preparation of Si-doped hydroxyapatite (Si-HA) coatings on H2O2-treated carbon/carbon composites (C/C) was developed. HA coating was prepared on C/C through chemical liquid vaporization deposition (CLVD)/hydrothermal treatment. HA coating was immersed in an H2SiO3 solution at an autoclave at 413 K for transformation into Si-HA coating. The effects of H2SiO3 mass contents on the phase, morphology, and composition of the Si-HA coatings were studied through SEM, EDS,XRD, and FTIR. Their bonding performance to C/C was measured through a scratch test. Under the optimal content condition, the in vitro skull osteoblast response behaviors of the Si-HA coating were evaluated. Results showed that SiO3(2-) could enter into the HA lattice and occupy the PO4(3-) sites. Doped SiO3(2-) significantly improved the bonding performance of the HA coating to C/C in comparison with the untreated HA. The adhesive strength of the coatings initially increased and then decreased with increasing H2SiO3 content. Meanwhile, the cohesive strength of the Si-HA coatings was almost nearly identical. The Si-HA coating achieved at a content of 90% H2SiO3 exhibited the best bonding performance, and its osteoblast compatibility in vitro was superior to that of the untreated HA coating on C/C through CLVD/hydrothermal treatment.

  11. A Novel Strategy for Preparation of Si-HA Coatings on C/C Composites by Chemical Liquid Vaporization Deposition/Hydrothermal Treatments

    Science.gov (United States)

    Xin-Bo, Xiong; Xin-Ye, Ni; Ya-Yun, Li; Cen-Cen, Chu; Ji-Zhao, Zou; Xie-Rong, Zeng

    2016-08-01

    A novel strategy for the preparation of Si-doped hydroxyapatite (Si-HA) coatings on H2O2-treated carbon/carbon composites (C/C) was developed. HA coating was prepared on C/C through chemical liquid vaporization deposition (CLVD)/hydrothermal treatment. HA coating was immersed in an H2SiO3 solution at an autoclave at 413 K for transformation into Si-HA coating. The effects of H2SiO3 mass contents on the phase, morphology, and composition of the Si-HA coatings were studied through SEM, EDS,XRD, and FTIR. Their bonding performance to C/C was measured through a scratch test. Under the optimal content condition, the in vitro skull osteoblast response behaviors of the Si-HA coating were evaluated. Results showed that SiO32‑ could enter into the HA lattice and occupy the PO43‑ sites. Doped SiO32‑ significantly improved the bonding performance of the HA coating to C/C in comparison with the untreated HA. The adhesive strength of the coatings initially increased and then decreased with increasing H2SiO3 content. Meanwhile, the cohesive strength of the Si-HA coatings was almost nearly identical. The Si-HA coating achieved at a content of 90% H2SiO3 exhibited the best bonding performance, and its osteoblast compatibility in vitro was superior to that of the untreated HA coating on C/C through CLVD/hydrothermal treatment.

  12. Association of poly(ADP-ribose) polymerase with the nuclear matrix: the role of intermolecular disulfide bond formation, RNA retention, and cell type.

    Science.gov (United States)

    Kaufmann, S H; Brunet, G; Talbot, B; Lamarr, D; Dumas, C; Shaper, J H; Poirier, G

    1991-02-01

    The recovery of the enzyme poly(ADP-ribose) polymerase (pADPRp) in the nuclease- and 1.6 M NaCl-resistant nuclear subfraction prepared from a number of different sources was assessed by Western blotting. When rat liver nuclei were treated with DNase I and RNase A followed by 1.6 M NaCl, approximately 10% of the nuclear pADPRp was recovered in the sedimentable fraction. The proportion of pADPRp recovered with the residual fraction decreased to less than 5% of the total nuclear polymerase when nuclei were prepared in the presence of the sulfhydryl blocking reagent iodoacetamide and increased to approximately 50% of the total nuclear pADPRp when nuclei were treated with the sulfhydryl cross-linking reagent sodium tetrathionate (NaTT) prior to fractionation. To determine whether this effect of disulfide bond formation was unique to rat liver nuclei, nuclear matrix/cytoskeleton structures were prepared in situ by sequentially treating monolayers of tissue culture cells with Nonidet-P40, DNase I and RNase A, and 1.6 M NaCl (S.H. Kaufmann and J.H. Shaper (1991) Exp. Cell Res. 192, 511-523). When nuclear monolayers were prepared from HTC rat hepatoma cells, CaLu-1 human lung carcinoma cells, and CHO hamster ovary cells in the absence of NaTT, pADPRp was undetectable in the nuclease- and 1.6 M NaCl-resistant fraction. In contrast, when nuclear monolayers were isolated in the presence of NaTT, from 5% (CaLu-1) to 26% (HTC cells) of the total nuclear pADPRp was recovered with the nuclease- and salt-resistant fraction. Examination of these residual structures by SDS-polyacrylamide gel electrophoresis under nonreducing conditions suggested that pADPRp was present as a component of disulfide cross-linked complexes. Further analysis by immunofluorescence revealed that the pADPRp was diffusely distributed throughout the CaLu-1 or CHO nuclear matrix. In addition, when matrices were prepared in the absence of RNase A, pADPRp was also observed in the residual nucleoli. These

  13. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  14. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  15. Crystal Structure of the 5-Chloro Salicylamides: Three Different Types of the H-bonding Influenced Linear Chain Formation in the Solid State

    Directory of Open Access Journals (Sweden)

    Jiří Hanusek

    2012-05-01

    Full Text Available Three N-substituted 5-chlorosalicylamides (4-chlorophenyl, 2a; benzyl, 2b; phenethyl 2c differing in the length of the 'linker' between the benzene ring and the amide moiety were prepared in order to compare their supramolecular architecture. The intramolecular NH···O(H hydrogen bond and the intermolecular C=O···H–O hydrogen bond were found in the crystal structure of 2a and 2c thus forming an infinite linear chain. Compound 2b had a different arrangement with the intramolecular C=O···H–O hydrogen bond and another intermolecular NH···O(H hydrogen forming a linear infinite chain.

  16. SOCIAL BONDING: REGULATION BY NEUROPEPTIDES

    Directory of Open Access Journals (Sweden)

    Claudia eLieberwirth

    2014-06-01

    Full Text Available Affiliative social relationships (e.g., among spouses, family members, and friends play an essential role in human society. These relationships affect psychological, physiological, and behavioral functions. As positive and enduring bonds are critical for the overall well-being of humans, it is not surprising that considerable effort has been made to study the neurobiological mechanisms that underlie social bonding behaviors. The present review details the involvement of the nonapeptides, oxytocin (OT and arginine vasopressin (AVP, in the regulation of social bonding in mammals including humans. In particular, we will discuss the role of OT and AVP in the formation of social bonds between partners of a mating pair as well as between parents and their offspring. Furthermore, the role of OT and AVP in the formation of interpersonal bonding involving trust is also discussed.

  17. Isopeptide bonds of the major pilin protein BcpA influence pilus structure and bundle formation on the surface of Bacillus cereus

    Energy Technology Data Exchange (ETDEWEB)

    Hendrickx, Antoni P.A.; Poor, Catherine B.; Jureller, Justin E.; Budzik, Jonathan M.; He, Chuan; Schneewind, Olaf (UC)

    2012-09-05

    Bacillus cereus strains elaborate pili on their surface using a mechanism of sortase-mediated cross-linking of major and minor pilus components. Here we used a combination of electron microscopy and atomic force microscopy to visualize these structures. Pili occur as single, double or higher order assemblies of filaments formed from monomers of the major pilin, BcpA, capped by the minor pilin, BcpB. Previous studies demonstrated that within assembled pili, four domains of BcpA -- CNA{sub 1}, CNA{sub 2}, XNA and CNA{sub 3} -- each acquire intramolecular lysine-asparagine isopeptide bonds formed via catalytic glutamic acid or aspartic acid residues. Here we showed that mutants unable to form the intramolecular isopeptide bonds in the CNA2 or CNA3 domains retain the ability to form pilus bundles. A mutant lacking the CNA{sub 1} isopeptide bond assembled deformed pilin subunits that failed to associate as bundles. X-ray crystallography revealed that the BcpA variant Asp{sup 312}Ala, lacking an aspartyl catalyst, did not generate the isopeptide bond within the jelly-roll structure of XNA. The Asp{sup 312}Ala mutant was also unable to form bundles and promoted the assembly of deformed pili. Thus, structural integrity of the CNA{sub 1} and XNA domains are determinants for the association of pili into higher order bundle structures and determine native pilus structure.

  18. Solvent effects on the formation of nanoparticles and multilayered coatings based on hydrogen-bonded interpolymer complexes of poly(acrylic acid) with homo- and copolymers of N-vinyl pyrrolidone.

    Science.gov (United States)

    Zhunuspayev, Daulet E; Mun, Grigoriy A; Hole, Patrick; Khutoryanskiy, Vitaliy V

    2008-12-02

    The formation of hydrogen-bonded interpolymer complexes between poly(acrylic acid) and poly(N-vinyl pyrrolidone) as well as amphiphilic copolymers of N-vinyl pyrrolidone with vinyl propyl ether has been studied in aqueous and organic solutions. It was demonstrated that introduction of vinyl propyl ether units into the macromolecules of the nonionic polymer enhances their ability to form complexes in aqueous solutions due to more significant contribution of hydrophobic effects. The complexation was found to be a multistage process that involves the formation of primary polycomplex particles, which further aggregate to form spherical nanoparticles. Depending on the environmental factors (pH, solvent nature), these nanoparticles may either form stable colloidal solutions or undergo further aggregation, resulting in precipitation of interpolymer complexes. In organic solvents, the intensity of complex formation increases in the following order: methanol complexes on glass surfaces. It was demonstrated that the solvent nature affects the efficiency of coating deposition.

  19. Unravelling the secrets of Cs controlled secondary ion formation: Evidence of the dominance of site specific surface chemistry, alloying and ionic bonding

    Science.gov (United States)

    Wittmaack, Klaus

    2013-03-01

    implantation can be evaluated as a function of Cs coverage. The summarised results imply that secondary ions are commonly not formed by charge transfer between an escaping atom and the electronic system of the sample but are already emitted as ions. The probability of ion formation appears to be controlled by the local ionic character of the alkali-target atom bonds, i.e., by the difference in electronegativity between the involved elements as well as by the electron affinity and the ionisation potential of the departing atom. This idea is supported by the finding that Si- yields exhibit the same very strong dependence on Cs coverage as Si+ and O- yields on the oxygen fraction in oxygen loaded Si. Most challenging to theoreticians is the finding that the ionisation probability is independent of the emission velocity of sputtered ions. This phenomenon cannot be rationalised along established routes of thinking. Different concepts need to be explored. An old, somewhat exotic idea takes account of the heavy perturbation created for a very short period of time at the site of ion emission (dynamic randomisation). Molecular dynamics simulations are desirable to clarify the issue. Ultimately it may be possible to describe all phenomena of enhanced or suppressed secondary ion formation, produced either by surface loading with alkali atoms or by enforced surface oxidation, on the basis of a single universal model. There is plenty of room for exciting new studies.

  20. Crystal Structure, Thermal Decomposition Behavior and the Standard Molar Enthalpy of Formation of a Novel 3D Hydrogen Bonded Supramolecular [Co(HnicO)2·(H2O)2

    Institute of Scientific and Technical Information of China (English)

    ZENG,Ming-Hua; WU,Mei-Chun; ZHU,Li-Hong; LIANG,Hong; YANG Xu-Wu

    2007-01-01

    Hydrothermal synthesis and X-ray characterized 3D supramolecular networks were constructed by [Co(HnicO)2·(H2O)2] (HnicOH=2-hydroxynicotinic acid) (1) as building block via abundant dimeric homomeric (N-H…O) and unusually cyclic tetrameric heteromeric (O-H…O) hydrogen-bonds. It is noted that there exist unusually linear metal-water chains comprised of tetrameric units linked by vertexes sharing cobalt centers through hydrogen-bonding. TG-DTG curves illustrated that thermal decomposition was completed by two steps, one is the loss of two terminal water molecules in the range of 156-234 ℃, and the other is the pyrolysis of HnicO ligand in the range of 234-730 ℃. The standard molar enthalpy of formation of the complex was determined to be (-1845.43±2.77) kJ·mol-1 by a rotary-bomb combustion calorimeter.

  1. Zeolite-Catalyzed Hydrocarbon Formation from Methanol: Density Functional Simulations

    Directory of Open Access Journals (Sweden)

    George Fitzgerald

    2002-04-01

    Full Text Available Abstract: We report detailed density functional theory (DFT calculations of important mechanisms in the methanol to gasoline (MTG process in a zeolite catalyst. Various reaction paths and energy barriers involving C-O bond cleavage and the first C-C bond formation are investigated in detail using all-electron periodic supercell calculations and recently developed geometry optimization and transition state search algorithms. We have further investigated the formation of ethanol and have identified a different mechanism than previously reported [1], a reaction where water does not play any visible role. Contrary to recent cluster calculations, we were not able to find a stable surface ylide structure. However, a stable ylide structure built into the zeolite framework was found to be possible, albeit a very high reaction barrier.

  2. The thermodynamics and kinetics of phosphoester bond formation, use, and dissociation in biology, with the example of polyphosphate in platelet activation, trasience, and mineralization.

    Science.gov (United States)

    Omelon, S. J.

    2014-12-01

    Mitochondria condense orthophosphates (Pi), forming phosphoester bonds for ATP production that is important to life. This represents an exchange of energy from dissociated carbohydrate bonds to phosophoester bonds. These bonds are available to phosphorylate organic compounds or hydrolyze to Pi, driving many biochemical processes. The benthic bacteria T. namibiensis 1 and Beggiatoa 2 condense Pi into phosphate polymers in oxygenated environments. These polyphosphates (polyPs) are stored until the environment becomes anoxic, when these bacteria retrieve the energy from polyP dissociation into Pi3. Dissociated Pi is released outside of the bacteria, where it precipitates as apatite.The Gibbs free energy of polyP phosphoester bond hydrolysis is negative, however, the kinetics are slow4. Diatoms contain a polyP pool that is stable until after death, after which the polyPs hydrolyze and form apatite5. The roles of polyP in eukaryotic organism biochemistry continue to be discovered. PolyPs have a range of biochemical roles, such as bioavailable P-storage, stress adaptation, and blood clotting6. PolyP-containing granules are released from anuclear platelets to activate factor V7 and factor XII in the blood clotting process due to their polyanionic charge8. Platelets have a lifespan of approximately 8 days, after which they undergo apoptosis9. Data will be presented that demonstrate the bioactive, thermodynamically unstable polyP pool within older platelets in vitro can spontaneously hydrolyze and form phosphate minerals. This process is likely avoided by platelet digestion in the spleen and liver, possibly recycling platelet polyPs with their phosphoester bond energy for other biochemical roles. 1 Schulz HN et al. Science (2005) 307: 416-4182 Brüchert V et al. Geochim Cosmochim Acta (2003) 67: 4505-45183 Goldhammer T et al. Nat Geosci (2010) 3: 557-5614 de Jager H-J et al. J Phys Chem A (1988) 102: 2838-28415 Diaz, J et al. Science (2008) 320: 652-6556 Mason KD et al

  3. Computational Study of Low-Temperature Catalytic C-C Bond Activation of Alkanes for Portable Power

    Science.gov (United States)

    2013-06-05

    the RhCl3 system. Our initial computations regarding this system showed that • RhII chloride salts are stable in a mixture of RhI and RhIII, so that...inhibiting the reaction. We found that Fluorinated phosphines are sufficiently π-accepting to satisfy this role. In our next step, we wanted to determine...flames” Proc. Comb. Inst. 2005, 30, 439–446 4. A. Onopchenko, J.G.D. Schulz “Oxidation of butane with cobalt salts and oxygen via electron

  4. Mutability-landscape guided enzyme engineering : Improving the promiscuous C-C bond-forming activities of 4-oxalocrotonate tautomerase

    NARCIS (Netherlands)

    van der Meer, Jan Ytzen

    2016-01-01

    Enzymes do not only play a crucial role in nature, they are also increasingly used as biocatalysts for the production of complex molecules such as pharmaceuticals. However, some of the reactions that are widely used in organic synthesis have not been observed in biological systems. Hence, there is n

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

    Science.gov (United States)

    Rajanbabu, T V

    2009-01-01

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

  6. Cu6Sn5-TiC-C nanocomposite anodes for high-performance sodium-ion batteries

    Science.gov (United States)

    Kim, Il Tae; Allcorn, Eric; Manthiram, Arumugam

    2015-05-01

    Cu6Sn5 alloy nanoparticles dispersed in a TiC and C conductive matrix have been developed via high energy mechanical milling (HEMM), and the resulting Cu6Sn5-TiC-C nanocomposite has been assessed as anodes for sodium-ion batteries. Composite anodes of Sn-C exhibit poor cyclic performance even with the introduction of 2 vol. % fluoroethylene carbonate (FEC) additive into the electrolyte. In contrast, Cu6Sn5-TiC-C nanocomposite anodes exhibit stable cycle life corresponding to a capacity retention of ∼80% at 40 cycles and high-rate performance with a capacity retention of ∼62% at 3000 mA g-1. These superior performance metrics is ascribed to the well-developed electrochemically active nanocrystalline material (Cu6Sn5) as well as a hybrid conductive matrix (TiC and C). The incorporation of 2 vol. % FEC additive into the electrolyte further improves the performance of Cu6Sn5-TiC-C nanocomposite to display a capacity retention of ∼94% at 250 cycles and high-rate capacity retention of ∼82% at 5000 mA g-1, which are attributed to the formation of a thin and stable SEI layer in presence of FEC.

  7. Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation.

    Science.gov (United States)

    Mullangi, Dinesh; Nandi, Shyamapada; Shalini, Sorout; Sreedhala, Sheshadri; Vinod, Chathakudath P; Vaidhyanathan, Ramanathan

    2015-06-09

    COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd(0) nanoparticles into it. An 18-20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) couplings and C-C couplings using 'non-boronic acid' substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 °C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable.

  8. Spheroidization behavior of dendritic b.c.c. phase in Zr-based モ-phase composite

    Directory of Open Access Journals (Sweden)

    Sun Guoyuan

    2013-03-01

    Full Text Available The spheroidization behavior of the dendritic b.c.c. phase dispersed in a bulk metallic glass (BMG matrix was investigated through applying semi-solid isothermal processing and a subsequent rapid quenching procedure to a Zr-based モ-phase composite. The Zr-based composite with the composition of Zr56.2Ti13.8Nb5.0Cu6.9Ni5.6Be12.5 was prefabricated by a water-cooled copper mold-casting method and characterized by X-ray diffraction (XRD and scanning electron microscope (SEM. The results show that the composite consists of a glassy matrix and uniformly distributed fine dendrites of the モ-Zr solid solution with the body-centered-cubic (b.c.c. structure. Based on the differential scanning calorimeter (DSC examination results, and in view of the b.c.c. モ-Zr to h.c.p. メ-Zr phase transition temperature, a semi-solid holding temperature of 900 ìC was determined. After reheating the prefabricated composite to the semi-solid temperature, followed by an isothermal holding process at this temperature for 5 min, and then quenching the semi-solid mixture into iced-water; the two-phase microstructure composed of a BMG matrix and uniformly dispersed spherical b.c.c. モ-Zr particles with a high degree of sphericity was achieved. The present spheroidization transition is a thermodynamically autonomic behavior, and essentially a diffusion process controlled by kinetic factors; and the formation of the BMG matrix should be attributed to the rapid quenching of the semi-solid mixture as well as the large glass-forming ability of the remaining melt in the semi-solid mixture.

  9. Effects of Preform Density on Structure and Property of C/C-SiC Composites Fabricated by Gaseous Silicon Infiltration

    Directory of Open Access Journals (Sweden)

    CAO Yu

    2016-07-01

    Full Text Available The 3-D needled C/C preforms with different densities deposited by chemical vapor infiltration (CVI method were used to fabricate C/C-SiC composites by gaseous silicon infiltration (GSI. The porosity and CVI C thickness of the preforms were studied, and the effects of preform density on the mechanical and thermal properties of C/C-SiC composites were analyzed. The results show that with the increase of preform density, the preform porosity decreases and the CVI C thickness increases from several hundred nanometers to several microns. For the C/C-SiC composites, as the preform density increases, the residual C content increases while the density and residual Si content decreases. The SiC content first keeps at a high level of about 40% (volume fraction, which then quickly reduces. Meanwhile, the mechanical properties increase to the highest values when the preform density is 1.085g/cm3, with the flexure strength up to 308.31MP and fracture toughness up to 11.36MPa·m1/2, which then decrease as the preform density further increases. The thermal conductivity and CTE of the composites, however, decrease with the increase of preform density. It is found that when the preform porosity is too high, sufficient infiltration channels lead to more residual Si, and thinner CVI C thickness results in the severe corrosion of the reinforcing fibers by Si and lower mechanical properties. When the preform porosity is relatively low, the contents of Si and SiC quickly reduce since the infiltration channels are rapidly blocked, resulting in the formation of large closed pores and not high mechanical properties.

  10. Thermoelectric properties of SiC/C composites from wood charcoal by pulse current sintering

    NARCIS (Netherlands)

    Fujisawa, M; Hata, T; Bronsveld, P; Castro, [No Value; Tanaka, F; Kikuchi, H; Imamura, Y

    2005-01-01

    SiC/C composites were investigated by sintering a mix of wood charcoal and SiO2 powder (32-45 mu m) at 1400, 1600 and 1800 degrees C under N-2 atmosphere with a pulse current sintering method. Thermoelectric properties of SiC/C composites were investigated by measuring the Seebeck coefficient and th

  11. 76 FR 44800 - Election of Reduced Research Credit Under Section 280C(c)(3)

    Science.gov (United States)

    2011-07-27

    ... [TD 9539] RIN 1545-BI09 Election of Reduced Research Credit Under Section 280C(c)(3) AGENCY: Internal... dates of applicability, see Sec. 1.280C- 4(c). FOR FURTHER INFORMATION CONTACT: David Selig, (202) 622... research credit under section 280C(c)(3). On July 16, 2009, a notice of proposed rulemaking...

  12. Ablation Resistance of C/C Composites with Atmospheric Plasma-Sprayed W Coating

    Science.gov (United States)

    Zhou, Zhe; Wang, Yuan; Gong, Jieming; Ge, Yicheng; Peng, Ke; Ran, Liping; Yi, Maozhong

    2016-12-01

    To improve the ablation resistance of carbon/carbon (C/C) composites, tungsten (W) coating with thickness of 1.2 mm was applied by atmospheric plasma spraying. The antiablation property of the coated composites was evaluated by oxyacetylene flame ablation experiments. The phase composition of the coating was investigated by a combination of x-ray diffraction analysis and scanning electron microscopy with energy-dispersive x-ray spectroscopy analysis. The ablation resistance of the coated C/C substrates was compared with that of uncoated C/C composites and C/C-CuZr composites after ablation for 30 s. The properties of the coated C/C composites after ablation time of 10, 30, 60, 90, 120, and 180 s were further studied. The results indicated that the mass and linear ablation rates of the W-coated C/C composites were lower than those of uncoated C/C or C/C-CuZr composites after ablation for 30 s. The coating exhibited heat stability after 120 s of ablation, with mass loss and linear ablation rates of 7.39 × 10-3 g/s and 3.50 × 10-3 mm/s, respectively. However, the W coating became ineffective and failed after ablation for 180 s. Three ablation regions could be identified, in which the ablation mechanism of the coating changed from thermochemical to thermophysical erosion to mechanical scouring with increasing ablation time.

  13. Proton stopping in C+C, d+C, C+Ta and d+Ta collisions at 4.2A GeV/c

    CERN Document Server

    Simic, L; Simic, Lj.

    1998-01-01

    The shape of proton rapidity distributions is analysed in terms of their Gaussian components, and the average rapidity loss is determined in order to estimate the amount of stopping in C+C, d+C, C+Ta and d+Ta collisions at 4.2A GeV/c. Three Gaussians correspond to the nuclear transparency and describe well all peripheral and also C+C central collisions. Two-component shape is obtained in case of d+C and C+Ta central collisions. Finally one Gaussian, found in d+Ta central collisions, corresponds to the full stopping. The calculated values of the average rapidity loss support the qualitative relationship between the number of Gaussian components and the corresponding stopping power. It is also observed, in central collisions, that the average rapidity loss increases with the ratio of the number of target and the number of projectile participants.

  14. Bond Alternation in Halogen Substituted Polyacetylene ---Possibility of C-F Bond Length Alternation in (CF)x---

    Science.gov (United States)

    Abdelaty, S. M.; Sasai, M.; Fukutome, H.

    1985-08-01

    Using the Hückel model, we study the π electronic and lattice structures of the ground state of halogen substituted polyacetylene (CX)x where X is F, Cl, Br or I. The halogen substitution always makes the C-C bond length alternation in the main chain and the corresponding band gap smaller than those in unsubstituted polyacetylene (CH)x. (CCl)x, (CBr)x and (CI)x have only the bond alternation in the main chain. (CF)x may take one of the three lattice structures depending on the value of the C-F σ bond force constant; the structure with the bond alternation in the main chain, the one with the bond length alternation in the C-F bonds and the one with coexistence of the two kinds of bond alternation. The structure with the C-F bond length alternation is ferroelectric.

  15. Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II–O and Ni(II–N coordination bonds

    Directory of Open Access Journals (Sweden)

    Vadim A. Soloshonok

    2012-11-01

    Full Text Available We describe herein the design and synthesis of asymmetric, pentadentate ligands, which are able to coordinate to Ni(II cations leading to quasi-diastereomeric complexes displaying two new elements of chirality: stereogenic axis and helix along with configurational stabilization of the stereogenic center on the nitrogen. Due to the stereocongested structural characteristics of the corresponding Ni(II complexes, the formation of quasi-diastereomeric products is highly stereoselective providing formation of only two, (Ra*,Mh*,Rc* and (Ra*,Ph*,Rc*, out of the four possible stereochemical combinations. The reversible quasi-diastereomeric transformation between the products (Ra*,Mh*,Rc* and (Ra*,Ph*,Rc* occurs by intramolecular trans-coordination of Ni–NH and Ni–O bonds providing a basis for a chiral switch model.

  16. 在MATLAB环境下创建C/C++外部应用程序的方法%The Method of Establishing C/C++ Exterior Application under MATLAB

    Institute of Scientific and Technical Information of China (English)

    刘东华

    2000-01-01

    介绍了利用MATLAB编译器和MATLAB的C/C++Math函数库以及C/C++编译器生成C/C++应用程序的优点及具体的编译链接流程,并通过实例分析了创建C/C++应用程序的方法.

