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Sample records for c-n bond formation

  1. Accelerated C-N Bond Formation in Dropcast Thin Films on Ambient Surfaces

    Science.gov (United States)

    Badu-Tawiah, Abraham K.; Campbell, Dahlia I.; Cooks, R. Graham

    2012-09-01

    The aza-Michael addition and the Mannich condensation occur in thin films deposited on ambient surfaces. The reagents for both C-N bond formation reactions were transferred onto the surface by drop-casting using a micropipette. The surface reactions were found to be much more efficient than the corresponding bulk solution-phase reactions performed on the same scale in the same acetonitrile solvent. The increase in rate of product formation in the thin film is attributed to solvent evaporation in the open air which results in reagent concentration and produces rate acceleration similar to that seen in evaporating droplets in desorption electrospray ionization. This thin film procedure has potential for the rapid synthesis of reaction products on a small scale, as well as allowing rapid derivatization of analytes to produce forms that are easily ionized by electrospray ionization. Analysis of the derivatized sample directly from the reaction surface through the use of desorption electrospray ionization is also demonstrated.

  2. 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

    2016-08-01

    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. PMID:27439145

  3. 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. PMID:26332253

  4. Tetra-bonding of C, N and O at solid surface

    OpenAIRE

    Sun, Chang Q.

    2008-01-01

    In order to gain advanced understanding of the kinetics and dynamics of C, N, and O reacting with a solid surface, it is necessary to consider the reaction from the perspectives of bond formation, bond dissociation, bond relaxation, bond vibration, and the associated charge redistribution and polarization and the energetic response of the involved atoms and valence electrons. The sp-orbital hybridization is found necessary for these concerned reactions associated with strongly anisotropic bon...

  5. Synthesis of Indolizines through Oxidative Linkage of C-C and C-N Bonds from 2-Pyridylacetates.

    Science.gov (United States)

    Mohan, Darapaneni Chandra; Ravi, Chitrakar; Pappula, Venkatanarayana; Adimurthy, Subbarayappa

    2015-07-01

    Synthesis of indolizine-1-carboxylates through the Ortoleva-King reaction of 2-pyridylacetate followed by the Aldol condensation under mild reaction conditions has been described. This protocol is compatible with a broad range of functional groups, and it has been also successfully extended to unsaturated ketones, bringing about the regioselective formation of benzoyl-substituted indolizines through Michael addition followed by C-N bond formation, which are difficult to prepare by previous methods in a single step. PMID:26044904

  6. Synthesis of sulfonamides via copper-catalyzed oxidative C-N bond cleavage of tertiary amines.

    Science.gov (United States)

    Ji, Jing; Liu, Zhengyi; Liu, Ping; Sun, Peipei

    2016-08-01

    A copper-catalyzed coupling reaction of sulfonyl chlorides with tertiary amines via the oxidative C-N bond cleavage of tertiary amines was developed. Sulfonamides were synthesized using this strategy in moderate to good yields. The reaction was applicable to various tertiary amines, as well as sulfonyl chlorides. PMID:27356858

  7. Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

    KAUST Repository

    Elshewy, Ahmed M.

    2013-12-01

    Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

  8. 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).

  9. Protein folding guides disulfide bond formation

    OpenAIRE

    Qin, Meng; Wang, Wei; Thirumalai, D.

    2015-01-01

    Anfinsen inferred the principles of protein folding by studying a protein containing four disulfide bonds in the native state. However, how protein folding drives disulfide bond formation is poorly understood despite the role such proteins play in variety of extracellular and intracellular functions. We developed a method to mimic the complex chemistry of disulfide bond formation in molecular simulations, which is used to decipher the mechanism of folding of bovine pancreatic trypsin inhibito...

  10. Halogen-bonding-triggered supramolecular gel formation.

    OpenAIRE

    Meazza, L.; Foster, J. A.; Fucke, K.; Metrangolo, P.; Resnati, G.; Steed, J. W.

    2013-01-01

    Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger sup...

  11. Orbital entanglement in bond-formation processes

    CERN Document Server

    Boguslawski, Katharina; Barcza, Gergely; Legeza, Ors; Reiher, Markus

    2013-01-01

    The accurate calculation of the (differential) correlation energy is central to the quantum chemical description of bond-formation and bond-dissociation processes. In order to estimate the quality of single- and multi-reference approaches for this purpose, various diagnostic tools have been developed. In this work, we elaborate on our previous observation [J. Phys. Chem. Lett. 3, 3129 (2012)] that one- and two-orbital-based entanglement measures provide quantitative means for the assessment and classification of electron correlation effects among molecular orbitals. The dissociation behavior of some prototypical diatomic molecules features all types of correlation effects relevant for chemical bonding. We demonstrate that our entanglement analysis is convenient to dissect these electron correlation effects and to provide a conceptual understanding of bond-forming and bond-breaking processes from the point of view of quantum information theory.

  12. Orbital entanglement in bond-formation processes

    OpenAIRE

    Boguslawski, Katharina; Tecmer, Pawel; Barcza, Gergely; Legeza, Ors; Reiher, Markus

    2013-01-01

    The accurate calculation of the (differential) correlation energy is central to the quantum chemical description of bond-formation and bond-dissociation processes. In order to estimate the quality of single- and multi-reference approaches for this purpose, various diagnostic tools have been developed. In this work, we elaborate on our previous observation [J. Phys. Chem. Lett. 3, 3129 (2012)] that one- and two-orbital-based entanglement measures provide quantitative means for the assessment a...

  13. Halogen-bonding-triggered supramolecular gel formation

    Science.gov (United States)

    Meazza, Lorenzo; Foster, Jonathan A.; Fucke, Katharina; Metrangolo, Pierangelo; Resnati, Giuseppe; Steed, Jonathan W.

    2013-01-01

    Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a two-component gel (‘co-gel’) is essentially unexplored, and forms the basis for this study. Here, we show that halogen bonding between a pyridyl substituent in a bis(pyridyl urea) and 1,4-diiodotetrafluorobenzene brings about gelation, even in polar media such as aqueous methanol and aqueous dimethylsulfoxide. This demonstrates that halogen bonding is sufficiently strong to interfere with competing gel-inhibitory interactions and create a ‘tipping point’ in gel assembly. Using this concept, we have prepared a halogen bond donor bis(urea) gelator that forms co-gels with halogen bond acceptors.

  14. Shedding light on disulfide bond formation

    DEFF Research Database (Denmark)

    Ostergaard, H; Henriksen, A; Hansen, F 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 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...... reorganization of residues in the immediate chromophore environment. By combining this information with spectroscopic data, we propose a detailed mechanism accounting for the observed redox state-dependent fluorescence. The redox potential of the cysteine couple was found to be within the physiological range...

  15. Antibody catalysis of peptide bond formation.

    OpenAIRE

    Jacobsen, J R; Schultz, P. G.

    1994-01-01

    An antibody generated against a neutral phosphonate diester transition-state (TS not equal to) analog catalyzes the formation of an amide bond between a phenylalanyl amino group and an acyl azide derived from L-alanine. The antibody is selective for L- vs. D-alanine and does not catalyze the hydrolysis of the acyl azide to an appreciable degree. A rate acceleration of 10,000-fold relative to the uncatalyzed reaction is observed. The antibody may achieve its catalytic efficiency both by acting...

  16. Centreline formation of Nb(C, N eutectic in structural steel

    Directory of Open Access Journals (Sweden)

    J. Bernetič

    2010-01-01

    Full Text Available The reduction of area in the through thickness direction is an essential mechanical property of thick steel heavy plates. By a routine control, a very small through thickness reduction of area was found for tensile specimen of a 90 mm plate. Careful investigations of the fracture and section of specimens cut from the as solidified continuously cast 250mmthick slab showed that the cause was the presence of coarse particles of niobium carbonitride as constituent of the quasi eutectic Fe-Nb(C, N that form because of the centerline segregation of niobium.

  17. Centreline formation of Nb(C, N) eutectic in structural steel

    OpenAIRE

    J. Bernetič; Bradaškja, B.; G. Kosec; Bricelj, E.; B. Kosec; F. Vodopivec; Kosec, L.

    2010-01-01

    The reduction of area in the through thickness direction is an essential mechanical property of thick steel heavy plates. By a routine control, a very small through thickness reduction of area was found for tensile specimen of a 90 mm plate. Careful investigations of the fracture and section of specimens cut from the as solidified continuously cast 250mmthick slab showed that the cause was the presence of coarse particles of niobium carbonitride as constituent of the quasi eutectic Fe-Nb(C, N...

  18. Formation of Si-C-N ceramics from melamine-carbosilazane single source precursors

    International Nuclear Information System (INIS)

    A series of melamine-carbosilazane pre-ceramic macromolecules (Mel-CSZs) were prepared by the condensation of melamine with different organochlorosilanes (RxSiCl4-x where R is CH3/C6H5 and x is 1, 2 or 3) using pyridine as a solvent under nitrogen atmosphere. These melamine-based carbosilazane macromolecules (Mel-CSZs) were characterized by infrared spectroscopy (FT-IR), mass spectrometry (MS), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The backbone of the resulting Mel-CSZs consists of melamine and carbosilazane building blocks. Pyrolysis of these Mel-CSZs at 600 deg. C under nitrogen and vacuum afforded the corresponding silicon-based nonoxide carbonitride ceramics (Si-C-N). The microstructure and textural morphology of the resulting fine ceramic materials were examined using FT-IR, powder X-ray diffraction (XRD), and scanning electron microscopy (SEM). - Graphical abstract: Pyrolysis of the prepared melamine-organosilane macromolecules afforded Si-C-N ceramics with different textural morphology

  19. Alkyl Aryl Ether Bond Formation with PhenoFluor**

    OpenAIRE

    Shen, Xiao; Neumann, Constanze N.; Kleinlein, Claudia; Claudia, Nathaniel W.; Ritter, Tobias

    2015-01-01

    An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation.

  20. 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...

  1. Double Pancake Versus Long Chalcogen-Chalcogen Bonds in Six-Membered C,N,S-Heterocycles.

    Science.gov (United States)

    Haberhauer, Gebhard; Gleiter, Rolf

    2016-06-13

    The double "pancake" bonding in the dimers of the six-membered heterocycles 1,3-dithia-2,4,6-triazine (4) and 1,3-dithia-2,4-diazine (16) were investigated by means of high-level quantum chemical calculations (B3LYP and CCSD(T)). It was found that the S-S dimers, 20 a and 27, are not the most stable isomers, but the dimers showing short S-N (21 a) and S-C (25, 28) bonds. An investigation of the 5-phenyl-1,3-dithia-2,4,6-triazine (4 b) yields that the syn dimer with two S-S bonds (2.57 Å) is the most stable one. In this dimer, the phenyl groups are placed on top of each other. The additional dispersion energy of the phenyl rings causes a stabilization of the syn-S-S (C2v -like) isomer. As a result, two weak albeit relevant single S-S bonds (2.57 Å) are predicted. These findings contradict the recently published concept of double "pancake" bonding in the dimer 4 b2 . PMID:27172139

  2. Formation of halogenated C-, N-DBPs from chlor(am)ination and UV irradiation of tyrosine in drinking water

    International Nuclear Information System (INIS)

    The formation of regulated and emerging halogenated carbonaceous (C-) and nitrogenous disinfection by-products (N-DBPs) from the chlor(am)ination and UV irradiation of tyrosine (Tyr) was investigated. Increased chlorine contact time and/or Cl2/Tyr ratio increased the formation of most C-DBPs, with the exception of 4-chlorophenol, dichloroacetonitrile, and dichloroacetamideChloroform and dichloroacetic acid increased with increasing pH, dichloroacetonitrile first increased and then decreased, and other DBPs had maximum yields at pH 7 or 8. The addition of ammonia significantly reduced the formation of most C-DBPs but increased 4-chlorophenol, dichloroacetonitrile, dichloroacetamide, and trichloroacetonitrile yields for short prechlorination contact times before dosing ammonia. When UV irradiation and chlorination were performed simultaneously, the concentrations of the relatively stable C-DBPs increased, and the concentrations of dichloroacetonitrile, dichloroacetamide, and 4-chlorophenol decreased with increasing UV dose. This information was used to develop a mechanistic model for the formation of intermediate DBPs and end products from the interaction of disinfectants with tyrosine. Highlights: ► Increased contact time and/or Cl2/Tyr decreased the formation of some N-DBPs. ► Changing the pH of disinfection decreases the formation of some N-DBPs. ► N-DBP yields increased for short prechlorination contact time before dosing ammonia. ► Low pressure UV before chlorination did not impact the formation of DBPs from Tyr. ► A novel integrated formation pathway of halogenated C-, N-DBPs is proposed. - Exploring the integrated formation mechanism of regulated and emerging highly toxic DBPs, which is expected to preferably reduce their occurrence in drinking water.

  3. Protein nanopatterns by oxime bond formation.

    Science.gov (United States)

    Christman, Karen L; Broyer, Rebecca M; Schopf, Eric; Kolodziej, Christopher M; Chen, Yong; Maynard, Heather D

    2011-02-15

    Patterning proteins on the nanoscale is important for applications in biology and medicine. As feature sizes are reduced, it is critical that immobilization strategies provide site-specific attachment of the biomolecules. In this study, oxime chemistry was exploited to conjugate proteins onto nanometer-sized features. Poly(Boc-aminooxy tetra(ethylene glycol) methacrylate) was synthesized by free radical polymerization. The polymer was patterned onto silicon wafers using an electron beam writer. Trifluoroacetic acid removal of the Boc groups provided the desired aminooxy functionality. In this manner, patterns of concentric squares and contiguous bowtie shapes were fabricated with 150-170-nm wide features. Ubiquitin modified at the N-terminus with an α-ketoamide group and N(ε)-levulinyl lysine-modified bovine serum albumin were subsequently conjugated to the polymer nanopatterns. Protein immobilization was confirmed by fluorescence microscopy. Control studies on protected surfaces and using proteins presaturated with O-methoxyamine indicated that attachment occurred via oxime bond formation. PMID:21192671

  4. Cooperative domain type interlayer $sp^3$-bond formation in graphite

    OpenAIRE

    Nishioka, Keita; Nasu, Keiichiro

    2010-01-01

    Using the classical molecular dynamics and the semiempirical Brenner's potential, we theoretically study the interlayer sigma bond formation, as cooperative and nonlinear phenomena induced by visible light excitations of a graphite crystal. We have found several cases, wherein the excitations of certain lattice sites result in new interlayer bonds even at non-excited sites. We have also found that, a new interlayer bond is easier to be formed around a bond, if it is already existing. As many ...

  5. Kinetico-mechanistic studies on the formation of seven-membered [C,N]-platinacycles: the effect of methyl or fluoro substituents on the aryl ancillary ligands.

    Science.gov (United States)

    Crespo, Margarita; Font-Bardia, Mercè; Martínez, Manuel

    2015-12-01

    The reactions of dinuclear [Pt2(4-RC6H4)4(μ-SEt2)2] (R = Me or F), or mononuclear [Pt(4-RC6H4)2(SMe2)2] (R = Me or H), platinum(ii) compounds with imines of the general formula 2-X,6-YC6H3CH[double bond, length as m-dash]NCH2Ph (X = Br, Y = F; X = Cl, Y = F; X = Br, Y = H) produced seven-membered [C,N]-platinacycles. The reaction consists of the initial formation of cyclometallated platinum(iv) compounds followed by a three step process: reductive elimination, isomerisation of the resulting non-cyclometallated intermediate and a final cycloplatination process. Combined (1)H NMR and UV-Vis kinetico-mechanistic studies indicated that the rate determining step of the process depends on the nature of the aryl-Pt ligand (phenyl, p-tolyl or p-fluorophenyl). PMID:26158624

  6. Sequential C-H and C-Ru Bond Formation and Cleavage During the Thermally Induced Rearrangement of Aryl Ruthenium(II) Complexes with [C6H3(CH2NMe2)2-2,6]-as a Bidentate n2-C,N Coordinated Ligand. The Crystal Structures of the Isomeric Pairs [RuCI{n6-C10H14 n2-C,n-C6H3(CH2NMe2)2,n}] (N=4 or 6) and [Ru(n5-C5H5){n2-C,N-C6H3(CH2NMe2)2-2,n}(PPh)] (n= 4 or 6)

    NARCIS (Netherlands)

    Koten, G. van; Steenwinkel, P.; James, S.L.; Gossage, R.A.; Grove, D.M.; Kooijman, H.; Smeets, W.J.J.; Spek, A.L.

    1998-01-01

    New air-stable ruthenium(II) complexes that contain the aryldiamine ligand [C6H3(CH2NMe2)2-2,6]- (NCN) are described. These complexes are [RuCl{2-C,N-C6H3(CH2NMe2)2-2,6}(6-C10H14)] (2; C10H14 = p-cymene = C6H4Me-iPr-4), [Ru{2-C,N-C6H3(CH2NMe2)2-2,6}(5-C5H5)(PPh3)] (5), and their isomeric forms [RuCl

  7. Sequential C-H and C-Ru Bond Formation and Cleavage During the Thermally Induced Rearrangement of Aryl Ruthenium(II) Complexes with [C6H3(CH2NMe2)2-2,6]-as a Bidentate n2-C,N Coordinated Ligand. The Crystal Structures of the Isomeric Pairs [RuCI{n6-C10H14 n2-C,n-C6H3(CH2NMe2)2,n}] (N=4 or 6) and [Ru(n5-C5H5){n2-C,N-C6H3(CH2NMe2)2-2,n}(PPh)] (n= 4 or 6)

    OpenAIRE

    van Koten, G.; Steenwinkel, P.; James, S. L.; Gossage, R. A.; Grove, D.M.; Kooijman, H.; Smeets, W.J.J.; Spek, A.L.

    1998-01-01

    New air-stable ruthenium(II) complexes that contain the aryldiamine ligand [C6H3(CH2NMe2)2-2,6]- (NCN) are described. These complexes are [RuCl{2-C,N-C6H3(CH2NMe2)2-2,6}(6-C10H14)] (2; C10H14 = p-cymene = C6H4Me-iPr-4), [Ru{2-C,N-C6H3(CH2NMe2)2-2,6}(5-C5H5)(PPh3)] (5), and their isomeric forms [RuCl{2-C,N-C6H3(CH2NMe2)2-2,4}(6-C10H14)] (3) and [Ru{2-C,N-C6H3(CH2NMe2)2-2,4}(5-C5H5)(PPh3)] (6), respectively. Complex 2 has been prepared from the reaction of [Li(NCN)]2 with [RuCl2(6-C10H14)]2, wh...

  8. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Makino, T. [NGK Insulators Ltd., Nagoya (Japan). Mater. Res. Lab.; Iwadachi, T. [NGK Insulators Ltd., Handa-city (Japan). New Metals Div.

    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{sub 2}Cu({delta}) phase on the Be side and Cu + BeCu({gamma}) phase on the DSCu side, Cu + BeCu({gamma}) 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{sub 2}Cu({delta}) phase on the Be side. (orig.) 2 refs.

  10. 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...

  11. Peptide Bond Formation in Water Mediated by Carbon Disulfide.

    Science.gov (United States)

    Leman, Luke J; Huang, Zheng-Zheng; Ghadiri, M Reza

    2015-09-01

    Demonstrating plausible nonenzymatic polymerization mechanisms for prebiotic monomers represents a fundamental goal in prebiotic chemistry. While a great deal is now known about the potentially prebiotic synthesis of amino acids, our understanding of abiogenic polymerization processes to form polypeptides is less well developed. Here, we show that carbon disulfide (CS2), a component of volcanic emission and sulfide mineral weathering, and a widely used synthetic reagent and solvent, promotes peptide bond formation in modest yields (up to ∼20%) from α-amino acids under mild aqueous conditions. Exposure of a variety of α-amino acids to CS2 initially yields aminoacyl dithiocarbamates, which in turn generate reactive 2-thiono-5-oxazolidone intermediates, the thio analogues of N-carboxyanhydrides. Along with peptides, thiourea and thiohydantoin species are produced. Amino acid stereochemistry was preserved in the formation of peptides. Our findings reveal that CS2 could contribute to peptide bond formation, and possibly other condensation reactions, in abiogenic settings. PMID:26308392

  12. Transition metal-catalyzed C(vinyl)-C(vinyl) bond formation via double C(vinyl)-H bond activation.

    Science.gov (United States)

    Shang, Xiaojie; Liu, Zhong-Quan

    2013-04-21

    Transition metal-catalyzed oxidative dehydrogenative coupling reactions of Caryl-H bonds with Cvinyl-H bonds to generate a Caryl-Cvinyl bonds have been well developed in recent decades. However, only a few studies have focused on the direct Cvinyl-Cvinyl bond formation via double Cvinyl-H bond activation. Recent developments in this active area have been highlighted in this tutorial review. PMID:23318664

  13. A theoretical study of the effects of polar substitution on the activation barriers for internal rotation around the C-N bond in p-substituted nitrosobenzenes: comparison of DFT and MP2 calculations

    OpenAIRE

    PİRİNÇÇİOĞLU, Şafak ÖZHAN KOCAKAYA and Necmettin

    2010-01-01

    The activation barriers for internal rotation around the C-N bond in p-substituted nitrosobenzenes were calculated using the density functional theory (DFT) and second-order Møller-Plesset (MP2) methods with the 6-31+g(d) basis set. The polarisable continuum model (PCM) was used to model the solvent effect. An explicit water molecule was also introduced to form a hydrogen bond with the nitrosogroup and its effect on the barrier was studied by DFT. The barriers were well-correlated wi...

  14. Ribosomal crystallography: peptide bond formation and its inhibition.

    Science.gov (United States)

    Bashan, Anat; Zarivach, Raz; Schluenzen, Frank; Agmon, Ilana; Harms, Joerg; Auerbach, Tamar; Baram, David; Berisio, Rita; Bartels, Heike; Hansen, Harly A S; Fucini, Paola; Wilson, Daniel; Peretz, Moshe; Kessler, Maggie; Yonath, Ada

    2003-09-01

    Ribosomes, the universal cellular organelles catalyzing the translation of genetic code into proteins, are protein/RNA assemblies, of a molecular weight 2.5 mega Daltons or higher. They are built of two subunits that associate for performing protein biosynthesis. The large subunit creates the peptide bond and provides the path for emerging proteins. The small has key roles in initiating the process and controlling its fidelity. Crystallographic studies on complexes of the small and the large eubacterial ribosomal subunits with substrate analogs, antibiotics, and inhibitors confirmed that the ribosomal RNA governs most of its activities, and indicated that the main catalytic contribution of the ribosome is the precise positioning and alignment of its substrates, the tRNA molecules. A symmetry-related region of a significant size, containing about two hundred nucleotides, was revealed in all known structures of the large ribosomal subunit, despite the asymmetric nature of the ribosome. The symmetry rotation axis, identified in the middle of the peptide-bond formation site, coincides with the bond connecting the tRNA double-helical features with its single-stranded 3' end, which is the moiety carrying the amino acids. This thus implies sovereign movements of tRNA features and suggests that tRNA translocation involves a rotatory motion within the ribosomal active site. This motion is guided and anchored by ribosomal nucleotides belonging to the active site walls, and results in geometry suitable for peptide-bond formation with no significant rearrangements. The sole geometrical requirement for this proposed mechanism is that the initial P-site tRNA adopts the flipped orientation. The rotatory motion is the major component of unified machinery for peptide-bond formation, translocation, and nascent protein progression, since its spiral nature ensures the entrance of the nascent peptide into the ribosomal exit tunnel. This tunnel, assumed to be a passive path for the

  15. Visible light induced C-C bond formation

    OpenAIRE

    Paria, Suva

    2015-01-01

    This Ph.D thesis demonstrates the development of new methodologies for C-C bond formation triggered by visible light photoredox catalysis. In Chapter 1, we have outlined a short overview on Copper in Photocatalysis. Starting from the photophysical properties of copper complexes, a comparison of main excited state aspects of prevalently used ruthenium and iridium complexes with that of copper has been shown. Several UV and visible light mediated synthetic transformation utilizing copper ca...

  16. Intermetallic compound formation at Cu-Al wire bond interface

    International Nuclear Information System (INIS)

    Intermetallic compound (IMC) formation and evolution at Cu-Al wire bond interface were studied using focused ion beam /scanning electron microscopy, transmission electron microscopy (TEM)/energy dispersive x-ray spectroscopy (EDS), nano beam electron diffraction (NBED) and structure factor (SF) calculation. It was found that discrete IMC patches were formed at the Cu/Al interface in as-packaged state and they grew toward Al pad after high temperature storage (HTS) environment at 150 °C. TEM/EDS and NBED results combined with SF calculation revealed the evidence of metastable θ′-CuAl2 IMC phase (tetragonal, space group: I4m2, a = 0.404 nm, c= 0.580 nm) formed at Cu/Al interfaces in both of the as-packaged and the post-HTS samples. Two feasible mechanisms for the formation of the metastable θ′-CuAl2 phase are discussed based on (1) non-equilibrium cooling of wire bond that is attributed to highly short bonding process time and (2) the epitaxial relationships between Cu and θ′-CuAl2, which can minimize lattice mismatch for θ′-CuAl2 to grow on Cu.

  17. Bond formation in ultrasonically welded aluminum sheet metal

    Science.gov (United States)

    Wilkosz, Daniel Edward

    Ultrasonic welding (USW), a solid state joining technology, has been used to bond aluminum alloys commonly used in the automotive industry. Bonding occurs due to USW's high frequency (˜20 kHz) in-plane vibration of sample interfaces while being held under moderate clamp pressure normal to the plane of vibration. Vibration and clamp pressure are transmitted into bond formation via contact with a weld-tip. To better understand how weld-tip geometry affected bond formation, experiments were conducted to quantify how tip geometry influenced plastic deformation characteristics between fully welded coupons of 0.9mm thick AA6111-T4 aluminum alloy. Weld-interface microstructure features were documented by optical microscopy and features quantified in a 19 point matrix. Correlation between microstructure features, such as rolling-wakes, and resulting weld bond strengths of more than 3.0kN is made. Weld zone microstructure features appear to result from deformation at and severe migration of the original weld interface during USW. To confirm this hypothesis, intrinsic and extrinsic markers were employed to monitor weld interface deformation characteristics. Various physical and analytical techniques were used in conjunction with these markers to show that joining of "like" and "dislike" aluminum samples is achieved through mechanical mixing of mating interfaces and not by elemental diffusion. It is also hypothesized that severe deformation of the original interface would result in areas of high residual strain within a formed weld zone. To investigate this and the influence that tip geometry may have on residual strain, fully welded samples were annealed at 500°C for a controlled period of time and recovery, recrystallization and grain growth characteristics were monitored. In all welds, initial recrystallization and grain growth occurred at the outer ends of weld zones and along weld interfaces where the most turbulent mixing and grain size reduction was observed

  18. Design and synthesis of multidentate ligands via metal promoted C-N bond formation processes and their coordination chemistry

    Indian Academy of Sciences (India)

    Kunal K Kamar; Amrita Saha; Sreebrata Goswami

    2002-08-01

    This presentation reports some novel examples of organic ring amination reactions via metal mediation. The organic transformations are highly regioselective and can be controlled by the proper selection of the mediator complex. The two isomeric organic ligands viz. HL1 and HL2 were isolated in their pure states by the removal of the metal ions. These were fully characterized. The ligand HL1 has low , 8.5. Upon deprotonation, it behaves as a potential bis chelating N,N,N-donors. The coordination chemistry of the HL1 ligand involving some 3-metal ions is described. Two unusual low-spin complexes of manganese(II) and iron(III) are reported. The ferric complex displayed a rhombic EPR while, the corresponding manganese compound showed a complex pattern due to hyperfine coupling. All the complexes displayed large number of redox responses. A brief mention about the future projection of this work is noted.

  19. Hydrogen Bond Formation between the Carotenoid Canthaxanthin and the Silanol Group on MCM-41 Surface.

    Science.gov (United States)

    Gao, Yunlong; Xu, Dayong; Kispert, Lowell D

    2015-08-20

    The formation of one or two hydrogen bonds (H-bonds) between canthaxanthin (CAN), a dye, and the silanol group(s) on the MCM-41 surface has been studied by density functional theory (DFT) calculations and calorimetric experiments. It was found that the formation of the H-bond(s) stabilized the CAN molecule more than its radical cation (CAN(•+)). The charge distribution, bond lengths, and the HOMO and LUMO energies of CAN are also affected. The formation of the H-bond(s) explains the lower photoinduced electron transfer efficiency of CAN imbedded in Cu-MCM-41 versus that for β-carotene (CAR) imbedded in Cu-MCM-41 where complex formation with Cu(2+) dominates. These calculations show that to achieve high electron transfer efficiency for a dye-sensitized solar cell, H-bonding between the dye and the host should be avoided. PMID:26230844

  20. Highly Efficient C--N Bond Forming Reactions in Water Catalyzed by Copper(I) Iodide with Calix[4]arene Supported Amino Acid Ionic Liquid%Highly Efficient C--N Bond Forming Reactions in Water Catalyzed by Copper(I) Iodide with Calix[4]arene Supported Amino Acid Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    黄利; 金灿; 苏为科

    2012-01-01

    A novel and effective protocol has been developed for the Ullmann-type C--N coupling reaction catalyzed by calix[4]arene supported amino acid ionic liquid and copper(I) iodide in water under microwave irradiation condition The protocol uses ealix[4]arene supported amino acid ionic liquid as double function of the ligand and phase-transfer catalyst, and shows good tolerance in good to excellent yields.

  1. Formation of Silicon-Gold Eutectic Bond Using Localized Heating Method

    Science.gov (United States)

    Lin, Liwei; Cheng, Yu-Ting; Najafi, Khalil

    1998-11-01

    A new bonding technique is proposed by using localized heating to supplythe bonding energy.Heating is achieved by applying a dc current through micromachined heaters made of gold which serves as both the heating and bonding material.At the interface of silicon and gold, the formation of eutectic bond takes place in about 5 minutes.Assembly of two substrates in microfabrication processescan be achieved by using this method.In this paper the following important results are obtained:1) Gold diffuses into silicon to form a strong eutectic bond by means of localized heating.2) The bonding strength reaches the fracture toughness of the bulk silicon.3) This bonding technique greatly simplifies device fabrication andassembly processes.

  2. High Charge Mobility of a Perylene Bisimide Dye with Hydrogen-bond Formation Group

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A perylene bisimide dye covalently bonded with a hydrogen-bond formation group of 1,3, 5-triazine-2, 4-diamine has been synthesized. Its casting films show a charge carrier mobility over 10-3 cm2/Vs, which is in the range of the highest values found for other promising charge transport materials suitable for solution processable technique.

  3. 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

  4. Molecular and ionic hydrogen bond formation in fluorous solvents.

    Science.gov (United States)

    O'Neal, Kristi L; Weber, Stephen G

    2009-01-01

    There are only a few studies of noncovalent association in fluorous solvents and even fewer that are quantitative. A full understanding, particularly of stoichiometry and binding strength of noncovalent interactions in fluorous solvents could be very useful in improved molecular-receptor-based extractions, advancements in sensor technologies, crystal engineering, and supramolecular chemistry. This work investigates hydrogen bonding between heterocyclic bases and a perfluoropolyether with a terminal carboxylic acid group (Krytox 157FSH (1)), chiefly in FC-72 (a mixture of perfluorohexanes). In particular, we were interested in whether or not proton transfer occurs, and if so, under what conditions in H-bonded complexes. Continuous variations experiments show that in FC-72 weaker bases (pyrazine, pyrimidine, and quinazoline) form 1:1 complexes with 1, whereas stronger bases (quinoline, pyridine, and isoquinoline) form 1:3 complexes. Ultraviolet and infrared spectral signatures reveal that the 1:1 complexes are molecular (B.HA) whereas the 1:3 complexes are ionic (BH+.A-HAHA). Infrared spectra of 1:3 ionic complexes are discussed in detail. Literature and experimental data on complexes between N-heterocyclic bases and carboxylic acids in a range of solvents are compiled to compare solvent effects on proton transfer. Polar solvents support ionic hydrogen bonds at a 1:1 mol ratio. In nonpolar organic solvents, ionic hydrogen bonds are only observed in complexes with 1:2 (base/acid) stoichiometries. In fluorous solvents, a larger excess of acid, 1:3, is necessary to facilitate proton transfer in hydrogen bonds between carboxylic acids and the bases studied. PMID:19195102

  5. Carbon–heteroatom bond formation catalysed by organometallic complexes

    OpenAIRE

    Hartwig, John F.

    2008-01-01

    At one time the synthetic chemist’s last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been ...