  17. Facile Formation and Dissociation Behaviour of C–C Bond Resulted from the Nucleophilic Attack of Carbanions on a Carbonyl Carbon in [Pt(hfac)2

    OpenAIRE

    2000-01-01

    [Pt(hfac)2] (hfac:hexafluoroacetylacetonate) reacts with MeNH2 in CH2Cl2/MeOH to give an –NHMe adduct complex on one of the carbonyl carbons, (MeNH3)[Pt(hfac)(hfac–NHMe)] 1 which is a tetrahedral intermediate of a Schiff base complex,[Pt(CF3COCHC(NMe)CF3)2] 2. Complex 1 activates H2O,MeOH, MeNO2 or acetone in solution to form the correspondingconjugate base adducts. The C–C bond in–CH2NO2 adduct 6, easily cleaves and generates nitromethane in solution.

  18. Calamistrin E, the First Annonaceous Acetogenin with Double Bond in Aliphatic Chain from Genus Uvaria

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Calamistrin E, the first Annonaceous acetogenin with C=C bond in the aliphatic chain from the genus Uvaria was isolated from U. calamistrata. Its structure including relative and absolute configurations was determined by chemical derivation and spectral analysis.

  19. Investigation of mechanisms of formation of biphenyls and benzonaphthothiophenes by simulation experiment

    Institute of Scientific and Technical Information of China (English)

    XIA; Yanqing(夏燕青); ZHANG; Gengxin(张更新)

    2002-01-01

    The formation mechanisms of biphenyl series and benzonaphthothiophene series are investigated by means of simulation experiment. Biphenyl series are likely formed in two ways: one is the aromatization of the chain compounds containing conjugated C== C double bonds or the compounds with such a kind of sidechains, and the other is the reaction of sulfur with ordinary chain compounds, in which sulphur acts on ordinary sidechain compounds by seizing some hydrogens and forming (H2S and) the intermediates with conjugated C== C double bonds first, and then the intermediates are aromatized. One of the basic precursors of benzonaphthothiophenes is likely the phenylnaphthalenes which may originate from the chain compounds containing conjugated C== C double bonds, the compounds with such sidechains and saturate or unsaturate chain compounds. Thermal stability of biphenyls is high, but they can become dibenzothiophenes and polycyclic aromatic hydrocarbons or dibenzofurans and polycyclic aromatic hydrocarbons respectively in the presence of sulphur or oxygen. The ratio of biphenyl and m-biphenyl to biphenyls may be employed to indicate the depositional environment in the mild to medium maturation, of which the higher value indicates a fresh water depositional environment and the lower indicates a saline depositional environment. The relative high content of benzonaphthothiophenes in the crude oil indicates that the crude oil has undergone an intense sulfurization in the source rock or reservoir.

  20. Characterization of Helicobacter pylori HP0231 (DsbK): role in disulfide bond formation, redox homeostasis and production of Helicobacter cystein-rich protein HcpE.

    Science.gov (United States)

    Lester, Jeffrey; Kichler, Sari; Oickle, Brandon; Fairweather, Spencer; Oberc, Alexander; Chahal, Jaspreet; Ratnayake, Dinath; Creuzenet, Carole

    2015-04-01

    Helicobacter pylori is a human gastric pathogen that colonizes ∼ 50% of the world's population. It can cause gastritis, gastric or duodenal ulcers and also gastric cancer. The numerous side effects of available treatments and the emergence of antibiotic resistant strains are severe concerns that justify further research into H. pylori's pathogenic mechanisms. H. pylori produces secreted proteins that may play a role in virulence, including the Helicobacter cysteine-rich protein HcpE (aka HP0235). We demonstrate herein that HcpE is secreted in the culture supernatant both as a soluble protein and in association with outer membrane vesicles. We show that the structure of HcpE comprises an organized array of disulfide bonds. We identify DsbK (aka HP0231) as a folding factor necessary for HcpE production and secretion in H. pylori and show that recombinant DsbK can interact with and refold unprocessed, reduced HcpE in vitro. These experiments highlight the first biologically relevant substrate for DsbK. Furthermore, we show that DsbK has disulfide bond (Dsb) forming activity on reduced lysozyme and demonstrate a DsbA-type of activity for DsbK upon expression in E. coli, despite its similarity with DsbG. Finally, we show a role of DsbK in maintaining redox homeostasis in H. pylori.

  1. A computational study on the N-heterocyclic carbene-catalyzed Csp(2)-Csp(3) bond activation/[4+2] cycloaddition cascade reaction of cyclobutenones with imines: a new application of the conservation principle of molecular orbital symmetry.

    Science.gov (United States)

    Wang, Yang; Wu, Bohua; Zhang, Haoyang; Wei, Donghui; Tang, Mingsheng

    2016-07-20

    A comprehensive density functional theory (DFT) investigation has been performed to interrogate the mechanisms and stereoselectivities of the Csp(2)-Csp(3) single bond activation of cyclobutenones and their [4+2] cycloaddition reaction with imines via N-heterocyclic carbene (NHC) organocatalysis. According to our calculated results, the fundamental reaction pathway contains four steps: nucleophilic addition of NHC to cyclobutenone, C-C bond cleavage for the formation of an enolate intermediate, [4+2] cycloaddition of the enolate intermediate with isatin imine, and the elimination of the NHC catalyst. In addition, the calculated results also reveal that the second reaction step is the rate-determining step, whereas the third step is the regio- and stereo-selectivity determining step. For the regio- and stereo-selectivity determining step, all four possible attack modes were considered. The addition of the C[double bond, length as m-dash]N bond in isatin imine to the dienolate intermediate is more energy favorable than the addition of the C[double bond, length as m-dash]O bond to a dienolate intermediate. Moreover, the Re face addition of the C[double bond, length as m-dash]N bond in isatin imine to the Re face of the dienolate intermediate leading to the SS configuration N-containing product was demonstrated to be most energy favorable, which is mainly due to the stronger second-order perturbation energy value in the corresponding transition state. Furthermore, by tracking the frontier molecular orbital (FMO) changes in the rate-determining C-C bond cleavage step, we found that the reaction obeys the conservation principle of molecular orbital symmetry. We believe that the present work would provide valuable insights into this kind of reaction.

  2. Electron attachment properties of c-C4F8O in different environments

    Science.gov (United States)

    Chachereau, A.; Fedor, J.; Janečková, R.; Kočišek, J.; Rabie, M.; Franck, C. M.

    2016-09-01

    The electron attachment properties of octafluorotetrahydrofuran (c-C4F8O) are investigated using two complementary experimental setups. The attachment and ionization cross sections of c-C4F8O are measured using an electron beam experiment. The effective ionization rate coefficient, electron drift velocity and electron diffusion coefficient in c-C4F8O diluted to concentrations lower than 0.6% in the buffer gases N2, CO2 and Ar, are measured using a pulsed Townsend experiment. A kinetic model is proposed, which combines the results of the two experiments.

  3. Redox-controlled hydrogen bonding: turning a superbase into a strong hydrogen-bond donor.

    Science.gov (United States)

    Wild, Ute; Neuhäuser, Christiane; Wiesner, Sven; Kaifer, Elisabeth; Wadepohl, Hubert; Himmel, Hans-Jörg

    2014-05-12

    Herein the synthesis, structures and properties of hydrogen-bonded aggregates involving redox-active guanidine superbases are reported. Reversible hydrogen bonding is switched on by oxidation of the hydrogen-donor unit, and leads to formation of aggregates in which the hydrogen-bond donor unit is sandwiched by two hydrogen-bond acceptor units. Further oxidation (of the acceptor units) leads again to deaggregation. Aggregate formation is associated with a distinct color change, and the electronic situation could be described as a frozen stage on the way to hydrogen transfer. A further increase in the basicity of the hydrogen-bond acceptor leads to deprotonation reactions.

  4. Oxidative formation of phosphinyl radicals from a trigonal pyramidal terminal phosphide Rh(i) complex, with an unusually long Rh-P bond.

    Science.gov (United States)

    Fischbach, Urs; Trincado, M; Grützmacher, Hansjörg

    2017-03-14

    A rhodium complex containing a tetrapodal triolefin ligand (trop3P) and a phosphanyl ligand (PPh2(-)) has been prepared and characterised. The special structural confinements of the tetradentate ligand impose an unusually long Rh-PPh2 bond. Chemical oxidation of the complex with FcOTf affords [Rh(OTf)(trop3P)] and plausibly phosphanyl radicals, which react instantly with a spin trap reagent forming a nitroxide-based persistent radical, undergo HAT with silanes or dimerise to the corresponding diphosphine (PPh2)2. Chemical oxidation with a peroxide leads to complex [Rh(POPh2)(trop3P)] which is photolabile and loses the Ph2PO moiety upon irradiation with UV/Vis light in CH2Cl2.

  5. An Iterated GMM Procedure for Estimating the Campbell-Cochrane Habit Formation Model, with an Application to Danish Stock and Bond Returns

    DEFF Research Database (Denmark)

    Engsted, Tom; Møller, Stig Vinther

    2010-01-01

    We suggest an iterated GMM approach to estimate and test the consumption based habit persistence model of Campbell and Cochrane, and we apply the approach on annual and quarterly Danish stock and bond returns. For comparative purposes we also estimate and test the standard constant relative risk......-aversion (CRRA) model. In addition, we compare the pricing errors of the different models using Hansen and Jagannathan's specification error measure. The main result is that for Denmark the Campbell-Cochrane model does not seem to perform markedly better than the CRRA model. For the long annual sample period...... covering more than 80 years there is absolutely no evidence of superior performance of the Campbell-Cochrane model. For the shorter and more recent quarterly data over a 20-30 year period, there is some evidence of counter-cyclical time-variation in the degree of risk-aversion, in accordance...

  6. An iterated GMM procedure for estimating the Campbell-Cochrane habit formation model, with an application to Danish stock and bond returns

    DEFF Research Database (Denmark)

    Engsted, Tom; Møller, Stig V.

    We suggest an iterated GMM approach to estimate and test the consumption based habit persistence model of Campbell and Cochrane (1999), and we apply the approach on annual and quarterly Danish stock and bond returns. For comparative purposes we also estimate and test the standard CRRA model....... In addition, we compare the pricing errors of the different models using Hansen and Jagannathan's (1997) specification error measure. The main result is that for Denmark the Campbell-Cochrane model does not seem to perform markedly better than the CRRA model. For the long annual sample period covering more...... than 80 years there is absolutely no evidence of superior performance of the Campbell-Cochrane model. For the shorter and more recent quarterly data over a 20-30 year period, there is some evidence of counter-cyclical time-variation in the degree of risk-aversion, in accordance with the Campbell...

  7. Disulfide bond formation between the COOH-terminal domain of the beta subunits and the gamma and epsilon subunits of the Escherichia coli F1-ATPase. Structural implications and functional consequences.

    Science.gov (United States)

    Aggeler, R; Haughton, M A; Capaldi, R A

    1995-04-21

    A set of mutants of the Escherichia coli F1F0-type ATPase has been generated by site-directed mutagenesis as follows: beta E381C, beta S383C, beta E381C/epsilon S108C, and beta S383C/epsilon S108C. Treatment of ECF1 isolated from any of these mutants with CuCl2 induces disulfide bond formation. For the single mutants, beta E381C and beta S383C, a disulfide bond is formed in essentially 100% yield between a beta subunit and the gamma subunit, probably at Cys87 based on the recent structure determination of F1 (Abrahams, J. P., Leslie, A. G. W., Lutter, R., and Walker, J. E. (1994) Nature 370, 621-628). In the double mutants, two disulfide bonds are formed, again in essentially full yield, one between beta and gamma, the other between a beta and the epsilon subunit via Cys108. The same two cross-links are produced with CuCl2 treatment of ECF1F0 isolated from either of the double mutants. These results show that the parts of gamma around residue 87 (a short alpha-helix) and the epsilon subunit interact with different beta subunits. The yield of covalent linkage of beta to gamma is nucleotide dependent and highest in ATP and much lower with ADP in catalytic sites. The yield of covalent linkage of beta to epsilon is also nucleotide dependent but in this case is highest in ADP and much lower in ATP. Disulfide bond formation between either beta and gamma, or beta and epsilon inhibits the ATPase activity of the enzyme in proportion to the yield of the cross-linked product. Chemical modification of the Cys at either position 381 or 383 of the beta subunit inhibits ATPase activity in a manner that appears to be dependent on the size of the modifying reagent. These results are as expected if movements of the catalytic site-containing beta subunits relative to the gamma and epsilon subunits are an essential part of the cooperativity of the enzyme.

  8. Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3 and Ammonia (NH3 Donor-Acceptor Complex

    Directory of Open Access Journals (Sweden)

    Dulal C. Ghosh

    2004-09-01

    Full Text Available The formation of the F3B–NH3 supermolecule by chemical interaction of its fragment parts, BF3 and NH3, and the dynamics of internal rotation about the ‘B–N’ bond have been studied in terms of parameters provided by the molecular orbital and density functional theories. It is found that the pairs of frontier orbitals of the interacting fragments have matching symmetry and are involved in the charge transfer interaction. The donation process stems from the HOMO of the donor into the LUMO of the acceptor and simultaneously, back donation stems from the HOMO of acceptor into the LUMO of the donor. The density functional computation of chemical activation in the donor and acceptor fragments, associated with the physical process of structural reorganization just prior to the event of chemical reaction, indicates that BF3 becomes more acidic and NH3 becomes more basic, compared to their separate equilibrium states. Theoretically it is observed that the chemical reaction event of the formation of the supermolecule from its fragment parts is in accordance with the chemical potential equalization principle of the density functional theory and the electronegativity equalization principle of Sanderson. The energetics of the chemical reaction, the magnitude of the net charge transfer and the energy of the newly formed bond are quite consistent, both internally and with the principle of maximum hardness, PMH. The dynamics of the internal rotation of one part with respect to the other part of the supermolecule about the ‘B–N’ bond mimics the pattern of the conformational isomerism of the isostructural ethane molecule. It is also observed that the dynamics and evolution of molecular conformations as a function of dihedral angles is also in accordance with the principle of maximum hardness, PMH. Quite consistent with spectroscopic predictions, the height of the molecule

  9. Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes

    KAUST Repository

    Chen, Shuli

    2013-09-17

    Phenylbis(phenylethynyl)phosphane PhP(C≡CPh)2 coordinates regiospecifically to the α-methyl-chiral ortho-platinated and -palladated naphthylamine units at the positions trans to the nitrogen donors. The P→Pt coordination bond is kinetically inert, whereas the P→Pd bond is labile. Upon heating of these phosphane complexes at 70 °C, one of the C≡C bonds in the coordinated PhP(C≡CPh)2 was activated towards an intermolecular Pd-C bond insertion reaction with an external ortho-palladated naphthylamine ring. No intramolecular insertion reaction occurred. In contrast to its palladium analogue, the ortho-platinated ring is not reactive towards coordinated PhP(C≡CPh)2, although it can promote the Pd-C bond insertion reaction. However, despite the high kinetic stability of the P→Pt coordination, the organoplatinum unit is a noticeably weaker activator than its organopalladium counterpart. The chirality of the reacting ortho-metallated naphthylamine ligand exhibited high stereochemical influence on the formation of the new stereogenic phosphorus center during the course of these C-C bond-formation reactions. The coordination chemistry and the absolute stereochemistry of the dimetallic products were determined by single-crystal X-ray crystallographic analysis. The asymmetric monoinsertion of PhP(C≡CPh)2 coordinated to a cyclometallated N,N-dimethyl naphthyl/benzylamine template into the Pd-C bonds of N,N-dimethylnaphthylamine palladacycles has been demonstrated for the synthesis of a variety of new P-stereogenic homo- or heterodimetallic complexes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A dense and strong bonding collagen film for carbon/carbon composites

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Sheng; Li, Hejun, E-mail: lihejun@nwpu.edu.cn; Li, Kezhi; Lu, Jinhua; Zhang, Leilei

    2015-08-30

    Graphical abstract: - Highlights: • Significantly enhancement of biocompatibility on C/C composites by preparing a collagen film. • The dense and continuous collagen film had a strong bonding strength with C/C composites after dehydrathermal treatment (DHT) crosslink. • Numerous oxygen-containing functional groups formed on the surface of C/C composites without matrix damage. - Abstract: A strong bonding collagen film was successfully prepared on carbon/carbon (C/C) composites. The surface conditions of the modified C/C composites were detected by contact angle measurements, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectra. The roughness, optical morphology, bonding strength and biocompatibility of collagen films at different pH values were detected by confocal laser scanning microscope (CLSM), universal test machine and cytology tests in vitro. After a 4-h modification in 30% H{sub 2}O{sub 2} solution at 100 °C, the contact angle on the surface of C/C composites was decreased from 92.3° to 65.3°. Large quantities of hydroxyl, carboxyl and carbonyl functional groups were formed on the surface of the modified C/C composites. Then a dense and continuous collagen film was prepared on the modified C/C substrate. Bonding strength between collagen film and C/C substrate was reached to 8 MPa level when the pH value of this collagen film was 2.5 after the preparing process. With 2-day dehydrathermal treatment (DHT) crosslinking at 105 °C, the bonding strength was increased to 12 MPa level. At last, the results of in vitro cytological test showed that this collagen film made a great improvement on the biocompatibility on C/C composites.

  11. Manganese(I)-Catalyzed Dispersion-Enabled C-H/C-C Activation.

    Science.gov (United States)

    Meyer, Tjark H; Liu, Weiping; Feldt, Milica; Wuttke, Axel; Mata, Ricardo A; Ackermann, Lutz

    2017-03-20

    C-H/C-C Functionalizations were achieved with the aid of a versatile manganese(I) catalyst. Thus, an organometallic manganese-catalyzed C-H activation set the stage for silver-free C-H/C-C transformations with ample substrate scope and excellent levels of chemo-, site-, and diastereo-selectivities. The robust nature of the manganese(I) catalysis regime was reflected by the first C-H/C-C functionalization on amino acids under racemization-free reaction conditions. Detailed experimental and computational mechanistic studies provided strong evidence for a facile C-H activation and a rate-determining C-C cleavage, with considerable contribution from London dispersion interactions.

  12. Observation of the decay $\\psi(3686)$ $\\rightarrow$ $\\Lambda\\bar\\Sigma^{\\pm}\\pi^{\\mp}+c.c.$

    CERN Document Server

    Ablikim, M; Ai, X C; Albayrak, O; Ambrose, D J; An, F F; An, Q; Bai, J Z; A, R Baldini Ferroli; Ban, Y; Bennett, J V; A, M Bertani; Bian, J M; Boger, E; Bondarenko, O; Boyko, I; Braun, S; Briere, R A; Cai, H; Cai, X; A, O Cakir; A, A Calcaterra; Cao, G F; B, S A Cetin; Chang, J F; Chelkov, G; Chen, G; Chen, H S; Chen, J C; Chen, M L; Chen, S J; Chen, X; Chen, X R; Chen, Y B; Cheng, H P; Chu, X K; Chu, Y P; Cronin-Hennessy, D; Dai, H L; Dai, J P; Dedovich, D; Deng, Z Y; Denig, A; Denysenko, I; Destefanis, M; Ding, W M; Ding, Y; Dong, C; Dong, J; Dong, L Y; Dong, M Y; Du, S X; Fang, J; Fang, S S; Fang, Y; Fava, L; Feng, C Q; Fu, C D; Fu, J L; Fuks, O; Gao, Q; Gao, Y; Geng, C; Goetzen, K; Gong, W X; Gradl, W; Greco, M; Gu, M H; Gu, Y T; Guan, Y H; Guo, A Q; Guo, L B; Guo, T; Guo, Y P; Han, Y L; Harris, F A; He, K L; He, M; He, Z Y; Held, T; Heng, Y K; Hou, Z L; Hu, C; Hu, H M; Hu, J F; Hu, T; Huang, G M; Huang, G S; Huang, J S; Huang, L; Huang, X T; Hussain, T; Ji, C S; Ji, Q; Ji, Q P; Ji, X B; Ji, X L; Jiang, L L; Jiang, X S; Jiao, J B; Jiao, Z; Jin, D P; Jin, S; Jing, F F; Johansson, T; Kalantar-Nayestanaki, N; Kang, X L; Kavatsyuk, M; Kloss, B; Kopf, B; Kornicer, M; Kuehn, W; Kupsc, A; Lai, W; Lange, J S; Lara, M; Larin, P; Leyhe, M; Li, C H; Li, Cheng; Li, Cui; Li, D; Li, D M; Li, F; Li, G; Li, H B; Li, J C; Li, K; Li, Lei; Li, P R; Li, Q J; Li, T; Li, W D; Li, W G; Li, X L; Li, X N; Li, X Q; Li, X R; Li, Z B; Liang, H; Liang, Y F; Liang, Y T; Liao, G R; Lin, D X; Liu, B J; Liu, C L; Liu, C X; Liu, F H; Liu, Fang; Liu, Feng; Liu, H B; Liu, H H; Liu, H M; Liu, J; Liu, J P; Liu, K; Liu, K Y; Liu, P L; Liu, Q; Liu, S B; Liu, X; Liu, Y B; Liu, Z A; Liu, Zhiqiang; Liu, Zhiqing; Loehner, H; Lou, X C; Lu, G R; Lu, H J; Lu, H L; Lu, J G; Lu, X R; Lu, Y; Lu, Y P; Luo, C L; Luo, M X; Luo, T; Luo, X L; Lv, M; Ma, F C; Ma, H L; Ma, Q M; Ma, S; Ma, T; Ma, X Y; Maas, F E; Maggiora, M; Malik, Q A; Mao, Y J; Mao, Z P; Messchendorp, J G; Min, J; Min, T J; Mitchell, R E; Mo, X H; Moeini, H; Morales, C Morales; Moriya, K; Muchnoi, N Yu; Nefedov, Y; Nikolaev, I B; Ning, Z; Nisar, S; Niu, X Y; Olsen, S L; Ouyang, Q; B, S Pacetti; Pelizaeus, M; Peng, H P; Peters, K; Ping, J L; Ping, R G; Poling, R; Prencipe, E; Qi, M; Qian, S; Qiao, C F; Qin, L Q; Qin, X S; Qin, Y; Qin, Z H; Qiu, J F; Rashid, K H; Redmer, C F; Ripka, M; Rong, G; Ruan, X D; Sarantsev, A; Schinning, K; Schumann, S; Shan, W; Shao, M; Shen, C P; Shen, X Y; Sheng, H Y; Shepherd, M R; Song, W M; Song, X Y; Spataro, S; Spruck, B; Sun, G X; Sun, J F; Sun, S S; Sun, Y J; Sun, Y Z; Sun, Z J; Sun, Z T; Tang, C J; Tang, X; Tapan, I; Thorndike, E H; Toth, D; Ullrich, M; B, I Uman; Varner, G S; Wang, B; Wang, D; Wang, D Y; Wang, K; Wang, L L; Wang, L S; Wang, M; Wang, P; Wang, P L; Wang, Q J; Wang, S G; Wang, W; Wang, X F; A, Y D Wang; Wang, Y F; Wang, Y Q; Wang, Z; Wang, Z G; Wang, Z H; Wang, Z Y; Wei, D H; Wei, J B; Weidenkaff, P; Wen, S P; Werner, M; Wiedner, U; Wolke, M; Wu, G G; Wu, L H; Wu, N; Wu, W; Wu, Z; Xia, L G; Xia, Y; Xiao, D; Xiao, Z J; Xie, Y G; Xiu, Q L; Xu, G F; Xu, L; Xu, Q J; Xu, Q N; Xu, X P; Xue, Z; Yan, L; Yan, W B; Yan, W C; Yan, Y H; Yang, H X; Yang, Y; Yang, Y X; Ye, H; Ye, M; Ye, M H; Yu, B X; Yu, C X; Yu, H W; Yu, J S; Yu, S P; Yuan, C Z; Yuan, W L; Yuan, Y; Zafar, A A; A, A Zallo; Zang, S L; Zeng, Y; Zhang, B X; Zhang, B Y; Zhang, C; Zhang, C B; Zhang, C C; Zhang, D H; Zhang, H H; Zhang, H Y; Zhang, J J; Zhang, J L; Zhang, J Q; Zhang, J W; Zhang, J Y; Zhang, J Z; Zhang, S H; Zhang, X J; Zhang, X Y; Zhang, Y; Zhang, Y H; Zhang, Z H; Zhang, Z P; Zhang, Z Y; Zhao, G; Zhao, J W; Zhao, Lei; Zhao, Ling; Zhao, M G; Zhao, Q; Zhao, Q W; Zhao, S J; Zhao, T C; Zhao, X H; Zhao, Y B; Zhao, Z G; Zhemchugov, A; Zheng, B; Zheng, J P; Zheng, Y H; Zhong, B; Zhou, L; Zhou, Li; Zhou, X; Zhou, X K; Zhou, X R; Zhou, X Y; Zhu, K; Zhu, K J; Zhu, X L; Zhu, Y C; Zhu, Y S; Zhu, Z A; Zhuang, J; Zou, B S; Zou, J H

    2013-01-01

    Using a sample of $1.06\\times10^{8}$ $\\psi(3686)$ events collected with the BESIII detector, we present the first observation of the decays of $\\psi(3686)$ $\\rightarrow$ $\\Lambda\\bar\\Sigma^{+}\\pi^{-}+c.c.$ and $\\psi(3686)$ $\\rightarrow$ $\\Lambda\\bar\\Sigma^{-}\\pi^{+}+c.c.$. The branching fractions are measured to be $\\mathcal{B}(\\psi(3686) \\rightarrow \\Lambda\\bar\\Sigma^{+}\\pi^{-} + c.c.)=(1.40\\pm 0.03 \\pm 0.13)\\times10^{-4}$ and $\\mathcal{B}(\\psi(3686) \\rightarrow \\Lambda\\bar\\Sigma^{-}\\pi^{+}+c.c.)=(1.54\\pm 0.04 \\pm 0.13)\\times10^{-4}$, where the first errors are statistical and the second ones systematic.

  13. Computational study of the enthalpies of formation, DeltafH degrees, and mean bond enthalpies, mBEs, of H4-nEXn0/- and H3-nEXn+/0 (E=C, B; X=F-I).

    Science.gov (United States)

    Raabe, Ines; Himmel, Daniel; Krossing, Ingo

    2007-12-20

    To compensate for lacking experimental standard enthalpies of formation DeltafH degrees of haloboranes/-boranates as well as the isoelectronic halocarbenium ions and halomethanes, high-level quantum chemical calculations up to the ccsd(t)/(SDB-)aug-cc-pVQZ level have been performed to establish these values. Very reliable experimental data (e.g., DeltafH degrees of HCl, F, and CH4) or at the G3 level established values (e.g., DeltafH degrees of CF3+=410 kJ mol(-1)) were used as anchor points to obtain accurate absolute DeltafH degrees and mean bond enthalpy (mBE) values. To further minimize systematic errors of the protocol, all derived quantities were assessed in isodesmic reactions at the G3 and ccsd(t) level using the (SDB-)aug-cc-PVTZ basis set. The obtained DeltafH degrees values are in very good agreement to (scarcely available) accurate experimental and computational data. Almost all B-containing compounds have been assessed for the first time. We derived "best" DeltafH degrees values and used them to determine the mean E-X bond enthalpies in H4-nEXn-/0 and H3-nEXn0/+ (with n=1-3, E=B, C, and X=F-I). In each of the series, the DeltafH degrees values increase from fluorine to iodine, and except for the iodine-containing carbenium ions and the bromo- and iodomethanes, the DeltafH degrees values become lower with the more halogen atoms that are present in the particle. The boron containing species always have a lower DeltafH degrees than the isoelectronic carbenium ions and methanes, and the H4-nEXn-/0 are lower in energy than the parent H3-nEXn+/0. This reflects the greater average B-X bond strengths.