  6. DNA Charge Transport Leading to Disulfide Bond Formation

    OpenAIRE

    Takada, Tadao; Barton, Jacqueline K.

    2005-01-01

    Here, we show that DNA-mediated charge transport (CT) can lead to the oxidation of thiols to form disulfide bonds in DNA. DNA assemblies were prepared possessing anthraquinone (AQ) as a photooxidant spatially separated on the duplex from two SH groups incorporated into the DNA backbone. Upon AQ irradiation, HPLC analysis reveals DNA ligated through a disulfide. The reaction efficiency is seen to vary in assemblies containing intervening DNA mismatches, confirming that the reaction is DNA-medi...

  7. 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

    that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.

  8. Covalent bonding and bandgap formation in intermetallic compounds: a case study for Al3V

    International Nuclear Information System (INIS)

    We demonstrate that a special hybridization between the Al(s, p) and V(d) orbitals which is responsible for forming of a deep pseudogap near the Fermi level in the Al3V compound is also associated with the formation of covalent bonds. We analyse the charge distribution in the elementary cell and find an enhanced charge density along the Al-V bonds and certain Al-Al bonds which is characteristic for covalent bonding. The role of the point-group symmetry and the character of the hybrid orbitals forming the covalent bonds are investigated. It is demonstrated that the deep pseudogap close to the Fermi level arises from the bonding-antibonding of the hybrid orbitals. (author)

  9. "Pnicogen bonds" or "chalcogen bonds": exploiting the effect of substitution on the formation of PSe noncovalent bonds.

    Science.gov (United States)

    Shukla, Rahul; Chopra, Deepak

    2016-05-18

    In this article, we have analyzed the nature and characteristics of PSe noncovalent interactions by studying the effect of substitution on XH2PSeH2, H3PSeHX and XH2PSeHX (X= -H, -F, -CH3, -CF3, -Cl, -OH, -OCH3, -NH2, -NHCH3, and -CN) as our systems of interest at MP2/aug-cc-pVDZ level of theory. Binding energy calculations depict that binding energy increases in the order XH2PSeH2 < H3PSeHX < XH2PSeHX with the nature of the substituent having a direct effect on the strength of the interactions. PSe contacts as short as 2.52 Å were observed and analyzed in our study. The energy values for PSe contacts were found to exist in the range of -1.20 kcal mol(-1) to -7.89 kcal mol(-1). The topological analysis confirms the presence of PSe contacts in all the complexes with characteristics similar to hydrogen bonds. NBO analysis helped in categorizing these interactions into pnicogen and chalcogen bonds, depending on the strength of P(lp) to σ*(Se-X) orbitals or Se(lp) to σ*(P-X) orbitals. PMID:27145973

  10. Phase formation at bonded vanadium and stainless steel interfaces

    International Nuclear Information System (INIS)

    The interface between vanadium bonded to stainless steel was studies to determine whether a brittle phase formed during three joining operations. Inertia friction welds between V and 21-6-9 stainless steel were examined using TEM. In the as-welded condition, a continuous, polygranular intermetallic layer about 0.25 μm thick was present at the interface. This layer grew to about 50 μm thick during heat treatment at 1000 degrees C for two hours. Analysis of electron diffraction patterns confirmed that this intermetallic was the ω phase. The interface between vanadium and type 304, SANDVIK SAF 2205, and 21-6-9 stainless steel bonded by a co-extrusion process had intermetallic particles at the interface in the as-extruded condition. Heat treatment at 1000 degrees C for two hours caused these particles to grow into continuous layers in all three cases. Based on the appearance, composition and hardness of this interfacial intermetallic, it was also concluded to be ω phase. Bonding V to type 430 stainless steel by co-extrusion caused V-rich carbides to form at the interface due to the higher concentration of C in the type 430 than in the other stainless steels investigated. The carbide particles initially present grew into a continuous layer during a two-hour heat treatment at 1000 degrees C. Co-hipping 21-6-9 stainless steel tubing with V rod resulted in slightly more concentric specimens than the co-extruded ones, but a continuous layer of the ω phase formed during the hipping operation. This brittle layer could initiate failure during subsequent forming operations. The vanadium near the stainless steel interface in the co-extruded and co-hipped tubing in some cases was harder than before heat treatment. It was concluded that this hardening was due to thermal straining during cooling following heat treatment and that thermal strains might present a greater problem than seen here when longer tubes are used in actual applications

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    in self-organised environment, a water-ice eutectic phase, with low concentrations of reactants. Incubation periods up to 30 days resulted in the formation of short oligomers of RNA. During the oligomerisation, an active intermediate (dipeptide-mononucleotide) is produced, which is the reactive species...

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

    OpenAIRE

    Jongsma, Marije A.; van der Mei, Henny C.; Atema-Smit, Jelly; Busscher, Henk J.; 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 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 we...

  13. Monitoring Backbone Hydrogen-Bond Formation in β-Barrel Membrane Protein Folding.

    Science.gov (United States)

    Raschle, Thomas; Rios Flores, Perla; Opitz, Christian; Müller, Daniel J; Hiller, Sebastian

    2016-05-10

    β-barrel membrane proteins are key components of the outer membrane of bacteria, mitochondria and chloroplasts. Their three-dimensional structure is defined by a network of backbone hydrogen bonds between adjacent β-strands. Here, we employ hydrogen-deuterium (H/D) exchange in combination with NMR spectroscopy and mass spectrometry to monitor backbone hydrogen bond formation during folding of the outer membrane protein X (OmpX) from E. coli in detergent micelles. Residue-specific kinetics of interstrand hydrogen-bond formation were found to be uniform in the entire β-barrel and synchronized to formation of the tertiary structure. OmpX folding thus propagates via a long-lived conformational ensemble state in which all backbone amide protons exchange with the solvent and engage in hydrogen bonds only transiently. Stable formation of the entire OmpX hydrogen bond network occurs downhill of the rate-limiting transition state and thus appears cooperative on the overall folding time scale. PMID:27062600

  14. Iterative reactions of transient boronic acids enable sequential C-C bond formation

    Science.gov (United States)

    Battilocchio, Claudio; Feist, Florian; Hafner, Andreas; Simon, Meike; Tran, Duc N.; Allwood, Daniel M.; Blakemore, David C.; Ley, Steven V.

    2016-04-01

    The ability to form multiple carbon-carbon bonds in a controlled sequence and thus rapidly build molecular complexity in an iterative fashion is an important goal in modern chemical synthesis. In recent times, transition-metal-catalysed coupling reactions have dominated in the development of C-C bond forming processes. A desire to reduce the reliance on precious metals and a need to obtain products with very low levels of metal impurities has brought a renewed focus on metal-free coupling processes. Here, we report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting flow-generated diazo compounds with boronic acids, and their application in controlled iterative C-C bond forming reactions is described. Thus far we have shown the formation of up to three C-C bonds in a sequence including the final trapping of a reactive boronic acid species with an aldehyde to generate a range of new chemical structures.

  15. Toxin-induced pore formation is hindered by intermolecular hydrogen bonding in sphingomyelin bilayers.

    Science.gov (United States)

    García-Linares, Sara; Palacios-Ortega, Juan; Yasuda, Tomokazu; Åstrand, Mia; Gavilanes, José G; Martínez-Del-Pozo, Álvaro; Slotte, J Peter

    2016-06-01

    Sticholysin I and II (StnI and StnII) are pore-forming toxins that use sphingomyelin (SM) for membrane binding. We examined how hydrogen bonding among membrane SMs affected the StnI- and StnII-induced pore formation process, resulting in bilayer permeabilization. We compared toxin-induced permeabilization in bilayers containing either SM or dihydro-SM (lacking the trans Δ(4) double bond of the long-chain base), since their hydrogen-bonding properties are known to differ greatly. We observed that whereas both StnI and StnII formed pores in unilamellar vesicles containing palmitoyl-SM or oleoyl-SM, the toxins failed to similarly form pores in vesicles prepared from dihydro-PSM or dihydro-OSM. In supported bilayers containing OSM, StnII bound efficiently, as determined by surface plasmon resonance. However, StnII binding to supported bilayers prepared from dihydro-OSM was very low under similar experimental conditions. The association of the positively charged StnII (at pH7.0) with unilamellar vesicles prepared from OSM led to a concentration-dependent increase in vesicle charge, as determined from zeta-potential measurements. With dihydro-OSM vesicles, a similar response was not observed. Benzyl alcohol, which is a small hydrogen-bonding compound with affinity to lipid bilayer interfaces, strongly facilitated StnII-induced pore formation in dihydro-OSM bilayers, suggesting that hydrogen bonding in the interfacial region originally prevented StnII from membrane binding and pore formation. We conclude that interfacial hydrogen bonding was able to affect the membrane association of StnI- and StnII, and hence their pore forming capacity. Our results suggest that other types of protein interactions in bilayers may also be affected by hydrogen-bonding origination from SMs. PMID:26975250

  16. 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 intrinsic fluorescence. Inter conversion between the two redox states could thus be followed in vitro as well as in vivoby non- invasive fluorimetric measurements. The 1.5 Angstrom crystal structure of the oxidized protein revealed a disulfide bond- induced distortion of the beta -barrel, as well...... as a structural reorganization of residues in the immediate chromophore environment. By combining this information with spectroscopic data, we propose a detailed mechanism accounting for the observed redox state-dependent fluorescence. The redox potential of the cysteine couple was found to be within...

  17. The formation process of the pellet-cladding bonding layer in high burnup BWR fuels

    International Nuclear Information System (INIS)

    The bonding formation process was studied by EPMA analysis, XRD measurements, and SEM/TEM observations for the oxide layer on a cladding inner surface and the pellet-cladding bonding layer in irradiated fuel rods. Specimens were prepared from fuels which had been irradiated to the pellet average burnups of 15, 27, 42 and 49 GWd/t in BWRs. In the lower burnup specimens of 15 and 27 GWd/t, no bonding layer was found, while the higher burnup specimens of 42 and 49 GWd/t had a typical bonding layer about 10 to 20 μm thick. A bonding layer which consisted of two regions was found in the latter fuels. One region of the inner surface of the Zr liner cladding was made up mainly of ZrO2 with a small amount of dissolved UO2. The structure of this ZrO2 consisted of cubic polycrystals a few nanometers in size, while no monoclinic crystals were found. The other region, near the pellet surface, had both a cubic solid solution of (U,Zr)O2 and amorphous phase in which the concentrations of UO2 and ZrO2 changed continuously. Even in the lower burnup specimens having no bonding layer, cubic ZrO2 phase was identified in the cladding inner oxide layer. The XRD measurements were consistent with the TEM results of the absence of the monoclinic ZrO2 phase. Phase transformation and amorphization were attributed to fission damage, since such phenomena have never been observed in the cladding outer surface. Phase transformation from monoclinic to cubic ZrO2 and amorphization by irradiation damage of fission products were discussed in connection with the formation mechanism and conditions of the bonding layer. (author)

  18. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures

    International Nuclear Information System (INIS)

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ∼140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C–Br bonds and formation of C–Cu–C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands

  19. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures

    Science.gov (United States)

    Fan, Qitang; Wang, Tao; Liu, Liming; Zhao, Jin; Zhu, Junfa; Gottfried, J. Michael

    2015-03-01

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ˜140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C-Br bonds and formation of C-Cu-C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.

  20. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Qitang; Wang, Tao; Zhu, Junfa, E-mail: jfzhu@ustc.edu.cn [National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei 230029 (China); Liu, Liming; Zhao, Jin [Department of Physics, University of Science and Technology of China, Hefei, Anhui 230026,People’s Republic of China (China); Gottfried, J. Michael, E-mail: michael.gottfried@chemie.uni-marburg.de [Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032 Marburg (Germany)

    2015-03-14

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ∼140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C–Br bonds and formation of C–Cu–C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.

  1. Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure on phosphodiester bond formation

    Science.gov (United States)

    Ferris, James P.; KAMALUDDIN

    1989-01-01

    The formation of oligomers from deoxynucleotides, catalyzed by Na(+)-montmorillonite, was investigated with special attention given to the effect of the monomer structure on the phosphodiester bond formation. It was found that adenine deoxynucleotides bind more strongly to montmorillonite than do the corresponding ribonucleotides and thymidine nucleotides. Tetramers of 2-prime-dpA were detected in the reaction of 2-prime-d-5-prime-AMP with a water-soluble carbodiimide EDAC in the presence of Na(+)-montmorillonite, illustrating the possible role of minerals in the formation of biopolymers on the primitive earth.

  2. Practical carbon-carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation.

    Science.gov (United States)

    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei

    2016-01-01

    New carbon-carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  3. 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. PMID:24711424

  4. C–C Bond formation catalyzed by natural gelatin and collagen proteins

    OpenAIRE

    Dennis Kühbeck; Basab Bijayi Dhar; Eva-Maria Schön; Carlos Cativiela; Vicente Gotor-Fernández; David Díaz Díaz

    2013-01-01

    The activity of gelatin and collagen proteins towards C-C bond formation via Henry (nitroaldol) reaction between aldehydes and nitroalkanes is demonstrated for the first time. Among other variables, protein source, physical state and chemical modification influence product yield and kinetics, affording the nitroaldol products in both aqueous and organic media under mild conditions. Significantly, the scale-up of the process between 4-nitrobenzaldehyde and nitromethane is successfully achieved...

  5. Highly Shocked Polymer Bonded Explosives at a Nonplanar Interface: Hot-Spot Formation Leading to Detonation

    OpenAIRE

    An, Qi; Goddard, William A.; Zybin, Sergey V.; Jaramillo-Botero, Andres; Zhou, Tingting

    2013-01-01

    We report reactive molecular dynamics simulations using the ReaxFF reactive force field to examine shock-induced hot-spot formation followed by detonation initiation in realistic (2.7 million atoms) models of polymer bonded explosives (PBX) with nonplanar interfaces. We considered here two energetic materials (EMs) pentaerythritol tetranitrate (PETN), a common EM for PBX, and silicon pentaerythritol tetranitrate (Si-PETN), which is so extremely sensitive that it has not been possible to chara...

  6. Formation of metalsbnd F bonds during frictional sliding: Influence of water and applied load

    Science.gov (United States)

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

    2016-04-01

    Effects of water lubrication and applied load on the formation of PTFE transfer films and metalsbnd 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 sliding interface inhibits the formation of PTFE transfer films and Alsbnd F bonds on the Al2O3 ball, leading to a detrimental effect on the tribo-performance. Under various normal loads in dry sliding condition, it is found that the smearing of PTFE onto the wear surface of the composite and the transfer of PTFE onto the surface of the steel counterpart are stimulated by a high load. During sliding, the contact pressure is found to be the driving force of the reaction between steel and PTFE. It is concluded that under various loads, the total amount of PTFE transfer films has a larger impact on the friction behavior than the formation of Fesbnd F bonds.

  7. Functionalized alkynyl-chlorogermanes: hydrometallation, Ge-Cl bond activation, Ge-H bond formation and chlorine-tert-butyl exchange via a transient germyl cation.

    Science.gov (United States)

    Honacker, Christian; Qu, Zheng-Wang; Tannert, Jens; Layh, Marcus; Hepp, Alexander; Grimme, Stefan; Uhl, Werner

    2016-04-14

    Treatment of alkynyl-arylchlorogermanes ArylnGe(Cl)(C[triple bond, length as m-dash]C-(t)Bu)3-n (n = 1, 2) with HM(t)Bu2 (M = Al, Ga) yielded mixed Al or Ga alkenyl-alkynylchlorogermanes via hydrometallation reactions. Intramolecular interactions between the Lewis-basic Cl atoms and the Lewis-acidic Al or Ga atoms afforded MCGeCl heterocycles. The endocyclic M-Cl distances were significantly lengthened compared to the starting compounds and indicated Ge-Cl bond activation. Dual hydrometallation succeeded only with HGa(t)Bu2. One Ga atom of the product was involved in a Ga-Cl bond, while the second one had an interaction to a C-H bond of a phenyl group. In two cases treatment of chlorogermanes with two equivalents of HAl(t)Bu2 resulted in hydroalumination of one alkynyl group and formation of unprecedented Ge-H functionalized germanes, Aryl-Ge(H)(C[triple bond, length as m-dash]C-(t)Bu)[C(Al(t)Bu2)[double bond, length as m-dash]C(H)-(t)Bu] (Aryl = mesityl, triisopropylphenyl). The Al atoms of these compounds interacted with the α-C atoms of the alkynyl groups. Ph(Cl)Ge(C[triple bond, length as m-dash]C-(t)Bu)[C(Al(t)Bu2}[double bond, length as m-dash]C(H)-(t)Bu] reacted in an unusual Cl/(t)Bu exchange to yield the tert-butylgermane Ph((t)Bu)Ge(C[triple bond, length as m-dash]C-(t)Bu)[C{Al((t)Bu)(Cl)}[double bond, length as m-dash]C(H)-(t)Bu]. Quantum chemical calculations suggested the formation of a germyl cation as a transient intermediate. PMID:26610394

  8. Mechanisms of formation of chemical bonding and defect formation at the a-SiO2/BaTiO3 interfaces

    International Nuclear Information System (INIS)

    The structure and mechanisms of bonding and defect formation at the interfaces between amorphous silica (a-SiO2) and BaTiO3(0 0 1) were investigated using ab initio molecular dynamics. It was found that the nature of interfacial bonds crucially depends on the BaTiO3 surface termination. In particular, the interface between silica and TiO2-terminated BaTiO3 (BTO) slab is characterised by strong covalent Ti–O–Si bonds, while the interface between silica and BaO-terminated BTO demonstrates ionic character of interfacial bonds and exhibits bond instability. In both cases, the dynamics of oxygen species at oxide interfaces is a driving force of the formation of interfacial bonds and defects. (paper)

  9. Correlation of particle impact conditions with bonding, nanocrystal formation and mechanical properties in kinetic sprayed nickel

    International Nuclear Information System (INIS)

    Owing to the specific high-strain-rate thermomechanical characteristics of Ni particle impact in kinetic spraying, the rebound phenomenon of the impacting particles hinders the formation of the first layer and impedes successful build-up of the coating. Even at higher impact velocities, the deposition efficiency of the coating is quite low because of excessive kinetic energy, which induces the rebound and/or erosion of the highly flattened particles. This paper reports noticeably improved bonding and deposition characteristics of Ni particles resulting from suppressed equivalent (von Mises) flow stress and enhanced interface heat-up as a result of powder preheating. Experimental observations coupled with finite-element modeling (FEM) corroborate the fact that the thermally softened Ni particle is very effective for enhanced adhesive and cohesive bonding. Based on the FEM results, the thermal boost-up zone, increased by thermally accelerated adiabatic shear instability, is proposed as a crucial factor for enhancing bonding between the particles, which is essential in producing better coating properties. Moreover, nanocrystal formation (<100 nm) in the coating was more pronounced than cases previously reported in the literature, mainly because of the enhanced thermal activation and straining of the severely deformed particles, which was verified by transmission electron microscopy investigations and nanoindentation tests.

  10. Effect of stacking fault energy on nanostructure formation under accumulative roll bonding (ARB) process

    International Nuclear Information System (INIS)

    In this study, the effect of stacking fault energy on the formation of nanostructure in aluminum, copper, and brass fabricated via the accumulative roll bonding (ARB) process was investigated. Evolution of microstructure of the samples was investigated by transmission electron microscopy (TEM). Occurrence of the recrystallization (both continuous and discontinuous) in the copper and brass led to the formation of nano grains with mean sizes of 80, and 40 nm, respectively; while, the mean grain size of aluminum was 250 nm. Differences in microstructural evolution during processing of aluminum, copper, and brass was related to their stacking fault energies. In order to facilitate nanostructure formation in the commercial purity aluminum, the second phase particles (alumina) were added to aluminum matrix. In this case, the mean grain size of the aluminum changed down to 90 nm

  11. Thioether bond formation by SPASM domain radical SAM enzymes: Cα H-atom abstraction in subtilosin A biosynthesis.

    Science.gov (United States)

    Benjdia, Alhosna; Guillot, Alain; Lefranc, Benjamin; Vaudry, Hubert; Leprince, Jérôme; Berteau, Olivier

    2016-05-01

    AlbA is a radical SAM enzyme catalyzing the formation of three unusual thioether bonds in the antibiotic subtilosin A. We demonstrate here that AlbA catalyzes direct Cα H-atom abstraction and likely contains three essential [4Fe-4S] centers. This leads us to propose novel mechanistic perspectives for thioether bond catalysis by radical SAM enzymes. PMID:27087315

  12. Cross-dehydrogenative coupling for the intermolecular C–O bond formation

    Directory of Open Access Journals (Sweden)

    Igor B. Krylov

    2015-01-01

    Full Text Available The present review summarizes primary publications on the cross-dehydrogenative C–O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C–O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C–O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on and compounds with activated C–H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety. An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C–O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C–H activation processes involving intermolecular C–O bond formation are discussed: acyloxylation reactions with ArI(O2CR2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc..

  13. Cross-dehydrogenative coupling for the intermolecular C-O bond formation.

    Science.gov (United States)

    Krylov, Igor B; Vil', Vera A; Terent'ev, Alexander O

    2015-01-01

    The present review summarizes primary publications on the cross-dehydrogenative C-O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C-O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C-O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on) and compounds with activated C-H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety). An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C-O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C-H activation processes involving intermolecular C-O bond formation are discussed: acyloxylation reactions with ArI(O2CR)2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc.). PMID:25670997

  14. Solid-state NMR studies on precursor derived Si-B-C-N and B-C-N ceramics

    OpenAIRE

    Tsetsgee, Otgontuul

    2009-01-01

    The precursor-derived Si-B-C-N and B-C-N ceramics are of special interest because of their covalent bonding providing mechanical reliability and high-temperature stability. In general, the precursor-derived ceramics posses several advantages, as compared to the ceramics obtained by conventional method. They exhibit a much better homogeneity on the molecular level. Moreover, the precursor route offers a better flexibility for the design of ceramic tools. More recently, it has been demonstrated...

  15. 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

  16. A free-standing condensation enzyme catalyzing ester bond formation in C-1027 biosynthesis.

    Science.gov (United States)

    Lin, Shuangjun; Van Lanen, Steven G; Shen, Ben

    2009-03-17

    Nonribosomal peptide synthetases (NRPSs) catalyze the biosynthesis of many biologically active peptides and typically are modular, with each extension module minimally consisting of a condensation, an adenylation, and a peptidyl carrier protein domain responsible for incorporation of an amino acid into the growing peptide chain. C-1027 is a chromoprotein antitumor antibiotic whose enediyne chromophore consists of an enediyne core, a deoxy aminosugar, a benzoxazolinate, and a beta-amino acid moiety. Bioinformatics analysis suggested that the activation and incorporation of the beta-amino acid moiety into C-1027 follows an NRPS mechanism whereby biosynthetic intermediates are tethered to the peptidyl carrier protein SgcC2. Here, we report the biochemical characterization of SgcC5, an NRPS condensation enzyme that catalyzes ester bond formation between the SgcC2-tethered (S)-3-chloro-5-hydroxy-beta-tyrosine and (R)-1-phenyl-1,2-ethanediol, a mimic of the enediyne core. SgcC5 uses (S)-3-chloro-5-hydroxy-beta-tyrosyl-SgcC2 as the donor substrate and exhibits regiospecificity for the C-2 hydroxyl group of the enediyne core mimic as the acceptor substrate. Remarkably, SgcC5 is also capable of catalyzing amide bond formation, albeit with significantly reduced efficiency, between (S)-3-chloro-5-hydroxy-beta-tyrosyl-(S)-SgcC2 and (R)-2-amino-1-phenyl-1-ethanol, an alternative enediyne core mimic bearing an amine at its C-2 position. Thus, SgcC5 is capable of catalyzing both ester and amide bond formation, providing an evolutionary link between amide- and ester-forming condensation enzymes. PMID:19246381

  17. 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

  18. 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. PMID

  19. A New Paradigm for Carbon-Carbon Bond Formation: Aerobic, Copper-Templated Cross-Coupling

    OpenAIRE

    Villalobos, Janette M.; Srogl, Jiri; Liebeskind, Lanny S.

    2007-01-01

    Thiol esters and boronic acids react to produce ketones under aerobic conditions in the presence of catalytic quantities of a CuI or CuII salt. The reaction occurs at reasonable rates between room temperature and 50 °C at neutral pH using thiol esters derived from bulky 2° amides of thiosalicylamides such as those based on N-tert-butyl-2-mercaptobenzamide. In this mechanistically unprecedented reaction system the carbon-carbon bond formation occurs through templating of the thiol ester and th...

  20. 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.

  1. Metalloenzyme-Like Zeolites as Lewis Acid Catalysts for C-C Bond Formation.

    Science.gov (United States)

    Van de Vyver, Stijn; Román-Leshkov, Yuriy

    2015-10-19

    The use of metalloenzyme-like zeolites as Lewis acid catalysts for C-C bond formation reactions has received increasing attention over the past few years. In particular, the observation of direct aldol condensation reactions enabled by hydrophobic zeolites with isolated framework metal sites has encouraged the development of catalytic approaches for producing chemicals from biomass-derived compounds. The discovery of new Diels-Alder cycloaddition/dehydration routes and experimental and computational studies of Lewis acid catalyzed carbonyl-ene reactions have given a further boost to this rapidly evolving field. PMID:26465652

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

    OpenAIRE

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

    2008-01-01

    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...

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

    International Nuclear Information System (INIS)

    Highlights: ► We dissect how individual disulfide bond affects the amyloidogenicity of insulin. ► A controlled reduction system for insulin is established in this study. ► Disulfide breakage is associated with unfolding and increased amyloidogenicity. ► Breakage of A6-A11 is associated with significantly increased cytotoxicity. ► 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-B7 induced more unfolding of the insulin structure and a higher amyloidogenicity than breakage of A6-A11, but breakage of A6

  4. 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

  5. Formation of III–V-on-insulator structures on Si by direct wafer bonding

    International Nuclear Information System (INIS)

    We have studied the formation of III–V-compound-semiconductors-on-insulator (III–V-OI) structures with thin buried oxide (BOX) layers on Si wafers by using developed direct wafer bonding (DWB). In order to realize III–V-OI MOSFETs with ultrathin body and extremely thin body (ETB) InGaAs-OI channel layers and ultrathin BOX layers, we have developed an electron-cyclotron resonance (ECR) O2 plasma-assisted DWB process with ECR sputtered SiO2 BOX layers and a DWB process based on atomic-layer-deposition Al2O3 (ALD-Al2O3) BOX layers. It is essential to suppress micro-void generation during wafer bonding process to achieve excellent wafer bonding. We have found that major causes of micro-void generation in DWB processes with ECR-SiO2 and ALD-Al2O3 BOX layers are desorption of Ar and H2O gas, respectively. In order to suppress micro-void generation in the ECR-SiO2 BOX layers, it is effective to introduce the outgas process before bonding wafers. On the other hand, it is a possible solution for suppressing micro-void generation in the ALD-Al2O3 BOX layers to increase the deposition temperature of the ALD-Al2O3 BOX layers. It is also another possible solution to deposit ALD-Al2O3 BOX layers on thermally oxidized SiO2 layers, which can absorb the desorption gas from ALD-Al2O3 BOX layers. (invited paper)

  6. Control of Reactivity and Regioselectivity for On-Surface Dehydrogenative Aryl-Aryl Bond Formation.

    Science.gov (United States)

    Kocić, Nemanja; Liu, Xunshan; Chen, Songjie; Decurtins, Silvio; Krejčí, Ondřej; Jelínek, Pavel; Repp, Jascha; Liu, Shi-Xia

    2016-05-01

    Regioselectivity is of fundamental importance in chemical synthesis. Although many concepts for site-selective reactions are well established for solution chemistry, it is not a priori clear whether they can easily be transferred to reactions taking place on a metal surface. A metal will fix the chemical potential of the electrons and perturb the electronic states of the reactants because of hybridization. Additionally, techniques to characterize chemical reactions in solution are generally not applicable to on-surface reactions. Only recent developments in resolving chemical structures by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) paved the way for identifying individual reaction products on surfaces. Here we exploit a combined STM/AFM technique to demonstrate the on-surface formation of complex molecular architectures built up from a heteroaromatic precursor, the tetracyclic pyrazino[2,3-f][4,7]phenanthroline (pap) molecule. Selective intermolecular aryl-aryl coupling via dehydrogenative C-H activation occurs on Au(111) upon thermal annealing under ultrahigh vacuum (UHV) conditions. A full atomistic description of the different reaction products based on an unambiguous discrimination between pyrazine and pyridine moieties is presented. Our work not only elucidates that ortho-hydrogen atoms of the pyrazine rings are preferentially activated over their pyridine equivalents, but also sheds new light onto the participation of substrate atoms in metal-organic coordination bonding during covalent C-C bond formation. PMID:27059121

  7. 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.

  8. Control of stability of polypeptide multilayer nanofilms by quantitative control of disulfide bond formation

    International Nuclear Information System (INIS)

    The crosslinking of polymers in a polymeric material will alter the mechanical properties of the material. Control over the mechanical properties of polyelectrolyte multilayer films (PEMs) could be useful for applications of the technology in medicine and other areas. Disulfide bonds are 'natural' polypeptide crosslinks found widely in wild-type proteins. Here, we have designed and synthesized three pairs of oppositely charged 32mer polypeptide to have 0, 4, or 8 cysteine (Cys) residues per molecule, and we have characterized physical properties of the peptides in a PEM context. The average linear density of free thiol in the designed peptides was 0, 0.125, or 0.25 per amino acid residue. The peptides were used to make 10-bilayer PEMs by electrostatic layer-by-layer self-assembly (LBL). Cys was included in the peptides to study specific effects of disulfide bond formation on PEM properties. Features of film assembly have been found to depend on the amino acid sequence, as in protein folding. Following polypeptide self-assembly into multilayer films, Cys residues were disulfide-crosslinked under mild oxidizing conditions. The stability of the crosslinked films at acidic pH has been found to depend on the number of Cys residues per peptide for a given crosslinking procedure. Crosslinked and non-crosslinked films have been analysed by ultraviolet spectroscopy (UVS), ellipsometry, and atomic force microscopy (AFM) to characterize film assembly, surface morphology, and disassembly. A selective etching model of the disassembly process at acidic pH is proposed on the basis of the experimental data. In this model, regions of film in which the disulfide bond density is low are etched at a higher rate than regions where the density is high

  9. Control of stability of polypeptide multilayer nanofilms by quantitative control of disulfide bond formation

    Science.gov (United States)

    Zhong, Yang; Li, Bingyun; Haynie, Donald T.

    2006-12-01

    The crosslinking of polymers in a polymeric material will alter the mechanical properties of the material. Control over the mechanical properties of polyelectrolyte multilayer films (PEMs) could be useful for applications of the technology in medicine and other areas. Disulfide bonds are 'natural' polypeptide crosslinks found widely in wild-type proteins. Here, we have designed and synthesized three pairs of oppositely charged 32mer polypeptide to have 0, 4, or 8 cysteine (Cys) residues per molecule, and we have characterized physical properties of the peptides in a PEM context. The average linear density of free thiol in the designed peptides was 0, 0.125, or 0.25 per amino acid residue. The peptides were used to make 10-bilayer PEMs by electrostatic layer-by-layer self-assembly (LBL). Cys was included in the peptides to study specific effects of disulfide bond formation on PEM properties. Features of film assembly have been found to depend on the amino acid sequence, as in protein folding. Following polypeptide self-assembly into multilayer films, Cys residues were disulfide-crosslinked under mild oxidizing conditions. The stability of the crosslinked films at acidic pH has been found to depend on the number of Cys residues per peptide for a given crosslinking procedure. Crosslinked and non-crosslinked films have been analysed by ultraviolet spectroscopy (UVS), ellipsometry, and atomic force microscopy (AFM) to characterize film assembly, surface morphology, and disassembly. A selective etching model of the disassembly process at acidic pH is proposed on the basis of the experimental data. In this model, regions of film in which the disulfide bond density is low are etched at a higher rate than regions where the density is high.

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

    Energy Technology Data Exchange (ETDEWEB)

    Roth, Justine P.

    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.

  11. Formation of porous surface layers in reaction bonded silicon nitride during processing

    Science.gov (United States)

    Shaw, N. J.; Glasgow, T. K.

    1979-01-01

    Microstructural examination of reaction bonded silicon nitride (RBSN) has shown that there is often a region adjacent to the as-nitrided surfaces that is even more porous than the interior of this already quite porous material. Because this layer of large porosity is considered detrimental to both the strength and oxidation resistance of RBSN, a study was undertaken to determine if its formation could be prevented during processing. All test bars studied were made from a single batch of Si powder which was milled for 4 hours in heptane in a vibratory mill using high density alumina cylinders as the grinding media. After air drying the powder, bars were compacted in a single acting die and hydropressed.

  12. Synthesis of nanostructured multiphase Ti(C,N)/a-C films by a plasma focus device

    International Nuclear Information System (INIS)

    Nanostructured multiphase Ti(C,N)/a-C films were deposited using a 3.3 kJ pulsed plasma focus device onto silicon (1 0 0) substrates at room temperature. The plasma focus device, fitted with solid titanium anode instead of usual hollow copper anode, was operated with nitrogen and Ar/CH4 as the filling gas. Films were deposited with different number of shots, at 80 mm from top of the anode and at zero angular position with respect to anode axis. X-ray diffraction results show the diffraction peaks related to different compounds such as TiC2, TiN, Ti2CN, Ti and TiC0.62 confirming the deposition of multiphase titanium carbo-nitride composite films on silicon. X-ray photoelectron spectroscopy confirms the formation of Ti-C, C-N, Ti-N, Ti-O and C-C bonds in the films. Scanning electron microscopy reveals that the nanostructure grains are agglomerates of smaller nanoparticles about 10-20 nm in size. Raman studies verify the formation of multiphase Ti(C,N) and also of amorphous graphite in the films. The maximum microhardness value of the composite film is 14.8 ± 1.3 GPa for 30 shots.

  13. Affiliation, reward, and immune biomarkers coalesce to support social synchrony during periods of bond formation in humans.

    Science.gov (United States)

    Ulmer-Yaniv, Adi; Avitsur, Ronit; Kanat-Maymon, Yaniv; Schneiderman, Inna; Zagoory-Sharon, Orna; Feldman, Ruth

    2016-08-01

    Social bonds are critical for survival and adaptation and periods of bond formation involve reorganization of neurobiological systems as mediated by social behavior. Theoretical accounts and animal studies suggest similarity between parent-infant and pair bonding, a hypothesis not yet directly tested in humans. In this study, we recruited three groups of human adults (N=189); parents who had their firstborn child in the last 4-6months, new lovers who began a romantic relationship within the past 4months, and non-attached singles. We measured plasma oxytocin (OT), beta endorphin (β-End), and interlukin-6 (IL-6), biomarkers of the affiliation, reward, and stress-response systems, and micro-coded gaze and affect synchrony between parents and infants and among new lovers during social interaction. OT significantly increased during periods of parental and romantic bonding and was highest in new lovers. In contrast, IL-6 and β-End were highest in new parents and lowest in singles. Biomarkers became more tightly coupled during periods of bond formation and inter-correlation among hormones was highest during romantic bonding. Structural equation modeling indicated that the effects of IL-6 and β-End on behavioral synchrony were mediated by their impact on OT, highlighting the integrative role of the oxytocinergic system in supporting human social affiliation. Findings suggest that periods of bond formation are accompanied by increased activity, as well as tighter cross-talk among systems underpinning affiliation, reward, and stress management and that research on the multidimensional process of bonding may shed further light on the effects of attachment on health. PMID:26902915

  14. Estimation of Abraham solvation equation coefficients for hydrogen bond formation from Abraham solvation parameters for solute acidity and basicity.

    Science.gov (United States)

    van Noort, Paul

    2013-01-01

    Abraham solvation equations find widespread use in environmental chemistry and pharmaco-chemistry. The coefficients in these equations, which are solvent (system) descriptors, are usually determined by fitting experimental data. To simplify the determination of these coefficients in Abraham solvation equations, this study derives equations, based on Abraham solvation parameters for hydrogen acidity and basicity of the solvents involved, to estimate the value of the coefficients for hydrogen bond formation. These equations were applied to calculate Abraham solvation parameters for hydrogen acidity and basicity for polyoxymethylene, polyacrylate, sodium dodecylsulfate, some ionic liquids, alkanoyl phosphatidyl cholines, and lipids for which fitted values for Abraham coefficients for hydrogen bond formation were available. PMID:22892357

  15. 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.

  16. Formation Mechanism of the First Carbon-Carbon Bond and the First Olefin in the Methanol Conversion into Hydrocarbons.

    Science.gov (United States)

    Liu, Yue; Müller, Sebastian; Berger, Daniel; Jelic, Jelena; Reuter, Karsten; Tonigold, Markus; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

    2016-05-01

    The elementary reactions leading to the formation of the first carbon-carbon bond during early stages of the zeolite-catalyzed methanol conversion into hydrocarbons were identified by combining kinetics, spectroscopy, and DFT calculations. The first intermediates containing a C-C bond are acetic acid and methyl acetate, which are formed through carbonylation of methanol or dimethyl ether even in presence of water. A series of acid-catalyzed reactions including acetylation, decarboxylation, aldol condensation, and cracking convert those intermediates into a mixture of surface bounded hydrocarbons, the hydrocarbon pool, as well as into the first olefin leaving the catalyst. This carbonylation based mechanism has an energy barrier of 80 kJ mol(-1) for the formation of the first C-C bond, in line with a broad range of experiments, and significantly lower than the barriers associated with earlier proposed mechanisms. PMID:27037603

  17. Anatomy of Bond Formation: Insights from the Analysis of Domain-Averaged Fermi Holes in Momentum Space

    Czech Academy of Sciences Publication Activity Database

    Cooper, D.L.; Ponec, Robert

    2009-01-01

    Roč. 109, č. 11 (2009), s. 2383-2392. ISSN 0020-7608 R&D Projects: GA AV ČR IAA4072403 Institutional research plan: CEZ:AV0Z40720504 Keywords : momentum space * domain averaged fermi holes * bond formation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.315, year: 2009

  18. Synthesis of isoquinolines via Rh-catalyzed C-H activation/C-N cyclization with diazodiesters or diazoketoesters as a C2 source.

    Science.gov (United States)

    Wang, Jie; Zha, Shanke; Chen, Kehao; Zhang, Feifei; Zhu, Jin

    2016-06-01

    Synthesis of isoquinolines based on efficient C-C and C-N bond formation through Rh(iii)-catalyzed C-H activation and subsequent intramolecular cyclization is reported. Diazodiesters serving as a C2 source in the newly formed heterocycles are first demonstrated. Additionally, the Rh(iii)-catalyzed direct C-H activation/cyclization of benzimidates with diazoketoesters is also described. PMID:27146107

  19. Ions colliding with clusters of fullerenes—Decay pathways and covalent bond formations

    International Nuclear Information System (INIS)

    We report experimental results for the ionization and fragmentation of weakly bound van der Waals clusters of n C60 molecules following collisions with Ar2+, He2+, and Xe20+ at laboratory kinetic energies of 13 keV, 22.5 keV, and 300 keV, respectively. Intact singly charged C60 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 [C60]n+→C60++(n−1)C60 evaporation model. Excitation energies in the range of only ∼0.7 eV per C60 molecule in a [C60]13+ 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 Ar2+ and He2+ collisions, we observe very efficient C119+ and C118+ formation and molecular dynamics simulations suggest that they are covalent dumb-bell systems due to bonding between C59+ or C58+ and C60 during cluster fragmentation. In the Ar2+ case, it is possible to form even smaller C120−2m+ molecules (m= 2–7), while no molecular fusion reactions are observed for the present Xe20+ collisions

  20. 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.

  1. 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-tRNA(Phe) 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-tRNA(Pro) isoacceptors at 4 different Pro codons help explain codon bias not accounted for by the "tRNA abundance" hypothesis. PMID:19104062

  2. Maternal nicotine exposure leads to impaired disulfide bond formation and augmented endoplasmic reticulum stress in the rat placenta.

    Directory of Open Access Journals (Sweden)

    Michael K Wong

    Full Text Available Maternal nicotine exposure has been associated with many adverse fetal and placental outcomes. Although underlying mechanisms remain elusive, recent studies have identified that augmented endoplasmic reticulum (ER stress is linked to placental insufficiency. Moreover, ER function depends on proper disulfide bond formation--a partially oxygen-dependent process mediated by protein disulfide isomerase (PDI and ER oxidoreductases. Given that nicotine compromised placental development in the rat, and placental insufficiency has been associated with poor disulfide bond formation and ER stress, we hypothesized that maternal nicotine exposure leads to both placental ER stress and impaired disulfide bond formation. To test this hypothesis, female Wistar rats received daily subcutaneous injections of either saline (vehicle or nicotine bitartrate (1 mg/kg for 14 days prior to mating and during pregnancy. Placentas were harvested on embryonic day 15 for analysis. Protein and mRNA expression of markers involved in ER stress (e.g., phosphorylated eIF2α, Grp78, Atf4, and CHOP, disulfide bond formation (e.g., PDI, QSOX1, VKORC1, hypoxia (Hif1α, and amino acid deprivation (GCN2 were quantified via Western blot and/or Real-time PCR. Maternal nicotine exposure led to increased expression of Grp78, phosphorylated eIF2α, Atf4, and CHOP (p<0.05 in the rat placenta, demonstrating the presence of augmented ER stress. Decreased expression of PDI and QSOX1 (p<0.05 reveal an impaired disulfide bond formation pathway, which may underlie nicotine-induced ER stress. Finally, elevated expression of Hif1α and GCN2 (p<0.05 indicate hypoxia and amino acid deprivation in nicotine-exposed placentas, respectively, which may also cause impaired disulfide bond formation and augmented ER stress. This study is the first to link maternal nicotine exposure with both placental ER stress and disulfide bond impairment in vivo, providing novel insight into the mechanisms underlying

  3. Dentin bonding performance using Weibull statistics and evaluation of acid-base resistant zone formation of recently introduced adhesives.

    Science.gov (United States)

    Guan, Rui; Takagaki, Tomohiro; Matsui, Naoko; Sato, Takaaki; Burrow, Michael F; Palamara, Joseph; Nikaido, Toru; Tagami, Junji

    2016-07-30

    Dentin bonding durability of recently introduced dental adhesives: Clearfil SE Bond 2 (SE2), Optibond XTR (XTR), and Scotchbond Universal (SBU) was investigated using Weibull analysis as well as analysis of the micromorphological features of the acid-base resistant zone (ABRZ) created for the adhesives. The bonding procedures of SBU were divided into three subgroups: self-etch (SBS), phosphoric acid (PA) etching on moist (SBM) or dry dentin (SBD). All groups were thermocycled for 0, 5,000 and 10,000 cycles followed by microtensile bond strength testing. Acid-base challenge was undertaken before SEM and TEM observations of the adhesive interface. The etch-and-rinse method with SBU (SBM and SBD) created inferior interfaces on the dentin surface which resulted in reduced bond durability. ABRZ formation was detected with the self-etch adhesive systems; SE2, XTR and SBS. In the PA etching protocols of SBM and SBD, a thick hybrid layer but no ABRZ was detected, which might affect dentin bond durability. PMID:27335136

  4. 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.

    2015-01-01

    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 to 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. PMID:25534767

  5. μ-Opioid receptors within subregions of the striatum mediate pair bond formation through parallel yet distinct reward mechanisms.

    Science.gov (United States)

    Resendez, Shanna L; Dome, Mackenzie; Gormley, Gwen; Franco, Dena; Nevárez, Natalie; Hamid, Arif A; Aragona, Brandon J

    2013-05-22

    The prairie vole is a socially monogamous rodent that is an excellent animal model for studies of the neurobiology of social attachment. Such studies have demonstrated that activation of reward circuitry during social interactions facilitates pair bond formation. Within this circuitry, μ-opioid receptors (MORs) modulate naturally rewarding behavior in an anatomically segregated manner; MORs located throughout the striatum (dorsal striatum, NAc core, and the entire NAc shell) are implicated in general motivational processes, whereas those located specifically within the dorsomedial NAc shell mediate positive hedonics (and are referred to as a "hedonic hotspot"). The purpose of the present study was to determine whether MORs within these distinct subregions differentially mediate pair bond formation. We first used receptor autoradiography to compare MOR binding densities between these regions. MOR binding was significantly higher in the NAc core and dorsomedial NAc shell compared with the ventral NAc shell. We next used partner preference testing to determine whether MORs within these subregions differentially mediate pair bonding. Blockade of MORs using 1 or 3 μg of H-d-Phe-Cys-Tyr-d-Trp-Arg-Thr-Pen-Thr-NH2 within the dorsal striatum decreased mating during the cohabitation period and inhibited partner preference formation. In contrast, blockade of MORs within dorsomedial NAc shell inhibited partner preference formation without effecting mating behavior, whereas other regions were not involved. Thus, MORs within the dorsal striatum mediate partner preference formation via impairment of mating, whereas those in the dorsomedial NAc shell appear to mediate pair bond formation through the positive hedonics associated with mating. PMID:23699524

  6. 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

  7. Palladium-Catalyzed Deaminative Phenanthridinone Synthesis from Aniline via C-H Bond Activation.

    Science.gov (United States)

    Yedage, Subhash L; Bhanage, Bhalchandra M

    2016-05-20

    This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level. PMID:27088815

  8. 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.

  9. 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.

  10. Investigation of biopolymer-based hydrogels as green and heterogeneous catalysts in C-C bond formation

    OpenAIRE

    Kühbeck, Dennis

    2015-01-01

    The present dissertation evaluates the efficacy of different polysaccharides (e.g. chitosan, alginate and kappa-carrageenan) and proteins (e.g. gelatin, collagen, silk fibroin) as possible catalysts for a variety of C-C bond formation reactions. These biopolymers can be obtained in different forms (e.g. hydrogels, mesoporous materials). Among different forms hydrogels are one of the most interesting since they could act as biphasic and heterogeneous systems in chemical transformations and fa...

  11. Evolution of the chemical bonding nature and electrode activity of indium selenide upon the composite formation with graphene nanosheets

    International Nuclear Information System (INIS)

    Graphical abstract: Display Omitted -- Highlights: • In4Se2.85@graphene nanocomposite is easily prepared by high energy mechanical milling process. • The bond covalency of In4Se2.85 is notably changed upon the composite formation with graphene. • In4Se2.85@graphene nanocomposite shows promising anode performance for lithium ion battery. -- Abstract: Evolution of the chemical bonding nature and electrochemical activity of indium selenide upon the composite formation with carbon species is systematically investigated. Nanocomposites of In4Se2.85@graphene and In4Se2.85@carbon-black are synthesized via a solid state reaction between In and Se elements, and the following high energy mechanical milling of In4Se2.85 with graphene and carbon-black, respectively. The high energy mechanical milling (HEMM) of In4Se2.85 with carbon species gives rise to a decrease of particle size with a significant depression of the crystallinity of In4Se2.85 phase. In contrast to the composite formation with carbon-black, that with graphene induces a notable decrease of (In−Se) bond covalency, underscoring significant chemical interaction between graphene and In4Se2.85. Both the nanocomposites of In4Se2.85@graphene and In4Se2.85@carbon-black show much better anode performance for lithium ion batteries with larger discharge capacity and better cyclability than does the pristine In4Se2.85 material, indicating the beneficial effect of composite formation on the electrochemical activity of indium selenide. Between the present nanocomposites, the electrode performance of the In4Se2.85@graphene nanocomposite is superior to that of the In4Se2.85@carbon-black nanocomposite, which is attributable to the weakening of (In−Se) bonds upon the composite formation with graphene as well as to the better mixing between In4Se2.85 and graphene. The present study clearly demonstrates that the composite formation with graphene has strong influence on the chemical bonds and electrode activity of indium

  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; Södervall, Ulf

    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...... resistance and current vs. temperature measurements. This suggests that the barrier is caused by inevitable dislocation networks due to wafer misorientation, as well as residual oxygen at the interface....

  13. Dissolution kinetics of tuff rock and mechanism of chemical bond formation at the interface with cement grout

    International Nuclear Information System (INIS)

    The interaction of tuff rock and cement was studied to evaluate the effectiveness of sealing of tuff boreholes with cementitious grouts. Previous studies indicated chemical bond formation between tuff and cement. Dissolution studies were carried out on Topopah Spring member tuff and on tuff with cement. The results indicate the formation of calcium silicate and calcium aluminosilicate hydrates; phase identification is confirmed by XRD studies. The significance of the results obtained and their implications on properties of the interfacial region are included. 7 refs., 6 figs

  14. Cooperativity between Al Sites Promotes Hydrogen Transfer and Carbon-Carbon Bond Formation upon Dimethyl Ether Activation on Alumina.

    Science.gov (United States)

    Comas-Vives, Aleix; Valla, Maxence; Copéret, Christophe; Sautet, Philippe

    2015-09-23

    The methanol-to-olefin (MTO) process allows the conversion of methanol/dimethyl ether into olefins on acidic zeolites via the so-called hydrocarbon pool mechanism. However, the site and mechanism of formation of the first carbon-carbon bond are still a matter of debate. Here, we show that the Lewis acidic Al sites on the 110 facet of γ-Al2O3 can readily activate dimethyl ether to yield CH4, alkenes, and surface formate species according to spectroscopic studies combined with a computational approach. The carbon-carbon forming step as well as the formation of methane and surface formate involves a transient oxonium ion intermediate, generated by a hydrogen transfer between surface methoxy species and coordinated methanol on adjacent Al sites. These results indicate that extra framework Al centers in acidic zeolites, which are associated with alumina, can play a key role in the formation of the first carbon-carbon bond, the initiation step of the industrial MTO process. PMID:27162986

  15. Mechanism for Forming B,C,N,O Rings from NH3BH3 and CO2 via Reaction Discovery Computations.

    Science.gov (United States)

    Li, Maxwell W; Pendleton, Ian M; Nett, Alex J; Zimmerman, Paul M

    2016-03-01

    This study employs computational reaction finding tools to probe the unique biphilic reactivity between ammonia-borane (AB) and CO2. The results show that sequential reactions involving multiple equivalents of AB and CO2 can lead to the formation of stable nonplanar B,C,N,O-heterocycles (Cy-BCN). Cy-BCN is shown to emerge through boron-oxygen bond formation, hydroboration, dative bond formation, and single- or double-hydrogen transfers. The most kinetically facile reactions (computed at the coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory) result from polarized nitrogen-boron double bonds whereas thermodynamic stability results from formation of covalent boron-oxygen bonds. An important structure, HCOOBHNH2 (DHFAB), contains both of these features and is the key intermediate involved in generation of Cy-BCN. Crucially, it is shown that favorable boron-oxygen bond formation results in production of Cy-BCN species that are more stable than polyaminoboranes. These types of reaction intermediates could serve as building blocks in the formation of B,N-codoped graphene oxide (BCN). PMID:26844585

  16. Evaluation of Bonding Shear Performance of Ultra-High-Performance Concrete with Increase in Delay in Formation of Cold Joints

    Directory of Open Access Journals (Sweden)

    Han-Seung Lee

    2016-05-01

    Full Text Available This study set out to derive the optimal conditions for ensuring the monolithicity of ultra-high-performance concrete (UHPC. Direct shear tests were performed to examine the influence on the bonding shear performance. The experimental variables included tamping and delay, which were set to 0, 15, 30, and 60 min. SEM and XRD analyses of the microstructure and composition were performed. The direct shear tests showed that the bonding shear strength was enhanced by the addition of tamping. For the normal-strength concrete (NSC, it is thought that a monolithicity of around 95% can be attained with a cold joint formation delay up to 60 min. In contrast, while the normalized bonding shear strength reduction of UHPC with a delay of 15 min was the lowest at around 8%, a dramatic degradation in the bonding shear performance was observed after 15 min. XRD analyses of the middle and surface sections revealed the composition of the thin film formed at the surface of the UHPC and, as a result, the main component appeared to be SiO2, which is believed to be a result of the rising of the SiO2-based filler, used as an admixture in this study, towards the surface, due to its low specific gravity.

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

    OpenAIRE

    Hideto Miyabe

    2015-01-01

    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 t...

  18. Mimicry of the regulatory role of urokinase in lamellipodia formation by introduction of a non-native interdomain disulfide bond in its receptor

    DEFF Research Database (Denmark)

    Gårdsvoll, Henrik; Kjærgaard, Magnus; Jacobsen, Benedikte; Kriegbaum, Mette Camilla; Huang, Mingdong; Ploug, Michael

    2011-01-01

    adhesive function of uPAR is allosterically regulated via a "tightening" of its three-domain structure elicited by uPA binding. To challenge this proposition, we redesigned the uPAR structure to limit its inherent conformational flexibility by covalently tethering domains DI and DIII via a non......-natural interdomain disulfide bond (uPAR(H47C-N259C)). The corresponding soluble receptor has 1) a smaller hydrodynamic volume, 2) a higher content of secondary structure, and 3) unaltered binding kinetics towards uPA. Most importantly, the purified uPAR(H47C-N259C) also displays a gain in affinity for the...

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

    International Nuclear Information System (INIS)

    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)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

  20. 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.

  1. Anatomy of Bond Formation. Insights from the DAFH Analysis in Momentum Space

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert; Cooper, D.L.

    -: -, 2009, Poster 33. ISBN N. [Central European Symposium on Theoretical Chemistry. Dobogókö (HU), 25.09.2009-28.09.2009] R&D Projects: GA ČR GA203/09/0118 Institutional research plan: CEZ:AV0Z40720504 Keywords : chemical bond * analysis of domain averaged fermi holes * momentum space Subject RIV: CC - Organic Chemistry

  2. Ruthenium-Catalyzed Transfer Hydrogenation for C-C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs.

    Science.gov (United States)

    Perez, Felix; Oda, Susumu; Geary, Laina M; Krische, Michael J

    2016-06-01

    Merging the chemistry of transfer hydrogenation and carbonyl or imine addition, a broad new family of redox-neutral or reductive hydrohydroxyalkylations and hydroaminomethylations have been developed. In these processes, hydrogen redistribution between alcohols and π-unsaturated reactants is accompanied by C-C bond formation, enabling direct conversion of lower alcohols to higher alcohols. Similarly, hydrogen redistribution between amines to π-unsaturated reactants results in direct conversion of lower amines to higher amines. Alternatively, equivalent products of hydrohydroxyalkylation and hydroaminomethylation may be generated through the reaction of carbonyl compounds or imines with π-unsaturated reactants under the conditions of 2-propanol-mediated reductive coupling. Finally, using vicinally dioxygenated reactants, that is, diol, ketols, or diones, successive transfer hydrogenative coupling occurs to generate 2 C-C bonds, resulting in products of formal [4+2] cycloaddition. PMID:27573275

  3. 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.

  4. Structure of DC sputtered Si-C-N thin films

    Energy Technology Data Exchange (ETDEWEB)

    Radnoczi, G.; Safran, G.; Czigany, Zs.; Berlind, T.; Hultman, L

    2003-09-01

    Si-C-N films of maximum 65 at.% of Si and maximum 40 at.% of N were prepared by reactive magnetron sputtering and their fine structure was investigated by high-resolution transmission electron microscopy. For compositions, where C-C and C-N bonds prevail, the films had anisotropic structure on the atomic scale, composed of curved graphitic layers, aligned parallel to the substrate normal. An isotropic structure was detected in the middle of the compositional triangle. On a larger scale, a columnar morphology, aligned in the direction of the deposition flux was formed in films containing more than 15 at.% of Si. Singular or simultaneous appearance of the above structures depended on film composition.

  5. Regularities in the formation of dislocation networks on the boundary of bonded Si(001) wafers

    International Nuclear Information System (INIS)

    The dislocation networks in structures with hydrophilically bonded Si (001) wafers are investigated by transmission electron microscopy. Networks with differing geometry and type of dominant dislocations are observed. One type of networks, which is typical of bonded structures, is formed on the basis of a square network of screw dislocations and contains a system of unidirectional 60° zigzag-shaped dislocations. It is established that such dislocation networks are flat in structures with an azimuthal misorientation of wafers exceeding 2°, whereas they are three-dimensional at smaller misorientation angles. A unique network of another type is formed only by 60° dislocations, the majority of which are extended along one direction, which does not coincide with the 〈110〉 directions in the boundary plane and has a number of specific features, the explanation of which is impossible within the framework of conventional representations.

  6. Palladium-Catalyzed C–C Bond Formations via Activation of Carboxylic Acids and Their Derivatives

    OpenAIRE

    Song, Bingrui

    2013-01-01

    Applications of carboxylic acids and their derivatives in transition metal-catalyzed cross-coupling reactions regio-selectively forming Csp3-Csp2, and Csp2-Csp2 bonds were explored in this thesis. Several important organic building blocks such as aryl acetates, diaryl acetates, imines, ketones, biaryls, styrenes and polysubstituted alkenes were successfully accessed from carboxylic acids and their derivatives by the means of C–H activation and decarboxylative cross-couplings. An efficient ...

  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; Felby, Claus

    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. This...

  8. Probabilistic modeling of shear-induced formation and breakage of doublets cross-linked by receptor-ligand bonds.

    OpenAIRE

    Long, M.; Goldsmith, H L; Tees, D. F.; C. Zhu

    1999-01-01

    A model was constructed to describe previously published experiments of shear-induced formation and breakage of doublets of red cells and of latexes cross-linked by receptor-ligand bonds (. Biophys. J. 65:1318-1334; Tees and Goldsmith. 1996. Biophys. J. 71:1102-1114;. Biophys. J. 71:1115-1122). The model, based on McQuarrie's master equations (1963. J. Phys. Chem. 38:433-436), provides unifying treatments for three distinctive time periods in the experiments of particles in a Couette flow in ...

  9. Concurrent Formation of Carbon-Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction.

    Science.gov (United States)

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-01-01

    Oxidative C-H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C-C bond formation via C-H transformation and production of functionalized graphene. PMID:27181191

  10. Solvent-Free Selective Condensations Based on the Formation of the Olefinic (C=C Bond Catalyzed by Organocatalyst

    Directory of Open Access Journals (Sweden)

    Heyuan Song

    2016-07-01

    Full Text Available Pyrrolidine and its derivatives were used to catalyze aldol and Knoevenagel condensations for the formation of the olefinic (C=C bond under solvent-free conditions. The 3-pyrrolidinamine showed high activity and afforded excellent yields of α,β-unsaturated compounds. The aldol condensation of aromatic/heterocyclic aldehydes with ketones affords enones in high conversion (99.5% and selectivity (92.7%. Good to excellent yields of α,β-unsaturated compounds were obtained in the Knoevenagel condensation of aldehydes with methylene-activated substrates.

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

    OpenAIRE

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

    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 ...

  12. Characterization of Sviceucin from Streptomyces Provides Insight into Enzyme Exchangeability and Disulfide Bond Formation in Lasso Peptides.

    Science.gov (United States)

    Li, Yanyan; Ducasse, Rémi; Zirah, Séverine; Blond, Alain; Goulard, Christophe; Lescop, Ewen; Giraud, Caroline; Hartke, Axel; Guittet, Eric; Pernodet, Jean-Luc; Rebuffat, Sylvie

    2015-11-20

    Lasso peptides are bacterial ribosomally synthesized and post-translationally modified peptides. They have sparked increasing interest in peptide-based drug development because of their compact, interlocked structure, which offers superior stability and protein-binding capacity. Disulfide bond-containing lasso peptides are rare and exhibit highly sought-after activities. In an effort to expand the repertoire of such molecules, we heterologously expressed, in Streptomyces coelicolor, the gene cluster encoding sviceucin, a type I lasso peptide with two disulfide bridges originating from Streptomyces sviceus, which allowed it to be fully characterized. Sviceucin and its reduced forms were characterized by mass spectrometry and peptidase digestion. The three-dimensional structure of sviceucin was determined using NMR. Sviceucin displayed antimicrobial activity selectively against Gram-positive bacteria and inhibition of fsr quorum sensing in Enterococcus faecalis. This study adds sviceucin to the type I lasso peptide family as a new representative. Moreover, new clusters encoding disulfide-bond containing lasso peptides from Actinobacteria were identified by genome mining. Genetic and functional analyses revealed that the formation of disulfide bonds in sviceucin does not require a pathway-encoded thiol-disulfide oxidoreductase. Most importantly, we demonstrated the functional exchangeability of the sviceucin and microcin J25 (a non-disulfide-bridged lasso peptide) macrolactam synthetases in vitro, highlighting the potential of hybrid lasso synthetases in lasso peptide engineering. PMID:26343290

  13. 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.

  14. 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.

  15. Alternative pathways of disulfide bond formation yield secretion-competent, stable and functional immunoglobulins

    OpenAIRE

    Elkabetz, Yechiel; Ofir, Ayala; Argon, Yair; Bar-Nun, Shoshana

    2008-01-01

    Disulfide bonds within and between proteins are responsible for stabilizing folding and covalent assembly. They are thought to form by an obligatory pathway that leads to a single native structure compatible with secretion. We have previously demonstrated that the intradomain disulfide in the CH1 domain of the Ig γ2b heavy chains was dispensable for secretion (Elkabetz et al., 2005). Here we show that the heavy chain-light chain interchain disulfide is also dispensable. γ2b with mutated Cys12...

  16. 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.

  17. Alcohol and group formation: a multimodal investigation of the effects of alcohol on emotion and social bonding.

    Science.gov (United States)

    Sayette, Michael A; Creswell, Kasey G; Dimoff, John D; Fairbairn, Catharine E; Cohn, Jeffrey F; Heckman, Bryan W; Kirchner, Thomas R; Levine, John M; Moreland, Richard L

    2012-08-01

    We integrated research on emotion and on small groups to address a fundamental and enduring question facing alcohol researchers: What are the specific mechanisms that underlie the reinforcing effects of drinking? In one of the largest alcohol-administration studies yet conducted, we employed a novel group-formation paradigm to evaluate the socioemotional effects of alcohol. Seven hundred twenty social drinkers (360 male, 360 female) were assembled into groups of 3 unacquainted persons each and given a moderate dose of an alcoholic, placebo, or control beverage, which they consumed over 36 min. These groups' social interactions were video recorded, and the duration and sequence of interaction partners' facial and speech behaviors were systematically coded (e.g., using the facial action coding system). Alcohol consumption enhanced individual- and group-level behaviors associated with positive affect, reduced individual-level behaviors associated with negative affect, and elevated self-reported bonding. Our results indicate that alcohol facilitates bonding during group formation. Assessing nonverbal responses in social contexts offers new directions for evaluating the effects of alcohol. PMID:22760882

  18. 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.

    2015-08-01

    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.

  19. Enzyme mediated silicon-oxygen bond formation; the use of Rhizopus oryzae lipase, lysozyme and phytase under mild conditions.

    Science.gov (United States)

    Abbate, Vincenzo; Bassindale, Alan R; Brandstadt, Kurt F; Lawson, Rachel; Taylor, Peter G

    2010-10-21

    The potential for expanding the variety of enzymic methods for siloxane bond formation is explored. Three enzymes, Rhizopus oryzae lipase (ROL), lysozyme and phytase are reported to catalyse the condensation of the model compound, trimethylsilanol, formed in situ from trimethylethoxysilane, to produce hexamethyldisiloxane in aqueous media at 25 °C and pH 7. Thermal denaturation and reactant inhibition experiments were conducted to better understand the catalytic role of these enzyme candidates. It was found that enzyme activities were significantly reduced following thermal treatment, suggesting a potential key-role of the enzyme active sites in the catalysis. Similarly, residue-specific modification of the key-amino acids believed to participate in the ROL catalysis also had a significant effect on the silicon bio-catalysis, indicating that the catalytic triad of the lipase may be involved during the enzyme-mediated formation of the silicon-oxygen bond. E. coli phytase was found to be particularly effective at catalysing the condensation of trimethylsilanol in a predominantly organic medium consisting of 95% acetonitrile and 5% water. Whereas the use of enzymes in silicon chemistry is still very much a developing and frontier activity, the results presented herein give some grounds for optimism that the variety of enzyme mediated reactions will continue to increase and may one day become a routine element in the portfolio of the synthetic silicon chemist. PMID:20683529

  20. 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; Andersen, Rikke; Hansen, Steffen V F; Ulven, Trond

    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.......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....