  14. Linux平台C/C++和汇编昆合编程%C/C++ Language and Assemble Language Combination Programming Based on Linux

    Institute of Scientific and Technical Information of China (English)

    郝丽花; 张世禄; 张杨军

    2004-01-01

    Linux的核心代码大部分是用C语言编写的,不可避免的其中还有一部分是用汇编语言写成的.有些汇编语言代码是利用gcc的内嵌语句直接嵌在C语言程序中的;还有一些则是写在汇编源程序中的,特别是Linux的启动代码部分.文章介绍了在Linux的gcc/g++环境下,C/C++程序中如何内嵌汇编代码;分析了汇编源程序如何与调用它的C/C++程序接口.

  15. Spectroscopic and thermodynamic evidence of dimer and trimer hydrogen bonded complex formation between chloroform and 2-butanone. Excess Molar enthalpy for the chloroform + 2-butanone binary system at 303 K.

    Science.gov (United States)

    Gómez Marigliano, Ana C; Campos, Viviana del Valle; Fernández, Lis; Roldán, M L; Sólimo, Horacio N

    2013-05-02

    FT-Raman and FT-infrared spectra of pure chloroform (A) and 2-butanone (B), as well as of the binary system chloroform + 2-butanone, were recorded to investigate the type and nature of the intermolecular complexes formed when both chemicals are mixed. The optimized structures and vibrational frequencies for 2-butanone, chloroform, and their 1:1 and 1:2 complexes were calculated by means of density functional theory (DFT) techniques using the B3LYP functional combined with the 6-31G(d,p) and 6-311++G(d,p) basis set. The recorded FTIR and Raman spectra confirm the existence of these types of hydrogen-bonded complexes, making it possible, furthermore, to calculate the heteroassociation constants. Heat of mixing at 303 K over the whole mole fraction range at atmospheric pressure was also measured. The excess molar enthalpy was fitted to a Redlich-Kister-type equation, using least-squares to obtain its dependence on concentration. The ideal associated solution model was also used to calculate these equilibrium constants among the chemical species in solution, which compare well with that calculated with the spectral determinations and the enthalpy of hydrogen bond formation. Furthermore, the McGlashan-Rastogi linearization test was also used to provide thermodynamic evidence about the stoichiometry of the formed complexes.

  16. Effectiveness of Diffusion Barrier Coatings for Mo-Re Embedded in C/SiC and C/C

    Science.gov (United States)

    Glass, David E.; Shenoy, Ravi N.; Wang, Zeng-Mei; Halbig, Michael C.

    2001-01-01

    Advanced high-temperature cooling applications may often require the elevated-temperature capability of carbon/silicon carbide or carbon/carbon composites in combination with the hermetic capability of metallic tubes. In this paper, the effects of C/SiC and C/C on tubes fabricated from several different refractory metals were evaluated. Though Mo, Nb, and Re were evaluated in the present study, the primary effort was directed toward two alloys of Mo-Re, namely, arc cast Mo-41Re and powder metallurgy Mo-47.5Re. Samples of these refractory metals were subjected to either the PyC/SiC deposition or embedding in C/C. MoSi2(Ge), R512E, and TiB2 coatings were included on several of the samples as potential diffusion barriers. The effects of the processing and thermal exposure on the samples were evaluated by conducting burst tests, microhardness surveys, and scanning electron microscopic examination (using either secondary electron or back scattered electron imaging and energy dispersive spectroscopy). The results showed that a layer of brittle Mo-carbide formed on the substrates of both the uncoated Mo-41Re and the uncoated Mo-47.5Re, subsequent to the C/C or the PyC/SiC processing. Both the R512E and the MoSi2(Ge) coatings were effective in preventing not only the diffusion of C into the Mo-Re substrate, but also the formation of the Mo-carbides. However, none of the coatings were effective at preventing both C and Si diffusion without some degradation of the substrate.

  17. 使用Visual Leak Detector检测c/c++程序内存泄漏%Memory Leak Detection in c/c++ Programs with Visual Leak Detector

    Institute of Scientific and Technical Information of China (English)

    杨磊; 汪仁煌; 刘洪江; 黄颖怡

    2008-01-01

    针对内存泄漏检测问题,本文通过示例说明使用软件Visual Leal Detector 来检测泄漏点的方法.通过实验说明该方法在检测一般的c/c++程序内存泄漏时,可以提高检测效率.

  18. The interface between C/C++ and assembler in gcc/g++%gcc/g++下C/C++和汇编的接口

    Institute of Scientific and Technical Information of China (English)

    陈付龙; 汪迅宝; 李明东

    2004-01-01

    汇编语言是低级语言,与硬件和操作系统紧密联系.它能够完成许多其他语言所不能完成的功能.笔者较详细地分析了在Linux平台的gcc/g++开发环境下,汇编程序与调用它的C/C++程序的接口约定.

  19. Formation and High Reactivity of the anti-Dioxo Form of High-Spin μ-Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C-H Bonds.

    Science.gov (United States)

    Kodera, Masahito; Ishiga, Shin; Tsuji, Tomokazu; Sakurai, Katsutoshi; Hitomi, Yutaka; Shiota, Yoshihito; Sajith, P K; Yoshizawa, Kazunari; Mieda, Kaoru; Ogura, Takashi

    2016-04-18

    Recently, it was shown that μ-oxo-μ-peroxodiiron(III) is converted to high-spin μ-oxodioxodiiron(IV) through O-O bond scission. Herein, the formation and high reactivity of the anti-dioxo form of high-spin μ-oxodioxodiiron(IV) as the active oxidant are demonstrated on the basis of resonance Raman and electronic-absorption spectral changes, detailed kinetic studies, DFT calculations, activation parameters, kinetic isotope effects (KIE), and catalytic oxidation of alkanes. Decay of μ-oxodioxodiiron(IV) was greatly accelerated on addition of substrate. The reactivity order of substrates is toluenecumenereaction with toluene/[D8 ]toluene is 95 at -30 °C, which the largest in diiron systems reported so far. The present diiron complex efficiently catalyzes the oxidation of various alkanes with H2 O2 .

  20. Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    Science.gov (United States)

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M.; Kassim, Mohammad B.

    2014-09-01

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-{3-(pyridin-2-yl)-pyrazolato} and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the CbenzoylN bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the {3-(pyridin-2-yl)-pyrazolato}{3-(pyridin-2-yl)-1H-pyrazole}Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ɛ = 116 dm3 mol-1 cm-1) supports the presence of Cu(II) centres.

  1. Bonding Character and Formation Energy of Point Defects of He and Vacancy on (001) Surface of bcc Iron by First Principle Calculations

    Institute of Scientific and Technical Information of China (English)

    Jun CAI; Daogang LU

    2013-01-01

    The structure and energy of He impurities and vacancy on (001) surface of bcc iron are investigated by an ab initio method.Three cases for stabilities of a He atom at the surface are found: some of He atoms at surface atomic layers (SAL) relax into vacuum gap; some of surface He atoms at octahedral interstitial site relax into more stable tetrahedral interstitial site; some of surface He atoms still stay at tetrahedral interstitial site.The un-stability of the He atom at the surface system can be explained by deformation mechanism of charge densities and electronic densities of states.It is found that formation energy of the point defects from the topmost SAL to bulk-like atomic layer increase gradually,for example,the formation energies of a monovacancy at the first five topmost SALs are equal to 0.33,1.56,2.04,2.02 and 2.11 eV,respectively.The magnetic moments of Fe atoms in the surface atomic layers are also calculated.

  2. Characteristics of an optimized active metal cast joint between copper and C/C

    Energy Technology Data Exchange (ETDEWEB)

    Schedler, B [Technology Centre of PLANSEE SE, A-6600 Reutte (Austria); Huber, T [Technology Centre of PLANSEE SE, A-6600 Reutte (Austria); Friedrich, T [Technology Centre of PLANSEE SE, A-6600 Reutte (Austria); Eidenberger, E [Department of Physical Metallurgy and Materials Testing, Montanuniversitaet Leoben, A-8700 Leoben (Austria); Kapp, M [Austrian Academy of Sciences, Erich-Schmid-Institute of Material Science, A-8700 Leoben (Austria); Scheu, C [Department of Physical Metallurgy and Materials Testing, Montanuniversitaet Leoben, A-8700 Leoben (Austria); Pippan, R [Austrian Academy of Sciences, Erich-Schmid-Institute of Material Science, A-8700 Leoben (Austria); Clemens, H [Department of Physical Metallurgy and Materials Testing, Montanuniversitaet Leoben, A-8700 Leoben (Austria)

    2007-03-15

    In this paper, an optimized active metal cast copper to carbon composite (C/C) joint is examined. Mechanical characterization by means of shear and tensile tests as well as fracture toughness measurements at ambient temperature are employed, which show that the obtained values are above those of the reference joint that has been used so far. The phases occurring at the interface region and the fracture surface of the optimized joint are investigated in detail to explain the improved mechanical behaviour. The composition and the morphology at the interface region are analysed by means of scanning electron microscopy. In addition, the crack path is analysed by stereomicroscopy. The improved properties can be explained by the circumstance that the fracture of the optimized joint is not restricted to the interface between the occurring carbide and the C/C but changes between C/C, the carbide to C/C interface and the copper, depending on the local structure in the C/C composite.

  3. Active Metal Brazing and Characterization of Brazed Joints in C-C and C-SiC Composites to Copper-Clad-Molybdenum System

    Science.gov (United States)

    Singh, M.; Asthana, R.

    2008-01-01

    Carbon/carbon composites with CVI and resin-derived matrices, and C/SiC composites reinforced with T-300 carbon fibers in a CVI SiC matrix were joined to Cu-clad Mo using two Ag-Cu braze alloys, Cusil-ABA (1.75% Ti) and Ticusil (4.5% Ti). The brazed joints revealed good interfacial bonding, preferential precipitation of Ti at the composite/braze interface, and a tendency toward delamination in resin-derived C/C composite. Extensive braze penetration of the inter-fiber channels in the CVI C/C composites was observed. The Knoop microhardness (HK) distribution across the C/C joints indicated sharp gradients at the interface, and a higher hardness in Ticusil than in Cusil-ABA. For the C/SiC composite to Cu-clad-Mo joints, the effect of composite surface preparation revealed that ground samples did not crack whereas unground samples cracked. Calculated strain energy in brazed joints in both systems is comparable to the strain energy in a number of other ceramic/metal systems. Theoretical predictions of the effective thermal resistance suggest that such joined systems may be promising for thermal management applications.

  4. Comprehensive analysis of individual pulp fiber bonds quantifies the mechanisms of fiber bonding in paper

    Science.gov (United States)

    Hirn, Ulrich; Schennach, Robert

    2015-05-01

    The process of papermaking requires substantial amounts of energy and wood consumption, which contributes to larger environmental costs. In order to optimize the production of papermaking to suit its many applications in material science and engineering, a quantitative understanding of bonding forces between the individual pulp fibers is of importance. Here we show the first approach to quantify the bonding energies contributed by the individual bonding mechanisms. We calculated the impact of the following mechanisms necessary for paper formation: mechanical interlocking, interdiffusion, capillary bridges, hydrogen bonding, Van der Waals forces, and Coulomb forces on the bonding energy. Experimental results quantify the area in molecular contact necessary for bonding. Atomic force microscopy experiments derive the impact of mechanical interlocking. Capillary bridges also contribute to the bond. A model based on the crystal structure of cellulose leads to values for the chemical bonds. In contrast to general believe which favors hydrogen bonding Van der Waals bonds play the most important role according to our model. Comparison with experimentally derived bond energies support the presented model. This study characterizes bond formation between pulp fibers leading to insight that could be potentially used to optimize the papermaking process, while reducing energy and wood consumption.

  5. Assembly of an allenylidene ligand, a terminal alkyne, and an acetonitrile molecule: formation of osmacyclopentapyrrole derivatives.

    Science.gov (United States)

    Bolaño, Tamara; Castarlenas, Ricardo; Esteruelas, Miguel A; Oñate, Enrique

    2006-03-29

    Treatment in acetonitrile at -30 C of the hydride-alkenylcarbyne complex [OsH([triple bond]CCH=CPh2)(CH3CN)2(P(i)Pr3)2][BF4]2 (1) with (t)BuOK produces the selective deprotonation of the alkenyl substituent of the carbyne and the formation of the bis-solvento hydride-allenylidene derivative [OsH(=C=C=CPh2)(CH3CN)2(P(i)Pr3)2]BF4 (2), which under carbon monoxide atmosphere is converted into [Os(CH=C=CPh2)(CO)(CH3CN)2(P(i)Pr3)2]BF4 (3). When the treatment of 1 with (t)BuOK is carried out in dichloromethane at room temperature, the fluoro-alkenylcarbyne [OsHF([triple bond]CCH=CPh2)(CH3CN)(P(i)Pr3)2]BF4 (4) is isolated. Complex 2 reacts with terminal alkynes. The reactions with phenylacetylene and cyclohexylacetylene afford [Os[(E)-CH=CHR](=C=C=CPh2)(CH3CN)2(P(i)Pr3)2]BF4 (R = Ph (5), Cy (6)), containing an alkenyl ligand beside the allenylidene, while the reaction with acetylene in dichloromethane at -20 degrees C gives the hydride-allenylidene-pi-alkyne [OsH(=C=C=CPh2)(eta2-HC[triple bond]CH)(P(i)Pr3)2]BF4 (7), with the alkyne acting as a four-electron donor ligand. In acetonitrile under reflux, complexes 5 and 6 are transformed into the osmacyclopentapyrrole compounds [Os[C=C(CPh2CR=CH)CMe=NH](CH3CN)2]BF4 (R = Ph (8), Cy (9)), as a result of the assembly of the allenylidene ligand, the alkenyl group, and an acetonitrile molecule. The X-ray structures of 2, 5, and 8 are also reported.

  6. Diagraphies de cimentation : vers une analyse de la qualité du contact ciment-formation Cement Logging: Toward an Analysis of the Quality of Cement-Formation Bonding

    Directory of Open Access Journals (Sweden)

    Isambourg P.

    2006-11-01

    Full Text Available Les compagnies pétrolières ont un réel besoin d'évaluer correctement les cimentations de leurs puits : l'étanchéité entre les différentes zones est-elle assurée? Pour ce faire, les outils soniques et ultra-soniques ont été mis au point. Jusqu'à présent, la qualité du contactcasing-ciment était analysée quantitativement et celle du contactciment-formation était analysée qualitativement par les spécialistes (outil VDL. Le progrès le plus important que l'on pouvait apporter dans les logsde cimentation était de détecter les défauts à l'interface ciment-formation. C'est ce que nous avons fait dans le cadre d'un projet financé par l'ARTEP (Association de Recherche sur les Techniques d'Exploitation du Pétrole comprenant Total, Gaz de France GDF, Institut Français du Pétrole (IFP, et Elf Aquitaine Production (EAP. Les expériences laboratoires effectuées au Service Analyse FLuides de Boussens ont été conçues en injectant du ciment entre un casing et une formation-simulée avec présence, ou non, de boue d'épaisseur variable. Des formations rapides ou lentes, ainsi que des ciments, rapides ou lents, ont été utilisés. Les échos ultrasoniques, obtenus à l'aide d'une sonde CET en céramique, ont été enregistrés et analysés. La théorie, comme les expériences, ont montré que les échos ultrasoniques sont modifiés en présence de boue et/ou de gaz. Les relations entre la forme de l'onde ultrasonique et la présence de boue et de gaz entre le ciment et la formation ont été établies. Une procédure de traitement est proposée avec ses limites. Oil companies have a real need to make a correct assessment of cementing jobs in their wells. Is the seal ensured between different zones? To do this, sonic and ultrasonic logging tools have been developed. Up to now, the quality of the casing-cement contacthas been analyzed quantitatively, and that of the cement-formation contacthas been analyzed qualitatively by

  7. Monitoring and Diagnostics for C/C++ Real-Time Applications

    CERN Document Server

    Fischer, Yves

    Knowledge about the internal state of computational processes is essential for problem diagnostics as well as for constant monitoring and pre-failure recognition. The CMX li- brary provides monitoring capabilities similiar to the Java Management Extensions (JMX) for C and C++ applications. This thesis provides a detailed analysis of the requirements for monitoring and diagnos- tics of the C/C++ processes at CERN. The developed CMX library enables real-time C/C++ processes to expose values with- out harming their normal execution. CMX is portable and can be integrated in different monitoring architectures.

  8. Experimental study on thermophysical properties of C/C composites at high temperature

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wei; YI Fa-jun; HAN Jie-cai; MENG Song-he

    2006-01-01

    The coefficient of thermal expansion, thermal diffusivity and specific heat of C/C composites from room temperature to ultra high temperature were experimentally investigated. Thermal conductivity and thermal stress resistance of the composites were therefore computed based on experimental results. The results show that the composite has a very low thermal expansion coefficient. Thermal diffusivity decreases exponentially with temperature increase. The specific heat increases linearly as the temperature rises, and the variation trend of thermal conductivity is similar to that of thermal diffusivity. The thermal stress coefficient of C/C composite has little change with temperature variation, and thermal stress resistance of the composite at high temperature is stable.

  9. Mo2C改性涂层制备温度对C/C-Cu复合材料组织和性能的影响%Influence of preparation temperature of Mo2C interlayer on microstructure and properties of C/C-Cu composites

    Institute of Scientific and Technical Information of China (English)

    周文艳; 易茂中; 冉丽萍; 彭可; 葛毅成

    2015-01-01

    In order to improve the wetting ability between molten copper and C/C preform, Mo2C interlayer was fabricated on the internal surface of C/C preform via molten salt deposition using ammonium paramolybdate as reactant. Then, C/C-Cu composites were prepared by pressureless infiltration. The influences of preparation temperature of Mo2C interlayer on the microstructure and properties of Mo2C interlayer and C/C-Cu composite were investigated. The results show that the Mo2C interlayer covered internal pore surface of the C/C preform uniformly has a good interface bonding with C/C substrate and Cu. With the increase of preparation temperature in the range of 950−1150℃, the thickness of the Mo2C interlayer increases from 2.0 μm to 6.5 μm, the density of C/C-Cu composite increases, the electrical resistivity decreases, the flexural strength firstly increases and then decreases, and reaches the maximum value (251.83 MPa) at 1000 ℃. The friction coefficient of the C/C-Cu composite firstly increases and then decreases to a stable value with friction time increasing. With the increase of the reaction temperature, the friction coefficient increases, the volume abrasion rate firstly decreases and then increases, and reaches the minimum value at 1000℃.%以仲钼酸铵为反应物,采用熔盐法在低密度C/C复合材料孔隙表面制备Mo2C涂层,改善Cu与C/C坯体的润湿性,然后通过无压熔渗Cu制备C/C-Cu复合材料,研究了Mo2C改性层制备温度对Mo2C涂层和C/C-Cu复合材料组织结构及性能的影响。结果表明:Mo2C涂层在坯体内部孔隙表面分布均匀,且与炭基体和Cu均有良好的界面结合。在950~1150℃范围内,随涂层反应温度的提高,Mo2C层厚度由2.0μm逐渐增大到6.5μm,C/C-Cu复合材料的密度逐渐增大,电阻率逐渐降低;抗弯强度呈现先增大后减小趋势,在涂层反应温度为1000℃时呈现最大值251.83 MPa。复合材料的摩擦因数均随磨损时

  10. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;

    1994-01-01

    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  11. Eco-Friendly Smokeless Al2O3-SiC-C Brick for Hot Metal Ladle

    Institute of Scientific and Technical Information of China (English)

    Santanu MUKHOPADHYAY; Shankha CHATYERJEE; Manoj K NANDA

    2008-01-01

    Hot metal transfer ladles were historically lined with high alumina refractories because of compatibility of high alumina refractories with the highly acidic slag, which is transferred from the iron making plant along with hot metal. With the introduction of higher capacity ladles, technological advancement in the process and increased productivity, calls for a higher campaign life of hot metal ladles, which could not be performed by ordinary high alumina refractories. Resin bonded Al2O3-SiC-C(hereinafter ASC)bricks gradually developed which at present taking place replacing the conventional refractories. Considerable work has been carried out in developing the ASC refractory to reach the present state. However, for higher capacity ladles still there is a lot of scope for improvement The present paper deals with the newly developed ASC bricks, which was used in 165 ton capacity hot metal ladles in one European plant and has given a substantial increase in performance. But, the customer was not fully satisfied since the brick was reported to produce smokes during preheating of the ladle. In the subsequent supply the smoke generation problem was taken care by adjusting the binders and additives and eco-friendly bricks were re-engineered and supplied to the same plant, which also performed splendidly and created all time record in their plant history.

  12. Lead Screening for HIV of C-C Chemokine Receptor Type 5 Receptor Inhibited by Traditional Chinese Medicine

    Directory of Open Access Journals (Sweden)

    Tzu-Chieh Hung

    2014-01-01

    Full Text Available The acquired immunodeficiency syndrome (AIDS, caused by the human immunodeficiency virus (HIV, has become a serious world-wide problem because of this disease's rapid propagation and incurability. Recent research has pointed out that the C-C chemokine receptor type 5 (CCR5 is an important target for HIV infection. The traditional Chinese medicine (TCM database (http://tcm.cmu.edu.tw/ has been screened for molecular compounds that, by simulating molecular docking and molecular dynamics, may protect CCR5 against HIV. Saussureamine C, 5-hydroxy-L-tryptophan, and abrine are selected based on the docking score being higher than Maraviroc and other TCM compounds. The molecular dynamics are helpful in the analysis and detection of protein-ligand interactions. According to the docking poses, hydrophobic interactions, and hydrogen bond variations, this research surmises TRP86, TYR108, GLN194, TYR251, and GLU283 are the main regions of important amino acids in CCR5. In addition to the detection of TCM compound efficacy, we suggest saussureamine C is better than the others for maintaining protein composition during protein-ligand interaction, based on the structural variation.

  13. Hairy carbon nanotube@nano-Pd heterostructures: design, characterization, and application in Suzuki C-C coupling reaction.

    Science.gov (United States)

    Mahouche Chergui, Samia; Ledebt, Alexandre; Mammeri, Fayna; Herbst, Frédéric; Carbonnier, Benjamin; Ben Romdhane, Hatem; Delamar, Michel; Chehimi, Mohamed M

    2010-10-19

    Poly(glycidyl methacrylate), PGMA, was prepared via ATRP in bulk solution, and its epoxy groups were further acid-hydrolyzed in order to obtain a polymer with glycerol moieties (noted POH). The POH chain end C-Br bonds were subjected to a nucleophilic attack by NaN(3), resulting in azide-terminated POH (POH-N(3)). The CNTs were modified by in-situ-generated alkynylated diazonium cations from the para-alkynylated aniline of the formulas H(2)N-C(6)H(4)-C≡C-H, yielding CNT-C(6)H(4)-C≡C-H nanotubes. The azide-functionalized polymer POH-N(3) was clicked to the alkynyl-modified CNTs giving CNT@POH hybrids, which were further subjected to an oxidation resulting in carboxylated polymer-modified CNTs (noted CNT@PCOOH). The as-designed hairy CNTs served as efficient platforms for the in-situ synthesis and massive loading of 3 nm sized palladium nanoparticles (NPs). The CNT@PCOOH@Pd heterostructures prepared so far exhibited an efficient catalytic effect in the C-C Suzuki coupling reaction and were regenerated up to four times without any significant loss of catalytic activity.

  14. Cold pressure welding - the mechanisms governing bonding

    DEFF Research Database (Denmark)

    Bay, Niels

    1979-01-01

    Investigations of the bonding surface in scanning electron microscope after fracture confirm the mechanisms of bond formation in cold pressure welding to be: fracture of work-hardened surface layer, surface expansion increasing the area of virgin surface, extrusion of virgin material through cracks...... of the original surface layer, and establishment of real contact and bonding between virgin material. This implies that normal pressure as well as surface expansion are basic parameters governing the bond strength. Experimental investigations of pressure welding Al-Al under plane strain compression in a specially...

  15. Development of C/C composite for the core component of the high temperature gas cooled reactor

    Energy Technology Data Exchange (ETDEWEB)

    Park, J. Y.; Kim, W. J.; Ryu, W. S.; Jang, J. H

    2005-01-15

    This report reviewed a state of the art on development of C/C composite for the core components for VHTR and described the followings items. The fabrication methods of C/C composites. Summary on the JAERI report (JAERI-Res 2002-026) on the process screening test for the selection of a proper C/C composite material. Review of the proceedings presented at the GEN-IV VHTR material PMB meeting. A status of the domestic commercial C/C composite. The published property data and the characteristics of the commercial C/C composite.

  16. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  17. Preparation of Biomorphic SiC/C Ceramics from Pine Wood via Supercritical Ethanol Infiltration

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Biomorphic (wood derived) carbide ceramics with an overall composition in the SiC/C was produced by supercritical ethanol infiltration of low viscosity tetraethylorthosilicate/supercritical ethanol into biologically derived carbon templates (CB-templates) and in situ hydrolysis into Si(OH)4-gel, the Si(OH)4-gel was calcined at 1400℃ to promote the polycondensation of Si(OH)4-gel into SiO2-phase and then carbonthermal reduction of the SiO2 with the biocarbon template into highly porous, biomorphic SiC/C ceramics. The phases and morphology conversion mechanism of resulting porous SiC/C ceramics have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR). Experimental results showed that the biomorphic cellular morphology of pinewood charcoal was remained in the porous SiC/C ceramic with high precision that consisted of β-SiC with minority of α-SiC and the remain free carbon existed in amorphous phase.

  18. Revis\\~ao da Constru\\c{c}\\~ao de Modelos Supersim\\'etricos

    CERN Document Server

    Rodríguez, M C

    2001-01-01

    Foi com base neste estudo que fizemos a constru\\c{c}\\~ao da vers\\~ao supersim\\'etrica dos modelos de simetria $SU(3)_{C} \\otimes SU(3)_{L} \\otimes U(1)_{N}$ \\cite{susy331}, apresentado no final da minha tese de doutorado \\cite{mcr1}. Bem como dos estudos fenomenol\\'ogicos subsequente \\cite{mcr}.