  1. Formation of sulfido niobium complexes through C-S bond activation

    International Nuclear Information System (INIS)

    Upon reacting η5-C5H5)2 Nb CL2, η5-C5H5 = Cp, and (Ph)3 Sn (S Ph), in THF, (η5- C5H5)2 Nb (Cl) (μ-S) Sn (Ph)3 (Cl), 1, and (η5-C5 H5)2 Nb (S) Cl, 2, were obtained. Complexes 1 and 2 were characterized by IR, 1H-NMR, 13 C-NMR, Moessbauer spectroscopies, elemental analysis as well as by atomic absorption. Hydrolysis of 1 yielded the μ-oxo species, (η5-C5 H5)2 Nb (Cl) (μ-O) Sn (Ph)3 Cl, 3, which was characterized by IR, 1H-NMR, 13 C-NMR and Moessbauer spectroscopies, elemental analysis, atomic absorption as well as by X-ray crystallography. It crystallizes in the space group Pca21 with a= 17.282(3), b = 18.122(4), c 17.3269(2), V = 5426.2(16) angstrom3, and Z= 8. Additional studies indicated that the complexes were formed as a result of the nucleophilic displacement of the niobium-chloride bond by the thiolate ligand followed by a C-S bond cleavage. The cleavage occurs with an excess of the thiolate compound equal to or greater than 2:1. (author)

  2. Mechanistic insight into benzenethiol catalyzed amide bond formations from thioesters and primary amines

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Bork, Nicolai; Strømgaard, Kristian

    2014-01-01

    The influence of arylthiols on cysteine-free ligation, i.e. the reaction between an alkyl thioester and a primary amine forming an amide bond, was studied in a polar aprotic solvent. We reacted the ethylthioester of hippuric acid with cyclohexylamine in the absence or presence of various quantities...... state in the aromatic thioester amidation reaction. Under similar conditions, cysteine-free ligation was achieved by coupling a fully side-chain protected 15 amino acid phosphopeptide thioester to the free N-terminal of a side-chain protected 9 amino acid peptide producing the corresponding 24 amino...... of thiophenol (PhSH) in a slurry of disodium hydrogen phosphate in dry DMF. Quantitative conversions into the resulting amide were observed within a few hours in the presence of equimolar amounts of thiophenol. Ab initio calculations showed that the reaction mechanism in DMF is similar to the well...

  3. 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.

  4. Splitting and/or Formation of Chemical Bonds. Insights from Momentum Space

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert; Cooper, D.L.

    Prague : IOCHB ASCR, v.v.i, 2011, s. 1. ISBN N. [JCS Symposium on Theoretical Chemistry 2011 /4./. Liblice (CZ), 18.05.2011-20.05.2011] R&D Projects: GA ČR GA203/09/0118 Institutional research plan: CEZ:AV0Z40720504 Keywords : domain averaged fermi holes * momentum space * chemical bonding Subject RIV: CF - Physical ; Theoretical Chemistry http://www. google .cz/search?q=www.jh-inst.cas.cz%2Ftchem%2Fjcs-2011&rls=com.microsoft:cs:IE-Address&ie=UTF-8&oe=UTF-8&sourceid=ie7&rlz=1I7PRFA_cs&redir_esc=&ei=wqLfTa-cFseUOomzmY8K

  5. 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.

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

    International Nuclear Information System (INIS)

    Research highlights: → The presence of two electronegative elements viz. nitrogen and oxygen in its molecular architecture, ethanolamine has greater extent of interaction with PEG. → Ethanolamine and m-cresol may be involved in a complex type of network of hydrogen bonding. → 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. → The difference in molar volume between the components of the mixture control the mixture properties. - Abstract: Densities (ρ) 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 (ks), free volume (Vf), internal pressure (πi), relaxation time (τ) and surface tension (σ) 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 (VE), excess intermolecular free length (LfE), excess acoustic impedance (ZE) and excess pseudo-Grueneisen parameter (ΓE) 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.

  7. Enantioselective Formation of a Dynamic Hydrogen-Bonded Assembly Based on the Chiral Memory Concept

    NARCIS (Netherlands)

    Ishi-i, Tsutomu; Crego Calama, Mercedes; Timmerman, Peter; Reinhoudt, David N.; Shinkai, Seiji

    2002-01-01

    In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a3·(CYA)6 composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively wit

  8. 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

  9. The structure, surface topography and mechanical properties of Si-C-N films fabricated by RF and DC magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Shi Zhifeng, E-mail: scut0533@126.com [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 (China); Wang Yingjun, E-mail: imwangyj@163.com [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 (China); Du Chang [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 (China); Huang Nan [Key Lab. for Advanced Technologies of Materials, Ministry of Education, Southwest Jiaotong University, 610031 Chengdu (China); Wang Lin; Ning Chengyun [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 (China)

    2011-12-01

    Silicon carbon nitride thin films were deposited on Co-Cr alloy under varying deposition conditions such as sputtering power and the partial pressure ratio of N{sub 2} to Ar by radio frequency and direct current magnetron sputtering techniques. The chemical bonding configurations, surface topography and hardness were characterized by means of X-ray photoelectron spectroscopy, atomic force microscopy and nano-indentation technique. The sputtering power exhibited important influence on the film composition, chemical bonding configurations and surface topography, the electro-negativity had primary effects on chemical bonding configurations at low sputtering power. A progressive densification of the film microstructure occurring with the carbon fraction was increased. The films prepared by RF magnetron sputtering, the relative content of the Si-N bond in the films increased with the sputtering power increased, and Si-C and Si-Si were easily detachable, and C-O, N-N and N-O on the film volatile by ion bombardment which takes place very frequently during the film formation process. With the increase of sputtering power, the films became smoother and with finer particle growth. The hardness varied between 6 GPa and 11.23 GPa depending on the partial pressure ratio of N{sub 2} to Ar. The tribological characterization of Co-Cr alloy with Si-C-N coating sliding against UHMWPE counter-surface in fetal bovine serum, shows that the wear resistance of the Si-C-N coated Co-Cr alloy/UHMWPE sliding pair show much favourable improvement over that of uncoated Co-Cr alloy/UHMWPE sliding pair. This study is important for the development of advanced coatings with tailored mechanical and tribological properties.

  10. The structure, surface topography and mechanical properties of Si-C-N films fabricated by RF and DC magnetron sputtering

    Science.gov (United States)

    Shi, Zhifeng; Wang, Yingjun; Du, Chang; Huang, Nan; Wang, Lin; Ning, Chengyun

    2011-12-01

    Silicon carbon nitride thin films were deposited on Co-Cr alloy under varying deposition conditions such as sputtering power and the partial pressure ratio of N2 to Ar by radio frequency and direct current magnetron sputtering techniques. The chemical bonding configurations, surface topography and hardness were characterized by means of X-ray photoelectron spectroscopy, atomic force microscopy and nano-indentation technique. The sputtering power exhibited important influence on the film composition, chemical bonding configurations and surface topography, the electro-negativity had primary effects on chemical bonding configurations at low sputtering power. A progressive densification of the film microstructure occurring with the carbon fraction was increased. The films prepared by RF magnetron sputtering, the relative content of the Si-N bond in the films increased with the sputtering power increased, and Si-C and Si-Si were easily detachable, and C-O, N-N and N-O on the film volatile by ion bombardment which takes place very frequently during the film formation process. With the increase of sputtering power, the films became smoother and with finer particle growth. The hardness varied between 6 GPa and 11.23 GPa depending on the partial pressure ratio of N2 to Ar. The tribological characterization of Co-Cr alloy with Si-C-N coating sliding against UHMWPE counter-surface in fetal bovine serum, shows that the wear resistance of the Si-C-N coated Co-Cr alloy/UHMWPE sliding pair show much favourable improvement over that of uncoated Co-Cr alloy/UHMWPE sliding pair. This study is important for the development of advanced coatings with tailored mechanical and tribological properties.

  11. Interface microstructure and formation mechanism of diffusion-bonded joints of TiAl to steel 40Cr

    Institute of Scientific and Technical Information of China (English)

    何鹏; 冯吉才; 张炳刚; 钱乙余

    2002-01-01

    TiAl intermetallics was diffusion bonded to steel 40Cr in vacuum furnace. The results show that at the TiAl-40Cr interface the mixture reaction layer of Ti3Al+FeAl+FeAl2 is formed close to the TiAl base, TiC layer is formed in the middle and obvious decarbonized layer is formed closest to the steel 40Cr side. The whole reaction process can be divided into three stages. In the first stage, TiC layer is formed at the interface TiAl/40Cr, as well, decarbonized layer occurs on the steel 40Cr side. In the second stage, TiAl, FeAl2 and FeAl are formed adjacent to TiAl, in the mean, the continuous diffusion of Al atoms from TiAl to 40Cr gives rise to the formation of Ti3Al. In the last stage, the thickness of each reaction layer increases with bonding time according to a parabolic law. The growth energy Q and the growth velocity K0 of reaction layer Ti3Al+FeAl+FeAl2+TiC in the diffusion-bonded joints of the TiAl base alloy to steel 40Cr are 203.017kJ/mol and 6.074mm2/s, respectively, and the growth formula (thickness of reaction layer) is y2=6.074×10-6exp(-203017.48/RT)t. By virtue of this formula, the growth of reaction layer Ti3Al+FeAl+FeAl2+TiC can be presetted and controlled.

  12. Efficient Covalent Bond Formation in Gas-Phase Peptide-Peptide Ion Complexes with the Photoleucine Stapler

    Science.gov (United States)

    Shaffer, Christopher J.; Andrikopoulos, Prokopis C.; Řezáč, Jan; Rulíšek, Lubomír; Tureček, František

    2016-04-01

    Noncovalent complexes of hydrophobic peptides GLLLG and GLLLK with photoleucine (L*) tagged peptides G(L* n L m )K (n = 1,3, m = 2,0) were generated as singly charged ions in the gas phase and probed by photodissociation at 355 nm. Carbene intermediates produced by photodissociative loss of N2 from the L* diazirine rings underwent insertion into X-H bonds of the target peptide moiety, forming covalent adducts with yields reaching 30%. Gas-phase sequencing of the covalent adducts revealed preferred bond formation at the C-terminal residue of the target peptide. Site-selective carbene insertion was achieved by placing the L* residue in different positions along the photopeptide chain, and the residues in the target peptide undergoing carbene insertion were identified by gas-phase ion sequencing that was aided by specific 13C labeling. Density functional theory calculations indicated that noncovalent binding to GL*L*L*K resulted in substantial changes of the (GLLLK + H)+ ground state conformation. The peptide moieties in [GL*L*LK + GLLLK + H]+ ion complexes were held together by hydrogen bonds, whereas dispersion interactions of the nonpolar groups were only secondary in ground-state 0 K structures. Born-Oppenheimer molecular dynamics for 100 ps trajectories of several different conformers at the 310 K laboratory temperature showed that noncovalent complexes developed multiple, residue-specific contacts between the diazirine carbons and GLLLK residues. The calculations pointed to the substantial fluidity of the nonpolar side chains in the complexes. Diazirine photochemistry in combination with Born-Oppenheimer molecular dynamics is a promising tool for investigations of peptide-peptide ion interactions in the gas phase.

  13. Polymer GARD: computer simulation of covalent bond formation in reproducing molecular assemblies.

    Science.gov (United States)

    Shenhav, Barak; Bar-Even, Arren; Kafri, Ran; Lancet, Doron

    2005-04-01

    The basic Graded Autocatalysis Replication Domain (GARD) model consists of a repertoire of small molecules, typically amphiphiles, which join and leave a non-covalent micelle-like assembly. Its replication behavior is due to occasional fission, followed by a homeostatic growth process governed by the assembly's composition. Limitations of the basic GARD model are its small finite molecular repertoire and the lack of a clear path from a 'monomer world' towards polymer-based living entities. We have now devised an extension of the model (polymer GARD or P-GARD), where a monomer-based GARD serves as a 'scaffold' for oligomer formation, as a result of internal chemical rules. We tested this concept with computer simulations of a simple case of monovalent monomers, whereby more complex molecules (dimers) are formed internally, in a manner resembling biosynthetic metabolism. We have observed events of dimer 'take-over' - the formation of compositionally stable, replication-prone quasi stationary states (composomes) that have appreciable dimer content. The appearance of novel metabolism-like networks obeys a time-dependent power law, reminiscent of evolution under punctuated equilibrium. A simulation under constant population conditions shows the dynamics of takeover and extinction of different composomes, leading to the generation of different population distributions. The P-GARD model offers a scenario whereby biopolymer formation may be a result of rather than a prerequisite for early life-like processes. PMID:16010993

  14. Polymer Gard: Computer Simulation of Covalent Bond Formation in Reproducing Molecular Assemblies

    Science.gov (United States)

    Shenhav, Barak; Bar-Even, Arren; Kafri, Ran; Lancet, Doron

    2005-04-01

    The basic Graded Autocatalysis Replication Domain (GARD) model consists of a repertoire of small molecules, typically amphiphiles, which join and leave a non-covalent micelle-like assembly. Its replication behavior is due to occasional fission, followed by a homeostatic growth process governed by the assembly’ s composition. Limitations of the basic GARD model are its small finite molecular repertoire and the lack of a clear path from a ‘monomer world’ towards polymer-based living entities.We have now devised an extension of the model (polymer GARD or P-GARD), where a monomer-based GARD serves as a ‘scaffold’ for oligomer formation, as a result of internal chemical rules. We tested this concept with computer simulations of a simple case of monovalent monomers, whereby more complex molecules (dimers) are formed internally, in a manner resembling biosynthetic metabolism. We have observed events of dimer ‘take-over’ the formation of compositionally stable, replication-prone quasi stationary states (composomes) that have appreciable dimer content. The appearance of novel metabolism-like networks obeys a time-dependent power law, reminiscent of evolution under punctuated equilibrium. A simulation under constant population conditions shows the dynamics of takeover and extinction of different composomes, leading to the generation of different population distributions. The P-GARD model offers a scenario whereby biopolymer formation may be a result of rather than a prerequisite for early life-like processes.

  15. 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.

  16. 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

  17. 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.

  18. Dispersion-corrected first-principles calculation of terahertz vibration, and evidence for weak hydrogen bond formation

    Science.gov (United States)

    Takahashi, Masae; Ishikawa, Yoichi; Ito, Hiromasa

    2013-03-01

    A weak hydrogen bond (WHB) such as CH-O is very important for the structure, function, and dynamics in a chemical and biological system WHB stretching vibration is in a terahertz (THz) frequency region Very recently, the reasonable performance of dispersion-corrected first-principles to WHB has been proven. In this lecture, we report dispersion-corrected first-principles calculation of the vibrational absorption of some organic crystals, and low-temperature THz spectral measurement, in order to clarify WHB stretching vibration. The THz frequency calculation of a WHB crystal has extremely improved by dispersion correction. Moreover, the discrepancy in frequency between an experiment and calculation and is 10 1/cm or less. Dispersion correction is especially effective for intermolecular mode. The very sharp peak appearing at 4 K is assigned to the intermolecular translational mode that corresponds to WHB stretching vibration. It is difficult to detect and control the WHB formation in a crystal because the binding energy is very small. With the help of the latest intense development of experimental and theoretical technique and its careful use, we reveal solid-state WHB stretching vibration as evidence for the WHB formation that differs in respective WHB networks The research was supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan (Grant No. 22550003).

  19. Structural Control of Nonadiabatic Photochemical Bond Formation: Photocyclization in Structurally Modified ortho-Terphenyls.

    Science.gov (United States)

    Molloy, Molly S; Snyder, Joshua A; DeFrancisco, Justin R; Bragg, Arthur E

    2016-06-16

    Understanding how molecular structure impacts the shapes of potential energy surfaces and prospects for nonadiabatic photochemical dynamics is critical for predicting and controlling the chemistry of molecular excited states. Ultrafast transient absorption spectroscopy was used to interrogate photoinduced, nonadiabatic 6π cyclization of a collection of ortho-terphenyls (OTP) modified with alkyl substituents of different sizes and electron-donating/withdrawing character positioned on its central and pendant phenyl rings. OTP alkylated at the 4,4″ and 4',5' positions of the pendant and central rings, respectively, exhibiting biphasic excited-state relaxation; this is qualitatively similar to relaxation of OTP itself, including a fast decrease in excited-state absorption (τ1 = 1-4 ps) followed by formation of metastable cyclized photoproducts (τ2 = 3-47 ps) that share common characteristic spectroscopic features for all substitutions despite variations in chemical nature of the substituents. By contrast, anomalous excited-state dynamics are observed for 3',6'dimethyl-OTP, in which the methyl substituents crowd the pendant rings sterically; time-resolved spectral dynamics and low photochemical reactivity with iodine reveal that methylation proximal to the pendant rings impedes nonadiabatic cyclization. Results from transient measurements and quantum-chemical calculations are used to decipher the nature of excited state relaxation mechanisms in these systems and how they are perturbed by mechanical, electronic, and steric interactions induced by substituents. PMID:27171560

  20. High N-content a-C:N films elaborated by femtosecond PLD with plasma assistance

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Nitrogen doped amorphous carbon films were deposited by DC reactive plasma femtosecond (fs) -PLD and conventional fs-PLD. • High nitrogen content in plasma assisted films. • More ordered sp2 rich graphitic clusters both in terms of structural and topological order. • Correlation length La of the clusters increases with nitrogen incorporation. • Formation of CN bonds at the expense of CC bonds with N content. • At the highest nitrogen concentration, terminal C≡N groups are incorporated in the film. • Correlation between film composition and plasma process. - Abstract: Amorphous carbon nitride (a-C:N) thin films are a interesting class of carbon-based electrode materials. Therefore, synthesis and characterization of these materials have found lot of interest in environmental analytical microsystems. Herein, we report the nitrogen-doped amorphous carbon thin film elaboration by femtosecond pulsed laser deposition (fs-PLD) both with and without a plasma assistance. The chemical composition and atomic bonding configuration of the films were investigated by multi-wavelength (MW) Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and electron energy-loss spectroscopy (EELS). The highest nitrogen content, 28 at.%, was obtained with plasma assistance. The I(D)/I(G) ratio and the G peak position increased as a function of nitrogen concentration, whereas the dispersion and full width at half maximum (FWHM) of G peak decreased. This indicates more ordered graphitic like structures in the films both in terms of topological and structural, depending on the nitrogen content. EELS investigations were correlated with MW Raman results. The interpretation of XPS spectra of carbon nitride films remains a challenge. Plasma assisted PLD in the femtosecond regime led to a significant high nitrogen concentration, which is highlighted on the basis of collisional processes in the carbon plasma plume interacting with the nitrogen

  1. High N-content a-C:N films elaborated by femtosecond PLD with plasma assistance

    Energy Technology Data Exchange (ETDEWEB)

    Maddi, C. [Université de Lyon, F-69003, Lyon, France, Université de Saint-Étienne, Laboratoire Hubert Curien (UMR 5516 CNRS) , 42000 Saint-Étienne (France); Donnet, C., E-mail: Christophe.Donnet@univ-st-etienne.fr [Université de Lyon, F-69003, Lyon, France, Université de Saint-Étienne, Laboratoire Hubert Curien (UMR 5516 CNRS) , 42000 Saint-Étienne (France); Loir, A.-S.; Tite, T. [Université de Lyon, F-69003, Lyon, France, Université de Saint-Étienne, Laboratoire Hubert Curien (UMR 5516 CNRS) , 42000 Saint-Étienne (France); Barnier, V. [Laboratoire Georges Friedel, Ecole Nationale Supérieure des Mines, 42023 Saint-Etienne (France); Rojas, T.C.; Sanchez-Lopez, J.C. [Instituto de Ciencia de Materiales de Sevilla (CSIC-US) , Avda. Américo Vespucio 49, 41092 Sevilla (Spain); Wolski, K. [Laboratoire Georges Friedel, Ecole Nationale Supérieure des Mines, 42023 Saint-Etienne (France); Garrelie, F. [Université de Lyon, F-69003, Lyon, France, Université de Saint-Étienne, Laboratoire Hubert Curien (UMR 5516 CNRS) , 42000 Saint-Étienne (France)

    2015-03-30

    Graphical abstract: - Highlights: • Nitrogen doped amorphous carbon films were deposited by DC reactive plasma femtosecond (fs) -PLD and conventional fs-PLD. • High nitrogen content in plasma assisted films. • More ordered sp2 rich graphitic clusters both in terms of structural and topological order. • Correlation length La of the clusters increases with nitrogen incorporation. • Formation of CN bonds at the expense of CC bonds with N content. • At the highest nitrogen concentration, terminal C≡N groups are incorporated in the film. • Correlation between film composition and plasma process. - Abstract: Amorphous carbon nitride (a-C:N) thin films are a interesting class of carbon-based electrode materials. Therefore, synthesis and characterization of these materials have found lot of interest in environmental analytical microsystems. Herein, we report the nitrogen-doped amorphous carbon thin film elaboration by femtosecond pulsed laser deposition (fs-PLD) both with and without a plasma assistance. The chemical composition and atomic bonding configuration of the films were investigated by multi-wavelength (MW) Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and electron energy-loss spectroscopy (EELS). The highest nitrogen content, 28 at.%, was obtained with plasma assistance. The I(D)/I(G) ratio and the G peak position increased as a function of nitrogen concentration, whereas the dispersion and full width at half maximum (FWHM) of G peak decreased. This indicates more ordered graphitic like structures in the films both in terms of topological and structural, depending on the nitrogen content. EELS investigations were correlated with MW Raman results. The interpretation of XPS spectra of carbon nitride films remains a challenge. Plasma assisted PLD in the femtosecond regime led to a significant high nitrogen concentration, which is highlighted on the basis of collisional processes in the carbon plasma plume interacting with the nitrogen

  2. Observations on size confinement effect in B-C-N nanoparticles embedded in mesoporous silica channels

    International Nuclear Information System (INIS)

    Fluorescent B-C-N/silica nanoparticles were synthesized by solution impregnation method. Effect of B-C-N particle size on the optical properties was investigated by varying the silica pore sizes. Formation of B-C-N nanoparticles within the mesoporous matrix is confirmed by x-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. Furthermore, a remarkable blue-shift in emission peak centres with decreasing pore size in conjugation with band gap modification, ascribed to the size confinement effect. A detailed analysis of experimental results by theoretically defined confinement models demonstrates that the B-C-N nanoparticles in the size range of 3–13 nm falls within the confinement regime. This work demonstrated the experimental evidence of the size confinement effect in smaller size B-C-N nanoparticles.

  3. The first organocatalytic carbonyl-ene reaction: isomerisation-free C-C bond formations catalysed by H-bonding thio-ureas

    Directory of Open Access Journals (Sweden)

    Jones Charlotte ES

    2007-09-01

    Full Text Available Abstract Intramolecular carbonyl ene reactions of highly activated enophiles can be catalysed by H-bonding thio-ureas to give tertiary alcohols in high yields without extensive isomerisation side products. An asymmetric variant of this reaction was realised using a chiral thiourea but was limited by low enantioselectivity (up to 33% e.e. and low turnover frequencies.

  4. 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...

  5. 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.

  6. Bond formation and slow heterogeneous dynamics in adhesive spheres with long-ranged repulsion: quantitative test of mode coupling theory.

    Science.gov (United States)

    Henrich, O; Puertas, A M; Sperl, M; Baschnagel, J; Fuchs, M

    2007-09-01

    A colloidal system of spheres interacting with both a deep and narrow attractive potential and a shallow long-ranged barrier exhibits a prepeak in the static structure factor. This peak can be related to an additional mesoscopic length scale of clusters and/or voids in the system. Simulation studies of this system have revealed that it vitrifies upon increasing the attraction into a gel-like solid at intermediate densities. The dynamics at the mesoscopic length scale corresponding to the prepeak represents the slowest mode in the system. Using mode coupling theory with all input directly taken from simulations, we reveal the mechanism for glassy arrest in the system at 40% packing fraction. The effects of the low-q peak and of polydispersity are considered in detail. We demonstrate that the local formation of physical bonds is the process whose slowing down causes arrest. It remains largely unaffected by the large-scale heterogeneities, and sets the clock for the slow cluster mode. Results from mode-coupling theory without adjustable parameters agree semiquantitatively with the local density correlators but overestimate the lifetime of the mesoscopic structure (voids). PMID:17930244

  7. 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. PMID:27158901

  8. Role of covalent Fe-As bonding in the magnetic moment formation and exchange mechanisms in iron-pnictide superconductors

    OpenAIRE

    Belashchenko, K. D.; Antropov, V. P.

    2008-01-01

    The electronic origin of the huge magnetostructural effect in layered Fe-As compounds is elucidated using LiFeAs as a prototype. The crucial feature of these materials is the strong covalent bonding between Fe and As, which tends to suppress the exchange splitting. The bonding-antibonding splitting is very sensitive to the distance between Fe and As nuclei. We argue that the fragile interplay between bonding and magnetism is universal for this family of compounds. The exchange interaction is ...

  9. A theoretical model investigation of peptide bond formation involving two water molecules in ribosome supports the two-step and eight membered ring mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qiang [School of Chemistry & Chemical Engineering, Shandong University, Jinan 250100 (China); Gao, Jun, E-mail: gaojun@sdu.edu.cn [Agricultural Bioinformatics Key Laboratory of Hubei Province, College of Informatics, Huazhong Agricultural University, Wuhan 430070 (China); School of Chemistry & Chemical Engineering, Shandong University, Jinan 250100 (China); Zhang, Dongju; Liu, Chengbu [School of Chemistry & Chemical Engineering, Shandong University, Jinan 250100 (China)

    2015-04-01

    Highlights: • We theoretical studied peptide bond formation reaction mechanism with two water molecules. • The first water molecule can decrease the reaction barriers by forming hydrogen bonds. • The water molecule mediated three-proton transfer mechanism is the favorable mechanism. • Our calculation supports the two-step and eight membered ring mechanism. - Abstract: The ribosome is the macromolecular machine that catalyzes protein synthesis. The kinetic isotope effect analysis reported by Strobel group supports the two-step mechanism. However, the destination of the proton originating from the nucleophilic amine is uncertain. A computational simulation of different mechanisms including water molecules is carried out using the same reaction model and theoretical level. Formation the tetrahedral intermediate with proton transfer from nucleophilic nitrogen, is the rate-limiting step when two water molecules participate in peptide bond formation. The first water molecule forming hydrogen bonds with O9′ and H15′ in the A site can decrease the reaction barriers. Combined with results of the solvent isotope effects analysis, we conclude that the three-proton transfer mechanism in which water molecule mediate the proton shuttle between amino and carbon oxygen in rate-limiting step is the favorable mechanism. Our results will shield light on a better understand the reaction mechanism of ribosome.

  10. Formation of the Si-B bond: insertion reactions of silylenes into B-X(X = F, Cl, Br, O, and N) bonds.

    Science.gov (United States)

    Geng, Bing; Xu, Chongjuan; Chen, Zhonghe

    2016-06-01

    The insertion reactions of the silylene H2Si with H2BXHn-1 (X = F, Cl, Br, O, N; n = 1, 1, 1, 2, 3) have been studied by DFT and MP2 methods. The calculations show that the insertions occur in a concerted manner, forming H2Si(BH2)(XHn-1). The essences of H2Si insertions with H2BXHn-1 are the transfers of the σ electrons on the Si atom to the positive BH2 group and the electrons of X into the empty p orbital on the Si atom in H2Si. The order of reactivity in vacuum shows the barrier heights increase for the same-family element X from up to down and the same-row element X from right to left in the periodic table. The energies relating to the B-X bond in H2BXHn-1, and the bond energies of Si-X and Si-B in H2Si(BH2)(XHn-1) may determine the preference of insertions of H2Si into B-X bonds for the same-column element X or for the same-row element X. The insertion reactions in vacuum are similar to those in solvents, acetone, ether, and THF. The barriers in vacuum are lower than those in solvents and the larger polarities of solvents make the insertions more difficult to take place. Both in vacuum and in solvents, the silylene insertions are thermodynamically exothermic. Graphical Abstract The insertion process of H2Si and H2BXHn-1(X = F, Cl, Br, O, and N; n = 1, 1 , 1, 2, 3). PMID:27184004

  11. Triplex formation at physiological pH by 5-Me-dC-N4-(spermine) [X] oligodeoxynucleotides: non protonation of N3 in X of X*G:C triad and effect of base mismatch/ionic strength on triplex stabilities.

    OpenAIRE

    Barawkar, D A; Rajeev, K. G.; Kumar, V A; Ganesh, K N

    1996-01-01

    Oligodeoxynucleotide (ODN) directed triplex formation has therapeutic importance and depends on Hoogsteen hydrogen bonds between a duplex DNA and a third DNA strand. T*A:T triplets are formed at neutral pH and C+*G:C are favoured at acidic pH. It is demonstrated that spermine conjugation at N4 of 5-Me-dC in ODNs 1-5 (sp-ODNs) imparts zwitterionic character, thus reducing the net negative charge of ODNs 1-5. sp-ODNs form triplexes with complementary 24mer duplex 8:9 show foremost stability at ...

  12. S-OO bond dissociation energies and enthalpies of formation of the thiomethyl peroxyl radicals CH3S(O)nOO (n=0,1,2)

    International Nuclear Information System (INIS)

    Optimized geometries, S-OO bond dissociation energies and enthalpies of formation for a series of thiomethyl peroxyl radicals are investigated using high level ab initio and density functional theory methods. The results show that the S-OO bond dissociation energy is largest in the methylsulfonyl peroxyl radical, CH3S(O)2OO, which contains two sulfonic type oxygen atoms followed by the methylthiyl peroxyl radical, CH3SOO. The methylsulfinyl peroxyl radical, CH3S(O)OO, which contains only one sulfonic type oxygen shows the least stability with regard to dissociation to CH3S(O)+O2. This stabilization trend is nicely reflected in the variations of the S-OO bond distance which is found to be shortest in CH3S(O)2OO and longest in CH3S(O)OO

  13. LAMMPS Framework for Directional Dynamic Bonding

    DEFF Research Database (Denmark)

    2012-01-01

    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 li...

  14. Isotopic studies of trans- and cis-HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures.

    Science.gov (United States)

    McCarthy, Michael C; Martinez, Oscar; McGuire, Brett A; Crabtree, Kyle N; Martin-Drumel, Marie-Aline; Stanton, John F

    2016-03-28

    HOCO is an important intermediate in combustion and atmospheric processes because the OH + CO → H + CO2 reaction represents the final step for the production of CO2 in hydrocarbon oxidation, and theoretical studies predict that this reaction proceeds via various intermediates, the most important being this radical. Isotopic investigations of trans- and cis-HOCO have been undertaken using Fourier transform microwave spectroscopy and millimeter-wave double resonance techniques in combination with a supersonic molecular beam discharge source to better understand the formation, chemical bonding, and molecular structures of this radical pair. We find that trans-HOCO can be produced almost equally well from either OH + CO or H + CO2 in our discharge source, but cis-HOCO appears to be roughly two times more abundant when starting from H + CO2. Using isotopically labelled precursors, the OH + C(18)O reaction predominately yields HOC(18)O for both isomers, but H(18)OCO is observed as well, typically at the level of 10%-20% that of HOC(18)O; the opposite propensity is found for the (18)OH + CO reaction. DO + C(18)O yields similar ratios between DOC(18)O and D(18)OCO as those found for OH + C(18)O, suggesting that some fraction of HOCO (or DOCO) may be formed from the back-reaction H + CO2, which, at the high pressure of our gas expansion, can readily occur. The large (13)C Fermi-contact term (aF) for trans- and cis-HO(13)CO implicates significant unpaired electronic density in a σ-type orbital at the carbon atom, in good agreement with theoretical predictions. By correcting the experimental rotational constants for zero-point vibration motion calculated theoretically using second-order vibrational perturbation theory, precise geometrical structures have been derived for both isomers. PMID:27036445

  15. Isotopic studies of trans- and cis-HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures

    Science.gov (United States)

    McCarthy, Michael C.; Martinez, Oscar; McGuire, Brett A.; Crabtree, Kyle N.; Martin-Drumel, Marie-Aline; Stanton, John F.

    2016-03-01

    HOCO is an important intermediate in combustion and atmospheric processes because the OH + CO → H + CO2 reaction represents the final step for the production of CO2 in hydrocarbon oxidation, and theoretical studies predict that this reaction proceeds via various intermediates, the most important being this radical. Isotopic investigations of trans- and cis-HOCO have been undertaken using Fourier transform microwave spectroscopy and millimeter-wave double resonance techniques in combination with a supersonic molecular beam discharge source to better understand the formation, chemical bonding, and molecular structures of this radical pair. We find that trans-HOCO can be produced almost equally well from either OH + CO or H + CO2 in our discharge source, but cis-HOCO appears to be roughly two times more abundant when starting from H + CO2. Using isotopically labelled precursors, the OH + C18O reaction predominately yields HOC18O for both isomers, but H18OCO is observed as well, typically at the level of 10%-20% that of HOC18O; the opposite propensity is found for the 18OH + CO reaction. DO + C18O yields similar ratios between DOC18O and D18OCO as those found for OH + C18O, suggesting that some fraction of HOCO (or DOCO) may be formed from the back-reaction H + CO2, which, at the high pressure of our gas expansion, can readily occur. The large 13C Fermi-contact term (aF) for trans- and cis-HO13CO implicates significant unpaired electronic density in a σ-type orbital at the carbon atom, in good agreement with theoretical predictions. By correcting the experimental rotational constants for zero-point vibration motion calculated theoretically using second-order vibrational perturbation theory, precise geometrical structures have been derived for both isomers.

  16. Thermal characteristics of a Zr(B,C,N) coated layer manufactured by the PACVD process

    Energy Technology Data Exchange (ETDEWEB)

    You, J.S.; Kang, C.-S. (Seoul Nat. Univ., Seoul (Korea, Republic of). Sch. of Mater. Sci. and Eng.); Lee, S.-H.; Pfohl, C.; Rie, K.-T.

    1999-02-01

    In this study, thermal characteristics of a Zr(B,C,N) coated layer manufactured by DC-pulse plasma-assisted chemical vapour deposition (PACVD) were investigated by thermal fatigue test. To examine the phase evolution and thermal stress effect, cyclic thermal fatigue test was done, and X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses were also performed. Conclusions have been made as follows. The as-coated sample showed an amorphous structure, while monoclinic-ZrO[sub 2], tetragonal-ZrO[sub 2], and cubic-ZrO[sub 2] structures were formed after 20 h holding at 700 C. XPS analysis showed that in the as-coated sample, ZrO[sub 2-x] suboxide had already existed and carbon partially substituted Zr on Zr-O bonding configuration. However, after 20 h holding at 700 C, the suboxide disappeared and boride was formed. As for the thermal stress effect, the fraction of the stable monoclinic phase increased as the heat treatment time increased without thermal stress. On the other hand, after cyclic thermal stress, the formation of a monoclinic phase was retarded. (orig.) 15 refs.

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

    Science.gov (United States)

    Kim, Kyung Hwan; Kim, Jong Goo; Oang, Key Young; Kim, Tae Wu; Ki, Hosung; Jo, Junbeom; Kim, Jeongho; Sato, Tokushi; Nozawa, Shunsuke; Adachi, Shin-Ichi; Ihee, Hyotcherl

    2016-07-01

    The [Au(CN)2 (-)]3 trimer in water experiences a strong van der Waals interaction between the d(10) 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. PMID:27191012

  18. Effect of interlayer configurations on joint formation in TLP bonding of Ti-6Al-4V to Mg-AZ31

    International Nuclear Information System (INIS)

    In this research work, the transient liquid phase (TLP) bonding process was utilized to fabricate joints using thin (20μm) nickel and copper foils placed between two bonding surfaces to help facilitate joint formation. Two joint configurations were investigated, first, Ti-6Al-4V/CuNi/Mg-AZ31 and second, Ti-6Al-4V/NiCu/Mg-AZ3L The effect of bonding time on microstructural developments across the joint and the changes in mechanical properties were studied as a function of bonding temperature and pressure. The bonded specimens were examined by metallographic analysis, scanning electron microscopy (SEM), and X-ray diffraction (XRD). In both cases, intermetallic phase of CuMg2 and Mg3AlNi2 was observed inside the joint region. The results show that joint shear strengths for the Ti-6Al-4V/CuNi/Mg-AZ31 setup produce joints with shear strength of 57 MPa compared to 27MPa for joints made using the Ti-6Al-4V/NiCu/Mg-AZ31 layer arrangement

  19. Recent advances in copper-catalyzed C-H bond amidation.

    Science.gov (United States)

    Wan, Jie-Ping; Jing, Yanfeng

    2015-01-01

    Copper catalysis has been known as a powerful tool for its ubiquitous application in organic synthesis. One of the fundamental utilities of copper catalysis is in the C-N bond formation by using carbon sources and nitrogen functional groups such as amides. In this review, the recent progress in the amidation reactions employing copper-catalyzed C-H amidation is summarized. PMID:26664644

  20. Formation and characterization of two interconvertible side-on and end-on bonded beryllium ozonide complexes.

    Science.gov (United States)

    Zhou, Zijian; Li, Yuzhen; Zhuang, Jia; Wang, Guanjun; Chen, Mohua; Zhao, Yanying; Zheng, Xuming; Zhou, Mingfei

    2011-09-01

    The reactions of beryllium atoms with dioxygen were reinvestigated by matrix isolation infrared absorption spectroscopy. Besides the previously reported linear OBeO and cyclic Be(2)O(2) molecules, two interconvertible beryllium ozonide complexes were prepared and characterized. The BeOBe(η(2)-O(3)) complex was formed on annealing, which is characterized to be a side-on bonded ozonide complex with a planar C(2v) structure. The BeOBe(η(2)-O(3)) complex isomerized to the BeOBe(η(1)-O(3)) isomer under visible light excitation, which is an end-on bonded ozonide complex with planar C(s) symmetry. These two isomers are interconvertible; that is, visible light induces the conversion of the side-on bonded complex to the end-on bonded isomer, and vice versa on annealing. In addition, evidence is also presented for the linear BeOBeOBe cluster. PMID:21806010

  1. Covalent bonding and bandgap formation in transition-metal aluminides: di-aluminides of group VIII transition metals

    International Nuclear Information System (INIS)

    In this paper we study the electronic structure, electron density distribution and bonding mechanism in transition-metal (TM) di-aluminides Al2TM formed by metals of group VIII (TM=Fe,Ru,Os) and crystal structures of TM di-silicides C11b (MoSi2), C40 (CrSi2) and C54 (TiSi2). A peculiar feature of the electronic structure of these TM di-aluminides is the existence of a semiconducting gap at the Fermi level. A substitution of a 3d TM by 4d or 5d metal enhances the width of the gap. From the analysis of the charge-density distribution and the crystal-orbital overlap population we conclude that the bonding between atoms has strong covalent character. This is confirmed not only from the enhanced charge density halfway between atoms, but also by a clear bonding-antibonding splitting of the electronic states. Groups of bonding and antibonding states corresponding to a particular bonding configuration of atoms are separated by a gap. As such a gap is observed in all bonding configurations among atoms in the unit cell it results in a gap in the total density of states. The bandgap exists at a certain electron per atom ratio e/A∼4.67 and also occurs in TM di-aluminides of groups VII and IX. For group VIII TM di-aluminides the Fermi level falls just in the gap. (author)

  2. Hydrogen bonded supramolecular structures

    CERN Document Server

    Li, Zhanting

    2015-01-01

    This book covers the advances in the studies of hydrogen-bonding-driven supramolecular systems  made over the past decade. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. The second part covers molecular recognition and supramolecular structures driven by hydrogen bonding. The third part introduces the formation of hollow and giant macrocycles directed by hydrogen bonding, while the last part summarizes hydrogen bonded supramolecular polymers. This book is designed to b

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

    Science.gov (United States)

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

    2016-05-25

    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, commercially available nickel catalyst (NiBr2·diglyme) can achieve couplings of alkyl bromides with nucleophilic silicon reagents under unusually mild conditions (e.g., -20 °C); especially noteworthy is our ability to employ unactivated tertiary alkyl halides as electrophilic coupling partners, which is still relatively uncommon in the field of cross-coupling chemistry. Stereochemical, relative reactivity, and radical-trap studies are consistent with a homolytic pathway for C-X bond cleavage. PMID:27187869

  4. Substrate Controlled Synthesis of Benzisoxazole and Benzisothiazole Derivatives via PhI(OAc)2-Mediated Oxidation Followed by Intramolecular Oxidative O-N/S-N Bond Formation.

    Science.gov (United States)

    Anand, Devireddy; Patel, Om P S; Maurya, Rahul K; Kant, Ruchir; Yadav, Prem P

    2015-12-18

    A phenyliodine(III) diacetate (PIDA)-mediated, highly efficient and tandem approach for the synthesis of aryldiazenylisoxazolo(isothiazolo)arenes from simple 2-amino-N'-arylbenzohydrazides has been developed. The reaction proceeds via formation of (E)-(2-aminoaryl)(aryldiazenyl)methanone as the key intermediate, followed by intramolecular oxidative O-N/S-N bond formation in one pot at room temperature. The quiet different reactivity of the substrate is due to the formation of a diazo intermediate which encounters a nucleophilic attack by carbonyl oxygen on the electrophilic amine to produce isoxazole products, as compared to the previous reportsa,b,4 in which an N-acylnitrenium ion intermediate is intramolecularly trapped by an amine group. PMID:26565748

  5. An alternative synthesis of the breast cancer drug fulvestrant (Faslodex®): catalyst control over C-C bond formation.

    Science.gov (United States)

    Caprioglio, Diego; Fletcher, Stephen P

    2015-10-14

    Fulvestrant (Faslodex®) was synthesized in four steps (35% overall yield) from 6-dehydronandrolone acetate. Catalyst controlled, room temperature, diastereoselective 1,6-addition of the zirconocene derived from commercially available 9-bromonon-1-ene was used in the key C-C bond forming step. PMID:26300021

  6. Anatomy of Bond Formation. Insights from the Analysis of Domain-Averaged Fermi holes in Momentum Space

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert; Cooper, D.L.

    2010, s. 27. ISBN N. [Girona Seminar Electron Density, Density Matrices and Density Functional Theory /9./. Girona (ES), 05.07.2010-08.07.2010] R&D Projects: GA ČR GA203/09/0118 Institutional research plan: CEZ:AV0Z40720504 Keywords : chemical bonding * fermi holes * momentum space Subject RIV: CF - Physical ; Theoretical Chemistry

  7. New chromogenic and fluorogenic reagents and sensors for neutral and ionic analytes based on covalent bond formation--a review of recent developments.

    Science.gov (United States)

    Mohr, Gerhard J

    2006-11-01

    To date, hydrogen bonding and Coulomb, van der Waals and hydrophobic interactions are the major contributors to non-covalent analyte recognition using ionophores, ligands, aptamers and chemosensors. However, this article describes recent developments in the use of (reversible) covalent bond formation to detect analyte molecules, with special focus on optical signal transduction. Several new indicator dyes for analytes such as amines and diamines, amino acids, cyanide, formaldehyde, hydrogen peroxide, organophosphates, nitrogen oxide and nitrite, peptides and proteins, as well as saccharides have become available. New means of converting analyte recognition into optical signals have also been introduced, such as colour changes of chiral nematic layers. This article gives an overview of recent developments and discusses response mechanisms, selectivity and sensitivity. PMID:17039383

  8. Silicon carbonitride by remote microwave plasma CVD from organosilicon precursor: Growth mechanism and structure of resulting Si:C:N films

    Energy Technology Data Exchange (ETDEWEB)

    Blaszczyk-Lezak, I. [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, PL-90-363 Lodz (Poland); Wrobel, A.M. [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, PL-90-363 Lodz (Poland)]. E-mail: amwrobel@bilbo.cbmm.lodz.pl; Kivitorma, M.P.M. [Department of Physics, University of Turku, FIN-20014 Turku (Finland); Vayrynen, I.J. [Department of Physics, University of Turku, FIN-20014 Turku (Finland); Tracz, A. [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, PL-90-363 Lodz (Poland)

    2007-06-30

    The remote microwave hydrogen plasma chemical vapor deposition (RP-CVD) from bis(dimethylamino)methylsilane precursor was used for the synthesis of silicon carbonitride (Si:C:N) films. The effect of thermal activation on the RP-CVD process was examined by determining the mass- and the thickness-based film growth rate and film growth yield, at different substrate temperature (T {sub S}). It was found that the mechanism of the process depends on T {sub S} and for low substrate temperature regime, 30 deg. C {<=} T {sub S} {<=} 100 deg. C, RP-CVD is limited by desorption of film-forming precursors, whereas for high substrate temperature regime, 100 deg. C < T {sub S} {<=} 400 deg. C, RP-CVD is a non-thermally activated and mass-transport limited process. The Si:C:N films were characterized by X-ray photoelectron and Fourier transform infrared spectroscopies, as well as by atomic force microscopy. The increase of T {sub S} enhances crosslinking in the film via the formation of nitridic Si-N and carbidic Si-C bonds. On the basis of the structural data a hypothetical crsosslinking reactions contributing to silicon carbonitride network formation have been proposed.

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

    International Nuclear Information System (INIS)

    Combining ab initio modeling and 57Fe 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

  10. 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.

  11. C-C Bond Formation: Synthesis of C5 Substituted Pyrimidine and C8 Substituted Purine Nucleosides Using Water Soluble Pd-imidate Complex.

    Science.gov (United States)

    Gayakhe, Vijay; Ardhapure, Ajaykumar V; Kapdi, Anant R; Sanghvi, Yogesh S; Serrano, Jose Luis; Schulzke, Carola

    2016-01-01

    The synthesis of a highly efficient, water soluble [Pd(Sacc)2 (TPA)2 ] complex for C-C bond formation is described. Additionally, application of the [Pd(Sacc)2 (TPA)2 ] complex for Suzuki-Miyaura arylation of all four nucleosides (5-iodo-2'-deoxyuridine [5-IdU], 5-iodo-2'-deoxycytidine [5-IdC], 8-bromo-2'-deoxyadenosine, and 8-bromo-2'-deoxyguanosine) with various aryl/heteroaryl boronic acids in plain water under milder conditions is demonstrated. © 2016 by John Wiley & Sons, Inc. PMID:27248782

  12. B-N, B-O, and B-CN Bond Formation via Palladium-Catalyzed Cross-Coupling of B-Bromo-Carboranes.

    Science.gov (United States)

    Dziedzic, Rafal M; Saleh, Liban M A; Axtell, Jonathan C; Martin, Joshua L; Stevens, Simone L; Royappa, A Timothy; Rheingold, Arnold L; Spokoyny, Alexander M

    2016-07-27

    Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, and -CN) and multiple functional groups onto the boron-rich clusters. PMID:27384544

  13. Hydrogen bonding of the dissociated histidine ligand is not required for formation of a proximal NO adduct in cytochrome c'.

    Science.gov (United States)

    Ghafoor, Dlzar D; Kekilli, Demet; Abdullah, Gaylany H; Dworkowski, Florian S N; Hassan, Hamid G; Wilson, Michael T; Strange, Richard W; Hough, Michael A

    2015-09-01

    Cytochromes c', that occur in methanotrophic, denitrifying and photosynthetic bacteria, form unusual proximal penta-coordinate NO complexes via a hexa-coordinate distal NO intermediate. Their NO binding properties are similar to those of the eukaryotic NO sensor, soluble guanylate cyclase, for which they provide a valuable structural model. Previous studies suggested that hydrogen bonding between the displaced proximal histidine (His120) ligand (following its dissociation from heme due to trans effects from the distally bound NO) and a conserved aspartate residue (Asp121) could play a key role in allowing proximal NO binding to occur. We have characterized three variants of Alcaligenes xylosoxidans cytochrome c' (AXCP) where Asp121 has been replaced by Ala, Ile and Gln, respectively. In all variants, hydrogen bonding between residue 121 and His120 is abolished yet 5-coordinate proximal NO species are still formed. Our data therefore demonstrate that the His120-Asp121 bond is not essential for proximal NO binding although it likely provides an energy minimum for the displaced His ligand. All variants have altered proximal pocket structure relative to native AXCP. PMID:26100643

  14. Nitrogen self-diffusion in magnetron sputtered Si-C-N films

    International Nuclear Information System (INIS)

    Self-diffusion was studied in magnetron sputtered nitrogen-rich amorphous compounds of the system Si-C-N by using nitrogen as a model tracer. As shown by infra-red spectroscopy a transient metastable region exists, where the structure of the material can be visualized as silicon nitride tetrahedra which are connected by carbo-diimide (-N=C=N-) bonds to a three dimensional amorphous network. In this region diffusion studies are carried out by neutron reflectometry and isotope multilayers as a function of annealing time, temperature and chemical composition. Low diffusivities between 10-20 and 10-24 m2/s were found. In the metastable region, diffusion is faster than diffusion in amorphous silicon nitride by 1 to 2 orders of magnitude, while the activation enthalpies of diffusion between 3.1 and 3.4 eV are the same within error limits. This can be explained by the fact that the diffusion mechanism along SiN4 tetrahedra is identical to that in amorphous silicon nitride, however, the carbo-diimide bonds seem to widen the structure, allowing faster diffusion. A correlation between diffusivities and the number of carbo-diimid bonds present in the material is found, where the highest diffusivities are observed for materials with the highest number of carbo-diimid bonds, close to the composition Si2CN4.

  15. Intramolecular electron density redistribution upon hydrogen bond formation in the anion methyl orange at the water/1,2-dichloroethane interface probed by phase interference second harmonic generation

    Science.gov (United States)

    Rinuy; Piron; Brevet; Blanchard-Desce; Girault

    2000-09-15

    Surface second harmonic generation (SSHG) studies of the azobenzene derivative p-dimethylaminoazobenzene sulfonate, often referred as Methyl Orange (MO), at the neat water/1,2-dichloroethane (DCE) interface is reported. The two forms of the anionic MO dye, which are usually observed in bulk solution, with one form being hydrogen bonded to a water molecule through the azo nitrogens (MO/H2O) and the other form not being hydrogen bonded (MO) have also been observed at the water/DCE interface. Their equilibrium constant has been compared with the corresponding bulk solution and found to be identical. The adsorption equilibrium of the two forms has been determined and the Gibbs energy of adsorption measured to be -30 kJmol(-1) for both forms. From a light polarisation analysis of the SH signal, the angle of orientation of the MO transition dipole moment was found to be 34 +/- 2 degrees for MO and 43 +/- 2 degrees for MO/H2O under the assumption of a Dirac delta function for the angle distribution, a difference explained by the different solvation properties of the two forms. Furthermore, the wavelength dependence analysis of these data revealed an interference pattern resulting from the electronic density redistribution within the hydrated anionic form occurring upon the formation of the hydrogen bond with a water molecule. This interference pattern was clearly evidenced with the use of another dye at the interface in order to define a phase reference to both forms of Methyl Orange. PMID:11039537

  16. Investigations on ternary B-C-N materials

    Institute of Scientific and Technical Information of China (English)

    HE Ju-long; LIU Zhong-yuan; YU Dong-li; XU Bo; TIAN Yong-jun

    2007-01-01

    Isoelectronic BCxN compounds have been researched widelv.However,electron-deficient boron-rich B-C-N solids have also attracted much interest both theoretically and experimentally.In this paper,we introduce the synthesis,theoretical prediction,and physical properties of crystalline ternary B-C-N compounds.Our recent work reveals that the novel B-C-N materialS may have a wide variety of crystal structures with different characteristics.

  17. The Molybdenum Active Site of Formate Dehydrogenase Is Capable of Catalyzing C-H Bond Cleavage and Oxygen Atom Transfer Reactions.

    Science.gov (United States)

    Hartmann, Tobias; Schrapers, Peer; Utesch, Tillmann; Nimtz, Manfred; Rippers, Yvonne; Dau, Holger; Mroginski, Maria Andrea; Haumann, Michael; Leimkühler, Silke

    2016-04-26

    Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal-containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pKa of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase. PMID:27054466

  18. 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. PMID:26685710

  19. Interaction of 1,2,5-chalcogenadiazole derivatives with thiophenolate: hypercoordination with formation of interchalcogen bond versus reduction to radical anion.

    Science.gov (United States)

    Suturina, Elizaveta A; Semenov, Nikolay A; Lonchakov, Anton V; Bagryanskaya, Irina Yu; Gatilov, Yuri V; Irtegova, Irina G; Vasilieva, Nadezhda V; Lork, Enno; Mews, Rüdiger; Gritsan, Nina P; Zibarev, Andrey V

    2011-05-12

    According to the DFT calculations, [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (4), [1,2,5]selenadiazolo[3,4-c][1,2,5]thiadiazole (5), 3,4-dicyano-1,2,5-thiadiazole (6), and 3,4-dicyano-1,2,5-selenadiazole (7) have nearly the same positive electron affinity (EA). Under the CV conditions they readily produce long-lived π-delocalized radical anions (π-RAs) characterized by EPR. Whereas 4 and 5 were chemically reduced into the π-RAs with thiophenolate (PhS(-)), 6 did not react and 7 formed a product of hypercoordination at the Se center (9) isolated in the form of the thermally stable salt [K(18-crown-6)][9] (10). The latter type of reactivity has never been observed previously for any 1,2,5-chalcogenadiazole derivatives. The X-ray structure of salt 10 revealed that the Se-S distance in the anion 9 (2.722 Å) is ca. 0.5 Å longer than the sum of the covalent radii of these atoms but ca. 1 Å shorter than the sum of their van der Waals radii. According to the QTAIM and NBO analysis, the Se-S bond in 9 can be considered a donor-acceptor bond whose formation leads to transfer of ca. 40% of negative charge from PhS(-) onto the heterocycle. For various PhS(-)/1,2,5-chalcogenadiazole reaction systems, thermodynamics and kinetics were theoretically studied to rationalize the interchalcogen hypercoordination vs reduction to π-RA dichotomy. It is predicted that interaction between PhS(-) and 3,4-dicyano-1,2,5-telluradiazole (12), whose EA slightly exceeds that of 6 and 7, will lead to hypercoordinate anion (17) with the interchalcogen Te-S bond being stronger than the Se-S bond observed in anion 9. PMID:21500829

  20. The reaction of iodoplatination of triple bond by platinum(4) complexes: formation of σ-vinyl derivatives

    International Nuclear Information System (INIS)

    According to IR and 1H NMR data, propargyl alcohol reacts with platinum(4) iodide complexes in aqueous solution at 10-15 deg C to yield the product of the addition of platinum(4) and iodine to the triple bond, which has been isolated in the form of Pt(CH=CI-CH2OH)2I2(CH3OH). The σ-vinyl ligands in the complex are situated in cis-position. The complex obtained decomposed at 80 deg C to form products of reductive elimination - E,E-2,5-diiodo-1,6-diolhexadiene-2,4 and PtI2. 3 refs

  1. 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

    Escherichia coli is widely used for the production of proteins, which are of interest in structure and function studies. The folding yield of inclusion body protein is, however, generally low (a few percent) for proteins such as the plant and fungal peroxidases, which contain four disulfide bonds......, 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...

  2. Post first dredge-up [C/N] ratio as age indicator. Theoretical calibration

    CERN Document Server

    Salaris, Maurizio; Piersimoni, Anna M; Cassisi, Santi

    2015-01-01

    We performed a detailed analysis of the use of [C/N] measured in red giant branch stars between the completion of the first dredge up and the red giant branch bump ([C/N]_{FDU}) as age indicator. [C/N]_{FDU} cannot give accurate ages for individual stars, but may provide a general chronology for the formation of composite populations and add constraints to analyses of red giants from surface gravity-effective temperature diagrams. We provide a theoretical calibration of [C/N]_{FDU} in terms of total metallicity [M/H] and age, for ages greater than 1 Gyr, which we tested against variations in the initial heavy element distribution (scaled-solar vs alpha-enhanced), efficiency of overshooting from MS convective cores and from the convective envelopes, variations in the initial He abundance and in the mixing length parameter. Our calibration is compared with a small sample of available measurements of [C/N]_{FDU} in star clusters and halo field stars, which at least qualitatively confirm the overall trend of the ...

  3. A nanosensor for in vivo selenol imaging based on the formation of AuSe bonds.

    Science.gov (United States)

    Hu, Bo; Cheng, Ranran; Liu, Xiaojun; Pan, Xiaohong; Kong, Fanpeng; Gao, Wen; Xu, Kehua; Tang, Bo

    2016-06-01

    Selenol is a key metabolite of Na2SeO3 and plays an important role in many physiological and pathological processes. The real-time monitoring of selenol is of scientific interest for understanding the anti-cancer mechanism of Na2SeO3. Based on selenol's ability to specifically break AuS bonds and form more stable AuSe bonds on the surfaces of gold nanoparticles (AuNPs), we developed a novel near-infrared fluorescent nanosensor (Cy5.5-peptide-AuNPs) for detecting selenol. The nanosensor exhibited rapid response to selenol with high selectivity and sensitivity, and it was successfully used to image changes in the selenol level in HepG2 cells during Na2SeO3-induced apoptosis. Moreover, in vivo fluorescence imaging of selenol was obtained from H22 tumor-bearing mice injected with both the nanosensor and sodium selenite. The results showed that the tumor cell apoptosis induced by Na2SeO3 is correlated with high-level of selenol under hypoxic conditions. We believe that this nanosensor could serve as a powerful tool for monitoring selenol and exploring the physiological function of selenol in a variety of physiological and pathological contexts and that the probe-designed strategy will provide a new platform for research on relevant selenium chemistry. PMID:27043769

  4. Thermal expansion of Ti5Si3 with Ge, B, C, N, or O additions

    International Nuclear Information System (INIS)

    The crystallographic thermal expansion coefficients of Ti5Si3 from 20 to 1000 degree sign C as a function of B, C, N, O, or Ge content were measured by high-temperature x-ray diffraction using synchrotron sources at Cornell University (Cornell High Energy Synchrotron Source; CHESS) and Argonne National Laboratory (Advanced Photon Source; APS). Whereas the ratio of the thermal expansion coefficients along the c and a axes was approximately 3 for pure Ti5Si3, this ratio decreased to about 2 when B, C, or N atoms were added. Additions of O and Ge were less efficient at reducing this thermal expansion anisotropy. The extent by which the thermal expansion was changed when B, C, N, or O atoms were added to Ti5Si3 correlated with their expected effect on bonding in Ti5Si3. (c) 2000 Materials Research Society

  5. Theoretical study on the transition-metal oxoboryl complex: M-BO bonding nature, mechanism of the formation reaction, and prediction of a new oxoboryl complex.

    Science.gov (United States)

    Zeng, Guixiang; Sakaki, Shigeyoshi

    2012-04-16

    The Pt-BO bonding nature and the formation reaction of the experimentally reported platinum(II) oxoboryl complex, simplified to PtBr(BO)(PMe(3))(2), were theoretically investigated with the density functional theory method. The BO(-) ligand was quantitatively demonstrated to have extremely strong σ-donation but very weak d(π)-electron-accepting abilities. Therefore, it exhibits a strong trans influence. The formation reaction occurs through a four-center transition state, in which the B(δ+)-Br(δ-) polarization and the Br → Si and O p(π) → B p(π) charge-transfer interactions play key roles. The Gibbs activation energy (ΔG°(++)) and Gibbs reaction energy (ΔG°) of the formation reaction are 32.2 and -6.1 kcal/mol, respectively. The electron-donating bulky phosphine ligand is found to be favorable for lowering both ΔG°(++) and ΔG°. In addition, the metal effect is examined with the nickel and palladium analogues and MBrCl[BBr(OSiMe(3))](CO)(PR(3))(2) (M = Ir and Rh). By a comparison of the ΔG°(++) and ΔG° values, the M-BO (M = Ni, Pd, Ir, and Rh) bonding nature, and the interaction energy between [MBrCl(CO)(PR(3))(2)](+) and BO(-) with those of the platinum system, MBrCl(BO)(CO)(PR(3))(2) (M = Ir and Rh) is predicted to be a good candidate for a stable oxoboryl complex. PMID:22458310

  6. Phase reactions in Ti(C,N)/(Ti,W)C, Ti(C,N)/(Ti,Mo)C, (Ti,W)(C,N)/Co and (Ti,W)(C,N)/Ni diffusion couples

    International Nuclear Information System (INIS)

    In order to investigate interactions of (Ti,W)(C,N) and (Ti,Mo)(C,N) with binder metals solid/solid diffusion couples were annealed. These two-dimensional arrangements provide good access to phase reactions occurring upon sintering already in the solid state. It was found in (Ti,W)(C,N)/Co- and (Ti,W)(C,N)/Ni-based couples that the reaction zone is thinner in contact with Co than with Ni. It was also observed that the reaction rate with both Co and Ni is lower if nitrogen is added to the hard phases. Beside a thickness variation of the diffusion zones a change in the microstructure was found. At the interface of nitrogen-free hard phases in contact with Co elongated microstructural constituents are formed with the main axis perpendicular to the interface, while at the interface of nitrogen-containing hard phases these elongated microstructural constituents were found in contact with Ni. Also phase reactions and the diffusion behavior between the different hard phases were studied by means of solid/solid diffusion couples of the type Ti(C,N)/(Ti,W)C and Ti(C,N)/(Ti,Mo)C with various concentrations. After 1008 h inside the Ti(C,N) phase of the Ti(C,N)/(Ti,W)C diffusion couple W-rich rims were found around Ti-rich cores. The thickness of these rims did not change with time. If W is exchanged by Mo it was observed that the well known core-rim structure is built by diffusion of Mo into the Ti(C,N) grains. But with time the Mo diffuses into the core of Ti(C,N) phase showing that the structure is not stable. (author)

  7. 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

    clear deviation from the behavior of the corresponding homogeneous system. In contrast, halogenated solvents are easily dehalogenated on Pd/Al2O3 and thus they favor leaching of the metal and formation of soluble compounds, analogous to classical metal corrosion in the presence of halide ions. The...

  8. Atomic mixing and chemical bond formation in MoSx/Fe thin-film system deposited from a laser plume in a high-intensity electrostatic field

    International Nuclear Information System (INIS)

    The potential of pulsed laser deposition in an applied uniform electrostatic field was investigated. A flat, positively charged, fine-celled-grid counter electrode was used to provide bias voltage of up to +50 kV with respect to the substrate. This enabled control of the atomic mixing and made it possible to initiate chemical bond formation at the interfaces of the films formed by deposition from the laser-induced plume. As an example, the results of multilayer 56Fe/MoSx/57Fe film deposition are presented. At first, a bilayer MoSx/57Fe film was grown in the absence of the electric field. This was followed by 56Fe film deposition in an applied field. A relatively sharp interface between the MoSx and 57Fe films was observed. In contrast, after 56Fe deposition, effective atom mixing was observed and new chemical bonds between Fe, S and Mo were detected. By penetrating through the interface, accelerated 56Fe ions gave rise to the growth of an amorphous layer of up to 50 nm in thickness. It consisted of rather evenly distributed Fe, S and Mo atoms (at total ion dose of 2.5x1016 cm-2). The ion flux destroyed Mo-S chemical bonds, and the S atoms released preferably bound Fe atoms, thus forming a FeS2-type phase. The Mo atoms, as a lower-oxidation-state species (apparently together with S atoms), were localized in the vicinity of Fe atoms and affected the hyperfine magnetic fields. The technique developed has made it possible to study the ion-induced processes occurring at the interfaces of multilayer films. It can also be applied to improve the tribological functionality of thin films

  9. $\\Lambda_c-N$ interaction from lattice QCD

    CERN Document Server

    Miyamoto, Takaya

    2016-01-01

    We investigate the s-wave $\\Lambda_c-N$ interaction for spin singlet systems($^1S_0$) using the HAL QCD method. In our lattice QCD simulations, we employ gauge configurations generated by the PACS-CS Collaboration at $a = 0.0907(13)$ fm on a $32^3 \\times 64$ lattice ($La = 2.902(42)$ fm). We employ two ensembles, one at $m_\\pi = 700(1)$ MeV and the other at $m_\\pi = 570(1)$ MeV to study the quark mass dependence of the $\\Lambda_c-N$ interactions. We calculate a $^1S_0$ central potential not only for the $\\Lambda_c-N$ system but also for $\\Lambda-N$ system to understand the role of heavy charm quarks in $\\Lambda_c-N$ system. We find repulsion at short distance and attraction at mid-range for both the $\\Lambda_c-N$ and the $\\Lambda-N$ potentials. The short range repulsion of the $\\Lambda_c-N$ potential is smaller than that of the $\\Lambda-N$ potential, and the attraction of the $\\Lambda_c-N$ potential is small compared with the $\\Lambda-N$ potential. The phase shift and scattering length calculated with these p...

  10. 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.

  11. 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.

  12. Palladium-catalyzed C–N and C–O bond formation of N-substituted 4-bromo-7-azaindoles with amides, amines, amino acid esters and phenols

    Directory of Open Access Journals (Sweden)

    Rajendra Surasani

    2012-11-01

    Full Text Available Simple and efficient procedures for palladium-catalyzed cross-coupling reactions of N-substituted 4-bromo-7-azaindole (1H-pyrrole[2,3-b]pyridine, with amides, amines, amino acid esters and phenols through C–N and C–O bond formation have been developed. The C–N cross-coupling reaction of amides, amines and amino acid esters takes place rapidly by using the combination of Xantphos, Cs2CO3, dioxane and palladium catalyst precursors Pd(OAc2/Pd2(dba3. The combination of Pd(OAc2, Xantphos, K2CO3 and dioxane was found to be crucial for the C–O cross-coupling reaction. This is the first report on coupling of amides, amino acid esters and phenols with N-protected 4-bromo-7-azaindole derivatives.