  19. Extraction and Visualization of Call Dependencies for Large C/C++ Code Bases : A Comparative Study

    NARCIS (Netherlands)

    Telea, Alexandru; Hoogendorp, Hessel; Ersoy, Ozan; Reniers, Dennie; Lanza, M; Storey, M; Muller, H

    2009-01-01

    Investigating program dependencies such as function calls is challenging for very large systems. We present here an integrated pipeline for extraction and visualization of call-and-hierarchy graphs for C/C++ programs. We present several adaptions and enhancements of a recent visualization method for

  20. Tribological characteristics of C/C-SiC braking composites under dry and wet conditions

    Institute of Scientific and Technical Information of China (English)

    LI Zhuan; XIAO Peng; XIONG Xiang; ZHU Su-hua

    2008-01-01

    C/C-SiC braking composites, based on reinforcement of carbon fibers and rnatrices of carbon and silicon carbide, were fabricated by warm compaction and in situ reaction process. The tribological characteristics of C/C-SiC braking composites under dry and wet conditions were investigated by means of MM-1000 type of friction testing machine. The influence of dry and wet conditions on the tribological characteristics of the C/C-SiC composites was ascertained. Under dry condition, C/C-SiC braking composites show superior tribological characteristics, including high coefficient of friction (0.38), good abrasive resistance (thickness loss is 1.10 μm per cycle) and steady breaking. The main wear mechanism is plastic deformation and abrasion caused by plough. Under wet condition, frictional films form on the worn surface. The coefficient of friction (0.35) could maintain mostly, and the thickness loss (0.70 μm per cycle) reduces to a certain extent. Furthermore, braking curves are steady and adhesion and oxidation are the main wear mechanisms.

  1. Al2O3-SiC-C Bricks for Hot Metal Pretreatment

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    @@ 1 Scope This standard specifies the classification,techni-cal requirements,test methods,inspection rules,packing,marking,transportation,storage and quality certificate of Al2O3-SiC-C bricks for hot metal pre-treatment.

  2. Al2O3 SiC-C Bricks for Hot Metal Pretreatment

    Institute of Scientific and Technical Information of China (English)

    Yu Lingyan; Peng Xigao

    2010-01-01

    @@ 1 Scope This standard specifies the classification,shape and dimensions,technical requirements,test methods,quality appraisal procedures,packing,marking,transportation,storage,and quality certificate of Al2O3SiC-C bricks for hot metal pretreatment.

  3. Re-mediated C-C coupling of pyridines and imidazoles.

    Science.gov (United States)

    Espinal Viguri, Maialen; Huertos, Miguel A; Pérez, Julio; Riera, Lucía; Ara, Irene

    2012-12-19

    Rhenium tricarbonyl complexes with three N-heterocyclic ligands (N-alkylimidazoles or pyridines) undergo deprotonation with KN(SiMe(3))(2) and then oxidation with AgOTf to afford complexes with pyridylimidazole or bipyridine bidentate ligands resulting from deprotonation, C-C coupling and rearomatization.

  4. Imidazole-nitrile or imidazole-isonitrile C-C coupling on rhenium tricarbonyl complexes.

    Science.gov (United States)

    Viguri, Maialen Espinal; Huertos, Miguel A; Pérez, Julio; Riera, Lucía

    2013-09-23

    Ligand activation: Deprotonation of the nitrile or isonitrile complexes [Re(CO)3(N-RIm)2(L)](+) (N-RIm = N-alkylimidazole; L = N≡CtBu, C≡NtBu) selectively afforded alkylidenamido or iminoacyl derivatives, respectively, in which C-C coupling has occurred. Protonation of the latter complex leads to aminocarbene products.

  5. 77 FR 10004 - C$ cMoney, Inc.; Order of Suspension of Trading

    Science.gov (United States)

    2012-02-21

    ... COMMISSION C$ cMoney, Inc.; Order of Suspension of Trading February 16, 2012. It appears to the Securities... the opinion that the public interest and the protection of investors require a suspension of trading... the Securities Exchange Act of 1934, that trading in the securities of the above-listed company...

  6. Task-Specific Ionic Liquids Catalyzed Carbon-Heteroatom Bond Formation Reactions%功能化离子液体催化碳-杂键形成反应

    Institute of Scientific and Technical Information of China (English)

    李满; 杨磊; 韩峰; 陈静; 夏春谷

    2013-01-01

    离子液体独特的溶剂性能使它在合成和催化领域得到了广泛的应用.然而,离子液体的经济问题和可能的环境友好性问题使得人们逐渐把目光投向了离子液体自身的催化性能.人们通过对离子液体结构的修饰设计出了各种具有特定催化性能的功能化离子液体.近年来功能化离子液体在催化碳-杂键形成反应方面有了相当多的应用.本文以形成的碳-杂原子键类型为主线,综述了功能化离子液体在催化碳-杂键形成反应方面的最新研究进展,涉及到了酸性离子液体、碱性离子液体、金属有机功能化离子液体、酸碱双功能离子液体、手性离子液体等多种类型的功能化离子液体.%Ionic liquids have emerged as excellent solvents for synthesis and catalysis in the past decades due to their special properties.However,their relatively high cost and potential risks to human health and environment make their function as catalysts rather than solvents more popular.Incorporating specific functional group(s) into one or both ions of ionic liquids to make them catalytic is highly important.Numerous so-called task-specific or functionalized ionic liquids are designed and successfully applied in catalyzing various reactions.In this review,we present the latest achievements in the carbon-heteroatom bond formation reactions catalyzed by task-specific ionic liquids.The contents are arranged according to the specific types of carbon-heteroatom bond formation reactions.As for the type of task-specific ionic liquids,this review focuses on acidic ionic liquids,basic ionic liquids,organometallic ionic liquids,acid-base bifunctional ionic liquids and chiral ionic liquids.

  7. Effectiveness of simplified dentin bonding systems.

    Science.gov (United States)

    Imai, T; Itoh, K; Tani, C; Manabe, A; Yamashita, T; Hisamitsu, H; Wakumoto, S

    1998-03-01

    The effectiveness of newly developed commercial dentin bonding systems (SB, MB II and KB) was evaluated by measuring the contraction gap width of a resin composite restored into a cylindrical dentin cavity prepared in an extracted human molar and by measuring the tensile bond strength to the flat dentin surface. In addition, calcium loss during dentin conditioning was analyzed using electron microanalyses. An experimental dentin bonding system composed of EDTA conditioning, GM solution priming and a bonding agent containing 10-MDP was employed as a control in which it was presumed that contraction gap formation was prevented completely. However, gap formation was observed using the three commercial simplified dentin bonding systems. SEM observation showed that the gap was formed between the resin composite and the top surface of the dentin cavity wall indicating that the fracture occurred at the adhesive interface, but never inside the dentin nor inside the resin composite.

  8. Temperature Dependence of a Period of the Modulated Structurein Atom-Vacancy Solid Solution Based on F.C.C. Nickel

    Directory of Open Access Journals (Sweden)

    V.A. Tatarenko

    2012-03-01

    Full Text Available The effective vacancy–vacancy interaction is considered. Based on the continuum approximation for the Fourier components of strain-induced vacancy–vacancy-interaction energies, approximating expressions for their expansion coefficients are obtained, depending on the elasticity moduli, longitudinal and transverse phonon frequencies, and vacancy-concentration-dependent lattice parameter. A non-analytical behaviour of the k-dependent Fourier components of the strain-induced vacancy–vacancy-interaction energies near the Brillouin zone centre, Avv(n + Bvv(n|k|2, is analysed. As shown, Avv(n  0 and Bvv(n  0 along all the high-symmetry [100], [110], [111] directions in reciprocal space for f.c.c. crystals with negative anisotropy factor. The criterion of modulated-structure formation for interacting vacancies in f.c.c. crystals is considered. Dependence of the f.c.c.-Ni–vacancies modulated-structure period on temperature is plotted. The effective vacancy–vacancy interaction is considered. Based on the continuum approximation for the Fourier components of strain-induced vacancy–vacancy-interaction energies, approximating expressions for their expansion coefficients are obtained, depending on the elasticity moduli, longitudinal and transverse phonon frequencies, and vacancy-concentration-dependent lattice parameter. A non-analytical behaviour of the k-dependent Fourier components of the strain-induced vacancy–vacancy-interaction energies near the Brillouin zone centre, Avv(n + Bvv(n|k|2, is analysed. As shown, Avv(n  0 and Bvv(n  0 along all the high-symmetry [100], [110], [111] directions in reciprocal space for f.c.c. crystals with negative anisotropy factor. The criterion of modulated-structure formation for interacting vacancies in f.c.c. crystals is considered. Dependence of the f.c.c.-Ni–vacancies modulated-structure period on temperature is plotted. The effective vacancy–vacancy interaction is considered

  9. Van Der Waals heterogeneous layer-layer carbon nanostructures involving π···H-C-C-H···π···H-C-C-H stacking based on graphene and graphane sheets.

    Science.gov (United States)

    Yuan, Kun; Zhao, Rui-Sheng; Zheng, Jia-Jia; Zheng, Hong; Nagase, Shigeru; Zhao, Sheng-Dun; Liu, Yan-Zhi; Zhao, Xiang

    2017-04-15

    Noncovalent interactions involving aromatic rings, such as π···π stacking, CH···π are very essential for supramolecular carbon nanostructures. Graphite is a typical homogenous carbon matter based on π···π stacking of graphene sheets. Even in systems not involving aromatic groups, the stability of diamondoid dimer and layer-layer graphane dimer originates from C - H···H - C noncovalent interaction. In this article, the structures and properties of novel heterogeneous layer-layer carbon-nanostructures involving π···H-C-C-H···π···H-C-C-H stacking based on [n]-graphane and [n]-graphene and their derivatives are theoretically investigated for n = 16-54 using dispersion corrected density functional theory B3LYP-D3 method. Energy decomposition analysis shows that dispersion interaction is the most important for the stabilization of both double- and multi-layer-layer [n]-graphane@graphene. Binding energy between graphane and graphene sheets shows that there is a distinct additive nature of CH···π interaction. For comparison and simplicity, the concept of H-H bond energy equivalent number of carbon atoms (noted as NHEQ), is used to describe the strength of these noncovalent interactions. The NHEQ of the graphene dimers, graphane dimers, and double-layered graphane@graphene are 103, 143, and 110, indicating that the strength of C-H···π interaction is close to that of π···π and much stronger than that of C-H···H-C in large size systems. Additionally, frontier molecular orbital, electron density difference and visualized noncovalent interaction regions are discussed for deeply understanding the nature of the C-H···π stacking interaction in construction of heterogeneous layer-layer graphane@graphene structures. We hope that the present study would be helpful for creations of new functional supramolecular materials based on graphane and graphene carbon nano-structures. © 2017 Wiley Periodicals, Inc.

  10. Log ASCII Standard (LAS) Files for Geophysical (Gamma Ray) Wireline Well Logs and Their Application to Geologic Cross Section C-C' Through the Central Appalachian Basin

    Science.gov (United States)

    Trippi, Michael H.; Crangle, Robert D.

    2009-01-01

    U.S. Geological Survey (USGS) regional geologic cross section C-C' (Ryder and others, 2008) displays key stratigraphic intervals in the central Appalachian basin. For this cross section, strata were correlated by using descriptions of well cuttings and gamma ray well log traces. This report summarizes the procedures used to convert gamma ray curves on paper well logs to the digital Log ASCII (American Standard Code for Information Interchange) Standard (LAS) format using the third-party software application Neuralog. The procedures could be used with other geophysical wireline logs also. The creation of digital LAS files from paper well logs by using Neuralog is very helpful, especially when dealing with older logs with limited or nonexistent digital data. The LAS files from the gamma ray logs of 11 wells used to construct cross section C-C' are included in this report. They may be downloaded from the index page as a single ZIP file.

  11. Supramolecular gel-assisted synthesis of double shelled Co@CoO@N-C/C nanoparticles with synergistic electrocatalytic activity for the oxygen reduction reaction

    Science.gov (United States)

    Wu, Zexing; Wang, Jie; Han, Lili; Lin, Ruoqian; Liu, Hongfang; Xin, Huolin L.; Wang, Deli

    2016-02-01

    Investigating active, stable, and low-cost materials for the oxygen reduction reaction is one of the key challenges in fuel-cell research. In this work, we describe the formation of N-doped carbon shell coated Co@CoO nanoparticles supported on Vulcan XC-72 carbon materials (Co@CoO@N-C/C) based on a simple supramolecular gel-assisted method. The double-shelled Co@CoO@N-C/C core-shell nanoparticles exhibit superior electrocatalytic activities for the oxygen reduction reaction compared to N-doped carbon and cobalt oxides, demonstrating the synergistic effect of the hybrid nanomaterials. Notably, the Co@CoO@N-C/C nanoparticles give rise to a comparable four-electron selectivity, long-term stability, and high methanol tolerance; all show a multi-fold improvement over the commercial Pt/C catalyst. The progress is of great importance in exploring advanced non-precious metal-based electrocatalysts for fuel cell applications.Investigating active, stable, and low-cost materials for the oxygen reduction reaction is one of the key challenges in fuel-cell research. In this work, we describe the formation of N-doped carbon shell coated Co@CoO nanoparticles supported on Vulcan XC-72 carbon materials (Co@CoO@N-C/C) based on a simple supramolecular gel-assisted method. The double-shelled Co@CoO@N-C/C core-shell nanoparticles exhibit superior electrocatalytic activities for the oxygen reduction reaction compared to N-doped carbon and cobalt oxides, demonstrating the synergistic effect of the hybrid nanomaterials. Notably, the Co@CoO@N-C/C nanoparticles give rise to a comparable four-electron selectivity, long-term stability, and high methanol tolerance; all show a multi-fold improvement over the commercial Pt/C catalyst. The progress is of great importance in exploring advanced non-precious metal-based electrocatalysts for fuel cell applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07929b

  12. Thermo-mechanical and tribological properties of phenolic polymers composites and C-C composites

    Directory of Open Access Journals (Sweden)

    Virgil MARINESCU

    2010-12-01

    Full Text Available Formaldehyde resin-based composites have been an inaugural step in obtaining and usingcomposite materials and they have grown rapidly because of their multiple uses, especially inelectrical and aeronautical field.Phenolic matrix composites represent a preliminary study to obtain mezophase carbon-carboncomposites for advanced materials as potential solutions for reentry shields of cosmic vehicles andlaunch subsystems, as elements of modern braking systems in aircraft or as potential solutions for thecomponents of the combustion chamber of rockets and also as hypersonic transport solutions for thefuture. Both phenolic matrix laminated composites and C-C mezophase matrix C-C composites wereobtained.This paper presents an evaluation of the mechanical and tribological behavior of the obtainedcomposites.

  13. IMPACT OF PHYSICAL AND CHEMICAL MUD CONTAMINATION ON WELLBORE CEMENT- FORMATION SHEAR BOND STRENGTH Authors: Arome Oyibo1 and Mileva Radonjic1 * 1. Craft and Hawkins Department of Petroleum Engineering, 2131 Patrick F. Taylor Hall, Louisiana State University, Baton Rouge, LA 70803, aoyibo1@tigers.lsu.edu, mileva@lsu.edu

    Science.gov (United States)

    Oyibo, A. E.

    2013-12-01

    Wellbore cement has been used to provide well integrity through zonal isolation in oil & gas wells and geothermal wells. Cementing is also used to provide mechanical support for the casing and protect the casing from corrosive fluids. Failure of cement could be caused by several factors ranging from poor cementing, failure to completely displace the drilling fluids to failure on the path of the casing. A failed cement job could result in creation of cracks and micro annulus through which produced fluids could migrate to the surface which could lead to sustained casing pressure, contamination of fresh water aquifer and blow out in some cases. In addition, cement failures could risk the release of chemicals substances from hydraulic fracturing into fresh water aquifer during the injection process. To achieve proper cementing, the drilling fluid should be completely displaced by the cement slurry. However, this is hard to achieve in practice, some mud is usually left on the wellbore which ends up contaminating the cement afterwards. The purpose of this experimental study is to investigate the impact of both physical and chemical mud contaminations on cement-formation bond strength for different types of formations. Physical contamination occurs when drilling fluids (mud) dries on the surface of the formation forming a mud cake. Chemical contamination on the other hand occurs when the drilling fluids which is still in the liquid form interacts chemically with the cement during a cementing job. We investigated the impact of the contamination on the shear bond strength and the changes in the mineralogy of the cement at the cement-formation interface to ascertain the impact of the contamination on the cement-formation bond strength. Berea sandstone and clay rich shale cores were bonded with cement cores with the cement-formation contaminated either physically or chemically. For the physically contaminated composite cores, we have 3 different sample designs: clean

  14. Influence of additives on oxidation resistance of binderless C/C composite

    Institute of Scientific and Technical Information of China (English)

    周声劢; 刘其城; 胡晓凯

    2003-01-01

    Experiment of adding B4C, SiC, and Si powders to improve oxidation resistance of the C/C compositeswas carried out. The results show that the increase of oxidation resistance is remarkable when the contents of B4C,SiC, and Si powders are 10%, 10%, and 5% in the composites, respectively. The regularities and mechanism ofthe effects of the ceramic powders on the oxidation resistance of the composites were also discussed.

  15. Long-term tropospheric trend of octafluorocyclobutane (c-C4F8 or PFC-318

    Directory of Open Access Journals (Sweden)

    T. Röckmann

    2012-01-01

    Full Text Available Air samples collected at Cape Grim, Tasmania between 1978 and 2008 and during a series of more recent aircraft sampling programmes have been analysed to determine the atmospheric abundance and trend of octafluorocyclobutane (c-C4F8 or PFC-318. c-C4F8 has an atmospheric lifetime in excess of 3000 yr and a global warming potential (GWP of 10 300 (100 yr time horizon, making it one of the most potent greenhouse gases detected in the atmosphere to date. The abundance of c-C4F8 in the Southern Hemisphere has risen from 0.35 ppt in 1978 to 1.2 ppt in 2010, and is currently increasing at a rate of around 0.03 ppt yr−1. It is the third most abundant perfluorocarbon (PFC in the present day atmosphere, behind CF4 (~75 ppt and C2F6 (~4 ppt. Although a number of potential sources of c-C4F8 have been reported, including the electronics and semi-conductor industries, there remains a large discrepancy in the atmospheric budget. Using a 2-D global model to derive top-down global emissions based on the Cape Grim measurements yields a recent (2007 emission rate of around 1.1 Gg yr−1 and a cumulative emission up to and including 2007 of 38.1 Gg. Emissions reported on the EDGAR emissions database for the period 1986–2005 represent less than 1% of the top-down emissions for the same period, which suggests there is a large unaccounted for source of this compound. It is also apparent that the magnitude of this source has varied considerably over the past 30 yr, declining sharply in the late 1980s before increasing again in the mid-1990s.

  16. Monte Carlo Simulation of Electron Swarms Parameters in c-C4F8/CF4 Gas Mixtures

    Institute of Scientific and Technical Information of China (English)

    LIU Xue-li; XIAO Deng-ming; WANG Yan-an; ZHANG Zhou-sheng

    2008-01-01

    The swarm parametes for c-C4F8/CF4 mixtures, including the density-normalized effective ionization coefficient, drift velocity and mean energy were calculated using Monte-Carlo method with the null collision technique. The overall density-reduced electric field strength could be varied between 150 and 500 Td,while the c-C4F8 content in gas mixtures is varied in the range of 0-100%. The value of the density-normalize deffective ionization coefficient shows a strong dependence on the c-C4F8 content, becoming more electronegative as the content of c-C4F8 is increased. The drift velocity of c-C4F4/CF4 mixtures is more affected by CF4. The calculated limiting field strength for c-C4F8/CF4 mixtures is higher than that of SF6/CF4.

  17. C/C-SiC Composites for Nozzle of Solid Propellant Ramjet

    Directory of Open Access Journals (Sweden)

    WANG Lingling

    2017-01-01

    Full Text Available Carbon fiber reinforced carbon and silicon carbide matrix composites for nozzle inner of solid propellant ramjet were prepared by using the hybrid process of "chemical vapor infiltration + precursor impregnation pyrolysis (CVI+PIP". The microstructure, flexural and anti-ablation properties of the C/C-SiC composites and hydraulic test and rocket motor hot firing test for nozzle inner of solid propellant ramjet were comprehensively investigated. The results show that when the flexural strength of the composite reachs 197 MPa, the fracture damage behavior of the composites presents typical toughness mode.Also the composites has excellent anti-ablative property, i.e., linear ablation rate is only 0.0063 mm·s-1 after 200 s ablation. The C/C-SiC component have excellent integral bearing performance with the hydraulic bursting pressure of 6.5 MPa, and the high temperature combination property of the C/C-SiC composite nozzle inner is verified through motor hot firing of solid propellant ramjet.

  18. A C/C++ Build System Based On Maven for the LHC Controls System

    CERN Document Server

    Nguyen Xuan, J; Dönszelmann, M

    2011-01-01

    The CERN accelerator controls system, mainly written in Java and C/C++, consists nowadays of 50 projects and 150 active developers. The controls group has decided to unify the development process and standards (e.g. project layout) using Apache Maven and Sonatype Nexus. Maven is the de-facto build tool for Java, it deals with versioning and dependency management, whereas Nexus is a repository manager. C/C++ developers were struggling to keep their dependencies on other CERN projects, as no versioning was applied, the libraries have to be compiled and available for several platforms and architectures, and finally there was no dependency management mechanism. This results in very complex Makefiles which were difficult to maintain. Even if Maven is primarily designed for Java, a plugin (Maven NAR) adapts the build process for native programming languages for different operating systems and platforms. However C/C++ developers were not keen to abandon their current Makefiles. Hence our approach was to combine the ...

  19. A new C=C embedded porphyrin sheet with superior oxygen reduction performance

    Institute of Scientific and Technical Information of China (English)

    Yawei Li[1; Shunhong Zhang[2; Jiabing Yu[1; Qian Wang[2; Qiang Sun[1,2,3; Puru Jena[3

    2015-01-01

    C2 is a well-known pseudo-oxygen unit with an electron affinity of 3.4 eV. We show that it can exhibit metal-ion like behavior when embedded in a porphyrin sheet and form a metal-free two-dimensional material with superior oxygen reduction performance. Here, the positively charged C=C units are highly active for oxygen reduction reaction (ORR) via dissociation pathways with a small energy barrier of 0.09 eV, much smaller than that of other non-platinum group metal (non-PGM) ORR catalysts. Using a microkinetics-based model we calculated the partial current density to be 3.0 mA/cm2 at 0.65 V vs. a standard hydrogen electrode (SHE), which is comparable to that of the state-of-the-art Pt/C catalyst. We further confirm that the C=C embedded porphyrin sheet is dynamically and thermally stable with a quasi-direct band gap of 1.14 eV. The superior catalytic performance and geometric stability make the metal-free C=C porphyrin sheet ideal for fuel cell applications.

  20. Determination of material properties for short fibre reinforced C/C-SiC

    Directory of Open Access Journals (Sweden)

    Hausherr J.-M.

    2015-01-01

    Full Text Available Determining the mechanical properties of short fibre reinforced CMC using standard sized coupons has always been a challenge due to a high statistical scattering of the measured values. Although the random orientation of short fibres results in a quasi-isotropic material behavior of 2D-structures with a sufficiently large volume, the small volume typical for test coupons usually results in a non-isotropic fibre orientation in the tested volume. This paper describes a method for manufacturing unidirectional oriented short fibre reinforced CMC materials and presents material properties of UD-C/C-SiC. After verifying the fibre orientation of the CMC using micro-computed tomography, coupons were extracted to determine the orthotropic material properties. These orthotropic material properties were then used to predict the properties of C/C-SiC with randomly distributed short fibres. To validate the method, micro-computed tomography is used to quantitatively determine the fibre orientation within coupons extracted from randomly distributed short fibre C/C-SiC. After mechanical three-point-bending tests, the measured stiffness and bending strength is compared with the predicted properties. Finally, the data are used to devise a method suited for reducing the inherent large spread of material properties associated with the measurement of CMC materials with randomly distributed short fibres.

  1. A first principles analysis of the effect of hydrogen concentration in hydrogenated amorphous silicon on the formation of strained Si-Si bonds and the optical and mobility gaps

    Energy Technology Data Exchange (ETDEWEB)

    Legesse, Merid; Nolan, Michael, E-mail: Michael.nolan@tyndall.ie; Fagas, Giorgos, E-mail: Georgios.fagas@tyndall.ie [Tyndall National Institute, University College Cork, Lee Maltings, Dyke Parade, Cork (Ireland)

    2014-05-28

    In this paper, we use a model of hydrogenated amorphous silicon generated from molecular dynamics with density functional theory calculations to examine how the atomic geometry and the optical and mobility gaps are influenced by mild hydrogen oversaturation. The optical and mobility gaps show a volcano curve as the hydrogen content varies from undersaturation to mild oversaturation, with largest gaps obtained at the saturation hydrogen concentration. At the same time, mid-gap states associated with dangling bonds and strained Si-Si bonds disappear at saturation but reappear at mild oversaturation, which is consistent with the evolution of optical gap. The distribution of Si-Si bond distances provides the key to the change in electronic properties. In the undersaturation regime, the new electronic states in the gap arise from the presence of dangling bonds and strained Si-Si bonds, which are longer than the equilibrium Si-Si distance. Increasing hydrogen concentration up to saturation reduces the strained bonds and removes dangling bonds. In the case of mild oversaturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structure shows that the extra hydrogen atoms form a bridge between neighbouring silicon atoms, thus increasing the Si-Si distance and increasing disorder in the sample.

  2. Functionalized olefin cross-coupling to construct carbon-carbon bonds

    Science.gov (United States)

    Lo, Julian C.; Gui, Jinghan; Yabe, Yuki; Pan, Chung-Mao; Baran, Phil S.

    2014-12-01

    Carbon-carbon (C-C) bonds form the backbone of many important molecules, including polymers, dyes and pharmaceutical agents. The development of new methods to create these essential connections in a rapid and practical fashion has been the focus of numerous organic chemists. This endeavour relies heavily on the ability to form C-C bonds in the presence of sensitive functional groups and congested structural environments. Here we report a chemical transformation that allows the facile construction of highly substituted and uniquely functionalized C-C bonds. Using a simple iron catalyst, an inexpensive silane and a benign solvent under ambient atmosphere, heteroatom-substituted olefins are easily reacted with electron-deficient olefins to create molecular architectures that were previously difficult or impossible to access. More than 60 examples are presented with a wide array of substrates, demonstrating the chemoselectivity and mildness of this simple reaction.

  3. Bonding with Your Baby

    Science.gov (United States)

    ... in infant massage in your area. Breastfeeding and bottle-feeding are both natural times for bonding. Infants respond ... activities include: participating together in labor and delivery feeding ( breast or bottle ); sometimes dad forms a special bond with baby ...

  4. Structural and Spectral Studies on the Ni(Ⅱ) Complexes of 1,5-Diazacyclooctane (DACO) Bearing Heterocyclic Pendants: Formation of a Two-dimensional Network Via Hydrogen Bonds and π-π Stacking Interactions

    Institute of Scientific and Technical Information of China (English)

    DU,Miao(杜淼); DU,Miao; XU,Qiang(徐强); XU,Qiang; GUO,Ya-Mei (郭亚梅); GUO,Ya-Mei; WENG,Lin-Hong(翁林红); WENG,Lin-Hong; BU,Xian-He (卜显和); BU,Xian-He

    2001-01-01

    A penta-coordinated Ni(II) complex with a 1,5-diazacyclooctane (DACO) ligand functionazed by two imidazole donor pendants, [NiiL1Cl] (ClO4)'HH2O (1) (where L1 = 1,5-bis (imidazol-4-ylmethyl)-1,S-diazacyclooctane) has been synthesized and characterized by X-ray diffraction, infrared spectra, elemental analyses, conductance, thermal analyses and UV-Vis techniques. Complex 1 crystallizes in triclinic crystal system, P-1 space group with a = 0.74782(7), b = 1.15082(10), c = 1.237s1(11) nm, a=82.090(2), β=73.011(2), γ=83.462(2)°, V= 1.00603(16) nn3, Mr = 486.00, Z=2,Dc=1.604 g/cm3, final R=0.0435, and wR=0.1244. The structures of 1 and its related complexes show that in all the three mononuclear complexes, each Ni(Ⅱ) center is penta-coordinated with a near regular square pyranid (RSP) to distorted square-pyramidal (DSP) coordination environment due to the boat/chair configuration of DACO ring in these complexes, and the degree of distortion increases with the augment of the size of the heterocyclic pendants. In addition, the most striking feature of complex 1 resides in the formation of a two-dimensional network structure through hydrogen bonds and stabilized by π-π stacking. The solution behaviors of the Ni(ⅡI) complexes are also discussed in detail.

  5. The catalytic role of uranyl in formation of polycatechol complexes

    Directory of Open Access Journals (Sweden)

    Halada Gary P

    2011-03-01

    Full Text Available Abstract To better understand the association of contaminant uranium with natural organic matter (NOM and the fate of uranium in ground water, spectroscopic studies of uranium complexation with catechol were conducted. Catechol provides a model for ubiquitous functional groups present in NOM. Liquid samples were analyzed using Raman, FTIR, and UV-Vis spectroscopy. Catechol was found to polymerize in presence of uranyl ions. Polymerization in presence of uranyl was compared to reactions in the presence of molybdate, another oxyion, and self polymerization of catechol at high pH. The effect of time and dissolved oxygen were also studied. It was found that oxygen was required for self-polymerization at elevated pH. The potential formation of phenoxy radicals as well as quinones was monitored. The benzene ring was found to be intact after polymerization. No evidence for formation of ether bonds was found, suggesting polymerization was due to formation of C-C bonds between catechol ligands. Uranyl was found to form outer sphere complexes with catechol at initial stages but over time (six months polycatechol complexes were formed and precipitated from solution (forming humic-like material while uranyl ions remained in solution. Our studies show that uranyl acts as a catalyst in catechol-polymerization.

  6. CYP719B1 is salutaridine synthase, the C-C phenol-coupling enzyme of morphine biosynthesis in opium poppy.

    Science.gov (United States)

    Gesell, Andreas; Rolf, Megan; Ziegler, Jörg; Díaz Chávez, María Luisa; Huang, Fong-Chin; Kutchan, Toni M

    2009-09-01

    Morphine is a powerful analgesic natural product produced by the opium poppy Papaver somniferum. Although formal syntheses of this alkaloid have been reported, the morphine molecule contains five stereocenters and a C-C phenol linkage that to date render a total synthesis of morphine commercially unfeasible. The C-C phenol-coupling reaction along the biosynthetic pathway to morphine in opium poppy is catalyzed by the cytochrome P450-dependent oxygenase salutaridine synthase. We report herein on the identification of salutaridine synthase as a member of the CYP719 family of cytochromes P450 during a screen of recombinant cytochromes P450 of opium poppy functionally expressed in Spodoptera frugiperda Sf9 cells. Recombinant CYP719B1 is a highly stereo- and regioselective enzyme; of forty-one compounds tested as potential substrates, only (R)-reticuline and (R)-norreticuline resulted in formation of a product (salutaridine and norsalutaridine, respectively). To date, CYP719s have been characterized catalyzing only the formation of a methylenedioxy bridge in berberine biosynthesis (canadine synthase, CYP719A1) and in benzo[c]phenanthridine biosynthesis (stylopine synthase, CYP719A14). Previously identified phenol-coupling enzymes of plant alkaloid biosynthesis belong only to the CYP80 family of cytochromes. CYP719B1 therefore is the prototype for a new family of plant cytochromes P450 that catalyze formation of a phenol-couple.

  7. Acrylic mechanical bond tests

    Energy Technology Data Exchange (ETDEWEB)

    Wouters, J.M.; Doe, P.J.

    1991-02-01

    The tensile strength of bonded acrylic is tested as a function of bond joint thickness. 0.125 in. thick bond joints were found to posses the maximum strength while the acceptable range of joints varied from 0.063 in. to almost 0.25 in. Such joints are used in the Sudbury Neutrino Observatory.

  8. Bond percolation in films

    Science.gov (United States)

    Korneta, W.; Pytel, Z.

    1988-04-01

    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  9. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot

    2014-01-01

    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  10. Does fluorine participate in halogen bonding?

    Science.gov (United States)

    Eskandari, Kiamars; Lesani, Mina

    2015-03-16

    When R is sufficiently electron withdrawing, the fluorine in the R-F molecules could interact with electron donors (e.g., ammonia) and form a noncovalent bond (F⋅⋅⋅N). Although these interactions are usually categorized as halogen bonding, our studies show that there are fundamental differences between these interactions and halogen bonds. Although the anisotropic distribution of electronic charge around a halogen is responsible for halogen bond formations, the electronic charge around the fluorine in these molecules is spherical. According to source function analysis, F is the sink of electron density at the F⋅⋅⋅N BCP, whereas other halogens are the source. In contrast to halogen bonds, the F⋅⋅⋅N interactions cannot be regarded as lump-hole interactions; there is no hole in the valence shell charge concentration (VSCC) of fluorine. Although the quadruple moment of Cl and Br is mainly responsible for the existence of σ-holes, it is negligibly small in the fluorine. Here, the atomic dipole moment of F plays a stabilizing role in the formation of F⋅⋅⋅N bonds. Interacting quantum atoms (IQA) analysis indicates that the interaction between halogen and nitrogen in the halogen bonds is attractive, whereas it is repulsive in the F⋅⋅⋅N interactions. Virial-based atomic energies show that the fluorine, in contrast to Cl and Br, stabilize upon complex formation. According to these differences, it seems that the F⋅⋅⋅N interactions should be referred to as "fluorine bond" instead of halogen bond.

  11. Core-level photoabsorption study of defects and metastable bonding configurations in boron nitride

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez, I.; Jankowski, A.F.; Terminello, L.J. [Lawrence Berkeley National Lab., CA (United States)] [and others

    1997-04-01

    Boron nitride is an interesting material for technological applications and for fundamental solid state physics investigations. It is a compound isoelectronic with carbon and, like carbon can possess sp{sup 2} and sp{sup 3} bonded phases resembling graphite and diamond. BN crystallizes in the sp{sup 2}-bonded hexagonal (h-BN), rhombohedral (r-BN) and turbostratic phases, and in the sp{sup 3}-bonded cubic (c-BN) and wurtzite (w-BN) phases. A new family of materials is obtained when replacing C-C pairs in graphite with isoelectronic B-N pairs, resulting in C{sub 2}BN compounds. Regarding other boron compounds, BN is exceptional in the sense that it has standard two-center bonds with conventional coordination numbers, while other boron compounds (e.g. B{sub 4}C) are based on the boron icosahedron unit with three-center bonds and high coordination numbers. The existence of several allotropic forms and fullerene-like structures for BN suggests a rich variety of local bonding and poses the questions of how this affects the local electronic structure and how the material accommodates the stress induced in the transition regions between different phases. One would expect point defects to play a crucial role in stress accommodation, but these must also have a strong influence in the electronic structure, since the B-N bond is polar and a point defect will thus be a charged structure. The study of point defects in relationship to the electronic structure is of fundamental interest in these materials. Recently, the authors have shown that Near-Edge X-ray Absorption Fine Structure (NEXAFS) is sensitive to point defects in h-BN, and to the formation of metastable phases even in amorphous materials. This is significant since other phase identification techniques like vibrational spectroscopies or x-ray diffraction yield ambiguous results for nanocrystalline and amorphous samples. Serendipitously, NEXAFS also combines chemical selectivity with point defect sensitivity.

  12. Long-term tropospheric trend of octafluorocyclobutane (c-C4F8 or PFC-318

    Directory of Open Access Journals (Sweden)

    T. Röckmann

    2011-07-01

    Full Text Available Air samples collected at Cape Grim, Tasmania between 1978 and 2008 and during a series of more recent aircraft sampling programmes have been analysed to determine the atmospheric abundance and trend of octafluorocyclobutane (-C4F8 or PFC-318. c-C4F8 has an atmospheric lifetime in excess of 3000 yr and a global warming potential (GWP of 10 300 (100 yr time horizon, making it one of the most potent greenhouse gases detected in the atmosphere to date. The abundance of c-C4F8 in the Southern Hemisphere has risen from 0.35 ppt in 1978 to 1.2 ppt in 2010, and is currently increasing at a rate of around 0.03 ppt yr−1. It is the third most abundant perfluorocarbon (PFC in the present day atmosphere, behind CF4 (~75 ppt and C2F6 (~4 ppt. The origin of c-C4F8 is unclear. Using a 2-D global model to derive top-down global emissions based on the Cape Grim measurements yields a recent (2007 emission rate of around 1.1 Gg yr−1 and a cumulative emission up to and including 2007 of 38.1 Gg. Emissions reported on the EDGAR emissions database for the period 1986–2005 represent less than 1 % of the top-down emissions for the same period, which suggests there is a large unaccounted for source of this compound. It is also apparent that the magnitude of this source has varied considerably over the past 30 yr, declining sharply in the late 1980s before increasing again in the mid-1990s.

  13. Measurement of Swarm Parameters of c-C4F8/CO2 and Its Insulation Characteristics Analysis

    Institute of Scientific and Technical Information of China (English)

    ZHANG Liu-chun; XIAO Deng-ming; ZHANG Dong; WU Bian-tao

    2008-01-01

    In c-C4F8 and c-C4F8/CO2 mixtures, the swarm parameters including ionization coefficient, attachment coefficient and effective ionization coefficient were obtained at the ratio of the electric field strength to the gas density between 150-550 Td by the steady-state Townsend (SST) method. Static breakdown voltages at each ratio were also measured at the SST condition. The limiting field strengths were obtained by two methods:computing the density-normalized effective ionization coefficient as a function of the overall density-reduced electric field strength; and measuring static breakdown voltages as a function of the product of gas density and electrode separation. Good agreement was obtained by these two methods, which ensures the correctness of the former method. The limiting field strengths of c-C4F8 and c-C4F8/CO2 mixtures were compared with those ofpure SF6, SF6/CO2 mixtures and pure c-C4Fs. It is found that buffer gas CO2 does not reduce the limiting field strengths of c-C4F8 greatly, the limiting field strengths of c-C4F8/CO2 mixtures are higher than those of SF6/CO2 mixtures or even pure SF6, and so c-C4F8/CO2 mixtures are suggested to be possible substitutes for SF6.

  14. 77 FR 12578 - Notice of Intent To Grant Exclusive Patent License; C&C Ventures, Doing Business as Randolph...

    Science.gov (United States)

    2012-03-01

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF DEFENSE Department of the Navy Notice of Intent To Grant Exclusive Patent License; C&C Ventures, Doing Business as... hereby gives notice of its intent to grant to C&C Ventures, doing business as Randolph Products,...

  15. Charged pion production in C+C and Ar+KCl collisions measured with HADES

    CERN Document Server

    Tlustý, P; Balanda, A; Bellia, G; Belver, D; Belyaev, A; Blanco, A; Boehmer, M; Boyard, J L; Braun-Munzinger, P; Cabanelas, P; Castro, E; Chernenko, S; Christ, T; Destefanis, M; Díaz, J; Dohrmann, F; Dybczak, A; Fabbietti, L; Fateev, O; Finocchiaro, P; Fonte, P; Friese, J; Fröhlich, I; Galatyuk, T; Garzón, J A; Gernhäuser, R; Gil, A; Gilardi, C; Golubeva, M; Gonzalez-Diaz, D; Grosse, E; Guber, F; Heilmann, M; Hennino, T; Holzmann, R; Ierusalimov, A; Iori, I; Ivashkin, A; Jurkovic, M; Kämpfer, B; Kanaki, K; Karavicheva, T; Kirschner, D; König, I; König, W; Kolb, B W; Kotte, R; Kozuch, A; Krasa, A; Krizek, F; Krücken, R; Kühn, W; Kugler, A; Kurepin, A; Lamas-Valverde, J; Lang, S; Lange, J S; Lapidus, K; Liu, T; Lopes, L; Lorenz, M; Maier, L; Mangiarotti, A; Marin, J; Markert, J; Metag, V; Michalska, B; Michel, J; Mishra, D; Moriniere, E; Mousa, J; Müntz, C; Naumann, L; Novotny, R; Otwinowski, J; Pachmayer, Y C; Palka, M; Parpottas, Y; Pechenov, V; Pechenova, O; Cavalcanti, T Perez; Pietraszko, J; Przygoda, W; Ramstein, B; Reshetin, A; Rustamov, A; Sadovskii, A; Salabura, P; Schmah, A; Simon, R; Sobolev, Yu G; Spataro, S; Spruck, B; Ströbele, H; Stroth, J; Sturm, C; Sudol, M; Tarantola, A; Teilab, K; Traxler, M; Trebacz, R; Tsertos, H; Veretenkin, I; Wagner, V; Weber, M; Wisniowski, M; Wüstenfeld, J; Yurevich, S; Zanevsky, Y; Zhou, P; Zumbruch, P

    2009-01-01

    Results of a study of charged pion production in 12C+12C collisions at incident beam energies of 1A GeV and 2A GeV, and 40Ar+natKCl at 1.76AGeV, using the spectrometer HADES at GSI, are presented. We have performed a measurement of the transverse momentum distributions of pi+- mesons covering a fairly large rapidity interval, in case of the C+C collision system for the first time. The yields, transverse mass and angular distributions are compared with a transport model as well as with existing data from other experiments.

  16. Study of dielectron production in C+C collisions at 1 AGeV

    CERN Document Server

    Agakichiev, G; Pol, H Alvarez; Balanda, A; Bassini, R; Bellia, G; Belver, D; Belyaev, A; Blanco, A; Boehmer, M; Bortolotti, A; Boyard, J L; Braun-Munzinger, P; Cabanelas, P; Castro, E; Christ, T; Destefanis, M; Díaz, J; Dohrmann, F; Dybczak, A; Eberl, T; Fabbietti, L; Finocchiaro, P; Fonte, Paulo J R; Friese, J; Fröhlich, I; Galatyuk, T; Garzón, J A; Gernhäuser, R; Gil, A; Gilardi, C; Golubeva, M; Diaz, D Gonzalez; Grosse, E; Guber, F; Heilmann, M; Hennino, T; Holzmann, R; Ierusalimov, A; Iori, I; Ivashkin, A; Jurkovic, M; Kämpfer, B; Kanaki, K; Karavicheva, T; Kirschner, D; König, I; König, W; Kolb, B W; Kotte, R; Kozuch, A; Krasa, A; Krizek, F; Krücken, R; Kühn, W; Kugler, A; Kurepin, A; Valverde, J Lamas; Lang, S; Lange, J S; Lapidus, K; Lopes, L; Maier, L; Mangiarotti, A; Marin, J; Markert, J; Metag, V; Michalska, B; Mishra, D; Moriniere, E; Mousa, J; Münch, M; Müntz, C; Naumann, Lutz; Novotny, R; Otwinowski, J; Pachmayer, Y C; Palka, M; Parpottas, Y; Pechenov, V; Pechenova, O; Perez, T; Pietraszko, J; Pleskac, R; Przygoda, W; Ramstein, B; Reshetin, A; Stephan, M Roy; Rustamov, A; Sadovskii, A; Sailer, B; Salabura, P; Schmah, A; Simon, R; Sobolev, Y; Spataro, S; Spruck, B; Ströbele, H; Stroth, J; Sturm, C; Sudol, M; Tarantola, A; Teilab, K; Tlustý, P; Toia, A; Traxler, M; Trebacz, R; Tsertos, H; Veretenkin, I; Wagner, V; Weber, M; Wen, H; Wisniowski, M; Wojcik, T; Wüstenfeld, J; Yurevich, S; Zanevsky, Y; Zhou, P; Zumbruch, P

    2007-01-01

    The emission of e+e- pairs from C+C collisions at an incident energy of 1 GeV per nucleon has been investigated. The measured production probabilities, spanning from the pi0-Dalitz to the rho/omega! invariant-mass region, display a strong excess above the cocktail of standard hadronic sources. The bombarding-energy dependence of this excess is found to scale like pion production, rather than like eta production. The data are in good agreement with results obtained in the former DLS experiment.

  17. Microanalysis on the Hydrogen Ion Irradiated 50 wt pct TiC-C Films

    Institute of Scientific and Technical Information of China (English)

    Hui JIANG; Yaoguang LIU; Ningkang HUANG

    2007-01-01

    The 50 wt pct TiC-C films were prepared on stainless steel substrates by using a technique of ion beam mixing.These films were irradiated by hydrogen ion beam with a dose of 1×1018 ions/cm2 and an energy of 5 keV.Microanalysis of X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) were used to analyze the films before and after hydrogen ion irradiation and to study the mechanism of hydrogen resistance.

  18. Oxidation mechanisms and kinetics of 1D-SiC/C/SiC composite materials; 1: An experimental approach

    Energy Technology Data Exchange (ETDEWEB)

    Filipuzzi, L.; Camus, G.; Naslain, R. (Domaine Univ., Pessac (France). Lab. des Composites Thermostructuraux); Thebault, J. (Societe Europeenne de Propulsion, Saint Medard en Jalles (France))

    1994-02-01

    The oxidation of unidirectional SiC/C/SiC model composites has been investigated through thermogravimetric analysis, optical/electron microscopy, and electrical measurements. The influence of temperature and carbon interphase thickness on the oxidation of the composites is discussed. The oxidation involves three phenomena: (1) reaction of oxygen with the carbon interphase resulting in pores around the fibers, (2) diffusion of oxygen and carbon oxides along the pores, and (3) reaction of oxygen with the pore walls leading to the growth of silica layers on both the fibers and matrix. In composites with a thin carbon interphase treated at T > 1,000 C the pores are rapidly sealed by silica. Under such conditions, the oxidation damages are limited to the vicinity of the external surface and the materials exhibit a self-healing character. Conversely, long exposures at 900 C give rise to the formation of microcracks in the matrix related to mechanical stresses arising from the in situ SiC/SiO[sub 2] conversion. Finally, the self-heating character is not observed in composites with a thick interphase since carbon is totally consumed before silica can seal the pores.

  19. Body of Knowledge (BOK) for Copper Wire Bonds

    Science.gov (United States)

    Rutkowski, E.; Sampson, M. J.

    2015-01-01

    Copper wire bonds have replaced gold wire bonds in the majority of commercial semiconductor devices for the latest technology nodes. Although economics has been the driving mechanism to lower semiconductor packaging costs for a savings of about 20% by replacing gold wire bonds with copper, copper also has materials property advantages over gold. When compared to gold, copper has approximately: 25% lower electrical resistivity, 30% higher thermal conductivity, 75% higher tensile strength and 45% higher modulus of elasticity. Copper wire bonds on aluminum bond pads are also more mechanically robust over time and elevated temperature due to the slower intermetallic formation rate - approximately 1/100th that of the gold to aluminum intermetallic formation rate. However, there are significant tradeoffs with copper wire bonding - copper has twice the hardness of gold which results in a narrower bonding manufacturing process window and requires that the semiconductor companies design more mechanically rigid bonding pads to prevent cratering to both the bond pad and underlying chip structure. Furthermore, copper is significantly more prone to corrosion issues. The semiconductor packaging industry has responded to this corrosion concern by creating a palladium coated copper bonding wire, which is more corrosion resistant than pure copper bonding wire. Also, the selection of the device molding compound is critical because use of environmentally friendly green compounds can result in internal CTE (Coefficient of Thermal Expansion) mismatches with the copper wire bonds that can eventually lead to device failures during thermal cycling. Despite the difficult problems associated with the changeover to copper bonding wire, there are billions of copper wire bonded devices delivered annually to customers. It is noteworthy that Texas Instruments announced in October of 2014 that they are shipping microcircuits containing copper wire bonds for safety critical automotive applications

  20. Effect of Treated Graphite on Properties of Al2 O3-SiC-C Castables

    Institute of Scientific and Technical Information of China (English)

    SHI Huiying; ZHANG Yang; BU Xiangjuan; CAO Xiying; HE Jiasong; WANG Lei

    2009-01-01

    Al2O3-SiC-C castables with 2 % pitch or 2 %,4% and 6% treated graphite,respectively,were prepared based on the basic formulation of traditional Al2O3-SiC-C castables.The flowability of castables,and bulk density,volume stability,strength,oxidation resistance and slag resistance of specimens fired at 110 ℃,1 100 ℃ and 1 500 ℃ respectively were comparatively studied.The results showed that:(1) With carbon source changing from pitch to treated graphite and the increase of treated graphite addition,water addition of castables increased,bulk density of specimens fired at different temperatures increased firstly and then decreased,strength after drying decreased obviously,strength after firing and oxidation resistance changed slightly,hot modulus of rupture increased obviously;(2) Slag resistance of specimen with treated graphite was worse than that of specimen with the same amount of pitch,but the former was obviously improved with the increase of treated graphite addition.

  1. Benefits of X-Ray CMT for the modeling of C/C composites

    Energy Technology Data Exchange (ETDEWEB)

    Coindreau, Olivia; Lachaud, Jean; Vignoles, Gerard L. [LCTS - UMR 5801 CNRS-Universite Bordeaux 1-Safran-CEA 3, Allee La Boetie, Pessac, F33600 (France); Mulat, Christianne [LCTS - UMR 5801 CNRS-Universite Bordeaux 1-Safran-CEA 3, Allee La Boetie, Pessac, F33600 (France); IMS - UMR5218 CNRS-Universite Bordeaux 1-IPB 351, Avenue de la Liberation, Talence, F33410 (France); Germain, Christian [IMS - UMR5218 CNRS-Universite Bordeaux 1-IPB 351, Avenue de la Liberation, Talence, F33410 (France)

    2011-03-15

    C/C composites have application in very demanding areas like aerospace, fusion technology, etc. and thus their optimization is crucial, both in the control of processing routes and in the prediction of their behavior in use. Intense modeling efforts have been performed in these directions. To help a direct application on actual materials, with possibly complex reinforcement architectures, X-ray computerized micro-tomography (CMT) is a beneficial technique, since it allows producing extremely detailed representations of these architectures. However, there is a long way from the crude X-ray projections to the information that is directly usable in C/C composite modeling. This paper summarizes several achievements in this domain and discusses the obtained results, concerning (i) composites imaging by phase contrast CMT and holographic CMT, (ii) evaluation of effective geometrical and transfer properties in fiber arrangements and actual fiber-reinforced composites, (iii) modeling of degradation by ablation, and (iv) modeling of processing by chemical vapor infiltration. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Molecular dynamics prediction of phonon-mediated thermal conductivity of f.c.c. Cu

    Science.gov (United States)

    Evteev, Alexander V.; Momenzadeh, Leila; Levchenko, Elena V.; Belova, Irina V.; Murch, Graeme E.

    2014-03-01

    The phonon-mediated thermal conductivity of f.c.c. Cu is investigated in detail in the temperature range 40-1300 K. The calculations are performed in the framework of equilibrium molecular dynamics making use of the Green-Kubo formalism and one of the most reliable embedded-atom method potentials for Cu. It is found that the temporal decay of the heat current autocorrelation function (HCACF) of the Cu model at low and intermediate temperatures demonstrate a more complex behaviour than the two-stage decay observed previously for the f.c.c. Ar model. After the first stage of decay, it demonstrates a peak in the temperature range 40-800 K. A decomposition model of the HCACF is introduced. In the framework of that model we demonstrate that a classical description of the phonon thermal transport in the Cu model can be used down to around one quarter of the Debye temperature (about 90 K). Also, we find that above 300 K the thermal conductivity of the Cu model varies with temperature more rapidly than ?, following an exponent close to -1.4 in agreement with previous calculations on the Ar model. Phonon thermal conductivity of Cu is found to be about one order of magnitude higher than Ar. The phonon contribution to the total thermal conductivity of Cu can be estimated to be about 0.5% at 1300 K and about 10% at 90 K.

  3. A spectroscopic and computational investigation of the conformational structural changes induced by hydrogen bonding networks in the glycidol-water complex.

    Science.gov (United States)

    Conrad, A R; Teumelsan, N H; Wang, P E; Tubergen, M J

    2010-01-14

    Rotational spectra were recorded in natural abundance for the (13)C isotopomers of two conformers of glycidol. Moments of inertia from the (13)C isotopomers were used to calculate the substitution coordinates and C-C bond lengths of two glycidol monomer conformations. The structures of seven different conformational minima were found from ab initio (MP2/6-311++G(d,p)) optimizations of glycidol-water. The rotational spectrum of glycidol-water was recorded using microwave spectroscopy, and the rotational constants were determined to be A = 3902.331 (11) MHz, B = 2763.176 (3) MHz, and C = 1966.863 (3) MHz. Rotational spectra were also recorded for glycidol-H(2)(18)O, glycidol-D(b)OH, and glycidol-d(O)-D(2)O. The rotational spectra were assigned to the lowest-energy ab initio structure, and the structure was improved by fitting to the experimental moments of inertia. The best-fit structure shows evidence for structural changes in glycidol to accommodate formation of the intermolecular hydrogen bonding network: the O-C-C-O torsional angle in glycidol was found to increase from 40.8 degrees for the monomer to 49.9 degrees in the water complex.

  4. Hydrogen bonds in PC61BM solids

    Science.gov (United States)

    Sheng, Chun-Qi; Li, Wen-Jie; Du, Ying-Ying; Chen, Guang-Hua; Chen, Zheng; Li, Hai-Yang; Li, Hong-Nian

    2015-09-01

    We have studied the hydrogen bonds in PC61BM solids. Inter-molecular interaction is analyzed theoretically for the well-defined monoclinic (P21/n) structure. The results indicate that PC61BM combines into C-H⋯Od bonded molecular chains, where Od denotes the doubly-bonded O atom of PC61BM. The molecular chains are linked together by C-H⋯Os bonds, where Os denotes the singly-bonded O atom of PC61BM. To reveal the consequences of hydrogen bond formation on the structural properties of PC61BM solids (not limited to the monoclinic structure), we design and perform some experiments for annealed samples with the monoclinic (P21/n) PC61BM as starting material. The experiments include differential scanning calorimetry, X-ray diffraction and infrared absorption measurements. Structural phase transitions are observed below the melting point. The C-H⋯Od bonds seem persisting in the altered structures. The inter-molecular hydrogen bonds can help to understand the phase separation in polymer/PC61BM blends and may be responsible for the existence of liquid PC61BM.

  5. The role of hydrogen bonds in the melting points of sulfonate-based protic organic salts

    DEFF Research Database (Denmark)

    Luo, Jiangshui

    2016-01-01

    there is evidence of bond formation [6]. Hydrogen bonds in the solid state fall into the classification of strong, moderate, and weak hydrogen bonds [7]. In molecular systems like H2O (vs. H2S) or NH3 (vs. PH3), strong hydrogen bonds lead to higher melting points. However, in organic salts, the situation may...