  13. Formation of C═C bond via knoevenagel reaction between aromatic aldehyde and barbituric acid at liquid/HOPG and vapor/HOPG interfaces.

    Science.gov (United States)

    Geng, Yanfang; Dai, Hongliang; Chang, Shaoqing; Hu, Fangyun; Zeng, Qingdao; Wang, Chen

    2015-03-01

    Controlling chemical reactions on surface is of great importance to constructing self-assembled covalent nanostructures. Herein, Knoevenagel reaction between aromatic aldehyde compound 2,5-di(5-aldehyde-2-thienyl)-1,4-dioctyloxybenzene (PT2) and barbituric acid (BA) has been successfully performed for the first time at liquid/HOPG interface and vapor/HOPG interface. The resulting surface nanostructures and the formation of C═C bond are recorded through scanning tunneling microscopy (STM), and confirmed by attenuated total reflectance Fourier-transform infrared (ATR/FT-IR) spectrometer and UV-vis absorption. The obtained results reveal that Knoevenagel condensation reaction can efficiently occur at both interfaces. This surface reaction would be an important step toward further reaction to produce innovative conjugated nanomaterial on the surface. PMID:25664650

  14. On peptide bond formation, translocation, nascent protein progression and the regulatory properties of ribosomes. Derived on 20 October 2002 at the 28th FEBS Meeting in Istanbul.

    Science.gov (United States)

    Agmon, Ilana; Auerbach, Tamar; Baram, David; Bartels, Heike; Bashan, Anat; Berisio, Rita; Fucini, Paola; Hansen, Harly A S; Harms, Joerg; Kessler, Maggie; Peretz, Moshe; Schluenzen, Frank; Yonath, Ada; Zarivach, Raz

    2003-06-01

    High-resolution crystal structures of large ribosomal subunits from Deinococcus radiodurans complexed with tRNA-mimics indicate that precise substrate positioning, mandatory for efficient protein biosynthesis with no further conformational rearrangements, is governed by remote interactions of the tRNA helical features. Based on the peptidyl transferase center (PTC) architecture, on the placement of tRNA mimics, and on the existence of a two-fold related region consisting of about 180 nucleotides of the 23S RNA, we proposed a unified mechanism integrating peptide bond formation, A-to-P site translocation, and the entrance of the nascent protein into its exit tunnel. This mechanism implies sovereign, albeit correlated, motions of the tRNA termini and includes a spiral rotation of the A-site tRNA-3' end around a local two-fold rotation axis, identified within the PTC. PTC features, ensuring the precise orientation required for the A-site nucleophilic attack on the P-site carbonyl-carbon, guide these motions. Solvent mediated hydrogen transfer appears to facilitate peptide bond formation in conjunction with the spiral rotation. The detection of similar two-fold symmetry-related regions in all known structures of the large ribosomal subunit, indicate the universality of this mechanism, and emphasizes the significance of the ribosomal template for the precise alignment of the substrates as well as for accurate and efficient translocation. The symmetry-related region may also be involved in regulatory tasks, such as signal transmission between the ribosomal features facilitating the entrance and the release of the tRNA molecules. The protein exit tunnel is an additional feature that has a role in cellular regulation. We showed by crystallographic methods that this tunnel is capable of undergoing conformational oscillations and correlated the tunnel mobility with sequence discrimination, gating and intracellular regulation. PMID:12787020

  15. Toward Design Principles for Diffusionless Transformations: The Frustrated Formation of Co-Co Bonds in a Low-Temperature Polymorph of GdCoSi2.

    Science.gov (United States)

    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 source of compounds exhibiting diffusionless transformations

  16. Velocity Map Imaging Study of Ion-Radical Chemistry: Charge Transfer and Carbon-Carbon Bond Formation in the Reactions of Allyl Radicals with C(.).

    Science.gov (United States)

    Pei, Linsen; Farrar, James M

    2016-08-11

    We present an experimental and computational study of the dynamics of collisions of ground state carbon cations with allyl radicals, C3H5, at a collision energy of 2.2 eV. Charge transfer to produce the allyl cation, C3H5(+), is exoergic by 3.08 eV and proceeds via energy resonance such that the electron transfer occurs without a significant change in nuclear velocities. The products have sufficient energy to undergo the dissociation process C3H5(+) → C3H4(+) + H. Approximately 80% of the reaction products are ascribed to charge transfer, with ∼40% of those products decaying via loss of a hydrogen atom. We also observe products arising from the formation of new carbon-carbon bonds. The experimental velocity space flux distributions for the four-carbon products are symmetric about the centroid of the reactants, providing direct evidence that the products are mediated by formation of a C4H5(+) complex living at least a few rotational periods. The primary four-carbon reaction products are formed by elimination of molecular hydrogen from the C4H5(+) complex. More than 75% of the nascent C4H3(+) products decay by C-H bond cleavage to yield a C4H2(+) species. Quantum chemical calculations at the MP2/6-311+g(d,p) level of theory support the formation of a nonplanar cyclic C4H5(+) adduct that is produced when the p-orbital containing the unpaired electron on C(+) overlaps with the unpaired spin density on the terminal carbon atoms in allyl. Product formation then occurs by 1,2-elimination of molecular hydrogen from the cyclic intermediate to form a planar cyclic C4H3(+) product. The large rearrangement in geometry as the C4H3(+) products are formed is consistent with high vibrational excitation in that product and supports the observation that the majority of those products decay to form the C4H2(+) species. PMID:27434380

  17. Real-time Monitoring of Intermediates Reveals the Reaction Pathway in the Thiol-Disulfide Exchange between Disulfide Bond Formation Protein A (DsbA) and B (DsbB) on a Membrane-immobilized Quartz Crystal Microbalance (QCM) System*

    Science.gov (United States)

    Yazawa, Kenjiro; Furusawa, Hiroyuki; Okahata, Yoshio

    2013-01-01

    Disulfide bond formation protein B (DsbBS-S,S-S) is an inner membrane protein in Escherichia coli that has two disulfide bonds (S-S, S-S) that play a role in oxidization of a pair of cysteine residues (SH, SH) in disulfide bond formation protein A (DsbASH,SH). The oxidized DsbAS-S, with one disulfide bond (S-S), can oxidize proteins with SH groups for maturation of a folding preprotein. Here, we have described the transient kinetics of the oxidation reaction between DsbASH,SH and DsbBS-S,S-S. We immobilized DsbBS-S,S-S embedded in lipid bilayers on the surface of a 27-MHz quartz crystal microbalance (QCM) device to detect both formation and degradation of the reaction intermediate (DsbA-DsbB), formed via intermolecular disulfide bonds, as a mass change in real time. The obtained kinetic parameters (intermediate formation, reverse, and oxidation rate constants (kf, kr, and kcat, respectively) indicated that the two pairs of cysteine residues in DsbBS-S,S-S were more important for the stability of the DsbA-DsbB intermediate than ubiquinone, an electron acceptor for DsbBS-S,S-S. Our data suggested that the reaction pathway of almost all DsbASH,SH oxidation processes would proceed through this stable intermediate, avoiding the requirement for ubiquinone. PMID:24145032

  18. Real-time monitoring of intermediates reveals the reaction pathway in the thiol-disulfide exchange between disulfide bond formation protein A (DsbA) and B (DsbB) on a membrane-immobilized quartz crystal microbalance (QCM) system.

    Science.gov (United States)

    Yazawa, Kenjiro; Furusawa, Hiroyuki; Okahata, Yoshio

    2013-12-13

    Disulfide bond formation protein B (DsbBS-S,S-S) is an inner membrane protein in Escherichia coli that has two disulfide bonds (S-S, S-S) that play a role in oxidization of a pair of cysteine residues (SH, SH) in disulfide bond formation protein A (DsbASH,SH). The oxidized DsbAS-S, with one disulfide bond (S-S), can oxidize proteins with SH groups for maturation of a folding preprotein. Here, we have described the transient kinetics of the oxidation reaction between DsbASH,SH and DsbBS-S,S-S. We immobilized DsbBS-S,S-S embedded in lipid bilayers on the surface of a 27-MHz quartz crystal microbalance (QCM) device to detect both formation and degradation of the reaction intermediate (DsbA-DsbB), formed via intermolecular disulfide bonds, as a mass change in real time. The obtained kinetic parameters (intermediate formation, reverse, and oxidation rate constants (kf, kr, and kcat, respectively) indicated that the two pairs of cysteine residues in DsbBS-S,S-S were more important for the stability of the DsbA-DsbB intermediate than ubiquinone, an electron acceptor for DsbBS-S,S-S. Our data suggested that the reaction pathway of almost all DsbASH,SH oxidation processes would proceed through this stable intermediate, avoiding the requirement for ubiquinone. PMID:24145032

  19. $\\mathbf{\\bar{C}_{n,n-1}}$ revisited

    OpenAIRE

    Fujino, Osamu

    2005-01-01

    The main purpose of this paper is to make $\\bar{C}_{n,n-1}$, which is the main theorem of [Ka1] Y.Kawamata, Addition formula of logarithmic Kodaira dimensions for morphisms of relative dimension one, more accessible.

  20. Si-C-N-Fe nanostuctured ceramics from inorganic polymer precursors obtained by plasma polymerization

    International Nuclear Information System (INIS)

    Multicomponent powders based on SiCN and SiCN containing iron systems are of great interest as starting materials for sintering advanced ceramics and composites with improved properties for high temperature applications. We report a versatile method by which are designed inorganic polymers with a defined composition as precursors for a ceramic with induced properties. The synthesis of Si-C-N and Si-C-N-iron polymer precursors are performed in improved configuration of plasma assisted chemical vapor deposition (CVD) coupled with chemical transport reaction (CTR) with inorganic monomers, hexamethyldisilazane and ferrocene/hexamethyldisilazane as precursors. Further, the resulted polymers are then pyrolysed at 1200 deg. C under nitrogen atmosphere into nanostructured ceramics (such as Si3N4, Fe3C). The conversion process of the polymer precursors into a nanostructured ceramic was followed mainly by FTIR, XRD, TEM and SEM investigation. Infrared spectroscopy of polymers revealed the presence of Si-C, Si-N, C-N and hydrogenated bonds. Transmission electron microscopy showed that the polymers are made of nanometric round-shape particles with the average particle size around 20-40 nm for SiCN and 40-80 nm for SiCN containing iron

  1. Si-C-N-Fe nanostuctured ceramics from inorganic polymer precursors obtained by plasma polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Dumitru, Anca [3 Nano-SAE Research Centre, University of Bucharest, MG-38, 077125, Bucharest-Magurele (Romania)], E-mail: anka.dumitru@gmail.com; Stamatin, Ioan; Morozan, Adina [3 Nano-SAE Research Centre, University of Bucharest, MG-38, 077125, Bucharest-Magurele (Romania); Mirea, C. [National Institute of Forensic Expertise, Bd. Regina Elisabeta 53, Bucharest (Romania); Ciupina, V. [Ovidius University of Constanta, Bd. Mamaia 124, Constanta (Romania)

    2007-09-15

    Multicomponent powders based on SiCN and SiCN containing iron systems are of great interest as starting materials for sintering advanced ceramics and composites with improved properties for high temperature applications. We report a versatile method by which are designed inorganic polymers with a defined composition as precursors for a ceramic with induced properties. The synthesis of Si-C-N and Si-C-N-iron polymer precursors are performed in improved configuration of plasma assisted chemical vapor deposition (CVD) coupled with chemical transport reaction (CTR) with inorganic monomers, hexamethyldisilazane and ferrocene/hexamethyldisilazane as precursors. Further, the resulted polymers are then pyrolysed at 1200 deg. C under nitrogen atmosphere into nanostructured ceramics (such as Si{sub 3}N{sub 4}, Fe{sub 3}C). The conversion process of the polymer precursors into a nanostructured ceramic was followed mainly by FTIR, XRD, TEM and SEM investigation. Infrared spectroscopy of polymers revealed the presence of Si-C, Si-N, C-N and hydrogenated bonds. Transmission electron microscopy showed that the polymers are made of nanometric round-shape particles with the average particle size around 20-40 nm for SiCN and 40-80 nm for SiCN containing iron.

  2. Crystallization behavior and controlling mechanism of iron-containing Si-C-N ceramics.

    Science.gov (United States)

    Francis, Adel; Ionescu, Emanuel; Fasel, Claudia; Riedel, Ralf

    2009-11-01

    The crystallization behavior and controlling mechanism of the Si-Fe-C-N system based on polymer-derived SiCN ceramic filled with iron metal powder has been studied. The composite preparation conditions allow the formation of a random distribution of metallic particles in the polymer matrix volume for the Si-C-N system. Pyrolysis of the composite material at 1100 degrees C indicates the presence of one crystalline phase Fe(3)Si. While the sample pyrolyzed at 1200 degrees C reveals the formation of both Fe(3)Si and Fe(5)Si(3) phases, a crystallization of beta-SiC is additionally observed by increasing the temperature up to 1300 degrees C. The propensity for the formation of SiC is due to the presence of Fe(5)Si(3), where a solid-liquid-solid (SLS) growth mechanism was suggested to occur. X-ray diffraction (XRD), scanning electron microscopy (SEM), differential thermal analysis (DTA), and thermal gravimetric analysis with mass spectroscopic detection (TGA-MS) were employed to investigate the crystallization behavior of the Si-Fe-C-N system. PMID:19788256

  3. Suppression of Boride Formation in Transient Liquid Phase Bonding of Pairings of Parent Superalloy Materials with Different Compositions and Grain Structures and Resulting Mechanical Properties

    Science.gov (United States)

    Steuer, Susanne; Singer, Robert F.

    2014-07-01

    Two Ni-based superalloys, columnar grained Alloy 247 and single-crystal PWA1483, are joined by transient liquid phase bonding using an amorphous brazing foil containing boron as a melting point depressant. At lower brazing temperatures, two different morphologies of borides develop in both base materials: plate-like and globular ones. Their ratio to each other is temperature dependent. With very high brazing temperatures, the deleterious boride formation in Alloy 247 can be totally avoided, probably because the three-phase-field moves to higher alloying element contents. For the superalloy PWA1483, the formation of borides cannot be completely avoided at high brazing temperatures as incipient melting occurs. During subsequent solidification of these areas, Chinese-script-like borides precipitate. The mechanical properties (tensile tests at room and elevated temperatures and short-term creep rupture tests at elevated temperatures) for brazed samples without boride precipitation are very promising. Tensile strengths and creep times to 1 pct strain are comparable, respectively, higher than the ones of the weaker parent material for all tested temperatures and creep conditions (from 90 to 100 pct rsp. 175 to 250 pct).

  4. Acetaldehyde partial oxidation on the Au(111) model catalyst surface: C-C bond activation and formation of methyl acetate as an oxidative coupling product

    Science.gov (United States)

    Karatok, Mustafa; Vovk, Evgeny I.; Shah, Asad A.; Turksoy, Abdurrahman; Ozensoy, Emrah

    2015-11-01

    Partial oxidation of acetaldehyde (CH3CHO) on the oxygen pre-covered Au(111) single crystal model catalyst was investigated via Temperature Programmed Desorption (TPD) and Temperature Programmed Reaction Spectroscopy (TPRS) techniques, where ozone (O3) was utilized as the oxygen delivery agent providing atomic oxygen to the reacting surface. We show that for low exposures of O3 and small surface oxygen coverages, two partial oxidation products namely, methyl acetate (CH3COOCH3) and acetic acid (CH3COOH) can be generated without the formation of significant quantities of carbon dioxide. The formation of methyl acetate as the oxidative coupling reaction product implies that oxygen pre-covered Au(111) single crystal model catalyst surface can activate C-C bonds. In addition to the generation of these products; indications of the polymerization of acetaldehyde on the gold surface were also observed as an additional reaction route competing with the partial and total oxidation pathways. The interplay between the partial oxidation, total oxidation and polymerization pathways reveals the complex catalytic chemistry associated with the interaction between the acetaldehyde and atomic oxygen on catalytic gold surfaces.

  5. Thermal Expansion Behavior of Precursor-Derived Amorphous Si-C-N and Si-B-C-N Ceramics

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Thermal expansion behaviors of some precursor-derived amorphous Si-C-N and Si-B-C-N ceramics, which were shaped by plastic forming after crosslink, were studied. To complete the shrinkage and densification, after thermolysis specimens were heat treated at a temperature of 1400℃ for 10 h in nitrogen atmosphere. The thermal expansion coefficient of VT50-derived amorphous Si-C-N ceramic increases from 1.98×10-6/K at 400℃ to 3.09×10-6/K at 1000℃, of NCP200-derived amorphous Si-C-N ceramic increases from 2.35× 10-6/K at 400℃ to 3.45×10-6/K at1000℃, and of T2-1-derived amorphous Si-B-C-N ceramic increases from 2.08×10-6/K at 400℃ to 3.18×10-6/K at 1000℃. No glass transition for these amorphous ceramic materials was detected, indicating that as-thermolyzed precursor-derived Si-(B-)C-N ceramic materials are amorphous solids, but not glasses.

  6. Preferential formation of 13C- 18O bonds in carbonate minerals, estimated using first-principles lattice dynamics

    Science.gov (United States)

    Schauble, Edwin A.; Ghosh, Prosenjit; Eiler, John M.

    2006-05-01

    Equilibrium constants for internal isotopic exchange reactions of the type: Ca12C18O16O2+Ca13C16O3↔Ca13C18O16O2+Ca12C16O3 for individual CO 32- groups in the carbonate minerals calcite (CaCO 3), aragonite (CaCO 3), dolomite (CaMg(CO 3) 2), magnesite (MgCO 3), witherite (BaCO 3), and nahcolite (NaHCO 3) are calculated using first-principles lattice dynamics. Calculations rely on density functional perturbation theory (DFPT) with norm-conserving planewave pseudopotentials to determine the vibrational frequencies of isotopically substituted crystals. Our results predict an ˜0.4‰ excess of 13C18O16O22- groups in all studied carbonate minerals at room-temperature equilibrium, relative to what would be expected in a stochastic mixture of carbonate isotopologues with the same bulk 13C/ 12C, 18O/ 16O, and 17O/ 16O ratios. The amount of excess 13C18O16O22- decreases with increasing temperature of equilibration, from 0.5‰ at 0 °C to <0.1‰ at 300 °C, suggesting that measurements of multiply substituted isotopologues of carbonate could be used to infer temperatures of ancient carbonate mineral precipitation and alteration events, even where the δ 18O of coexisting fluids is uncertain. The predicted temperature sensitivity of the equilibrium constant is ˜0.003‰/°C at 25 °C. Estimated equilibrium constants for the formation of 13C18O16O22- are remarkably uniform for the variety of minerals studied, suggesting that temperature calibrations will also be applicable to carbonate minerals not studied here without greatly compromising accuracy. A related equilibrium constant for the reaction: Ca12C18O16O2+Ca12C17O16O2↔Ca12C18O17O16O+Ca12C16O3 in calcite indicates formation of 0.1‰ excess 12C 18O 17O 16O 2- at 25 °C. In a conventional phosphoric acid reaction of carbonate to form CO 2 for mass-spectrometric analysis, molecules derived from 13C18O16O22- dominate (˜96%) the mass 47 signal, and 12C 18O 17O 16O 2- contributes most of the remainder (3%). This suggests

  7. Slow rate of phosphodiester bond formation accounts for the strong bias that Taq DNA polymerase shows against 2',3'-dideoxynucleotide terminators.

    Science.gov (United States)

    Brandis, J W; Edwards, S G; Johnson, K A

    1996-02-20

    Taq and T7 DNA polymerases have become basic molecular biology "tools" for DNA sequence analysis. However, Taq, unlike T7 DNA polymerase, is strongly biased against the incorporation of 2',3'-dideoxynucleotide triphosphates (ddNTPs) indicating very different substrate selectivities. Equilibrium binding and rate constants were measured for 2',3'-ddNTPs as well as for several other 3'-substituted terminators and compared to 2'-deoxynucleotide substrates (dNTPs). In steady-state experiments, Taq Pol I was strongly biased in favor of dATP1 over ddATP incorporation by about 700 to 1, in contrast to T7 DNA polymerase which showed a preference of only about 4 to 1. Manganese reduced but did not eliminate selectivity against 2',3'-ddNTPs. Transient kinetic traces indicated different rate-limiting steps for substrate and terminator incorporation. Further mechanistic studies showed that the binding constants for substrates and terminators were equivalent. However, the rate constants for phosphodiester bond formation for 2',3'-ddNTPs were 200-3000-fold lower than for dNTPs. Alternative terminators showed only slight improvements. The data were consistent with a model in which both substrates and terminators undergo ground-state binding followed by formation of a tight-binding Enz.DNA.Nucleotide complex. Immediately after complex formation, substrates undergo a rapid nucleoside phosphoryl transfer reaction. However, the reaction rates for terminators were slower presumably due to misalignment of reactive groups in the active site. Thus, the strong bias that Taq DNA polymerase shows against terminators is due to a very slow "chemistry" step. Such a strong bias has several kinetic consequences for DNA sequence patterns. These consequences are discussed in the text. PMID:8652560

  8. 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...

  9. The effect of nitrogen incorporation on the bonding structure of hydrogenated carbon nitride films

    International Nuclear Information System (INIS)

    This work describes the composition and bonding structure of hydrogenated carbon nitride (a-CNx:H) films synthesized by electron cyclotron resonance chemical vapor deposition using as precursor gases argon, methane, and nitrogen. The composition of the films was derived from Rutherford backscattering and elastic recoil detection analysis and the bonding structure was examined by infrared (IR) spectroscopy and x-ray absorption near edge spectroscopy (XANES). By varying the nitrogen to methane ratio in the applied gas mixture, polymeric a-CNx:H films with N/C contents varying from 0.06 to 0.49 were obtained. Remarkably, the H content of the films (∼40 at. %) was rather unaffected by the nitrogenation process. The different bonding states as detected in the measured XANES C(1s) and N(1s) spectra have been correlated with those of a large number of reference samples. The XANES and IR spectroscopy results indicate that N atoms are efficiently incorporated into the amorphous carbon network and can be found in different bonding environments, such as pyridinelike, graphitelike, nitrilelike, and amino groups. The nitrogenation of the films results in the formation of N-H bonding environments at the cost of C-H structures. Also, the insertion of N induces a higher fraction of double bonds in the structure at the expense of the linear polymerlike chains, hence resulting in a more cross-linked solid. The formation of double bonds takes place through complex C=N structures and not by formation of graphitic aromatic rings. Also, the mechanical and tribological properties (hardness, friction, and wear) of the films have been studied as a function of the nitrogen content. Despite the major modifications in the bonding structure with nitrogen uptake, no significant changes in these properties are observed

  10. Stacked base-pair structures of adenine nucleosides stabilized by the formation of hydrogen-bonding network involving the two sugar groups

    International Nuclear Information System (INIS)

    Highlights: ► A combination of laser desorption and supersonic jet-cooling is used to produce base pairs of adenine nucleosides. ► Stacked base-pair structure of N6,N6-dimethyladnosine is identified by IR vibrational spectroscopy. ► Anharmonic vibrational calculation is employed to analyze the vibrational mode coupling in the stacked base pair. - Abstract: We have employed a laser desorption technique combined with supersonic-jet cooling for producing base pairs of adenine nucleosides, adenosine (Ado) and N6,N6-dimethyladenosine (DMAdo) under low-temperature conditions. The resulting base pairs are then ionized through resonant two-photon ionization (R2PI) and analyzed by time-of-flight mass spectrometry. It is found that dimers of these adenine nucleosides are stable, especially in the case of DMAdo, with respect to those of the corresponding bases, i.e., adenine and N6,N6-dimethyladenine. Structural analysis of the DMAdo dimer is performed based on the IR–UV double resonance measurements and theoretical calculations. The result demonstrates that the dimer possesses a stacked structure being stabilized by the formation of hydrogen-bonding network involving the two sugar groups. The occurrence of the frequency shift and broadening is explained satisfactorily based on the anharmonic coupling of the OH stretching modes with specific bending modes and low-frequency modes of base and sugar moieties

  11. Palladium(ii)-catalyzed C-C and C-O bond formation for the synthesis of C1-benzoyl isoquinolines from isoquinoline N-oxides and nitroalkenes.

    Science.gov (United States)

    Li, Jiu-Ling; Li, Wei-Ze; Wang, Ying-Chun; Ren, Qiu; Wang, Heng-Shan; Pan, Ying-Ming

    2016-08-01

    C1-Benzoyl isoquinolines can be generated via a palladium(ii)-catalyzed C-C and C-O coupling of isoquinoline N-oxides with aromatic nitroalkenes. The reaction proceeds through remote C-H bond activation and subsequent intramolecular oxygen atom transfer (OAT). In this reaction, the N-O bond was designed as a directing group in the C-H bond activation as well as the source of an oxygen atom. PMID:27443150

  12. Structural basis for hyperactivity of cN-II mutants

    Czech Academy of Sciences Publication Activity Database

    Hnízda, Aleš; Škerlová, Jana; Šinalová, Martina; Pachl, Petr; Man, Petr; Novák, Petr; Fábry, Milan; Řezáčová, Pavlína; Veverka, Václav

    2015-01-01

    Roč. 22, č. 1 (2015), s. 4. ISSN 1211-5894. [Discussions in Structural Molecular Biology . Annual Meeting of the Czech Society for Structural Biology /13./. 19.03.2015-21.03.2015, Nové Hrady] Institutional support: RVO:61388963 ; RVO:68378050 ; RVO:61388971 Keywords : cN-II mutants * enzyme hyperactivity Subject RIV: CE - Biochemistry

  13. The electronic structures and photophysical properties of platinum complexes with C^N^N ligands: the influence of the carborane substituent.

    Science.gov (United States)

    Zhang, Wenting; Luo, Yafei; Xu, Yanyan; Tian, Li; Li, Ming; He, Rongxing; Shen, Wei

    2015-11-01

    Carboranes have attracted increasing interest in the scientific community due to their remarkable structures and strong electron-withdrawing abilities. In this article, four platinum complexes [(C^N^N)PtC[triple bond, length as m-dash]CPh](1), [(C^N^N)PtC[triple bond, length as m-dash]C-TPA](2), [(C^N^N)PtC[triple bond, length as m-dash]C-TAB](3), [(C^N^N)PtC[triple bond, length as m-dash]C-CB](4) (where TPA = triphenylamine, TAB = triarylboryl, CB = o-carborane) have been calculated via density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods to mainly explore the influence of carborane substituents on electronic structures, photophysical properties and radiative decay processes. The calculated results reveal that 2 with electron-donating triphenylamine has a low radiative decay rate constant and a red-shifted emission band, but 3 and 4 containing electron-withdrawing triarylboryl and o-carborane exhibit the opposite properties, especially 4 is supposed to have the highest phosphorescence quantum yield with the smallest nonradiative decay rate constant. These findings successfully illustrated the structure-property relationship and the designed complex 4 with carborane can serve as a highly efficient phosphorescent material in the future. PMID:26419292

  14. Hydrodenitrogenation chemistry. I. Cleavage of alkylcarbon-nitrogen bonds, methane and ammonia formation in the HDN reaction of 1,2,3,4-tetrahydroquinoline with a nickel oxide catalyst supported on silica/alumina

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.; Thormodsen, A.D.; Moore, R.S.; Perry, D.L.; Heinemann, H.

    1986-11-01

    The hydrodenitrogenation reaction (HDN) is one of the most important industrial processes used in the refining of petroleum feedstocks and involves the removal of the nitrogen atom, as ammonia, from polynuclear heteroaromatic nitrogen compounds at high temperatures and high pressures of hydrogen gas (350-500/sup 0/C and 2000 psi). It is interesting to note that most of the reported heterogeneous catalysts require the complete hydrogenation of both the nitrogen heterocyclic ring and the aromatic ring before carbon-nitrogen bond cleavage can occur. A major breakthrough in the technical and economic aspects of the HDN reaction would take place if, in fact a catalyst could be found that would selectively cleave the C-N bond din the saturated nitrogen ring and subsequently produce ammonia, without substantial reduction of the aromatic rings, at lower temperatures as well as lower pressures of hydrogen gas. In this note, the authors report on a highly loaded nickel oxide catalyst (50% by weight Ni), supported on silica/alumina, that will effectively provide some of the criteria for an ideal HDN catalyst. 8 references.

  15. 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.

  16. Deposition of and annealing effect on Ti(C, N) coatings

    International Nuclear Information System (INIS)

    The influence of annealing environment such as temperature and atmosphere on the microhardness of Ti(C, N) coatings has been studied. Complete solid solution between TiC and TiN was obtained on steel substrates by ion plating. The composition of the coatings was close to stoichiometric. A linear relationship between the hardness and the carbon content in the coatings was obtained. The values of the Vickers hardness varied from 2100 (TiN) to 5300 (TiC) which was harder than the reported values of bulk TiC. The possible origins of such high values of the hardness are the fine grains, the crystallographic orientation, high compressive residual stresses or the dense defect-free structure of the coatings. The hardness of the TiC coatings dropped rapidly after annealing in air at 673 K although Ti(C, N) coatings maintained their hardness even at 773 K. Titanium oxide was formed at the surface of annealed samples whose values of hardness rapidly decreased. It is suggested that this softening is due to formation of soft oxides such as TiO2. The oxidation was dependent upon the chemical composition of the coatings. The Ti(C, N) coatings which included larger amounts of TiN component could be more oxidation resistant and maintained a very hard surface. (orig.)

  17. Erythromycin, roxithromycin, and clarithromycin: use of slow-binding kinetics to compare their in vitro interaction with a bacterial ribosomal complex active in peptide bond formation.

    Science.gov (United States)

    Dinos, George P; Connell, Sean R; Nierhaus, Knud H; Kalpaxis, Dimitrios L

    2003-03-01

    In a cell-free system derived from Escherichia coli, it is shown that clarithromycin and roxithromycin, like their parent compound erythromycin, do not inhibit the puromycin reaction (i.e., the peptide bond formation between puromycin and AcPhe-tRNA bound at the P-site of 70S ribosomes programmed with heteropolymeric mRNA). Nevertheless, all three antibiotics compete for binding on the ribosome with tylosin, a 16-membered ring macrolide that behaves as a slow-binding, slowly reversible inhibitor of peptidyltransferase. The mutually exclusive binding of these macrolides to ribosomes is also corroborated by the fact that they protect overlapping sites in domain V of 23S rRNA from chemical modification by dimethyl sulfate. From this competition effect, detailed kinetic analysis revealed that roxithromycin or clarithromycin (A), like erythromycin, reacts rapidly with AcPhe-tRNA.MF-mRNA x 70S ribosomal complex (C) to form the encounter complex CA which is then slowly isomerized to a more tight complex, termed C*A. The value of the overall dissociation constant, K, encompassing both steps of macrolide interaction with complex C, is 36 nM for erythromycin, 20 nM for roxithromycin, and 8 nM for clarithromycin. Because the off-rate constant of C*A complex does not significantly differ among the three macrolides, the superiority of clarithromycin as an inhibitor of translation in E. coli cells and many Gram-positive bacteria may be correlated with its greater rate of association with ribosomes. PMID:12606769

  18. The spatial relationship between human activities and C, N, P, S in soil based on landscape geochemical interpretation.

    Science.gov (United States)

    Yu, Huan; He, Zheng-Wei; Kong, Bo; Weng, Zhong-Yin; Shi, Ze-Ming

    2016-04-01

    The development and formation of chemical elements in soil are affected not only by parent material, climate, biology, and topology factors, but also by human activities. As the main elements supporting life on earth system, the C, N, P, S cycles in soil have been altered by human activity through land-use change, agricultural intensification, and use of fossil fuels. The present study attempts to analyze whether and how a connection can be made between macroscopical control and microcosmic analysis, to estimate the impacts of human activities on C, N, P, S elements in soil, and to determine a way to describe the spatial relationship between C, N, P, S in soil and human activities, by means of landscape geochemical theories and methods. In addition, the disturbances of human activities on C, N, P, S are explored through the analysis of the spatial relationship between human disturbed landscapes and element anomalies, thereby determining the diversified rules of the effects. The study results show that the rules of different landscapes influencing C, N, P, S elements are diversified, and that the C element is closely related to city landscapes; furthermore, the elements N, P, and S are shown to be closely related to river landscapes; the relationships between mine landscapes and the elements C, N, P, S are apparent; the relationships between the elements C, N, P, S and road landscapes are quite close, which shows that road landscapes have significant effects on these elements. Therefore, the conclusion is drawn that the response mechanism analysis of human disturbance and soil chemical element aggregation is feasible, based on the landscape geochemical theories and methods. The spatial information techniques, such as remote sensing and geographic information systems, are effective for research on soil element migration. PMID:26055456

  19. The chemical composition and band gap of amorphous Si:C:N:H layers

    Science.gov (United States)

    Swatowska, Barbara; Kluska, Stanislawa; Jurzecka-Szymacha, Maria; Stapinski, Tomasz; Tkacz-Smiech, Katarzyna

    2016-05-01

    In this work we presented the correlation between the chemical composition of amorphous Si:C:N:H layers of various content of silicon, carbon and nitrogen, and their band gap. The series of amorphous Si:C:N:H layers were obtained by plasma assisted chemical vapour deposition method in which plasma was generated by RF (13.56 MHz, 300 W) and MW (2.45 GHz, 2 kW) onto monocrystalline silicon Si(001) and borosilicate glass. Structural studies were based on FTIR transmission spectrum registered within wavenumbers 400-4000 cm-1. The presence of Sisbnd C, Sisbnd N, Csbnd N, Cdbnd N, Cdbnd C, Ctbnd N, Sisbnd H and Csbnd H bonds was shown. The values band gap of the layers have been determined from spectrophotometric and ellipsometric measurements. The respective values are contained in the range between 1.64 eV - characteristic for typical semiconductor and 4.21 eV - for good dielectric, depending on the chemical composition and atomic structure of the layers.

  20. Structure of small TiC n clusters: A theoretical study

    International Nuclear Information System (INIS)

    A theoretical study of the TiC n (n = 1-8) clusters has been carried out at the B3LYP/6-311+G(d) level. Molecular properties for three different isomers, namely linear, cyclic, and fan species, have been determined. The fan isomers, where the titanium atom is essentially side-bonded to the entire C n unit, are predicted to be more stable than both linear and cyclic isomers. Only for the largest studied species, TiC8, the cyclic isomer is located lower in energy. An even-odd parity effect in the incremental binding energies is observed for the three isomers, n-even species being in general more stable for linear and fan isomers, whereas for the cyclic species n-odd clusters are favoured. A topological analysis of the electronic charge density shows that all cyclic isomers correspond to true monocyclic rings, whereas for the fan species a variety of different connectivities has been observed

  1. Structural, Mechanical and Optical Properties of Plasma-chemical Si-C-N Films

    Directory of Open Access Journals (Sweden)

    A.O. Kozak

    2014-11-01

    Full Text Available An influence of the substrate temperature in the range of 40-400 °C on the properties of the Si-C-N films deposited by plasma enhanced chemical vapor deposition (PECVD technique using hexamethyldisilazane is analyzed. Study of the structure, chemical bonding, surface morphology, mechanical properties and energy gap of the obtained films was carried out using X-ray diffraction, infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, optical measurements and nanoindentation. It was established that all the films were X-ray amorphous and had low surface roughness. Intensive hydrogen effusion from the films takes place, when substrate temperature increases up to 400 °C, which promotes a decrease of roughness and an increase in hardness and Young modules more than twice.

  2. Evolution of Ti(C,N)-based cermet microstructures

    Institute of Scientific and Technical Information of China (English)

    李晨辉; 熊惟皓; 余立新

    2002-01-01

    Two series of Ti(C,N)-based cermet materials originating from the same chemical composition but with different grain size distribution and sintered to different stages of the sintering cycle have been studied using SEM,TEM,EDX,and XRD.Much of the surrounding structure is formed during solid state sintering.During the solid state sintering,at first,the Mo and W rich (Ti,Mo,W)C inner rim is formed by the interaction among TiC,WC,and Mo2C;then the Mo and W lean (Ti,Mo,W)(C,N)outer rim is formed.During the liquid phase sintering,the outer rim of coarse grains grows rapidly throw a solution-reprecipitation process;also coarse grains grow by particle coalescence.The interface between coarse grain outer rim and binder is flat (crystal surface).

  3. Boundary Regularity of Correspondences in $\\mathbb{C}^n$

    Indian Academy of Sciences (India)

    Rasul Shafikov; Kaushal Verma

    2006-02-01

    Let ,′ be smooth, real analytic hypersurfaces of finite type in $\\mathbb{C}^n$ and $\\hat{f}$ a holomorphic correspondence (not necessarily proper) that is defined on one side of , extends continuously up to and maps to ′. It is shown that $\\hat{f}$ must extend across as a locally proper holomorphic correspondence. This is a version for correspondences of the Diederich–Pinchuk extension result for CR maps.

  4. Microstructure and tribological properties of TiN, TiC and Ti(C, N) thin films prepared by closed-field unbalanced magnetron sputtering ion plating

    International Nuclear Information System (INIS)

    TiN, TiC and Ti(C, N) films have been respectively prepared using closed-field unbalanced magnetron sputtering ion plating technology, with graphite target serving as the C supplier in an Ar-N2 mixture gas. Bonding states and microstructure of the films are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) in combination with transmission electron microscopy (TEM). The friction coefficients are measured by pin-on-disc test and the wear traces of deposited films are observed by optical microscope. Results show that the TiN film and Ti(C, N) film exhibit dense columnar structure while the TiC film exhibits a mixed microstructure of main nanocrystallite and little amorphous phases. The Ti(C, N) film has the highest microhardness value and the TiC film has the lowest. Because of small amount of pure carbon with sp2 bonds existing in the film, the friction coefficients of Ti(C, N) and TiC multilayer films are lower than that of TiN film. In addition, the multilayer structure of films also contributes visually to decrease of friction coefficients. The TiC film has extremely low friction coefficient while the wear ratio is the highest in all of the films. The results also show that the Ti(C, N) film has excellent anti-abrasion property.

  5. Possible interstellar formation of glycine through a concerted mechanism: a computational study on the reaction of CH2[double bond, length as m-dash]NH, CO2 and H2.

    Science.gov (United States)

    Nhlabatsi, Zanele P; Bhasi, Priya; Sitha, Sanyasi

    2016-07-27

    Glycine being the simplest amino acid and also having significant astrobiological implications, has meant that intensive investigations have been carried out in the past, starting from its detection in the interstellar medium (ISM) to analysis of meteorites and cometary samples and laboratory synthesis, as well as computational studies on the possible reaction paths. In this present work quantum chemical calculations have been performed to investigate the possible interstellar formation of glycine via two different paths; (1) in a two-step process via a dihydroxy carbene intermediate and (2) through a one-step concerted mechanism, starting from reactants like CH2[double bond, length as m-dash]NH, CO, CO2, H2O and H2. For the two reactions representing the carbene route, it was observed that the formation of dihydroxy carbene from either CO + H2O or CO2 + H2 is highly endothermic with large barrier heights, whereas the subsequent step of interaction of this carbene with CH2[double bond, length as m-dash]NH to give glycine is exothermic and the barrier is below the reactants. Based on this observation it is suggested that the formation of glycine via the carbene route is a least favourable or even unfavourable path. On the other hand, the two reactions CH2[double bond, length as m-dash]NH + CO + H2O and CH2[double bond, length as m-dash]NH + CO2 + H2 representing the concerted paths were found to be favourable in leading to the formation of glycine. After an extensive study on the first concerted reaction in our previous work (Phys. Chem. Chem. Phys., 2016, 18, 375-381), in this work a detailed investigation has been carried out for the second concerted reaction, CH2[double bond, length as m-dash]NH + CO2 + H2, which can possibly lead to the interstellar formation of glycine. It was observed that this reaction proceeds through a large barrier and at the same time the transition state shows prominent hydrogen dynamics, indicating a tunnelling possibility for this

  6. Inhibition of Hotspot Formation in Polymer Bonded Explosives Using an Interface Matching Low Density Polymer Coating at the Polymer–Explosive Interface

    OpenAIRE

    An, Qi; Goddard, William A.; Zybin, Sergey V.; Luo, Sheng-Nian

    2014-01-01

    In order to elucidate how shocks in heterogeneous materials affect decomposition and reactive processes, we used the ReaxFF reactive force field in reactive molecules dynamics (RMD) simulations of the effects of strong shocks (2.5 and 3.5 km/s) on a prototype polymer bonded explosive (PBX) consisting of cyclotrimethylene trinitramine (RDX) bonded to hydroxyl-terminated polybutadiene (HTPB). We showed earlier that shock propagation from the high density RDX to the low density polymer (RDX → Po...

  7. Does the Surface Matter? Hydrogen-Bonded Chain Formation of an Oxalic Amide Derivative in a Two- and Three-Dimensional Environment

    OpenAIRE

    Klappenberger, F.; Canas-Ventura, M. E.; Clair, S.; Pons, S.; Schlickum, U.; Qu, Z. R.; Strunskus, T.; Comisso, A.; Woll, C.; Brune, H.; Kern, K.; De Vita, A; Ruben, M.; Bartha, J. V.

    2008-01-01

    We report on a multi-technique investigation of the supramolecular organisation of N,N-diphenyl oxalic amide under differently dimensioned environments, namely three-dimensional (3D) in the bulk crystal, and in two dimensions on the Ag(111) surface as well as on the reconstructed Au(111) surface. With the help of Xray structure analysis and scanning tunneling microscopy (STM) we find that the molecules organize in hydrogen-bonded chains with the bonding motif qualitatively changed by the surf...

  8. Spatio-temporal patterns of C : N : P ratios in the northern Benguela upwelling regime

    Directory of Open Access Journals (Sweden)

    A. Flohr

    2013-06-01

    Full Text Available Dissolved carbon to nutrient ratios in the oceans' interior are remarkably consistent with the classical C : N : P : O2 Redfield ratio of 106 : 16 : 1 : 138 reflecting the mean composition of organic matter photosynthesized in the sunlit surface ocean. Deviations from the Redfield ratio indicate changes in the functioning of the biological carbon pump, which is driven and limited by the availability of nutrients. The northern Benguela coastal upwelling system (NBUS is known for losses of fixed nitrogen (N = NO3–, NO2– and NH4+ and the accumulation of phosphate (P in sub- and anoxic bottom waters and sediments of the Namibian shelf. To study the impact on the regional carbon cycle and consequences for the nutrient export from the BUS into the oligotrophic subtropical gyre of the South Atlantic Ocean we measured dissolved inorganic carbon (CT, oxygen (O2, and nutrient concentrations as well as the total alkalinity (AT in February 2011. Our results indicate that over the Namibian shelf the C : N : P : O2 ratio decreases to 106 : 16 : 1.6 : 138 because of phosphate efflux from sediments. N reduction further increase C : N and reduce N : P ratios in those regions where O2 concentrations in bottom waters are –1. However, off the shelf along the continental margin the mean C : N : P : O2 ratio is again close to the Redfield stoichiometry. Comparing the situation of 2011 with nutrient concentration data measured during 2 cruises in 2008 and 2009 implies that the amount of excess P that is created in the bottom waters on the shelf and its export into the subtropical gyre after upwelling varies through time. The magnitude of excess P formation and export is governed by inputs of excess N along with the South Atlantic Central Water (SACW flowing into the NBUS from the north as a poleward compensation current. Since excess N is produced by the remineralization of N-enriched biomass built up by N2-fixing organisms, factors controlling N2 fixation north

  9. 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.

  10. 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:

  11. Covalent bonding and band-gap formation in ternary transition-metal di-aluminides: Al4MnCo and related compounds

    International Nuclear Information System (INIS)

    In this paper we extend our previous study of the electronic structure of and bonding mechanism in transition-metal (TM) di-aluminides to ternary systems. We have studied the character of the bonding in Al4MnCo and related TM di-aluminides in the C11b (MoSi2) and C54 (TiSi2) crystal structures. A peculiar feature of the electronic structure of these TM di-aluminides is the existence of a semiconducting gap at the Fermi level. In our previous work we predicted a gap in Al2TM compounds where the TM atoms have eight valence electrons. Here we demonstrate that the semiconducting gap does not disappear if the TM sites are occupied by two different TMs, provided that the electron-per-atom ratio is conserved. Such a replacement substantially increases the class of possibly semiconducting TM di-aluminides. Substitution for 3d TMs of 4d or 5d TMs enhances the width of the gap. From the analysis of the charge density distribution and the crystal orbital overlap population, we conclude that the bonding between atoms has dominantly covalent character. This is confirmed not only by the enhanced charge density halfway between atoms, but also by the clear bonding-antibonding splitting of the electronic states. If the gaps between split states that correspond to all bonding configurations in the crystal have a common overlap at the Fermi level, the intermetallic compound becomes a semiconductor. However, the results of the total-energy calculations suggest that the existence of a band gap does not necessarily imply a stable structure. Strong covalent bonds can exist also in Al-TM structures where no band gap is observed. (author)

  12. A Phenomenographic Study on Chemical Bonding

    Directory of Open Access Journals (Sweden)

    Şenol Şen

    2013-12-01

    Full Text Available This study aims to reveal how students perceive and identify the concept of chemical bonding, and to identify and explain the misconceptions of students on this subject through phenomenographic research method, as well. The present study included 17 2nd grade students who enrolled to Inorganic Chemistry course in the Faculty of Education. Concept maps and lotus blossom technique were used as data collection tools in order to determine the perceptions and definitions of students about chemical bonding. Data analysis results determined the misconceptions of students about chemical bonding classified misconceptions under seven categories, which are, according to the results of the study, physical changes and bonding, ionic bond, formation of chemical bonding, the existence of chemical bonding, covalent bonds, metallic bonds and intermolecular bonding.

  13. Distinguishing Bonds.

    Science.gov (United States)

    Rahm, Martin; Hoffmann, Roald

    2016-03-23

    The energy change per electron in a chemical or physical transformation, ΔE/n, may be expressed as Δχ̅ + Δ(VNN + ω)/n, where Δχ̅ is the average electron binding energy, a generalized electronegativity, ΔVNN is the change in nuclear repulsions, and Δω is the change in multielectron interactions in the process considered. The last term can be obtained by the difference from experimental or theoretical estimates of the first terms. Previously obtained consequences of this energy partitioning are extended here to a different analysis of bonding in a great variety of diatomics, including more or less polar ones. Arguments are presented for associating the average change in electron binding energy with covalence, and the change in multielectron interactions with electron transfer, either to, out, or within a molecule. A new descriptor Q, essentially the scaled difference between the Δχ̅ and Δ(VNN + ω)/n terms, when plotted versus the bond energy, separates nicely a wide variety of bonding types, covalent, covalent but more correlated, polar and increasingly ionic, metallogenic, electrostatic, charge-shift bonds, and dispersion interactions. Also, Q itself shows a set of interesting relations with the correlation energy of a bond. PMID:26910496

  14. Features of microstructure formation of hard alloys on the base of TiC0.5N0.47 under nickel-molybdenum bond deficit

    International Nuclear Information System (INIS)

    Materials with low content of metal phase in TiCxNz-Ni-Mo system were prepared. Microstructure of solid alloys was studied. It is shown that sintering temperature should be increased in proportion to decrease of volumetric content of metallic bond when preparing low-porous solid alloys of TiC0.5N0.47-Ni-Mo system

  15. Discovery of molluscicidal and cercaricidal activities of 3-substituted quinazolinone derivatives by a scaffold hopping approach using a pseudo-ring based on the intramolecular hydrogen bond formation.

    Science.gov (United States)

    Guo, Wei; Zheng, Lv-Yin; Li, Yong-Dong; Wu, Ren-Miao; Chen, Qiang; Yang, Ding-Qiao; Fan, Xiao-Lin

    2016-06-10

    Discovery of novel topological agents against Oncomelania hupensis snails and cercariae remains a significant challenge in current Schistosomiasis control. A pseudo-ring formed from salicylanilide by an intramolecular hydrogen bond led to the discovery of 3-substituted quinazolinone derivatives which showed a potent molluscicidal and cercaricidal activities. PMID:27017555

  16. 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...

  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. 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.

  19. Sensor/ROIC Integration using Oxide Bonding

    OpenAIRE

    Ye, Zhenyu; Group, for the Fermilab Pixel R&D

    2009-01-01

    We explore the Ziptronix Direct Bond Interconnect technology for the integration of sensors and readout integrated circuits (ROICs) for high energy physics. The technology utilizes an oxide bond to form a robust mechanical connection between layers which serves to assist with the formation of metallic interlayer connections. We report on testing results of sample sensors bonded to ROICs and thinned to 100 microns.

  20. Thread bonds in molecules

    CERN Document Server

    Ivlev, B

    2015-01-01

    Unusual chemical bonds are proposed. Each bond is almost covalent but is characterized by the thread of a small radius $\\sim 0.6\\times 10^{-11}$cm, between two nuclei in a molecule. The main electron density is concentrated outside the thread as in a covalent bond. The thread is formed by the electron wave function which has a tendency to be singular on it. The singularity along the thread is cut off by electron "vibrations" due to the interaction with zero point electromagnetic oscillations. The electron energy has its typical value of (1-10)eV. Due to the small tread radius the uncertainty of the electron momentum inside the thread is large resulting in a large electron kinetic energy $\\sim 1 MeV$. This energy is compensated by formation of a potential well due to the reduction of the energy of electromagnetic zero point oscillations. This is similar to formation of a negative van der Waals potential. Thread bonds are stable and cannot be created or destructed in chemical or optical processes.

  1. Untersuchung der Struktur und des Kristallisationsverhaltens von Si-C-N- und Si-B-C-N-Precursorkeramiken mit Röntgen- und Neutronenbeugung

    OpenAIRE

    Haug, Jörg

    2002-01-01

    Die atomare Nahordnung und die mittelreiweitige Struktur amorpher Si-C-N- und Si-B-C-N-Keramiken wurde mit Röntgen- und Neutronenbeugung untersucht. Ein Vergleich der Strukturfaktoren S(Q) von Si-C-N-Keramiken, die sich in ihrer chemischen Zusammensetzung unterscheiden, mit den S(q) von amorphem Kohlenstoff und amorphem Si3N4, hat gezeigt, dass die S(q) der Keramiken ein gewichtetes Mittel dieser beiden S(q) darstellen. Die amorphen Si-C-N-Keramiken setzen sich also zuammen aus einer amorphen...

  2. Effect of fire on soil C, N and microbial biomass

    OpenAIRE

    Palese, Assunta; Giovannini, Giacomo; Lucchesi, Sergio; Dumontet, Stefano; Perucci, Piero

    2004-01-01

    - Effet des feux sur le C, N et sur la biomasse microbienne du sol. Le feu est un facteur écologique notable dans les environnements arbustifs et boisés. Dans cet article nous avons étudié les effets d'un feu expérimental. En particulier, nous avons étudié le carbone et l'azote soluble, le carbone et l'azote de la biomasse microbienne, le rapport champignons/bactéries et les activités enzymatiques 12 et 18 mois après le feu dans un sol classé Lithic Xerocrept. Le carbone soluble a été modifié...

  3. Study in electron microscopy the formation of the hybrid layer using adhesive systems One Coat and Single Bond Universal, at the Facultad de Medicina of the Universidad de Costa Rica

    International Nuclear Information System (INIS)

    The formation of the hybrid layer is observed in dental pieces in vitro, using systems of conventional adhesives (Single Bond 2 of 3M and One Coat of Coltene), with different times of acid etching, through the use of atomic force microscopy (AFM). The images of the hybrid layer obtained from samples prepared with adhesive systems are analyzed by AFM. Samples collected have been of dental pieces (molars and premolars) recently extracted and later placed in water. The pieces used have provided more surface to be observed under the microscope, greater accessibility to the be cut for its study, and to the great pieces have facilitated their placement on the Isomet low speed saw. The differences are evaluated between hybrid layers according the adhesive system used and the mode of application of the images obtained in the atomic force microscope. The adhesive system that has allowed the formation of a hybrid layer more appropriate between the adhesive system One Coat and the adhesive system Single Bond Universal is determined. The time of acid etching as variable of procedure is determined and has interfered with the formation of a hybrid layer more stable. The images evaluated that were provided by the atomic force microscope and compared with the images of electron microscopy of other studies, have determined that the AFM is without providing detailed information, as well as the appropriate images to evaluate the hybrid layer of the adhesive systems Single Bond 2 and One Coat of Coltene, or the different times of acid etching. Therefore, for this type of study, the image of choice must be of an electron microscope

  4. Effects of growing integrated layer [GIL] formation on bonding behavior between hydroxyapatite ceramics and Ti-based bulk metallic glasses via hydrothermal hot-pressing

    International Nuclear Information System (INIS)

    The authors successfully formed a bond between bioactive hydroxyapatite (HA) ceramics and titanium (Ti)-based bulk metallic glasses (Ti40Zr10Cu36Pd14: BMG) through a growing integrated layer (GIL) to develop a new type of biomaterial. The GILs were formed on the BMG surfaces by hydrothermal-electrochemical (HE) techniques. The BMG substrates were treated in a 5 mol/L NaOH solution at 90 deg. C for 10-120 min while a constant electric current of 0.5 mA/cm2 was maintained between the electrodes. Then the BMG disks with the GIL and a powder mixture of CaHPO4.2H2O and Ca(OH)2 were simultaneously treated with an autoclave for hydrothermal hot-pressing (HHP) (150 oC, 40 MPa, 2 h). Direct bonding between the HA ceramics and the BMG disks could be achieved through the above processing method. Consequently, to the best of our knowledge, this is the first demonstration of the usefulness of a series of hydrothermal techniques (HE and HHP) for direct bonding of bulk ceramics and bulk metallic materials.

  5. Thermally activated solvent bonding of polymers

    OpenAIRE

    Ng, S H; Tjeung, R. T.; Z. F. Wang; Lu, A. C. W.; Rodriguez, I.; de Rooij, Nicolaas F.

    2010-01-01

    We present a thermally activated solvent bonding technique for the formation of embedded microstructures 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 it...

  6. Diffusion bonding

    Science.gov (United States)

    Anderson, Robert C.

    1976-06-22

    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

  7. Preparation and sintering of Zr(C,N,O) phases

    International Nuclear Information System (INIS)

    The Zr(C,O,N) compounds form a great mono-phase zone belonging to the pseudoternary ZrO-ZrN-ZrC system.Theses phases have cubic crystalline structure with ao parameter depending on the C, O2 and N2 content.These phases have many potential applications in the manufacture of ceramic pieces utilizable as electronic conductors.The Zr (C,O,N) phases can be obtained from ZrO2 by carbonitriding reactions: that is carbothermal reduction and simultaneous nitriding.In this work a series of experiences of carbonitriding of zirconia under different conditions (temperatures between 1400 and 1600degC, times of 120 min, carbon content between 20 and 40%) in order to obtain suitable powders to be sintered.The XRD analysis shows the Zr(C,O,N) as the main products and β -ZrON as the only secondary product in proportions depending on the obtaining conditions.The variables employed were the C content and the reaction temperature.The Zr(C,O,N) content varies between 40 and 90% and tends to increase with the temperature and the carbon content whereas the β -ZrON phase varies between the 40 and 10 % decreasing its proportion with temperature and the carbon content.The oxidation resistance of these phases was studied by DTA-TG tests in air.Results show complete oxidation reaction at ∼500degC in air.The sintering of these materials was made on disks obtained by pressing of powders of Zr(C,N,O) contents higher than 90%.Sintering was performed in nitrogen atmosphere and temperatures between 1450 and 1620degC.Disks were characterized by pycnometry and Hg volumeter.The densities obtained were between 5 and 6,6g/cm3 with a tendency to increase with the Zr(C,N,O) phase content, the temperature and the sintering time.Sintered disks were characterized by dilatometry in N2

  8. Formation and Decomposition of Platinum–Thallium Bond, Kinetics and Mechanism. Structural Characterization of Some Metal Cyanides in the Solid State

    OpenAIRE

    Nagy, Péter

    2004-01-01

    The kinetic and mechanistic features of a new series ofplatinum-thallium cyano compounds containing a direct andunsupported by ligands metal-metal bond have been studied insolution, using standard mix–and–measurespectrophotometric technique and stopped–flow method.These reactions are interpreted as oxidative addition of the cspecies to the square planar Pt(CN)42-complex. Each of these processes was found to befirst-order in Pt(CN)42-, the corresponding TIIIIcomplex and a cyanide ion donating ...

  9. Formation of a Six-Coordinate fac-[Re(Co)3]+ Complex by the N-C bond cleavage of a potentially tetradentate ligand

    International Nuclear Information System (INIS)

    The rhenium(I) compound fac-[Re(CO)3(daa)]. Hpab.H2O (Hpab N,N'-(l,2-phenylene)bis(2'-aminobenzamide); Hdaa 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5,Br] with two equivalent of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. The compound was characterized by IR spectroscopy and X-ray crystallography, and daa is coordinated as a diamino amide via three nitrogen-donor atoms

  10. The kinetics of formation of single-stranded breaks and alkali-labile bonds in irradiated superhelical dna of PM 2 page

    International Nuclear Information System (INIS)

    The methods of neutral and alkaline agarose gel electrophoresis were used to study the dose-dependence of the concentration of different DNA species formed under the effect of X-irradiation of solutions of superhelical DNA of PM2 phage. The experimental results are described by a model in which a considerable role is attributed to conjugated lesions in both DNA strands (single-stranded breaks and alkali--labile-bonds). A study was made of the influence of metronidazole and TAN on radiation-induced changes in DNA

  11. First-principles study of B, C, N and F doped graphene-like MgO monolayer

    Science.gov (United States)

    Wu, Ping; Huang, Min; Cheng, Wenjing; Tang, Fuling

    2016-07-01

    Based on the first-principles calculations, we have investigated the stable geometries, electronic and magnetic properties of the graphene-like MgO monolayer with O atom substituted by B, C, N, and F atoms. The formation energy decreases in the order of B>C>N>F, which may be influenced by the different electronegativities. The band gaps of p-type doped MgO monolayers are tunable due to the emergence of impurity states within the band gap, while F-doped MgO monolayer realizes the transition from semiconductor to metal. The results show that p-type doped MgO monolayer exhibit magnetic behaviors due to polarizations of dopants and surrounding Mg or O atoms near the dopants, while no magnetism is observed in the case of F doped MgO monolayer. These results are potentially useful for spintronic applications and the development of magnetic nanostructures.

  12. Covalent Bond Formation of Uranium Ions in a LiCl-KCl Eutectic Melt at 450 .deg. C: Spectroscopic Evidence from Their UV-VIS Spectra

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Young Hwan; Bae, Sang Eun; Oh, Seung Yong; Kim, Jong Yun; Song, Kyu Seok; Yeon, Jei Won [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2012-05-15

    Molten salt based electrochemical processes, so called pyroprocessing, have been proposed as a new option for the advanced spent nuclear fuel cycle. One of the important steps in the pyroprocessing of the spent nuclear fuel is the electrorefining of uranium in molten LiCl based media. The knowledge on the electronic states of uranium ions in molten salt media is essential for understanding their optical, electrochemical properties. Electronic absorption spectra may provide detailed information on the chemical state of the ions. Several studies have been reported for the past decades on the electronic absorption spectra of uranium ion species in high temperature molten salt media. However, no attempts have been made to interpret the spectra with respect to the electronic state and chemical bonding point of view. Here, report the results of insitu measurement and interpretation of the electronic spectra of the U(III) and U(IV) ion species in a LiCl- KCl eutectic melt at in terms of chemical bonding

  13. Pi Bond Orders and Bond Lengths

    Science.gov (United States)

    Herndon, William C.; Parkanyi, Cyril

    1976-01-01

    Discusses three methods of correlating bond orders and bond lengths in unsaturated hydrocarbons: the Pauling theory, the Huckel molecular orbital technique, and self-consistent-field techniques. (MLH)

  14. Carbon–Hydrogen Bond Activation, C–N Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand

    OpenAIRE

    Mindiola, Daniel J.; Waterman, Rory; Iluc, Vlad M.; Cundari, Thomas R.; Hillhouse, Gregory L.

    2014-01-01

    The three-coordinate imidos (dtbpe)Ni=NR (dtbpe = t Bu2PCH2CH2P t Bu2, R = 2,6- i Pr2C6H3, 2,4,6-Me3C6H2 (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni–N double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC≡CPh to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C≡CPh). In the case of R = 2,6- i Pr2C6H3, reductive carbonylation results in formation of the (dtbpe)Ni(CO)2 along with the N–C coupled product keteneimine PhCH=C=N(2,6- i P...

  15. LAMMPS Framework for Dynamic Bonding and an Application Modeling DNA

    DEFF Research Database (Denmark)

    Svaneborg, Carsten

    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...

  16. Iodide, azide, and cyanide complexes of (N,C), (N,N), and (N,O) metallacycles of tetra- and pentavalent uranium

    International Nuclear Information System (INIS)

    In contrast to the neutral macrocycle [UN*2(N,C)] (1) [N* = N(SiMe3)3; N,C = CH2SiMe2N-(SiMe3)] which was quite inert toward I2, the anionic bismetallacycle [NaUN*(N,C)2] (2) was readily transformed into the enlarged monometallacycle [UN*(N,N)I] (4) [N,N = (Me3Si)NSiMe2CH2CH2SiMe2N(SiMe3)] resulting from C-C coupling of the two CH2 groups, and [NaUN*(N,O)2] (3) [N,O = OC(=CH2)SiMe2N(SiMe3)], which is devoid of any U-C bond, was oxidized into the UV bismetallacycle [Na{UN*(N,O)2}2(μ-I)] (5). Sodium amalgam reduction of 4 gave the U(III) compound [UN*(N,N)] (6). Addition of MN3 or MCN to the (N,C), (N,N), and (N,O) metallacycles 1, 4, and 5 led to the formation of the anionic azide or cyanide derivatives M[UN*2(N,C)(N3)] [M = Na, 7a or Na(15-crown-5), 7b], M[UN*2(N,C)(CN)] [M = NEt4, 8a or Na(15-crown-5), 8b or K(18-crown-6), 8c], M[UN*(N,N)(N3)2] [M = Na, 9a or Na(THF)4, 9b], [NEt4][UN*(N,N)(CN)2] (10), M[UN*(N,O)2(N3)] [M = Na, 11a or Na(15-crown-5), 11b], M[UN*(N,O)2(CN)] [M = NEt4, 12a or Na(15-crown-5), 12b]. In the presence of excess iodine in THF, the cyanide 12a was converted back into the iodide 5, while the azide 11a was transformed into the neutral UV complex [U(N{SiMe3}-SiMe2C{CHI}O)2I(THF)] (13). The X-ray crystal structures of 4, 7b, 8a-c, 9b, 10, 12b, and 13 were determined. (authors)

  17. Iodide, azide, and cyanide complexes of (N,C), (N,N), and (N,O) metallacycles of tetra- and pentavalent uranium.

    Science.gov (United States)

    Bénaud, Olivier; Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

    2011-12-01

    In contrast to the neutral macrocycle [UN*(2)(N,C)] (1) [N* = N(SiMe(3))(3); N,C = CH(2)SiMe(2)N(SiMe(3))] which was quite inert toward I(2), the anionic bismetallacycle [NaUN*(N,C)(2)] (2) was readily transformed into the enlarged monometallacycle [UN*(N,N)I] (4) [N,N = (Me(3)Si)NSiMe(2)CH(2)CH(2)SiMe(2)N(SiMe(3))] resulting from C-C coupling of the two CH(2) groups, and [NaUN*(N,O)(2)] (3) [N,O = OC(═CH(2))SiMe(2)N(SiMe(3))], which is devoid of any U-C bond, was oxidized into the U(V) bismetallacycle [Na{UN*(N,O)(2)}(2)(μ-I)] (5). Sodium amalgam reduction of 4 gave the U(III) compound [UN*(N,N)] (6). Addition of MN(3) or MCN to the (N,C), (N,N), and (N,O) metallacycles 1, 4, and 5 led to the formation of the anionic azide or cyanide derivatives M[UN*(2)(N,C)(N(3))] [M = Na, 7a or Na(15-crown-5), 7b], M[UN*(2)(N,C)(CN)] [M = NEt(4), 8a or Na(15-crown-5), 8b or K(18-crown-6), 8c], M[UN*(N,N)(N(3))(2)] [M = Na, 9a or Na(THF)(4), 9b], [NEt(4)][UN*(N,N)(CN)(2)] (10), M[UN*(N,O)(2)(N(3))] [M = Na, 11a or Na(15-crown-5), 11b], M[UN*(N,O)(2)(CN)] [M = NEt(4), 12a or Na(15-crown-5), 12b]. In the presence of excess iodine in THF, the cyanide 12a was converted back into the iodide 5, while the azide 11a was transformed into the neutral U(V) complex [U(N{SiMe(3)}SiMe(2)C{CHI}O)(2)I(THF)] (13). The X-ray crystal structures of 4, 7b, 8a-c, 9b, 10, 12b, and 13 were determined. PMID:22050237

  18. Access to novel fluorovinylidene ligands via exploitation of outer-sphere electrophilic fluorination: new insights into C-F bond formation and activation.