  6. Would be the photon a composed particle? / Sobre a possibilidade da quantiza\\c{c}\\~ao dos fluxos de campo na radia\\c{c}\\~ao eletromagn\\'etica

    CERN Document Server

    Duarte, Celso de Araujo

    2013-01-01

    Here it is made a comparative analysis between the classical and the quantum expressions for the energy of electromagnetic radiation (ER). The comparison points to the possibility of the quantization of the magnetic and the electric field fluxes in the ER. ----- Apresenta-se uma an\\'alise comparativa entre as express\\~oes cl\\'assica e qu\\^antica para a energia da radia\\c{c}\\~ao eletromagn\\'etica (RE). A compara\\c{c}\\~ao nos aponta para a possibilidade de haver uma quantiza\\c{c}\\~ao dos fluxos dos campos magn\\'etico e el\\'etrico na RE.

  7. Preliminary Discussion on C/C++Program Design Course Teaching in Higher Vocational Colleges%浅谈高职院校C/C++程序设计课程教学

    Institute of Scientific and Technical Information of China (English)

    徐立艳

    2013-01-01

    The C/C++program design is a basic course of computer specialty. The course is difficult to teach and learn, perplexes largeness teachers and students. Based on analyzing many years of teaching experience, summarizing the problems in the course of teaching, and drawing aged teachers’teaching views, the author puts forward some sugges-tions on C/C++program design teaching.%C/C++程序设计是计算机专业的一门基础课程,该课程难教、难学一直困扰着广大师生,根据多年的教学经验,总结自己在教学过程中存在的问题,听取老教师的教学观点,提出C/C++程序设计教学的几点建议。

  8. Bond length and charge density variations within extended arm chair defects in graphene.

    Science.gov (United States)

    Warner, Jamie H; Lee, Gun-Do; He, Kuang; Robertson, Alex W; Yoon, Euijoon; Kirkland, Angus I

    2013-11-26

    Extended linear arm chair defects are intentionally fabricated in suspended monolayer graphene using controlled focused electron beam irradiation. The atomic structure is accurately determined using aberration-corrected transmission electron microscopy with monochromation of the electron source to achieve ∼80 pm spatial resolution at an accelerating voltage of 80 kV. We show that the introduction of atomic vacancies in graphene disrupts the uniformity of C-C bond lengths immediately surrounding linear arm chair defects in graphene. The measured changes in C-C bond lengths are related to density functional theory (DFT) calculations of charge density variation and corresponding DFT calculated structural models. We show good correlation between the DFT predicted localized charge depletion and structural models with HRTEM measured bond elongation within the carbon tetragon structure of graphene. Further evidence of bond elongation within graphene defects is obtained from imaging a pair of 5-8-5 divacancies.

  9. Architectural Visualization of C/C++ Source Code for Program Comprehension

    Energy Technology Data Exchange (ETDEWEB)

    Panas, T; Epperly, T W; Quinlan, D; Saebjornsen, A; Vuduc, R

    2006-09-01

    Structural and behavioral visualization of large-scale legacy systems to aid program comprehension is still a major challenge. The challenge is even greater when applications are implemented in flexible and expressive languages such as C and C++. In this paper, we consider visualization of static and dynamic aspects of large-scale scientific C/C++ applications. For our investigation, we reuse and integrate specialized analysis and visualization tools. Furthermore, we present a novel layout algorithm that permits a compressive architectural view of a large-scale software system. Our layout is unique in that it allows traditional program visualizations, i.e., graph structures, to be seen in relation to the application's file structure.

  10. Diffusion and electrotransport of some transition elements in (B. C. C. ) thorium

    Energy Technology Data Exchange (ETDEWEB)

    Okafor, I.C.I.

    1987-03-01

    Diffusion and electrotransport parameters of the transition elements molybdenum, rhenium, tungsten and zirconium in ..beta.. thorium were measured for the temperature range 1660-1945 K. For each solute element, except zirconium, the measurement was made at four different temperatures, where as for zirconium, studies were performed for only two temperatures 1770 and 1870 K. The authors' results indicate that all four solute elements migrate to the anode in b.c.c. thorium with mean Z/sup */ values of -6.6 for Mo, -4.6 for Re, -8.2 for W and about -2.5 for Zr. The results also indicate that molybdenum, rhenium and tungsten diffuse much faster in ..beta.. thorium than zirconium.

  11. Two Photon Transition Form Factor of $\\bar{c}c $ Quarkonia

    CERN Document Server

    Chen, Jing; Chang, Lei; Liu, Yu-xin

    2016-01-01

    The two photon transition of $\\bar{c}c$ quarkonia are studied within a covariant approach based on the consistent truncation scheme of the quantum chromodynamics Dyson-Schwinger equation for the quark propagator and the Bethe--Salpeter equation for the mesons. We find the decay widths of $\\eta_{c}^{} \\to \\gamma\\gamma$ and $\\chi_{c0,2}^{} \\to \\gamma\\gamma$ in good agreement with experimental data. The obtained transition form factor of $\\eta_{c}^{} \\to \\gamma\\gamma^{\\ast}$ for a wide range of space-like photon momentum transfer squared is also in agreement with the experimental findings of the BABAR experiment. As a by-product, the decay widths of $\\eta_{b}^{},\\chi_{b0,2}^{} \\to \\gamma\\gamma$ and the transition form factor of $\\eta_{b}^{}, \\chi_{c0,b0}^{} \\to\\gamma\\gamma^{\\ast}$ are predicted, which await for experimental test.

  12. The 3D Lima\\c{c}on: Properties and Applications

    CERN Document Server

    Kreismann, Jakob; Sinzinger, Stefan

    2016-01-01

    We perform electromagnetic wave simulations of fully three-dimensional optical Lima\\c{c}on-microcavities, one basis for their future applications in microlasers and photonic devices. The analysis of the three-dimensional modes and far-fields reveals an increase of the quality factors as compared to the two-dimensional case. The structure of the far-field in the third dimension shows pronounced maxima in the emission directionality inclined to the resonator plane which may be exploited for coupling the resonator modes to the environment. This triggers ideas for technical applications, like the suggested sensor that can detect small changes in the environment based on changes in the emission profile.

  13. Fabrication of SiC-C composite from poycarbosilane, epoxy and polyvinyl butyral resin mixture

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Jin Wook; Park, Dong Won; Jeun, Joon Pyo; Kang, Phil Hyun [Korea Atomic Energy Research Institte, Jeongeup (Korea, Republic of)

    2009-06-15

    Silicon carbide (SiC) has wide application in various industrial fields because of their good high strength and modulus, low density, oxidation resistance and thermal stability. In this study, SiC-C composites were prepared from mixture of polycarbosilane (PCS), epoxy resin, and polyvinyl butyral (PVB) with weight ration of 2/1/1. PCS/epoxy/PVB mixture was cured by electron beam irradiation at 5,000 kGy. The cured composite was pyrolyzed by heat treatment in flowing argon at 1,300 .deg. C for 1 hr. As the result of TGA analysis, the oxidation resistance showed 95.2% residue at 1,500 .deg. C under air.

  14. Influence of substitutional atoms on the Snoek peak of carbon in b.c.c. iron

    Energy Technology Data Exchange (ETDEWEB)

    Saitoh, Hajime; Yoshinaga, Naoki; Ushioda, Kohsaku

    2004-03-08

    The influence of substitutional atoms (Mn, P, Si, Al, Cr, Co) on the C Snoek peak in b.c.c. iron was investigated. In the dilute range of the substitutes, the addition of Co, Mn, Cr, Si, P and Al resulted in the decreases in Snoek peak height in this ascending order. However, the addition of Mn to the Fe-C-P alloy hardly changes Snoek peak height. There is even a case that Snoek peak height is increased by further Mn addition to this alloy. They can be explained systematically by the proposed model wherein the solute carbon present in the influence region where the lattice distortion around the substitute is greater than the threshold value cannot contribute to the Snoek peak. The strain field generated by a substitutional atom due to the difference in atomic size is concluded to be the main reason for the reduction in Snoek peak height.

  15. Sintering Behaviour of Al2O3-SiC-C Ramming Mix

    Institute of Scientific and Technical Information of China (English)

    WUXingrong; CAOFeng

    2004-01-01

    Silicon fines, boron acid solid powders and microfine SiO2 as sintering agents were incorporated into Al2O3-SiC-C ramming mix in order to investigated their effects on the microstructure , mechanical properties and sintering behavior of the ramming mix. Results show that all the three agents could improved both densification and mehanical properties markedly, compared to that of non-agent specimens and the effect of the composite of boron acid solid powders and microfine SiO2 is the best. The oxidation resistance increased with the addition of agents, which is supported by densification. Microstructures showed that agent powders could fill pores or produce liquid phases at high temperature, therefore, improve the sintering of the ramming mix.

  16. Sintering Behaviour of Al2O3-SiC-C Ramming Mix

    Institute of Scientific and Technical Information of China (English)

    WU Xingrong; CAO Feng

    2004-01-01

    Silicon fines, boron acid solid powders and microfine SiO2 as sintering agents were incorporated into Al2O3-SiC-C ramming mix in order to investigated their effects on the microstructue,mechanical properties and sintering be-havior of the ramming mix.Results show that all the three agents could improved both densification and mehanical properties markedly,compared to that of non-agent speci-mens and the effect of the composite of boron acid solid powders and microfine SiO2 is the best.The oxidation re-sistance increased with the addition of agents,which is supported by densification.Microstructures shoued that a-gent powders could fill pores or produce liquid phases at high temperatuer,therefore,improve the sintering of the ramming mix.

  17. Overview of C/C-SiC Composite Development for the Orion Launch Abort System

    Science.gov (United States)

    Allen, Lee R.; Valentine, Peter G.; Schofield, Elizabeth S.; Beshears, Ronald D.; Coston, James E.

    2012-01-01

    Past and present efforts by the authors to further understanding of the ceramic matrix composite (CMC) material used in the valve components of the Orion Launch Abort System (LAS) Attitude Control Motor (ACM) will be presented. The LAS is designed to quickly lift the Orion Crew Exploration Vehicle (CEV) away from its launch vehicle in emergency abort scenarios. The ACM is a solid rocket motor which utilizes eight throttleable nozzles to maintain proper orientation of the CEV during abort operations. Launch abort systems have not been available for use by NASA on manned launches since the last Apollo ]Saturn launch in 1975. The CMC material, carbon-carbon/silicon-carbide (C/C-SiC), is manufactured by Fiber Materials, Inc. and consists of a rigid 4-directional carbon-fiber tow weave reinforced with a mixed carbon plus SiC matrix. Several valve and full system (8-valve) static motor tests have been conducted by the motor vendor. The culmination of these tests was the successful flight test of the Orion LAS Pad Abort One (PA ]1) vehicle on May 6, 2010. Due to the fast pace of the LAS development program, NASA Marshall Space Flight Center assisted the LAS community by performing a series of material and component evaluations using fired hardware from valve and full ]system development motor tests, and from the PA-1 flight ACM motor. Information will be presented on the structure of the C/C-SiC material, as well as the efficacy of various non ]destructive evaluation (NDE) techniques, including but not limited to: radiography, computed tomography, nanofocus computed tomography, and X-ray transmission microscopy. Examinations of the microstructure of the material via scanning electron microscopy and energy dispersive spectroscopy will also be discussed. The findings resulting from the subject effort are assisting the LAS Project in risk assessments and in possible modifications to the final ACM operational design.

  18. C,C'-bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: synthesis, structures, photophysics and electrochemistry.

    Science.gov (United States)

    Weber, Lothar; Kahlert, Jan; Brockhinke, Regina; Böhling, Lena; Halama, Johannes; Brockhinke, Andreas; Stammler, Hans-Georg; Neumann, Beate; Nervi, Carlo; Harder, Rachel A; Fox, Mark A

    2013-08-14

    Six new C,C'-bis(benzodiazaborolyl)dicarba-closo-dodecaboranes, 1,A-R2-1,A-C2B10H10, where R represents the group 2-(1,3-Et2-1,3,2-N2BC6H4) or 2-(1,3-Ph2-1,3,2-N2BC6H4) and A is 2, 7 or 12, were synthesized from o-, m-, and p-dicarbadodecaboranes (carboranes) by lithiation and subsequent treatment with the respective 2-bromo-1,3,2-benzodiazaboroles. UV-visible and fluorescence spectra of all carboranes display low energy charge transfer emissions. While such emissions with Stokes shifts between 17,330 and 21,290 cm(-1) are typical for C,C'-bis(aryl)-ortho-carboranes, the observed low-energy emissions with Stokes shifts between 8320 and 15,170 cm(-1) for the meta- and para-isomers are unusual as high-energy emissions are typical for meta- and para-dicarbadodecaboranes. Fluorescence quantum yields (φF) for the novel 1,7- and 1,12-bis(benzodiazaborolyl)-carboranes depend on the substituents at the nitrogen atoms of the heterocycle. Thus, the para-carborane with N-ethyl substituents 1,12-(1',3'-Et2-1',3',2'-N2BC6H4)2-1,12-C2B10H10 has a φF value of 41% in cyclohexane solution and only of 9% in the solid state, whereas the analogous 1,12-(1',3'-Ph2-1',3',2'-N2BC6H4)2-1,12-C2B10H10 shows quantum yields of 3% in cyclohexane solution and 72% in the solid state. X-ray crystallographic, computational and cyclic voltammetry studies for these carboranes are also presented.

  19. T47D Cells Expressing Myeloperoxidase Are Able to Process, Traffic and Store the Mature Protein in Lysosomes: Studies in T47D Cells Reveal a Role for Cys319 in MPO Biosynthesis that Precedes Its Known Role in Inter-Molecular Disulfide Bond Formation.

    Science.gov (United States)

    Laura, Richard P; Dong, David; Reynolds, Wanda F; Maki, Richard A

    2016-01-01

    Among the human heme-peroxidase family, myeloperoxidase (MPO) has a unique disulfide-linked oligomeric structure resulting from multi-step processing of the pro-protein monomer (proMPO) after it exits the endoplasmic reticulum (ER). Related family members undergo some, but not all, of the processing steps involved with formation of mature MPO. Lactoperoxidase has its pro-domain proteolytically removed and is a monomer in its mature form. Eosinophil peroxidase undergoes proteolytic removal of its pro-domain followed by proteolytic separation into heavy and light chains and is a heterodimer. However, only MPO undergoes both these proteolytic modifications and then is further oligomerized into a heterotetramer by a single inter-molecular disulfide bond. The details of how and where the post-ER processing steps of MPO occur are incompletely understood. We report here that T47D breast cancer cells stably transfected with an MPO expression plasmid are able to efficiently replicate all of the processing steps that lead to formation of the mature MPO heterotetramer. MPO also traffics to the lysosome granules of T47D cells where it accumulates, allowing in-depth immunofluorescent microscopy studies of MPO trafficking and storage for the first time. Using this novel cell model we show that formation of MPO's single inter-molecular disulfide bond can occur normally in the absence of the proteolytic events that lead to separation of the MPO heavy and light chains. We further demonstrate that Cys319, which forms MPO's unique inter-molecular disulfide bond, is important for events that precede this step. Mutation of this residue alters the glycosylation and catalytic activity of MPO and blocks its entry into the endocytic pathway where proteolytic processing and disulfide bonding occur. Finally, using the endocytic trafficking of lysosomal hydrolases as a guide, we investigate the role of candidate receptors in the endocytic trafficking of MPO.

  20. T47D Cells Expressing Myeloperoxidase Are Able to Process, Traffic and Store the Mature Protein in Lysosomes: Studies in T47D Cells Reveal a Role for Cys319 in MPO Biosynthesis that Precedes Its Known Role in Inter-Molecular Disulfide Bond Formation.

    Directory of Open Access Journals (Sweden)

    Richard P Laura

    Full Text Available Among the human heme-peroxidase family, myeloperoxidase (MPO has a unique disulfide-linked oligomeric structure resulting from multi-step processing of the pro-protein monomer (proMPO after it exits the endoplasmic reticulum (ER. Related family members undergo some, but not all, of the processing steps involved with formation of mature MPO. Lactoperoxidase has its pro-domain proteolytically removed and is a monomer in its mature form. Eosinophil peroxidase undergoes proteolytic removal of its pro-domain followed by proteolytic separation into heavy and light chains and is a heterodimer. However, only MPO undergoes both these proteolytic modifications and then is further oligomerized into a heterotetramer by a single inter-molecular disulfide bond. The details of how and where the post-ER processing steps of MPO occur are incompletely understood. We report here that T47D breast cancer cells stably transfected with an MPO expression plasmid are able to efficiently replicate all of the processing steps that lead to formation of the mature MPO heterotetramer. MPO also traffics to the lysosome granules of T47D cells where it accumulates, allowing in-depth immunofluorescent microscopy studies of MPO trafficking and storage for the first time. Using this novel cell model we show that formation of MPO's single inter-molecular disulfide bond can occur normally in the absence of the proteolytic events that lead to separation of the MPO heavy and light chains. We further demonstrate that Cys319, which forms MPO's unique inter-molecular disulfide bond, is important for events that precede this step. Mutation of this residue alters the glycosylation and catalytic activity of MPO and blocks its entry into the endocytic pathway where proteolytic processing and disulfide bonding occur. Finally, using the endocytic trafficking of lysosomal hydrolases as a guide, we investigate the role of candidate receptors in the endocytic trafficking of MPO.

  1. T47D Cells Expressing Myeloperoxidase Are Able to Process, Traffic and Store the Mature Protein in Lysosomes: Studies in T47D Cells Reveal a Role for Cys319 in MPO Biosynthesis that Precedes Its Known Role in Inter-Molecular Disulfide Bond Formation

    Science.gov (United States)

    Laura, Richard P.; Dong, David; Reynolds, Wanda F.; Maki, Richard A.

    2016-01-01

    Among the human heme-peroxidase family, myeloperoxidase (MPO) has a unique disulfide-linked oligomeric structure resulting from multi-step processing of the pro-protein monomer (proMPO) after it exits the endoplasmic reticulum (ER). Related family members undergo some, but not all, of the processing steps involved with formation of mature MPO. Lactoperoxidase has its pro-domain proteolytically removed and is a monomer in its mature form. Eosinophil peroxidase undergoes proteolytic removal of its pro-domain followed by proteolytic separation into heavy and light chains and is a heterodimer. However, only MPO undergoes both these proteolytic modifications and then is further oligomerized into a heterotetramer by a single inter-molecular disulfide bond. The details of how and where the post-ER processing steps of MPO occur are incompletely understood. We report here that T47D breast cancer cells stably transfected with an MPO expression plasmid are able to efficiently replicate all of the processing steps that lead to formation of the mature MPO heterotetramer. MPO also traffics to the lysosome granules of T47D cells where it accumulates, allowing in-depth immunofluorescent microscopy studies of MPO trafficking and storage for the first time. Using this novel cell model we show that formation of MPO’s single inter-molecular disulfide bond can occur normally in the absence of the proteolytic events that lead to separation of the MPO heavy and light chains. We further demonstrate that Cys319, which forms MPO’s unique inter-molecular disulfide bond, is important for events that precede this step. Mutation of this residue alters the glycosylation and catalytic activity of MPO and blocks its entry into the endocytic pathway where proteolytic processing and disulfide bonding occur. Finally, using the endocytic trafficking of lysosomal hydrolases as a guide, we investigate the role of candidate receptors in the endocytic trafficking of MPO. PMID:26890638

  2. Equilibrium CO bond lengths

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  3. Formation of unsaturated hydrocarbons in interstellar ice analogs by cosmic rays

    CERN Document Server

    Pilling, S; da Silveira, E F; Rothard, H; Domaracka, A; Boduch, P

    2012-01-01

    The formation of double and triple C-C bonds from the processing of pure c-C6H12 (cyclohexane) and mixed H2O:NH3:c-C6H12 (1:0.3:0.7) ices by highly-charged, and energetic ions (219 MeV O^{7+} and 632 MeV Ni^{24+}) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ices analogs. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accel\\'erat\\'eur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared (FTIR) spectrometry at different ion fluences. Dissociation cross section of cyclohexane and its half-life in astrophysical environments were determined. A comparison between spectra of bombarded ices and young stellar sources indicates that the initial composition of grains in theses environments should contain a mixture of H2O, NH3, CO (or CO2), simple al...

  4. Reducing the formation of disinfection by-products by pre-ozonation.

    Science.gov (United States)

    Chang, Cheng-Nan; Ma, Ying-Shih; Zing, Fang-Fong

    2002-01-01

    The objective of this study is to apply the pre-ozonation process to reduce the formation of disinfection by-products (DBPs). The raw water sample, collected from the Te-Chi Reservoir in central Taiwan, has been polluted by fertilizer. Three types of resins were used to isolate the natural organic matter into seven types of organic fractions. The pre-ozonation was used to oxidize each organic fraction to study the reduction of DBPs of each fraction. Experimental results indicated that the pre-ozonation could reduce the concentration of dissolved organic carbon resulting in the reduction of DBP formation. With the pre-ozonation, 9-54% of DOC and more than 40% of DBPs were reduced. With the analysis of UV adsorption and Fourier transform infrared spectrometer (FTIR), the reduction of A254 and unsaturated functional groups such as aromatic ring and C=C bond containing in the water sample is the major reaction mechanism.

  5. Direct conversion of cellulose using carbon monoxide and water on a Pt-Mo2C/C catalyst

    KAUST Repository

    Li, Jing

    2014-01-01

    CO and H2O were employed as the hydrogen source for cellulose conversion to polyols. Pt-Mo2C/C tandem catalyst with the Pt-Mo 2C domain responsible for H2 and/or H production and the Pt-C domain for cellulose conversion was fabricated. Considerable polyols were obtained over this tandem Pt-Mo2C/C catalyst. This journal is © 2014 The Royal Society of Chemistry.

  6. Simulation for F.C.C. deformation texture by modified pencil glide theory[Face Centered Cubic

    Energy Technology Data Exchange (ETDEWEB)

    Masui, H.

    1999-11-26

    Inspired by the pencil glide theory for b.c.c. metal, modified pencil glide theory for f.c.c. metal was proposed, dividing the 12 glide systems of f.c.c. metal into three groups individually composed of eight {l{underscore}brace}111{r{underscore}brace}{l{underscore}angle}110{r{underscore}angle} glide systems around the principal axes X[100], Y[010] and Z[001]. These assumptions yielded two mathematical solutions {Omega}(3) and {Omega}(1). In {Omega}(3), from the three groups with four complete conjugated glide systems composed of, respectively, two glide systems of common {l{underscore}angle}110{r{underscore}angle} direction, only one group with the maximum plastic work may operate if the requirements are satisfied, otherwise glide systems in {Omega}(1) where one of the four conjugated glide systems is zero are activated. The model considering the 12 glide systems of f.c.c. as a whole explained many experimentally stable orientations in axisymmetric and rolling deformation. The differences between the two pencil glide theories for b.c.c. and f.c.c. are also discussed with data.

  7. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter

    2009-01-01

    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  8. The dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  9. The samurai bond market

    OpenAIRE

    1997-01-01

    Issuance in the samurai bond market has more than tripled over the past several years. Some observers have attributed this growth to a systematic underestimation of credit risk in the market. A detailed review of credit quality, ratings differences, and initial issue pricing in the samurai bond market, however, turns up little evidence to support this concern.

  10. Pomegranate-like N,P-Doped Mo2C@C Nanospheres as Highly Active Electrocatalysts for Alkaline Hydrogen Evolution.

    Science.gov (United States)

    Chen, Yu-Yun; Zhang, Yun; Jiang, Wen-Jie; Zhang, Xing; Dai, Zhihui; Wan, Li-Jun; Hu, Jin-Song

    2016-09-27

    Well-defined pomegranate-like N,P-doped Mo2C@C nanospheres were prepared by simply using phosphomolybdic acid (PMo12) to initiate the polymerization of polypyrrole (PPy) and as a single source for Mo and P to produce N,P-doped Mo2C nanocrystals. The existence of PMo12 at the molecular scale in the polymer network allows the formation of pomegranate-like Mo2C@C nanospheres with a porous carbon shell as peel and Mo2C nanocrystals well-dispersed in the N-doped carbon matrix as seeds. This nanostructure provides several favorable features for hydrogen evolution application: (1) the conductive carbon shell and matrix effectively prevent the aggregation of Mo2C nanocrystals and facilitate electron transportation; (2) the uniform N,P-doping in the carbon shell/matrix and plenty of Mo2C nanocrystals provide abundant catalytically highly active sites; and (3) nanoporous structure allows the effective exposure of active sites and mass transfer. Moreover, the uniform distribution of P and Mo from the single source of PMo12 and N from PPy in the polymeric PPy-PMo12 precursor guarantees the uniform N- and P-co-doping in both the graphitic carbon matrix and Mo2C nanocrystals, which contributes to the enhancement of electrocatalytic performance. As a result, the pomegranate-like Mo2C@C nanospheres exhibit extraordinary electrocatalytic activity for the hydrogen evolution reaction (HER) in terms of an extremely low overpotential of 47 mV at 10 mA cm(-2) in 1 M KOH, which is one of the best Mo-based HER catalysts. The strategy for preparing such nanostructures may open up opportunities for exploring low-cost high-performance electrocatalysts for various applications.

  11. Solvent effects on hydrogen bonding between primary alcohols and esters

    Institute of Scientific and Technical Information of China (English)

    DHARMALINGAM K.; RAMACHANDRAN K.; SIVAGURUNATHAN P.

    2006-01-01

    The interaction by hydrogen bond formation of some primary alcohols (1-heptanol, 1-octanol and 1-decanol) with esters (methyl methacrylate, ethyl methacrylate and butyl methacrylate) was investigated in non-polar solvents viz., n-heptane,CCh and benzene by means of FTIR spectroscopy. Formation constants and free energy changes of complex formation were determined. The dependence of the equilibrium constants and free energy changes of complex formation on the alkyl chain length of both the alcohols and esters are discussed. The solvent effect on the hydrogen bond formation is discussed in terms of specific interaction between the solute and solvent.

  12. High-level ab initio predictions for the ionization energy, bond dissociation energies, and heats of formation of nickel carbide (NiC) and its cation (NiC+).

    Science.gov (United States)

    Lau, Kai-Chung; Chang, Yih Chung; Shi, Xiaoyu; Ng, C Y

    2010-09-21

    The ionization energy (IE) of NiC and the 0 K bond dissociation energies (D(0)) and heats of formation at 0 K (ΔH(o)(f0)) and 298 K (ΔH(o)(f298)) for NiC and NiC(+) are predicted by the wavefunction based CCSDTQ(Full)/CBS approach and the multireference configuration interaction (MRCI) method with Davidson correction (MRCI+Q). The CCSDTQ(Full)/CBS calculations presented here involve the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations along with the zero-point vibrational energy (ZPVE), high-order correlation, core-valence electronic (CV), spin-orbit coupling (SO), and scalar relativistic effect (SR) corrections. The present calculations provide the correct symmetry predictions for the ground states of NiC and NiC(+) to be (1)∑(+) and (2)∑(+), respectively. The CCSDTQ(Full)/CBS IE(NiC)=8.356 eV is found to compare favorably with the experimental IE value of 8.372 05±0.000 06 eV. The predicted IE(NiC) value at the MRCI+Q/cc-pwCV5Z level, including the ZPVE, SO, and SR effects is 8.00 eV, which is 0.37 eV lower than the experimental value. This work together with the previous experimental and theoretical investigations supports the conclusion that the CCSDTQ(Full)/CBS method is capable of providing reliable IE predictions for 3d-transition metal carbides, such as FeC and NiC. Furthermore, the CCSDTQ(Full)/CBS calculations give the prediction of D(0)(Ni-C)-D(0)(Ni(+)-C)=0.688 eV, which is also consistent with the experimental determination of 0.732 21±0.000 06 eV, whereas the MRCI+Q calculations (with relativistic and CV effects) predict a significantly lower value of 0.39 eV for D(0)(Ni-C)-D(0)(Ni(+)-C). The analysis of the correction terms shows that the CV and valence-valence electronic correlations beyond CCSD(T) wavefunction and the relativistic effect make significant contributions to the calculated thermochemical properties of NiC/NiC(+). For the experimental D(0) and ΔH(o)(f0) values of

  13. Functionalization of methyl (R)-phenylglycinate through orthopalladation: C-Hal, C-O, C-N, and C-C bond coupling.

    Science.gov (United States)

    Nieto, Sonia; Arnau, Palmira; Serrano, Elena; Navarro, Rafael; Soler, Tatiana; Cativiela, Carlos; Urriolabeitia, Esteban P

    2009-12-21

    The ortho functionalization of methyl R-phenylglycinate has been easily achieved using the known orthopalladated complex [Pd(mu-Cl){R-C(6)H(4)(CH(CO(2)Me)NH(2))-2}](2) (1) as synthetic tool. Different functional groups have been introduced at the ortho position of the aryl ring. The reaction of (R)-1 with X(2) or PhI(OAc)(2) gives XC(6)H(4)(CH(CO(2)Me)NH(2))-2 (X = I, Br, OMe, OEt) through oxidative coupling, while the reaction with CO gives an isoindolone. (R)-1 also reacts with one, two, or three alkyne molecules to give different metal-containing or metal-free heterocycles. The resulting functionalized amino esters or heterocycles retain the chirality of (R)-1, according with the values of the optical rotation and the obtained ee values ranging from 22%-87%. The X-ray structures of six representative compounds have also been determined.

  14. Bipodal surface organometallic complexes with surface N-donor ligands and application to the catalytic cleavage of C-H and C-C bonds in n -Butane

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa

    2013-11-27

    We present a new generation of "true vicinal" functions well-distributed on the inner surface of SBA15: [(Sî - Si-NH 2)(≡Si-OH)] (1) and [(≡Si-NH2)2] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [(≡Si-NH-)(≡Si-O-)]Zr(CH2tBu) 2 (3) and [(≡Si-NH-)2]Zr(CH2tBu) 2 (4) have been obtained by reaction with Zr(CH2tBu) 4. The surfaces were characterized with 2D multiple-quantum 1H-1H NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH2tBu)4 reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [(≡Si-NH-)2]Zr(H) 2 (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [(≡Si-NH-)2(≡Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an 1H NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [(≡Si-Nî)(≡Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [(≡Si-NH-)(≡Si-O-)] Zr(H)2 (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [(≡Si-NH-)(≡Si-O-)2]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N]. © 2013 American Chemical Society.

  15. Migrating C/C++ Software to Mobile Platforms in the ADM Context

    Directory of Open Access Journals (Sweden)

    Liliana Martinez

    2017-03-01

    Full Text Available Software technology is constantly evolving and therefore the development of applications requires adapting software components and applications in order to be aligned to new paradigms such as Pervasive Computing, Cloud Computing and Internet of Things. In particular, many desktop software components need to be migrated to mobile technologies. This migration faces many challenges due to the proliferation of different mobile platforms. Developers usually make applications tailored for each type of device expending time and effort. As a result, new programming languages are emerging to integrate the native behaviors of the different platforms targeted in development projects. In this direction, the Haxe language allows writing mobile applications that target all major mobile platforms. Novel technical frameworks for information integration and tool interoperability such as Architecture-Driven Modernization (ADM proposed by the Object Management Group (OMG can help to manage a huge diversity of mobile technologies. The Architecture-Driven Modernization Task Force (ADMTF was formed to create specifications and promote industry consensus on the modernization of existing applications. In this work, we propose a migration process from C/C++ software to different mobile platforms that integrates ADM standards with Haxe. We exemplify the different steps of the process with a simple case study, the migration of “the Set of Mandelbrot” C++ application. The proposal was validated in Eclipse Modeling Framework considering that some of its tools and run-time environments are aligned with ADM standards.

  16. Human C-C chemokine receptor 3 monoclonal antibody inhibits pulmonary inflammation in allergic mice

    Institute of Scientific and Technical Information of China (English)

    Kai WANG; Hua-hao SHEN; Wen LI; Hua-qiong HUANG

    2007-01-01

    Aim:To evaluate the effect of C-C chemokine receptor 3 (CCR3) blockade on pulmonary inflammation and mucus production in allergic mice. Methods:We used the synthetic peptide of the CCR3 NH2-terminal as the immunizing antigen and generated murine monoclonal antibody against the human CCR3. In addition,the generated antibody was administered to mice sensitized and challenged with ovalbumin. The inflammatory cells in bronchoalveolar lavage,cytokine levels,pulmonary histopathology,and mucus secretion were examined. Results:The Western blotting analysis indicated that the generated antibody bound to CCR3 specifically. The allergic mice treated with the antihuman CCR3 antibody exhibited a significant reduction of pulmonary inflammation accompanied with the alteration of cytokine. Conclusion:The antibody we generated was specific to CCR3. The inhibition of airway inflammation and mucus overproduction by the antibody suggested that the blockade of CCR3 is an appealing therapeutical target for asthma. The present research may provide an experimental basis for the further study of this agent.

  17. Effect of infiltrating Si on friction properties of C/C composites

    Institute of Scientific and Technical Information of China (English)

    马运柱; 黄伯云; 熊翔; 肖鹏; 李江鸿; 黄启忠; 易茂忠

    2003-01-01

    In order to improve the friction-wear properties of the C/C composites for aircraft brake pairs, the fric-tion behavior of samples with infiltrating Si was investigated. The influence of Si smearing thickness on frictionproperties was studied in detail. The results show that with the increase of Si smearing thickness and β-SiC content,the friction coefficient reduces from 0.40 to 0.30; the linear wear of stators increases from 2.0 μm to 18.9 μm percycle, and that of rotors increases from 1.4 μm to 22.6 μm per cycle; mass wear of stators increases from 20.6 mgto 126.9 mg per cycle, and that of rotors increases from 13.7 mg to 166.2 mg per cycle. On the other hand, whena large number of inhomogeneous β-SiC particulates are performed, friction surfaces of the samples flake off layer bylayer and many nicks are observed.

  18. Anti-oxidation mechanism of SiC-B4C-C composites

    Institute of Scientific and Technical Information of China (English)

    LIU Qi-cheng; XU Xie-wen; HUANG Qi-zhong; HUANG Bai-yun

    2005-01-01

    Mixture of green petroleum coke, B4C and SiC together with short carbon fiber were employed as starting materials, the mixture was press-formed without any binder after grinding, dense and homogeneous binderless SiC-B4C-C(carbon/ceramic) composites were then obtained after sintering. Composites thus prepared possess excellent anti-oxidation property, that is, mass loss less than 1% within the temperature range from 900 to 1100℃ for 10h. Anti-oxidation mechanism was also discussed from the viewpoint of thermodynamics, excellent anti-oxidation property of materials thus prepared can be discribed to 1) solid SiO2 formed from SiC, which restrains the filtering of oxygen and simultaneously, its volume expansion brought about by the reaction takes roles both walling up the original pores and making the material more compact; 2) liquid B2O3 from the reaction of B4C not only makes the combination with C, B4C and SiC tighter through forming solid solution, but also effect of reaction SiC(s)+2CO(g)=SiO2(s)+3C(s) is an expansive process, which improves the microstructure of the material.

  19. The Infiltration Process and Texture Transition of 2D C/C Composites

    Institute of Scientific and Technical Information of China (English)

    Hejun Li; Guozhong Xu; Kezhi Li; Chuang Wang; Wei Li; Miaoling Li

    2009-01-01

    2D needle-punched fiber felt was infiltrated by a kind of rapid isothermal chemical vapor infiltration technique. The infiltration process and texture transition of the infiltrated C/C composites were investigated. The porosity and the variations of the cumulative pore volume were determined by mercury porosimetry. The texture of matrix carbon was studied under a polarized light microscope. The results show that the relative mass gain of the sample increases directly as the infiltration time at the initial stage until 20 h, and subsequently the increasing rate of the relative mass gain decreases gradually with the prolonging of infiltration time. Three layers of pyrocarbon were formed around fibers. Low-textured pyrocarbon was obtained at the initial stage. With the densification going on, high-textured pyrocarbon was formed on the surface of low-textured pyrocarbon. Then, low-textured pyrocarbon was produced again during the final stage of densification. The texture transition is ascribed to the variation of the ratio of cumulative inner surface area to volume of pores and the gas partial pressure in pores.

  20. Binding of reactive organophosphate by oximes via hydrogen bond

    Indian Academy of Sciences (India)

    Andrea Pappalardo; Maria E Amato; Francesco P Ballistreri; Valentina La Paglia Fragola; Gaetano A Tomaselli; Rosa Maria Toscano; Giuseppe Trusso Sfrazzetto

    2013-07-01

    In this contribution, the ability of simple oximes to bind a well-known nerve agent simulant (dimethylmethylphosphonate, DMMP) via hydrogen bond is reported. UV/Vis measurements indicate the formation of 1:1 complexes. 1H-, 31P-NMR titrations and T-ROESY experiments confirm that oximes bind the organophosphate via hydrogen bond.

  1. Experimental Investigation of Second Interface Cement Bond Evaluation

    Institute of Scientific and Technical Information of China (English)

    Che Xiaohua; Qiao Wenxiao

    2007-01-01

    Cement bond model wells (1:10 scaled-down) were made with a gradually degrading cement annulus for cement bond evaluation of the first interface (between the casing and the cement annulus) and the second interface (between the cement annulus and the formation).Experimental simulation on cement bond logging was carried out with these model wells.The correlation of acoustic waveforms,casing wave energy and free casing area before and after cement bonding of the second interface was established.The experimental results showed that the arrival of the casing waves had no relationship with the cement bonding of the second interface,but the amplitude of the casing head wave decreased obviously after the second interface was bonded.So,cement bonding of the second interface had little effect on the evaluation of the cement bond quality of the first interface by using casing head wave arrivals.Strong cement annulus waves with early arrivals were observed before the second interface was bonded,while obvious "formation waves" instead of cement annulus waves were observed after the second interface was bonded.

  2. Effect of ultrasonic power and bonding force on the bonding strength of copper ball bonds

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Copper wire, serving as a cost-saving alternative to gold wire, has been used in many high-end thermosonic ball bonding applications. In this paper, the bond shear force, bond shear strength, and the ball bond diameter are adopted to evaluate the bonding quality. It is concluded that the efficient ultrasonic power is needed to soften the ball to form the copper bonds with high bonding strength. However, excessive ultrasonic power would serve as a fatigue loading to weaken the bonding. Excessive or less bonding force would cause cratering in the silicon.

  3. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik

    2012-01-01

    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...... non-linear fracture mechanics. The results indicated a good correlation between theory and tests. Furthermore, the model is suggested as theoretical base for determining load capacity of bonded anchorages with transverse pressure, in externally reinforced concrete structures....

  4. A Numerical Study on the Thermal Conductivity of 3D Woven C/C Composites at High Temperature

    Science.gov (United States)

    Shigang, Ai; Rujie, He; Yongmao, Pei

    2015-12-01

    Experimental data for Carbon/Carbon (C/C) constituent materials are combined with a three dimensional steady state heat transfer finite element analysis to demonstrate the average in-plane and out-of-plane thermal conductivities (TCs) of C/C composites. The finite element analysis is carried out at two distinct length scales: (a) a micro scale comparable with the diameter of carbon fibres and (b) a meso scale comparable with the carbon fibre yarns. Micro-scale model calculate the TCs at the fibre yarn scale in the three orthogonal directions ( x, y and z). The output results from the micro-scale model are then incorporated in the meso-scale model to obtain the global TCs of the 3D C/C composite. The simulation results are quite consistent with the theoretical and experimental counterparts reported in references. Based on the numerical approach, TCs of the 3D C/C composite are calculated from 300 to 2500 K. Particular attention is given in elucidating the variations of the TCs with temperature. The multi-scale models provide an efficient approach to predict the TCs of 3D textile materials, which is helpful for the thermodynamic property analysis and structure design of the C/C composites.

  5. GCC(g++)编译环境下C(C++)和汇编的接口分析%C/C++ Language and Assemble Language Ombination Programming Based on Linux

    Institute of Scientific and Technical Information of China (English)

    郝丽花; 陈付龙

    2004-01-01

    为了在gcc/g++环境下程序开发能顺利地进行C/C++与汇编语言的混合编程,本文给出了一种在该环境下的接口分析方法,并在此基础上分析了gcc/g++环境下汇编源程序如何与调用它的C/C++程序接口问题.

  6. C-C chemokine receptor-7 mediated endocytosis of antibody cargoes into intact cells

    Directory of Open Access Journals (Sweden)

    Xavier eCharest-Morin

    2013-09-01

    Full Text Available The C-C chemokine receptor-7 (CCR7 is a G protein coupled receptor that has a role in leukocyte homing, but that is also expressed in aggressive tumor cells. Preclinical research supports that CCR7 is a valid target in oncology. In view of the increasing availability of therapeutic monoclonal antibodies that carry cytotoxic cargoes, we studied the feasibility of forcing intact cells to internalize known monoclonal antibodies by exploiting the cycle of endocytosis and recycling triggered by the CCR7 agonist CCL19. Firstly, an anti-CCR7 antibody (CD197; clone 150503 labeled surface recombinant CCR7 expressed in intact HEK 293a cells and the fluorescent antibody was internalized following CCL19 treatment. Secondly, a recombinant myc-tagged CCL19 construction was exploited along the anti-myc monoclonal antibody 4A6. The myc-tagged ligand was produced as a conditioned medium of transfected HEK 293a cells that contained the equivalent of 430 ng/ml of immunoreactive CCL19 (average value, ELISA determination. CCL19-myc, but not authentic CCL19, carried the fluorophore-labeled antibody 4A6 into other recipient cells that expressed recombinant CCR7 (microscopy, cytofluorometry. The immune complexes were apparent in endosomal structures, colocalized well with the small GTPase Rab5 and progressed toward Rab7-positive endosomes. A dominant negative form of Rab5 (GDP-locked inhibited this endocytosis. Further, endosomes in CCL19-myc- or CCL19-stimulated cells were positive for β-arrestin2, but rarely for β-arrestin1. Following treatment with CCL19-myc and the 4A6 antibody, the melanoma cell line A375 that expresses endogenous CCR7 was specifically stained using a secondary peroxidase-conjugated antibody. Agonist-stimulated CCR7 can transport antibody-based cargoes, with possible therapeutic applications in oncology.

  7. Converting ultrasonic induction heating deposited monetite coating to Na-doped HA coating on H 2O 2-treated C/C composites by a two-step hydrothermal method

    Science.gov (United States)

    Xin-bo, Xiong; Jian-feng, Hung; Xie-rong, Zeng; Cen-cen, Chu

    2011-10-01

    a monetite coating on H 2O 2-treated C/C composites was prepared by ultrasonic induction heating (UIH) technology. Subsequently, this coating was subjected to an ammonia hydrothermal treatment to form a undoped hydroxyapatite (U-HA) coating. Finally, the as-prepared U-HA coating was placed in a NaOH solution and hydrothermally treated to produce the other hydroxyapatite (Na-HA) coating. The structure, morphology and chemical composition of the two HA coatings were characterized by XRD, FTIR, SEM and EDS, the adhesiveness and local mechanical properties, e.g. nanohardness and Young's modulus of the two HA coatings to C/C composites was evaluated by a scratch test and nanoindentation technique respectively. The results showed that the two HA coatings had the alike morphology and crystallization. But, compared with the U-HA coating, the Na-HA coating was doped with Na ions, and gave a Ca/P ratio close to a stoichiometric hydroxyapatite, and thus showed a higher nano-indentation value, Young's modulus, and larger bonding strength. These results verified the strengthened effect of Na ion in hydroxyapatite coating on carbon/carbon (C/C) composities.

  8. Handbook of wafer bonding

    CERN Document Server

    Ramm, Peter; Taklo, Maaike M V

    2011-01-01

    Written by an author and editor team from microsystems companies and industry-near research organizations, this handbook and reference presents dependable, first-hand information on bonding technologies.In the first part, researchers from companies and institutions around the world discuss the most reliable and reproducible technologies for the production of bonded wafers. The second part is devoted to current and emerging applications, including microresonators, biosensors and precise measuring devices.

  9. Diffusion bonding of titanium alloy to tin-bronze

    Institute of Scientific and Technical Information of China (English)

    李卓然; 冯吉才; 刘会杰

    2002-01-01

    The vacuum diffusion bonding of titanium alloy to tin-bronze has been studied and the feasibility and appropriate processing parameters have been investigated. The maximum tensile strength of the joints is bonded joint has been observed by SEM, X-ray and EPMA, and the main factors affecting diffusion bonding have been analyzed. The intermetallic compounds Ti2Cu and TiCu were formed near the interface. The width and quantity of the intermetallic compound increases with the increase of the bonding time. The formation of the intermetallic compounds results in embrittlement of the joint and the poor joint properties.

  10. Influence of charge and coordination number on bond dissociation energies, distances, and vibrational frequencies for the phosphorus-phosphorus bond.

    Science.gov (United States)

    Chitnis, Saurabh S; Whalen, J Marc; Burford, Neil

    2014-09-01

    We report a comprehensive and systematic experimental and computational assessment of the P-P bond in prototypical molecules that represent a rare series of known compounds. The data presented complement the existing solid-state structural data and previous computational studies to provide a thorough thermodynamic and electronic understanding of the P-P bond. Comparison of homolytic and heterolytic bond dissociation for tricoordinate-tricoordinate, tricoordinate-tetracoordinate, and tetracoordinate-tetracoordinate P-P bonds in frameworks 1-6 provides fundamental insights into covalent bonding. For all types of P-P bond discussed, homolytic dissociation is favored over heterolytic dissociation, although the distinction is small for 2(1+) and 6(1+). The presence of a single cationic charge in a molecule substantially strengthens the P-P bond (relative to analogous neutral frameworks) such that it is comparable with the C-C bond in alkanes. Nevertheless, P-P distances are remarkably independent of molecular charge or coordination number, and trends in values of d(PC) and νsymm(PC) imply that a molecular cationic charge is distributed over the alkyl substituents. In the gas phase, the diphosphonium dication 3(2+) has similar energy to two [PMe3](+) radical cations, so that it is the lattice enthalpy of 3[OTf]2 in the solid-state that enables isolation, highlighting that values from gas-phase calculations are poor guides for synthetic planning for ionic compounds. There are no relationships or correlations between bond lengths, strengths, and vibrational frequencies.

  11. Enthalpy of formation and anharmonic force field of diacetylene.

    Science.gov (United States)

    Simmonett, Andrew C; Schaefer, Henry F; Allen, Wesley D

    2009-01-28

    The enthalpy of formation of diacetylene (C4H2) is pinpointed using state-of-the-art theoretical methods, accounting for high-order electron correlation, relativistic effects, non-Born-Oppenheimer corrections, and vibrational anharmonicity. Molecular energies are determined from coupled cluster theory with single and double excitations (CCSD), perturbative triples [CCSD(T)], full triples (CCSDT), and perturbative quadruples [CCSDT(Q)], in concert with correlation-consistent basis sets (cc-pVXZ, X=D, T, Q, 5, 6) that facilitate extrapolations to the complete basis set limit. The first full quartic force field of diacetylene is determined at the highly accurate all-electron CCSD(T) level with a cc-pCVQZ basis, which includes tight functions for core correlation. Application of second-order vibrational perturbation theory to our anharmonic force field yields fundamental frequencies with a mean absolute difference of only 3.9 cm(-1) relative to the experimental band origins, without the use of any empirical scale factors. By a focal point approach, we converge on an enthalpy change for the isogyric reaction 2 H-C[triple bond]C-H-->H-C[triple bond]C-C[triple bond]C-H+H2 of (+0.03, +0.81) kcal mol(-1) at (0, 298.15) K. With the precisely established fHdegrees of acetylene, we thus obtain DeltafHdegrees(C4H2)=(109.4,109.7)+/-0.3 kcal mol(-1) at (0, 298.15) K. Previous estimates of the diacetylene enthalpy of formation range from 102 to 120 kcal mol(-1).

  12. Cloning and expression analysis of human reticulon 4c cDNA

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    RTNs (reticulons) is a gene family related to the growth and differentiation of neuroendocrine cell. This family is composed of several members such as RTN1, RTN2 and RTN3. RTN1 and RTN2 have been proved to have 3 transcripts with different length. Because the RTN1c cDNA was involved in the sologenesis of small cell lung carcinoma (SCLC), it was selected as a bioinformatic probe to clone novel members of RTN family with the electric hybridization assistant new-gene cloning method (EHAC). A 1677-bp cDNA was identified from human brain cDNA library. The cDNA contains an intact open reading frame (ORF) which encodes a protein of 199 amino acids. This deduced protein is highly homologous to RTN1c, RTN2c and RTN3 with identities of 64.4%, 45.8% and 50.0% respectively. This new gene was named RTN4c (GenBank accession number: AF087901). Northern hybridization showed that the full length of RTN4c transcript is about 1.8 kb. It is hardly expressed in heart, placenta, lung, spleen, thymus, testis, ovary, small intestine and peripheral blood white cells; but it is highly expressed in the tissues of skeletal muscle, brain, liver and kidney, and less expressed in the pancreas, prostate and colon. Furthermore, Northern results also showed that there is a 2.3 kb transcript expressed in 14 tissues except liver and skeletal muscle; while another 5.0 kb transcript in brain, skeletal muscle and testis. By the electric hybridization walking, we obtained two full-length contigs with a length of 4632 and 2235 bp respectively. The former encodes a protein with 1192 amino acids and was defined as RTN4a; the latter encodes another protein with 373 amino acids, and was named RTN4b. The RTN4 gene was mapped to human chromosome 2p14-p13 region by the radiation hybridization (RH).

  13. Minimal model for dynamic bonding in colloidal transient networks

    Science.gov (United States)

    Krinninger, Philip; Fortini, Andrea; Schmidt, Matthias

    2016-04-01

    We investigate a model for colloidal network formation using Brownian dynamics computer simulations. Hysteretic springs establish transient bonds between particles with repulsive cores. If a bonded pair of particles is separated by a cutoff distance, the spring vanishes and reappears only if the two particles contact each other. We present results for the bond lifetime distribution and investigate the properties of the van Hove dynamical two-body correlation function. The model displays crossover from fluidlike dynamics, via transient network formation, to arrested quasistatic network behavior.

  14. Crystal structure, ferromagnetostructural behavior and evidence of cooperative Jahn-Teller interactions of the complex [CuL]Cl·H 2O (L= N-glycyl-2(aminomethyl)benzimidazol), synthesized by a novel simple method of peptide bond formation.

    Science.gov (United States)

    García-Orozco, Ivan; Tapia-Benavides, Antonio Rafael; Alvarez-Toledano, Cecilio; Toscano, Ruben A.; Ramírez-Rosales, Daniel; Zamorano-Ulloa, Rafael; Reyes-Ortega, Yasmi

    2002-01-01

    [CuL]Cl·H 2O 1 (L= N-glycyl-2(aminomethyl)benzimidazol) compound crystallizes in the orthorhombic space group Pna2 1 with unit cell parameters a=7.140(5) Å, b=17.621(5) Å, c=9.941(5) Å. Its structure shows that the copper(II) ion is tetra coordinated with a square planar geometry. The ligand acts as a tridentate and the chloride ion is the fourth ligand. Symmetry related units stack into helicoidal columns along the ā direction producing weakly bonded strips with dihedral angles of 2.6° between two consecutive molecular planes. UV/VIS spectrum of 1 shows one broad and weak band at 622 nm, characteristic of d-d transitions, indicative of low local Cu(II) symmetry. X band ESR spectra of 1 at 300 and 77 K are axial exchange narrow lines with g∥=2.135 and g⊥=2.028. However, the axial spectrum at 6.4 K shows an increment Δ g∥=0.076(6) and Δ g⊥=0.028(4) which suggests a cooperative Jahn-Teller interactions between complexes via the hydrogen-bonding network. Magnetic susceptibility data at 18-300 K and fitted to the modified Bleany-Bowers equation indicate a weak ferromagnetic coupling with 2J≅+17 cm-1, which is compatible with the helium temperature ESR results and with the helicoidal stacking into columns of the molecules along the a-axis with 78.9° Cu'-Cl'-Cu and 81.2° Cu'-N( 1)-Cu bonds angles. The synthesis is a novel, simple and efficient method: in aqueous conditions and heterogeneous phase with basic copper(II) carbonate, which carries out the formation of the stable peptide bond.

  15. Fundamentals of fiber bonding in thermally point-bonded nonwovens

    Science.gov (United States)

    Chidambaram, Aparna

    Thermal point bonding (TPB) uses heat and pressure to bond a web of fibers at discrete points imparting strength to the manufactured fabric. This process significantly reduces the strength and elongation of the bridging fibers between bond points while strengthening the web. Single fiber experiments were performed with four structurally different polypropylene fibers to analyze the inter-relationships between fiber structure, fiber properties and bonding process. Two fiber types had a low birefringence sheath or surface layer while the remaining had uniform birefringence profiles through their thickness. Bonds were formed between isolated pairs of fibers by subjecting the fibers to a calendering process and simulating TPB process conditions. The dependence of bond strength on bonding temperature and on the type of fiber used was evaluated. Fiber strengths before and after bonding were measured and compared to understand the effect of bonding on fiber strength. Additionally, bonded fiber strength was compared to the strength of single fibers which had experienced the same process conditions as the bonded pairs. This comparison estimated the effect of mechanical damage from pressing fibers together with steel rolls while creating bonds in TPB. Interfiber bond strength increased with bonding temperature for all fiber types. Fiber strength decreased with increasing bonding temperature for all fiber types except for one type of low birefringent sheath fibers. Fiber strength degradation was unavoidable at temperatures required for successful bonding. Mechanical damage from compression of fibers between rolls was an insignificant factor in this strength loss. Thermal damage during bonding was the sole significant contributor to fiber strength degradation. Fibers with low birefringence skins formed strong bonds with minimal fiber strength loss and were superior to fibers without such surface layers in TPB performance. A simple model to predict the behavior of a two-bond

  16. Modelling longevity bonds: Analysing the Swiss Re Kortis bond

    OpenAIRE

    2015-01-01

    A key contribution to the development of the traded market for longevity risk was the issuance of the Kortis bond, the world's first longevity trend bond, by Swiss Re in 2010. We analyse the design of the Kortis bond, develop suitable mortality models to analyse its payoff and discuss the key risk factors for the bond. We also investigate how the design of the Kortis bond can be adapted and extended to further develop the market for longevity risk.

  17. Formation of a ruthenium(IV)-oxo complex by electron-transfer oxidation of a coordinatively saturated ruthenium(II) complex and detection of oxygen-rebound intermediates in C-H bond oxygenation.

    Science.gov (United States)

    Kojima, Takahiko; Nakayama, Kazuya; Ikemura, Kenichiro; Ogura, Takashi; Fukuzumi, Shunichi

    2011-08-03

    A coordinatively saturated ruthenium(II) complex having tetradentate tris(2-pyridylmethyl)amine (TPA) and bidentate 2,2'-bipyridine (bpy), [Ru(TPA)(bpy)](2+) (1), was oxidized by a Ce(IV) ion in H(2)O to afford a Ru(IV)-oxo complex, [Ru(O)(H(+)TPA)(bpy)](3+) (2). The crystal structure of the Ru(IV)-oxo complex 2 was determined by X-ray crystallography. In 2, the TPA ligand partially dissociates to be in a facial tridentate fashion and the uncoordinated pyridine moiety is protonated. The spin state of 2, which showed paramagnetically shifted NMR signals in the range of 60 to -20 ppm, was determined to be an intermediate spin (S = 1) by the Evans' method with (1)H NMR spectroscopy in acetone-d(6). The reaction of 2 with various oraganic substrates in acetonitrile at room temperature afforded oxidized and oxygenated products and a solvent-bound complex, [Ru(H(+)TPA)(bpy)(CH(3)CN)], which is intact in the presence of alcohols. The oxygenation reaction of saturated C-H bonds with 2 proceeds by two-step processes: the hydrogen abstraction with 2, followed by the dissociation of the alcohol products from the oxygen-rebound complexes, Ru(III)-alkoxo complexes, which were successfully detected by ESI-MS spectrometry. The kinetic isotope effects in the first step for the reaction of dihydroanthrathene (DHA) and cumene with 2 were determined to be 49 and 12, respectively. The second-order rate constants of C-H oxygenation in the first step exhibited a linear correlation with bond dissociation energies of the C-H bond cleavage.

  18. Formation and reactivity of a porphyrin iridium hydride in water: acid dissociation constants and equilibrium thermodynamics relevant to Ir-H, Ir-OH, and Ir-CH2- bond dissociation energetics.

    Science.gov (United States)

    Bhagan, Salome; Wayland, Bradford B

    2011-11-01

    Aqueous solutions of group nine metal(III) (M = Co, Rh, Ir) complexes of tetra(3,5-disulfonatomesityl)porphyrin [(TMPS)M(III)] form an equilibrium distribution of aquo and hydroxo complexes ([(TMPS)M(III)(D(2)O)(2-n)(OD)(n)]((7+n)-)). Evaluation of acid dissociation constants for coordinated water show that the extent of proton dissociation from water increases regularly on moving down the group from cobalt to iridium, which is consistent with the expected order of increasing metal-ligand bond strengths. Aqueous (D(2)O) solutions of [(TMPS)Ir(III)(D(2)O)(2)](7-) react with dihydrogen to form an iridium hydride complex ([(TMPS)Ir-D(D(2)O)](8-)) with an acid dissociation constant of 1.8(0.5) × 10(-12) (298 K), which is much smaller than the Rh-D derivative (4.3 (0.4) × 10(-8)), reflecting a stronger Ir-D bond. The iridium hydride complex adds with ethene and acetaldehyde to form organometallic derivatives [(TMPS)Ir-CH(2)CH(2)D(D(2)O)](8-) and [(TMPS)Ir-CH(OD)CH(3)(D(2)O)](8-). Only a six-coordinate carbonyl complex [(TMPS)Ir-D(CO)](8-) is observed for reaction of the Ir-D with CO (P(CO) = 0.2-2.0 atm), which contrasts with the (TMPS)Rh-D analog which reacts with CO to produce an equilibrium with a rhodium formyl complex ([(TMPS)Rh-CDO(D(2)O)](8-)). Reactivity studies and equilibrium thermodynamic measurements were used to discuss the relative M-X bond energetics (M = Rh, Ir; X = H, OH, and CH(2)-) and the thermodynamically favorable oxidative addition of water with the (TMPS)Ir(II) derivatives.

  19. Rotational spectra and properties of complexes B···ICF3 (B = Kr or CO) and a comparison of the efficacy of ICl and ICF3 as iodine donors in halogen bond formation.

    Science.gov (United States)

    Stephens, Susanna L; Walker, Nicholas R; Legon, Anthony C

    2011-12-14

    The ground-state rotational spectra of two weakly bound complexes B···ICF(3) (B = Kr or CO) formed by trifluoroiodomethane have been observed in pulsed jets by using two types of Fourier-transform microwave spectroscopy (chirped-pulse and Fabry-Perot cavity). Both complexes exhibit symmetric-top type spectra, thus indicating that the Kr atom in Kr···ICF(3) and both the C and O atoms in OC···ICF(3) lie along the C(3) axis of ICF(3). The rotational constant B(0), the centrifugal distortion constants D(J) and D(JK), and the iodine nuclear quadrupole coupling constant χ(aa)(I) were determined for each of the isotopologues (84)Kr···ICF(3), (86)Kr···ICF(3), (16)O(12)C···ICF(3), (16)O(13)C···ICF(3), and (18)O(12)C···ICF(3). Interpretation of the spectroscopic constants reveals that the carbon atom of CO is adjacent to I and participates in the weak bond in OC···ICF(3). Simple models based on unperturbed component geometries lead to the distances r(Kr···I) = 3.830(1) Å and r(C···I) = 3.428(1) Å in Kr···ICF(3) and OC···ICF(3), respectively, and to the quadratic force constants for stretching of the weak bond k(σ) = 2.80 N m(-1) and 3.96 N m(-1), respectively. The distances r(Z···I) (Z is the acceptor atom in B), the k(σ) values, and the angular geometries of the pair of complexes B···ICF(3) and B···ICl for a given B are compared when B = Kr, CO, H(2)O, H(2)S, or NH(3). The comparison reveals that the iodine bond in B···ICF(3) is systematically longer and weaker than that of B···ICl, while the angular geometry of the B···I moiety is isomorphic in B···ICF(3) and B···ICl for a given B. It is concluded that -CF(3) is less effective than -Cl as an electron-withdrawing group when attached to an I atom and that the angular geometries of the B···ICF(3) can be predicted by means of a simple rule that holds for many hydrogen- and halogen-bonded complexes.

  20. Romanian government bond market

    Directory of Open Access Journals (Sweden)

    Cornelia POP

    2012-12-01

    Full Text Available The present paper aims to present the level of development reached by Romanian government bond market segment, as part of the country financial market. The analysis will be descriptive (the data series available for Romania are short, based on the secondary data offered by the official bodies involved in the process of issuing and trading the Romanian government bonds (Romanian Ministry of Public Finance, Romanian National Bank and Bucharest Stock Exchange, and also on secondary data provided by the Federation of European Stock Exchanges.To enhance the market credibility as a benchmark, a various combination of measures is necessary; among these measures are mentioned: the extension of the yield curve; the issuance calendars in order to improve transparency; increasing the disclosure of information on public debt issuance and statistics; holding regular meetings with dealers, institutional investors and rating agencies; introducing a system of primary dealers; establishing a repurchase (repo market in the government bond market. These measures will be discussed based on the evolution presented inside the paper.The paper conclude with the fact that, until now, the Romanian government bond market did not provide a benchmark for the domestic financial market and that further efforts are needed in order to increase the government bond market transparency and liquidity.

  1. Computer Simulation of the E.C.C.S. Buckling Curve using a Monte-Carlo Method

    NARCIS (Netherlands)

    Strating, J.; Vos, H.

    1973-01-01

    The application of a Monte-Carlo simulation procedure to obtain the distribution function of the maximum load of a hinged column with imperfections is discussed. Buckling tests carried out by the E.C.C.S. on IPE 160 sections have been simulated. Information concerning the column variables is obtaine

  2. Highly Conductive, Mechanically Robust, and Electrochemically Inactive TiC/C Nanofiber Scaffold for High-Performance Silicon Anode Batteries

    KAUST Repository

    Yao, Yan

    2011-10-25

    Silicon has a high specific capacity of 4200 mAh/g as lithium-ion battery anodes, but its rapid capacity fading due to >300% volume expansion and pulverization presents a significant challenge for practical applications. Here we report a core-shell TiC/C/Si inactive/active nanocomposite for Si anodes demonstrating high specific capacity and excellent electrochemical cycling. The amorphous silicon layer serves as the active material to store Li+, while the inactive TiC/C nanofibers act as a conductive and mechanically robust scaffold for electron transport during the Li-Si alloying process. The core-shell TiC/C/Si nanocomposite anode shows ∼3000 mAh g-1 discharge capacity and 92% capacity retention after 100 charge/discharge cycles. The excellent cycling stability and high rate performance could be attributed to the tapering of the nanofibers and the open structure that allows facile Li ion transport and the high conductivity and mechanical stability of the TiC/C scaffold. © 2011 American Chemical Society.

  3. Safe and Liquid Mortgage Bonds

    DEFF Research Database (Denmark)

    Dick-Nielsen, Jens; Gyntelberg, Jacob; Lund, Jesper

    This paper shows that strict match pass-through funding of covered bonds provides safe and liquid mortgage bonds. Despite a 30% drop in house prices during the 2008 global crisis Danish mortgage bonds remained as liquid as most European government bonds. The Danish pass-through system effectively...... eliminates credit risk from the investor's perspective. Similar to other safe bonds, funding liquidity becomes the main driver of mortgage bond liquidity and this creates commonality in liquidity across markets and countries. These findings have implications for how to design a robust mortgage bond system...

  4. Time-dependent density functional theory study on the electronic excited-state geometric structure, infrared spectra, and hydrogen bonding of a doubly hydrogen-bonded complex.

    Science.gov (United States)

    Liu, Yufang; Ding, Junxia; Liu, Ruiqiong; Shi, Deheng; Sun, Jinfeng

    2009-12-01

    The geometric structures and infrared (IR) spectra in the electronically excited state of a novel doubly hydrogen-bonded complex formed by fluorenone and alcohols, which has been observed by IR spectra in experimental study, are investigated by the time-dependent density functional theory (TDDFT) method. The geometric structures and IR spectra in both ground state and the S(1) state of this doubly hydrogen-bonded FN-2MeOH complex are calculated using the DFT and TDDFT methods, respectively. Two intermolecular hydrogen bonds are formed between FN and methanol molecules in the doubly hydrogen-bonded FN-2MeOH complex. Moreover, the formation of the second intermolecular hydrogen bond can make the first intermolecular hydrogen bond become slightly weak. Furthermore, it is confirmed that the spectral shoulder at around 1700 cm(-1) observed in the IR spectra should be assigned as the doubly hydrogen-bonded FN-2MeOH complex from our calculated results. The electronic excited-state hydrogen bonding dynamics is also studied by monitoring some vibraitonal modes related to the formation of hydrogen bonds in different electronic states. As a result, both the two intermolecular hydrogen bonds are significantly strengthened in the S(1) state of the doubly hydrogen-bonded FN-2MeOH complex. The hydrogen bond strengthening in the electronically excited state is similar to the previous study on the singly hydrogen-bonded FN-MeOH complex and play important role on the photophysics of fluorenone in solutions.

  5. A mild route to mesoporous Mo2C-C hybrid nanospheres for high performance lithium-ion batteries

    Science.gov (United States)

    Gao, Qing; Zhao, Xinyu; Xiao, Ying; Zhao, Di; Cao, Minhua

    2014-05-01

    In this work, we have developed a mild route to fabricate typically mesoporous Mo2C-C hybrid nanospheres based on a solvothermal synthesis and reduction-carbonization process. This work opens a low-temperature route to synthesize valuable carbides. The resultant Mo2C-C hybrid, for the first time, is used as an anode material in lithium ion batteries (LIBs). Compared with bulk Mo2C, the Mo2C-C hybrid exhibits much better electrochemical performance. Remarkably, the hybrid electrode can deliver a specific capacity of over 670 mA h g-1 after 50 cycles at 100 mA g-1, which is much higher than that of the bulk material (113 mA h g-1). Even cycled at a high current density of 1000 mA g-1, high capacities of around 400-470 mA h g-1 can still be retained for the Mo2C-C hybrid. It might benefit from the synergistic effect of the nanohybridization, effectively relieving the volume change during the repeated lithium insertion-extraction reactions and maintaining the integrity of the electrical connections. It is expected that the present synthesis strategy for the Mo2C-C hybrid can be extended to other nanostructured carbides with good energy storage performance.In this work, we have developed a mild route to fabricate typically mesoporous Mo2C-C hybrid nanospheres based on a solvothermal synthesis and reduction-carbonization process. This work opens a low-temperature route to synthesize valuable carbides. The resultant Mo2C-C hybrid, for the first time, is used as an anode material in lithium ion batteries (LIBs). Compared with bulk Mo2C, the Mo2C-C hybrid exhibits much better electrochemical performance. Remarkably, the hybrid electrode can deliver a specific capacity of over 670 mA h g-1 after 50 cycles at 100 mA g-1, which is much higher than that of the bulk material (113 mA h g-1). Even cycled at a high current density of 1000 mA g-1, high capacities of around 400-470 mA h g-1 can still be retained for the Mo2C-C hybrid. It might benefit from the synergistic effect of

  6. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    Corporate financing is the choice between capital generated by the corporation and capital from external investors. However, since the financial crisis shook the markets in 2007–2008, financing opportunities through the classical means of financing have decreased. As a result, corporations have...... markets. However, NASDAQ OMX has introduced the First North Bond Market in December 2012 and new regulatory framework came into place in 2014, which may contribute to a Danish based corporate bond market. The purpose of this article is to present the regulatory changes in Denmark in relation to corporate...

  7. The Trouble With Bonds

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    @@ In early June,global financial markets gyrated downwards in the wake of central banks'tough language on inflation.At one point bond prices reflected expectations of four rate hikes by the US Federal Reserve (Fed) in the next 12 months.As a result,the dollar firmed,oil prices stabilized,and yield curves flattened around the world.If all these inflation-fighting measures are real,the situation bodes well for bonds.But,I think otherwise.

  8. Cooperativity in beryllium bonds.

    Science.gov (United States)

    Alkorta, Ibon; Elguero, José; Yáñez, Manuel; Mó, Otilia

    2014-03-07

    A theoretical study of the beryllium bonded clusters of the (iminomethyl)beryllium hydride and (iminomethyl)beryllium fluoride [HC(BeX)=NH, X = H, F] molecules has been carried out at the B3LYP/6-311++G(3df,2p) level of theory. Linear and cyclic clusters have been characterized up to the decamer. The geometric, energetic, electronic and NMR properties of the clusters clearly indicate positive cooperativity. The evolution of the molecular properties, as the size of the cluster increases, is similar to those reported in polymers held together by hydrogen bonds.

  9. Hydrogen-bonded proton transfer in the protonated guanine-cytosine (GC+H)+ base pair.

    Science.gov (United States)

    Lin, Yuexia; Wang, Hongyan; Gao, Simin; Schaefer, Henry F

    2011-10-13

    The single proton transfer at the different sites of the Watson-Crick (WC) guanine-cytosine (GC) DNA base pair are studied here using density functional methods. The conventional protonated structures, transition state (TS) and proton-transferred product (PT) structures of every relevant species are optimized. Each transition state and proton-transferred product structure has been compared with the corresponding conventional protonated structure to demonstrate the process of proton transfer and the change of geometrical structures. The relative energies of the protonated tautomers and the proton-transfer energy profiles in gas and solvent are analyzed. The proton-transferred product structure G(+H(+))-H(+)C(N3)(-H(+))(PT) has the lowest relative energy for which only two hydrogen bonds exist. Almost all 14 isomers of the protonated GC base pair involve hydrogen-bonded proton transfer following the three pathways, with the exception of structure G-H(+)C(O2). When the positive charge is primarily "located" on the guanine moiety (H(+)G-C, G-H(+)C(C4), and G-H(+)C(C6)), the H(1) proton transfers from the N(1) site of guanine to the N(3) site of cytosine. The structures G-H(+)C(C5) and G-H(+)C(C4) involve H(4a) proton transfer from the N(4) of cytosine to the O(6) site of guanine. H(2a) proton transfer from the N(2) site of guanine to the O(2) site of cytosine is found only for the structure G-H(+)C(C4). The structures to which a proton is added on the six-centered sites adjoining the hydrogen bonds are more prone to proton transfer in the gas phase, whereas a proton added on the minor groove and the sites adjoining the hydrogen bonds is favorable to the proton transfer in energy in the aqueous phase.

  10. Ordinary and partial differential equation routines in C, C++, Fortran, Java, Maple, and Matlab

    CERN Document Server

    Lee, HJ

    2003-01-01

    This book provides a set of ODE/PDE integration routines in the six most widely used computer languages, enabling scientists and engineers to apply ODE/PDE analysis toward solving complex problems. This text concisely reviews integration algorithms and then analyzes the widely used Runge-Kutta method. It first presents a complete code before discussing its components in detail, focusing on integration concepts such as error monitoring and control. The format allows readers to understand the basics of ODE/PDE integration, and then calculate sample numerical solutions within the targeted program

  11. Intramolecular hydrogen bonding in medicinal chemistry.

    Science.gov (United States)

    Kuhn, Bernd; Mohr, Peter; Stahl, Martin

    2010-03-25

    The formation of intramolecular hydrogen bonds has a very pronounced effect on molecular structure and properties. We study both aspects in detail with the aim of enabling a more rational use of this class of interactions in medicinal chemistry. On the basis of exhaustive searches in crystal structure databases, we derive propensities for intramolecular hydrogen bond formation of five- to eight-membered ring systems of relevance in drug discovery. A number of motifs, several of which are clearly underutilized in drug discovery, are analyzed in more detail by comparing small molecule and protein-ligand X-ray structures. To investigate effects on physicochemical properties, sets of closely related structures with and without the ability to form intramolecular hydrogen bonds were designed, synthesized, and characterized with respect to membrane permeability, water solubility, and lipophilicity. We find that changes in these properties depend on a subtle balance between the strength of the hydrogen bond interaction, geometry of the newly formed ring system, and the relative energies of the open and closed conformations in polar and unpolar environments. A number of general guidelines for medicinal chemists emerge from this study.

  12. Cross-coupling of C(sp)-H Bonds with Organometallic Reagents via Pd(II)/Pd(0) Catalysis**

    Science.gov (United States)

    Wasa, Masayuki; Engle, Keary M; Yu, Jin-Quan

    2010-12-01

    Palladium-catalyzed C-H activation/C-C bond-forming reactions have emerged as a promising class of synthetic tools in organic chemistry. Among the many different means of forging C-C bonds using Pd-mediated C-H activation, a new horizon in this field is Pd(II)-catalyzed cross-coupling of C-H bonds with organometallic reagents via a Pd(II)/Pd(0) catalytic cycle. While this type of reaction has proven to be effective for the selective functionalization of aryl C(sp(2))-H bonds, the focus of this review is on Pd(II)-catalyzed C(sp(3))-H activation/C-C cross-coupling, a topic of particular importance because reactions of this type enable fundamentally new methods for bond construction. Since our laboratory's initial report on cross-coupling of C-H bonds in 2006, this area has expanded rapidly, and the unique ability of Pd(II) catalysts to cleave and functionalize alkyl C(sp(3))-H bonds has been exploited to develop protocols for forming an array of C(sp(3))-C(sp(2)) and C(sp(3))-C(sp(3)) bonds. Furthermore, enantioselective C(sp(3))-H activation/C-C cross-coupling has been achieved through the use of chiral amino acid-derived ligands, offering a novel technique for producing enantioenriched molecules. Although this nascent field remains at an early stage of development, further investigations hold the potential to revolutionalize the way in which chiral molecules are synthesized in industrial and academic laboratories.

  13. Evidence of amino acid precursors: C-N bond coupling in simulated interstellar CO2/NH3 ices

    Science.gov (United States)

    Esmaili, Sasan

    2015-08-01

    Low energy secondary electrons are abundantly produced in astrophysical or planetary ices by the numerous ionizing radiation fields typically encountered in space environments and may thus play a role in the radiation processing of such ices [1]. One approach to determine their chemical effect is to irradiate nanometer thick molecular solids of simple molecular constituents, with energy selected electron beams and to monitor changes in film chemistry with the surface analytical techniques [2].Of particular interest is the formation of HCN, which is a signature of dense gases in interstellar clouds, and is ubiquitous in the ISM. Moreover, the chemistry of HCN radiolysis products such as CN- may be essential to understand of the formation of amino acids [3] and purine DNA bases. Here we present new results on the irradiation of multilayer films of CO2 and NH3 with 70 eV electrons, leading to CN bond formations. The electron stimulated desorption (ESD) yields of cations and anions are recorded as a function of electron fluence. The prompt desorption of cationic reaction/scattering products [4], is observed at low fluence (~4x1013 electrons/cm2). Detected ions include C2+, C2O2+, C2O+, CO3+, C2O3+ or CO4+ from pure CO2, and N+, NH+, NH2+, NH3+, NH4+, N2+, N2H+ from pure NH3, and NO+, NOH+ from CO2/NH3 mixtures. Most saliently, increasing signals of negative ion products desorbing during prolonged irradiation of CO2/NH3 films included C2-, C2H-, C2H2-, as well as CN-, HCN- and H2CN-. The identification of particular product ions was accomplished by using 13CO2 and 15NH3 isotopes. The chemistry induced by electrons in pure films of CO2 and NH3 and mixtures with composition ratios (3:1), (1:1), and (1:3), was also studied by X-ray photoelectron spectroscopy (XPS). Irradiation of CO2/NH3 mixed films at 22 K produces species containing the following bonds/functional groups identified by XPS: C=O, O-H, C-C, C-O, C=N and N=O. (This work has been funded by NSERC).

  14. Copper(I)- and copper(0)-promoted homocoupling and homocoupling-hydrodehalogenation reactions of dihalogenoclathrochelate precursors for C-C conjugated iron(II) bis-cage complexes.

    Science.gov (United States)

    Varzatskii, Oleg A; Shul'ga, Sergey V; Belov, Alexander S; Novikov, Valentin V; Dolganov, Alexander V; Vologzhanina, Anna V; Voloshin, Yan Z

    2014-12-28

    Iron(II) dibromo- and diiodoclathrochelates undergo copper(I)-promoted reductive homocoupling in HMPA at 70-80 °C leading to C-C conjugated dibromo- and diiodo-bis-clathrochelates in high yields. Under the same conditions, their dichloroclathrochelate analog does not undergo the same homocoupling reaction, so the target dichloro-bis-cage product was obtained in high yield via dimerization of its heterodihalogenide iodochloromonomacrobicyclic precursor. The use of NMP as a solvent at 120-140 °C gave the mixture of bis-clathrochelates resulting from a tandem homocoupling-hydrodehalogenation reaction: the initial acetonitrile copper(I) solvato-complex at a high temperature underwent re-solvatation and disproportionation leading to Cu(II) ions and nano-copper, which promoted the hydrodehalogenation process even at room temperature. The most probable pathway of this reaction in situ includes hydrodehalogenation of the already formed dihalogeno-bis-clathrochelate via the formation of reduced anion radical intermediates. As a result, chemical transformations of the iron(II) dihalogenoclathrochelates in the presence of an acetonitrile copper(I) solvato-complex were found to depend both on the nature of halogen atoms in their ribbed chelate fragments and on reaction conditions (i.e. solvent and temperature). The C-C conjugated iron(II) dihalogeno-bis-clathrochelates easily undergo nucleophilic substitution with various N,S-nucleophiles giving ribbed-functionalized bis-cage species. These iron(II) complexes were characterized by elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (1)H and (13)C NMR spectroscopy, and by X-ray diffraction; their electrochemical properties were studied by cyclic voltammetry. The isomeric shift values in (57)Fe Mössbauer spectra of such cage compounds allowed identifying them as low-spin iron(II) complexes, while those of the quadrupole splitting are the evidence for a significant TP distortion of their FeN6-coordination polyhedra

  15. C/C++代码自动生成脚本语言接口的实现%Implementation of Automatic Generating Scripting Language Interfaces with C/C++ Code

    Institute of Scientific and Technical Information of China (English)

    官尚元; 张芝萍; 徐立锋; 缪敬

    2005-01-01

    对于开发灵活的科学软件来说,脚本语言是一个强大的工具.然而开发人员经常遇到一个问题:如何将编译过的C/C++代码集成到一个解释器.为了解决上述问题,设计了一个可扩展的编译器--接口产生器(IG).IG主要任务是把编译过的C/C++代码集成到脚本语言解释器中.因此,该文的主要目的就是解决上述相关问题.

  16. Photochemical tissue bonding

    Science.gov (United States)

    Redmond, Robert W.; Kochevar, Irene E.

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  17. Bonding in cementitious composites

    Energy Technology Data Exchange (ETDEWEB)

    Mindess, S. (British Columbia Univ., Vancouver, BC (Canada)) Shah, S.P. (Northwestern Univ., Evanston, IL (USA))

    1988-01-01

    These proceedings discuss the papers presented at the symposium on the subject of high performance cement composites. Some of the topics discussed were; calcium hydroxides treated ceramics microspheres and mechanical properties of high temperature light weight cements; microstructure and chemical variations of class F fly ash; microstructure and bond strength of cement and crack propagation as detected by laser holography and acoustic emission.

  18. Thermal Bond System.

    Science.gov (United States)

    1995-10-31

    a twill weave, a crowfoot weave, a satin weave (FIG. 2), and a leno weave. Descriptions of the various weave types can be found in " Composite ...together to define a fabric mesh having first and second opposing woven surfaces. An adhesive bond that is flowable prior to drying is used to wet and

  19. Statically Detecting Likely Buffer Overflow Vulnerabilities in C/C++ Program%C/C++源程序缓冲区溢出漏洞的静态检测

    Institute of Scientific and Technical Information of China (English)

    杨小龙; 刘坚

    2004-01-01

    讨论了C/C++源程序中缓冲区溢出的常见表现;分析了其特性以及产生机理;提出了在源代码的AST上附加安全属性进行漏洞静态检测的方法;讨论了该方法的实现过程.

  20. Deep Analysis and Application of the Function Pointer in the C/C++ Language Programming%C/C++语言中函数指针的深入分析与应用

    Institute of Scientific and Technical Information of China (English)

    张海平

    2009-01-01

    C/C++语言程序设计中函数指针进行了详细的分析与研究,包括函数指针的概念、定义和调用,并着重通过回调函数与简单消息映射实例阐述函数指针的使用方法和技巧.