    Science.gov (United States)

    Milner, Lucy M; Hall, Lewis M; Pridmore, Natalie E; Skeats, Matthew K; Whitwood, Adrian C; Lynam, Jason M; Slattery, John M

    2016-01-19

    Metal vinylidene complexes are widely encountered, or postulated, as intermediates in a range of important metal-mediated transformations of alkynes. However, fluorovinylidene complexes have rarely been described and their reactivity is largely unexplored. By making use of the novel outer-sphere electrophilic fluorination (OSEF) strategy we have developed a rapid, robust and convenient method for the preparation of fluorovinylidene and trifluoromethylvinylidene ruthenium complexes from non-fluorinated alkynes. Spectroscopic investigations (NMR and UV/Vis), coupled with TD-DFT studies, show that fluorine incorporation results in significant changes to the electronic structure of the vinylidene ligand. The reactivity of fluorovinylidene complexes shows many similarities to non-fluorinated analogues, but also some interesting differences, including a propensity to undergo unexpected C-F bond cleavage reactions. Heating fluorovinylidene complex [Ru(η(5)-C5H5)(PPh3)2(C[double bond, length as m-dash]C{F}R)][BF4] led to C-H activation of a PPh3 ligand to form an orthometallated fluorovinylphosphonium ligand. Reaction with pyridine led to nucleophilic attack at the metal-bound carbon atom of the vinylidene to form a vinyl pyridinium species, which undergoes both C-H and C-F activation to give a novel pyridylidene complex. Addition of water, in the presence of chloride, leads to anti-Markovnikov hydration of a fluorovinylidene complex to form an α-fluoroaldehyde, which slowly rearranges to its acyl fluoride isomer. Therefore, fluorovinylidenes ligands may be viewed as synthetic equivalents of 1-fluoroalkynes providing access to reactivity not possible by other routes. PMID:26701305

  19. 3D micro-CT analysis of void formations and push-out bonding strength of resin cements used for fiber post cementation

    Science.gov (United States)

    2016-01-01

    PURPOSE To investigate the void parameters within the resin cements used for fiber post cementation by micro-CT (µCT) and regional push-out bonding strength. MATERIALS AND METHODS Twenty-one, single and round shaped roots were enlarged with a low-speed drill following by endodontic treatment. The roots were divided into three groups (n=7) and fiber posts were cemented with Maxcem Elite, Multilink N and Superbond C&B resin cements. Specimens were scanned using µCT scanner at resolution of 13.7 µm. The number, area, and volume of voids between dentin and post were evaluated. A method of analysis based on the post segmentation was used, and coronal, middle and apical thirds considered separately. After the µCT analysis, roots were embedded in epoxy resin and sectioned into 2 mm thick slices (63 sections in total). Push-out testing was performed with universal testing device at 0.5 mm/min cross-head speed. Data were analyzed with Kruskal–Wallis and Mann–Whitney U tests (α=.05). RESULTS Overall, significant differences between the resin cements and the post level were observed in the void number, area, and volume (P.05). CONCLUSION µCT proved to be a powerful non-destructive 3D analysis tool for visualizing the void parameters. Multilink N had the lowest void parameters. When efficiency of all cements was evaluated, direct relationship between the post region and push-out bonding strength was not observed. PMID:27141253

  20. 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

  1. Stabilization of (dG-dC)n.(dG-dC)n in the Z conformation by a crosslinking reaction.

    OpenAIRE

    Castleman, H; Hanau, L H; Erlanger, B. F.

    1983-01-01

    (dG-dC)n.(dG-dC) was converted to the Z conformer by heating in the presence of Mn++n. Reaction of this preparation with the crosslinking reagent, DL-diepoxybutane (DEB), stabilized this conformer so that it retained its structure even when returned to conditions that favored reversion to the B conformation. Treatment of the crosslinked Z conformer with periodate caused scission of the crosslink, allowing reversion to the B conformer. Reaction of (dG-dC)n.(dG-dC)n in the B conformation with D...

  2. Specific collapse followed by slow hydrogen-bond formation of β-sheet in the folding of single-chain monellin

    Science.gov (United States)

    Kimura, Tetsunari; Uzawa, Takanori; Ishimori, Koichiro; Morishima, Isao; Takahashi, Satoshi; Konno, Takashi; Akiyama, Shuji; Fujisawa, Tetsuro

    2005-01-01

    Characterization of the conformational landscapes for proteins with different secondary structures is important in elucidating the mechanism of protein folding. The folding trajectory of single-chain monellin composed of a five-stranded β-sheet and a helix was investigated by using a pH-jump from the alkaline unfolded to native state. The kinetic changes in the secondary structures and in the overall size and shape were measured by circular dichroism spectroscopy and small-angle x-ray scattering, respectively. The formation of the tertiary structure was monitored by intrinsic and extrinsic fluorescence. A significant collapse was observed within 300 μs after the pH-jump, leading to the intermediate with a small amount of secondary and tertiary structures but with an overall oblate shape. Subsequently, the stepwise formation of secondary and tertiary structures was detected. The current observation was consistent with the theoretical prediction that a more significant collapse precedes the formation of secondary structures in the folding of β-sheet proteins than that of helical proteins [Shea, J. E., Onuchic, J. N. & Brooks, C. L., III (2002) Proc. Natl. Acad. Sci. USA 99, 16064–16068]. Furthermore, it was implied that the initial collapse was promoted by the formation of some specific structural elements, such as tight turns, to form the oblate shape. PMID:15710881

  3. Specific collapse followed by slow hydrogen-bond formation of beta-sheet in the folding of single-chain monellin.

    Science.gov (United States)

    Kimura, Tetsunari; Uzawa, Takanori; Ishimori, Koichiro; Morishima, Isao; Takahashi, Satoshi; Konno, Takashi; Akiyama, Shuji; Fujisawa, Tetsuro

    2005-02-22

    Characterization of the conformational landscapes for proteins with different secondary structures is important in elucidating the mechanism of protein folding. The folding trajectory of single-chain monellin composed of a five-stranded beta-sheet and a helix was investigated by using a pH-jump from the alkaline unfolded to native state. The kinetic changes in the secondary structures and in the overall size and shape were measured by circular dichroism spectroscopy and small-angle x-ray scattering, respectively. The formation of the tertiary structure was monitored by intrinsic and extrinsic fluorescence. A significant collapse was observed within 300 micros after the pH-jump, leading to the intermediate with a small amount of secondary and tertiary structures but with an overall oblate shape. Subsequently, the stepwise formation of secondary and tertiary structures was detected. The current observation was consistent with the theoretical prediction that a more significant collapse precedes the formation of secondary structures in the folding of beta-sheet proteins than that of helical proteins [Shea, J. E., Onuchic, J. N. & Brooks, C. L., III (2002) Proc. Natl. Acad. Sci. USA 99, 16064-16068]. Furthermore, it was implied that the initial collapse was promoted by the formation of some specific structural elements, such as tight turns, to form the oblate shape. PMID:15710881

  4. Effect of heating rate on the mechanical properties and microstructure of Ti(C,N)-based cermets

    International Nuclear Information System (INIS)

    An appropriate heating rate in the sintering process is crucial to obtain the Ti(C,N)-based cermets with superior properties. In this paper, Ti(C,N)-based cermets were sintered to investigate the influence of heating rate on the mechanical properties and microstructure of the cermet materials. The transverse rupture strength (TRS), Vickers hardness (HV) and fracture toughness (KIC) were tested. The microstructure, indention crack, fracture morphology and phase composition of the cermets were also studied by scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The results reveal that the heating rate has a great influence on the mechanical properties and microstructure of Ti(C,N)-based cermets. The cermets sintered at the heating rate of 3 °C/min between 1300 °C and 1430 °C have the optimum comprehensive mechanical properties with a transverse rupture strength of 1605±107 MPa, a hardness of 12.02±0.25 GPa and a fracture toughness of 10.73±0.40 MPa m1/2. The heating rate can affect the reaction among the constituents of Ti(C,N)-based cermets and then influence the elements distribution in the core–rim microstructures and the lattice parameter of Ti(C,N) phase. When the heating rate is between 2 °C/min and 5 °C/min, the lower the heating rate is, the coarser the Ti(C,N) grains become. A higher heating rate is detrimental to the formation of core–rim microstructures, and a lower heating rate can result in grain coarsening and inhomogeneous microstructure. The observation of indention cracks and fracture surfaces show that the intergranular cracks and intergranular fractures mainly occur in the cermets with larger binder mean free path and medium grains. While the cleavage fractures appear more in the cermets with grain coarsening, and the transgranular fractures exist more in the cermets with non-fully developed fine grains

  5. Effect of heating rate on the mechanical properties and microstructure of Ti(C,N)-based cermets

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Qingzhong; Ai, Xing, E-mail: aixingsdu@163.com; Zhao, Jun; Zhang, Hongshan; Qin, Wenzhen; Gong, Feng

    2015-03-25

    An appropriate heating rate in the sintering process is crucial to obtain the Ti(C,N)-based cermets with superior properties. In this paper, Ti(C,N)-based cermets were sintered to investigate the influence of heating rate on the mechanical properties and microstructure of the cermet materials. The transverse rupture strength (TRS), Vickers hardness (HV) and fracture toughness (K{sub IC}) were tested. The microstructure, indention crack, fracture morphology and phase composition of the cermets were also studied by scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The results reveal that the heating rate has a great influence on the mechanical properties and microstructure of Ti(C,N)-based cermets. The cermets sintered at the heating rate of 3 °C/min between 1300 °C and 1430 °C have the optimum comprehensive mechanical properties with a transverse rupture strength of 1605±107 MPa, a hardness of 12.02±0.25 GPa and a fracture toughness of 10.73±0.40 MPa m{sup 1/2}. The heating rate can affect the reaction among the constituents of Ti(C,N)-based cermets and then influence the elements distribution in the core–rim microstructures and the lattice parameter of Ti(C,N) phase. When the heating rate is between 2 °C/min and 5 °C/min, the lower the heating rate is, the coarser the Ti(C,N) grains become. A higher heating rate is detrimental to the formation of core–rim microstructures, and a lower heating rate can result in grain coarsening and inhomogeneous microstructure. The observation of indention cracks and fracture surfaces show that the intergranular cracks and intergranular fractures mainly occur in the cermets with larger binder mean free path and medium grains. While the cleavage fractures appear more in the cermets with grain coarsening, and the transgranular fractures exist more in the cermets with non-fully developed fine grains.

  6. Molecular dynamics simulations of precursor-derived Si-C-N ceramics

    OpenAIRE

    Resta, Nicoletta

    2005-01-01

    The microscopic mechanisms behind the transformation from the amorphous Si-C-N ceramics to the polycrystalline material are studied by isolating its fundamental steps. Si-C-N amorphous ceramics, amorphous and crystalline silicon carbide, and carbon, are numerically modeled by means of classical molecular dynamics. The interatomic interactions are modeled by the Tersoff many-body empirical potential. In the first part amorphous Si-C-N materials are studied. We show how the atomic structures...

  7. The reaction mechanism of the enantioselective Tsuji allylation: inner-sphere and outer-sphere pathways, internal rearrangements, and asymmetric C–C bond formation

    OpenAIRE

    Keith, John A.; Behenna, Douglas C.; Sherden, Nathaniel; Mohr, Justin T.; Ma, Sandy; Marinescu, Smaranda C.; Nielsen, Robert J.; Oxgaard, Jonas; Stoltz, Brian M.; Goddard, William A.

    2012-01-01

    We use first principles quantum mechanics (density functional theory) to report a detailed reaction mechanism of the asymmetric Tsuji allylation involving prochiral nucleophiles and nonprochiral allyl fragments, which is consistent with experimental findings. The observed enantioselectivity is best explained with an inner-sphere mechanism involving the formation of a 5-coordinate Pd species that undergoes a ligand rearrangement, which is selective with regard to the prochiral faces of the int...

  8. Direct carbon-carbon bond formation via reductive soft enolization: a syn-selective Mannich addition of α-iodo thioesters.

    Science.gov (United States)

    Truong, Ngoc; Sauer, Scott J; Seraphin-Hatcher, Cyndie; Coltart, Don M

    2016-08-16

    The β-amino carboxylic acid moiety is a key feature of numerous important biologically active compounds. We describe a syn-selective direct Mannich addition reaction that uses α-iodo thioesters and sulfonyl imines and produces β-amino thioesters. Enolate formation is achieved by reductive soft enolization. The products of the reaction provide straightforward access to biologically important β-lactams through a variety of known reactions. PMID:27492274

  9. Kinetic effect of boron on the thermal stability of Si-(B-)C-N polymer-derived ceramics

    International Nuclear Information System (INIS)

    The isothermal mass loss of two polymer-derived ceramics with compositions SiC1.4N0.9 and SiC1.5N1.0B0.05 were measured as a function of time using thermal gravimetric analysis at various temperatures ranging between 1580 and 1720 deg. C. The process of mass loss, attributed to the reaction Si3N4 + 3C → 3SiC + 2N2↑, takes substantially more time for the boron-containing ceramic compared with the boron-free one. The continuous formation of SiC crystallites as the product of the reaction between Si3N4 and C was revealed through X-ray diffraction (XRD) measurements during the course of the reaction. The kinetics of this reaction was studied using a generalized model for the analysis of chemical reaction kinetics. Consequently, the effective activation energies for the Si3N4 degradation were estimated to be 11.6 ± 0.5 eV and 17.1 ± 0.7 eV for the Si-C-N and Si-B-C-N ceramics, respectively. Moreover, the results obtained indicate that the dominant mechanisms of the Si3N4 degradation are strongly influenced by the presence of boron. For the Si-C-N ceramic, the chemical reaction at interfaces of the reactants and the crystallization of SiC as the reaction product are proposed to be the main probable stages controlling the progress of the investigated reaction. However, the local diffusion of C out of BNCx turbostratic layers surrounding the Si3N4 nanocrystals and the gas (N2) release from the reaction zone are suggested to be the most plausible processes limiting the progress of Si3N4 degradation for the Si-B-C-N ceramic.

  10. Thermochemistry and constitution of precursor-derived Si-(B-)C-N ceramics

    OpenAIRE

    Peng, Jianqiang

    2002-01-01

    In the present work the phase equilibria and phase reactions of Si-C-N and Si-B-C-N precursor-derived ceramics were studied by means of the CALPHAD method combined with experimental studies: e. g. DTA/TG, XRD, HRTEM and SEM. Thermodynamic calculations of different types of phase diagrams, phase fraction diagrams and phase composition diagrams in regard to the reaction behavior of Si-C-N and Si-B-C-N ceramics were carried out using software such as THERMO-CALC. Consistent Scheil's reaction sch...

  11. 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 toluenebond cleavage of ethylbenzene than the most reactive diiron system reported so far. The KIE for the reaction 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 . PMID:26970337

  12. Study on Properties of Ti(C,N)/TiN Multi-Element-layer Films Plus Nanometer Lubrication Dry Films

    Institute of Scientific and Technical Information of China (English)

    HUANG Yuan-lin; MA Shi-ning; LI Chang-qing; ZHU You-li

    2004-01-01

    Ti(C,N)/TiN multi-element-layer films was deposited on aluminium alloy substrates by using multi-arc ion plating. The microhardness of the films was 2000HV0.1 which was nearly 21 times of that of the substrates. XRD analysis show that the main composition of the composite films system were Ti(C,N), TiN, Al3Ti, Al and a little Ti2N. The presence of Al3Ti new phase in the interface of the films/substrates indicated some metallurgical bonding between them, which implies higher adhesive strength of the films/substrates system. Pin-on-disc tests showed that the wear resistance of the substrates was improved substantially. However, the coefficient of friction of the films/substrate system was high (μ=0.66),which resulted in the wear of the counterparts. To reduce the coefficient of friction, nanometer lubrication dry films was applied on top of the multi-element-layer films to form composite films system and subsequent wear tests showed that the resulting composite films led to reduction of the coefficient of friction from 0.66 to 0.16. Meanwhile, wear mass loss of the counterpart was reduced from 1.29 mg to 0.02 mg, so that increased wear resistance and reduced friction effects were achieved.

  13. The Microstructure, Chemical Characteristic and Crystallization Behavior of the Polymer Derived Si-B-C-N Amorphous Ceramic

    Science.gov (United States)

    Gao, Dond; Zhang, Fanwei; Zhang, Yue; Song, Yang; Shi, Xiaobin

    Amorphous materials of the Si-(B)-C-N system have recently attracted considerable interest because of its hardness, low density, durability at extremely high temperature and easy to be prepared from precursor compounds by polymer route. The materials show a great potential to be used in the field of the Thermal Protective System (TPS) for the aircrafts, while the microstructure and chemical configuration are still not clearly revealed due to its complicated covalent character for this multi-component amorphous material. This paper focused on the characterization of polymer derived Si-(B)-C-N amorphous ceramic, various method were employed in order to obtain accurate information about the microstructure, chemical composition, bonding mode of components, such as TEM, EPMA, NMR and FT-IR. SiC crystalline was found existing in the amorphous glass, which indicates the preparation process was achieved accompanied by crystallization of SiC from polymer precursor. The microstructure of the researched material was analyzed and relative accurate chemical composition was obtained on the basis of characterization result, furthermore the covalent character of the amorphous material was deduced according to the characterization results obtained.

  14. Paint-Bonding Improvement for 2219 Aluminum Alloy

    Science.gov (United States)

    Daech, Alfred F.; Cibula, Audrey Y.

    1987-01-01

    Bonding of adhesives and primers to 2219 aluminum alloy improved by delaying rinse step in surface-treatment process. Delaying rinse allows formation of rougher surface for stronger bonding and greater oxide buildup.

  15. Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    International Nuclear Information System (INIS)

    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 (ε = 116 dm3 mol−1 cm−1) supports the presence of Cu(II) centres

  16. tri-n-butyltin hydride-mediated radical reaction of a 2-iodobenzamide: formation of an unexpected carbon-tin bond

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Marcelo T.; Alves, Rosemeire B.; Cesar, Amary [Universidade Federal de Minas Gerais, Belo Horizonte, MG (Brazil). Dept. de Quimica; Prado, Maria Auxiliadora F.; Alves, Ricardo J.; Queiroga, Carla G. [Federal de Minas Gerais, Belo Horizonte, MG (Brazil). Faculdade de Farmacia. Dept. de Produtos Farmaceuticos]. E-mail: pradora@farmacia.ufmg.br; Santos, Leonardo S. [Universidad de Talca (Chile). Inst. de Quimica de Recursos Naturales; Eberlin, Marcos N. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica

    2007-03-15

    The tri-n-butyltin hydride-mediated reaction of methyl 2,3-di-O-benzyl-4-O-trans-cinnamyl- 6-deoxy-6-(2-iodobenzoylamino)-{alpha}-D-galactopyranoside afforded an unexpected aryltributyltin compound. The structure of this new tetraorganotin(IV) product has been elucidated by {sup 1}H, {sup 13}C NMR spectroscopy, COSY and HMQC experiments and electrospray ionization mass spectrometry (ESI-MS). The formation of this new compound via a radical coupling reaction and a radical addition-elimination process is discussed. (author)

  17. FORMATION OF C-I COVALENT BOND BETWEEN THE SINGLE-WALL CARBON NANOTUBES AND SODIUM IODIDE%单壁碳纳米管与碘化钠形成C-I共价键

    Institute of Scientific and Technical Information of China (English)

    黄洁华; 林治卿; 刘丽华; 刘焕亮; 胡传禄; 程文文; 袭著革

    2011-01-01

    目的 探讨单壁碳纳米管与碘化钠反应后C-I共价键的生成及其表征,为单壁碳纳米管放射性碘标记及观察其在生物体内分布提供实验参考数据.方法 采用1odogen方法制备碘化的单壁碳纳米管(I-SWCNTs),然后用透射电子显微镜(TEM)及X射线光电子能谱仪(XPS)对碳碘结合及C-I共价键的形成进行表征.结果 TEM成像和成分分析显示,与未经处理的SWCNTs 对比,处理后的产物其管壁不再光滑,有缺口,其上结合有碘.XPS检测发现,碘与SWCNTs形成C-I共价键,处理后产物的碘电子结合能与具有C-I共价键的参考物硝基碘苯基本一致,而与具有离子性质的NaI的结合能不同.结论 用Iodogen法能使SWCNTs与NaI结合生成C-I共价键.%Objective To explore the formation and characterization of C-I covalent bond between the singlewall carbon nanotubes (SWCNTs) and NaI in order to provide experimental reference data for radioiodination of SWCNTs and oberving its biodistribution. Methods IMogen method was used to synthesize iodinated SWCNTs (I-SWCNTs) in which iodine was covalently bound to SWCNTs. The formation of C-I bond was proved by transmission electron microscope(TEM) as well as X-ray photoelectron spectroscopy (XPS) . Results The image and component analyses TEM showed that the wall of the tubes of I-SWCNTs became rough, with gaps, and bound iodine, as compared to that of the tmtreated products. XPS spectra showed that the binding energy of iodine of I-SWCNTs was analogous to that of nitroiodobenzene and different from that of ionic NaI. Conclusion The C-I covalent bond between the single-wall carbon nanotubes and NaI could be formed by the Iodogen method.

  18. Intramolecular versus intermolecular hydrogen bonding in solution

    OpenAIRE

    Vliegenthart, J. F. G.; Kroon, Jan; Kroon-Batenburg, L.M.J.; Leeflang, B.R.

    1994-01-01

    The balance between intra- and intermolecular hydrogen bonding is studied for a solution of methyl beta-cellobioside in water and dimethylsulfoxide by 1H NMR and molecular dynamics simulations. In water O(3) predominantly interacts with water molecules, whereas in dimethylsulfoxide it is intramolecularly hydrogen bonded to O(5Œ). The temperature coefficient of the chemical shift of the hydroxy groups appears to be a reliable indicator of intermolecular hydrogen-bond formation, whereas the ex...

  19. Sensor/ROIC Integration using Oxide Bonding

    International Nuclear Information System (INIS)

    We explore the Ziptronix Direct Bond Interconnect (DBI) technology (2) for the integration of sensors and readout integrated circuits (ROICs) for high energy physics. The technology utilizes an oxide bond to form a robust mechanical connection between layers which serves to assist with the formation of metallic interlayer connections. We report on testing results of sample sensors bonded to ROICs and thinned to 100 (micro)m

  20. Sensor/ROIC Integration using Oxide Bonding

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Zhenyu; /Fermilab

    2009-02-01

    We explore the Ziptronix Direct Bond Interconnect (DBI) technology [2] for the integration of sensors and readout integrated circuits (ROICs) for high energy physics. The technology utilizes an oxide bond to form a robust mechanical connection between layers which serves to assist with the formation of metallic interlayer connections. We report on testing results of sample sensors bonded to ROICs and thinned to 100 {micro}m.

  1. Formation, Characterization, and O-O Bond Activation of a Peroxomanganese(III) Complex Supported by a Cross-Clamped Cyclam Ligand.

    Science.gov (United States)

    Colmer, Hannah E; Howcroft, Anthony W; Jackson, Timothy A

    2016-03-01

    Although there have been reports describing the nucleophilic reactivity of peroxomanganese(III) intermediates, as well as their conversion to high-valent oxo-bridged dimers, it remains a challenge to activate peroxomanganese(III) species for conversion to high-valent, mononuclear manganese complexes. Herein, we report the generation, characterization, and activation of a peroxomanganese(III) adduct supported by the cross-clamped, macrocyclic Me2EBC ligand (4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). This ligand is known to support high-valent, mononuclear Mn(IV) species with well-defined spectroscopic properties, which provides an opportunity to identify mononuclear Mn(IV) products from O-O bond activation of the corresponding Mn(III)-peroxo adduct. The peroxomanganese(III) intermediate, [Mn(III)(O2)(Me2EBC)](+), was prepared at low-temperature by the addition of KO2 to [Mn(II)(Cl)2(Me2EBC)] in CH2Cl2, and this complex was characterized by electronic absorption, electron paramagnetic resonance (EPR), and Mn K-edge X-ray absorption (XAS) spectroscopies. The electronic structure of the [Mn(III)(O2)(Me2EBC)](+) intermediate was examined by density functional theory (DFT) and time-dependent (TD) DFT calculations. Detailed spectroscopic investigations of the decay products of [Mn(III)(O2)(Me2EBC)](+) revealed the presence of mononuclear Mn(III)-hydroxo species or a mixture of mononuclear Mn(IV) and Mn(III)-hydroxo species. The nature of the observed decay products depended on the amount of KO2 used to generate [Mn(III)(O2)(Me2EBC)](+). The Mn(III)-hydroxo product was characterized by Mn K-edge XAS, and shifts in the pre-edge transition energies and intensities relative to [Mn(III)(O2)(Me2EBC)](+) provide a marker for differences in covalency between peroxo and nonperoxo ligands. To the best of our knowledge, this work represents the first observation of a mononuclear Mn(IV) center upon decay of a nonporphyrinoid Mn(III)-peroxo center. PMID:26908013

  2. Formation versus Hydrolysis of the Peptide Bond from a Quantum-mechanical Viewpoint: The Role of Mineral Surfaces and Implications for the Origin of Life

    Directory of Open Access Journals (Sweden)

    2009-02-01

    Full Text Available The condensation (polymerization by water elimination of molecular building blocks to yield the first active biopolymers (e.g. of amino acids to form peptides during primitive Earth is an intriguing question that nowadays still remains open since these processes are thermodynamically disfavoured in highly dilute water solutions. In the present contribution, formation and hydrolysis of glycine oligopeptides occurring on a cluster model of sanidine feldspar (001 surface have been simulated by quantum mechanical methods. Results indicate that the catalytic interplay between Lewis and Brønsted sites both present at the sanidine surface, in cooperation with the London forces acting between the biomolecules and the inorganic surface, plays a crucial role to: i favour the condensation of glycine to yield oligopeptides as reaction products; ii inhibit the hydrolysis of the newly formed oligopeptides. Both facts suggest that mineral surfaces may have helped in catalyzing, stabilizing and protecting from hydration the oligopeptides formed in the prebiotic era.

  3. Effect of boron on the thermodynamic stability of amorphous polymer-derived Si-(B-)C-N ceramics

    International Nuclear Information System (INIS)

    The reason for the higher thermal persistence of amorphous polymer-derived Si-B-C-N ceramics (T ∼ 1700–2000 °C) compared to Si-C-N ones (T ∼ 1500 °C) has been a matter of debate for more than a decade. Despite recent experimental results which indicate a major kinetic effect of boron on the thermal persistence of the ceramics, no experimental investigation of the thermodynamic stability of the materials has been reported. In this work, we present measured energetics of a series of the amorphous ceramics with various boron contents (0–8.3 at.%) using high-temperature oxidative drop-solution calorimetry. Through measurement of the drop-solution enthalpies in molten sodium molybdate at 811 °C, the formation enthalpies of the amorphous ceramics from crystalline components (SiC, BN, Si3N4, C) at 25 °C were obtained and found to be between −1.4 and −26.6 kJ g-atom−1. The determined enthalpy data plus the estimated positive entropy of formation values point to the thermodynamic stability of the amorphous ceramics relative to the crystalline phases, but such stabilization diminishes with increasing boron content. In contrast, the higher boron content increases the temperature of Si3N4 crystallization despite less favorable energetics for the amorphous phase, implying more favorable energetics for crystallization. Thus the so-called “stability” of Si-B-C-N ceramics in terms of persistence against Si3N4 crystallization appears to be controlled by kinetics rather than by thermodynamic stability.

  4. 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...

  5. Modélisation et caractérisation des joints collés à hautes vitesses de déformation Modeling and characterization of bonded joints at high strain rates

    Directory of Open Access Journals (Sweden)

    Bourel B.

    2013-11-01

    Full Text Available Ce papier traite de la modélisation de joints collés pour les structures soumises à des sollicitations de type crash. Cette nouvelle modélisation basée sur un élément cohésif tient compte du comportement viscoplastique, de l'endommagement ainsi que de la rupture de l'adhésive. Sensible à la vitesse de déformation l'identification du critère de rupture nécessite une base expérimentale allant jusqu'à de très hautes vitesses de déformations. Un nouveau dispositif d'essais a donc été mis en place sur les barres de Hopkinson afin de solliciter des assemblages à haute vitesse et sous différents angles de chargement. This paper deals with the modeling of bonded joints for structures subjected to dynamic crash loading. This new model based on a cohesive element takes into account the viscoelastic behavior, the damage and the failure of the adhesive. Due to the strain rate sensitivity, the identification of failure criterion requires experimental tests, up to very high strain rates. A new testing device has then been set up on the Hopkinson bar in order to load the assemblies with high strain rates and with different angles.

  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. Bond-centered, bond-ordered stripes in doped antiferromagnets

    OpenAIRE

    Wrobel, P.; Maciag, A; Eder, R.

    2004-01-01

    Motivated by recent inelastic neutron scattering experiments on cuprates, we discuss the formation of bond order in the stripe phase. We suggest that the spin Peierls order emerges in hole-rich domain walls (DWs) formed between hole-poor regions in which long-range antiferromagnetic (AF) correlations exist. On the example of a single stripe we analyze the stability of such structures. The motion of a hole inside the DW which takes the form of a bond ordered ladder is in principle unrestricted...

  8. Metabolic Engineering to Develop a Pathway for the Selective Cleavage of Carbon-Nitrogen Bonds

    Energy Technology Data Exchange (ETDEWEB)

    John J. Kilbane II

    2005-10-01

    The objective of the project is to develop a biochemical pathway for the selective cleavage of C-N bonds in molecules found in petroleum. Specifically a novel biochemical pathway will be developed for the selective cleavage of C-N bonds in carbazole. The cleavage of the first C-N bond in carbazole is accomplished by the enzyme carbazole dioxygenase, that catalyzes the conversion of carbazole to 2-aminobiphenyl-2,3-diol. The genes encoding carbazole dioxygenase were cloned from Sphingomonas sp. GTIN11 and from Pseudomonas resinovorans CA10. The selective cleavage of the second C-N bond has been challenging, and efforts to overcome that challenge have been the focus of recent research in this project. Enrichment culture experiments succeeded in isolating bacterial cultures that can metabolize 2-aminobiphenyl, but no enzyme capable of selectively cleaving the C-N bond in 2-aminobiphenyl has been identified. Aniline is very similar to the structure of 2-aminobiphenyl and aniline dioxygenase catalyzes the conversion of aniline to catechol and ammonia. For the remainder of the project the emphasis of research will be to simultaneously express the genes for carbazole dioxygenase and for aniline dioxygenase in the same bacterial host and then to select for derivative cultures capable of using carbazole as the sole source of nitrogen.

  9. Frameshift Deletion by Sulfolobus solfataricus P2 DNA Polymerase Dpo4 T239W Is Selective for Purines and Involves Normal Conformational Change Followed by Slow Phosphodiester Bond Formation*

    Science.gov (United States)

    Zhang, Huidong; Beckman, Jeff W.; Guengerich, F. Peter

    2009-01-01

    The human DNA polymerase κ homolog Sulfolobus solfataricus DNA polymerase IV (Dpo4) produces “−1” frameshift deletions while copying unmodified DNA and, more frequently, when bypassing DNA adducts. As judged by steady-state kinetics and mass spectrometry, bypass of purine template bases to produce these deletions occurred rarely but with 10-fold higher frequency than with pyrimidines. The DNA adduct 1,N2-etheno-2′-deoxyguanosine, with a larger stacking surface than canonical purines, showed the highest frequency of formation of −1 frameshift deletions. Dpo4 T239W, a mutant we had previously shown to produce fluorescence changes attributed to conformational change following dNTP binding opposite cognate bases (Beckman, J. W., Wang, Q., and Guengerich, F. P. (2008) J. Biol. Chem. 283, 36711–36723), reported similar conformational changes when the incoming dNTP complemented the base following a templating purine base or bulky adduct (i.e. the “+1” base). However, in all mispairing cases, phosphodiester bond formation was inefficient. The frequency of −1 frameshift events and the associated conformational changes were not dependent on the context of the remainder of the sequence. Collectively, our results support a mechanism for −1 frameshift deletions by Dpo4 that involves formation of active complexes via a favorable conformational change that skips the templating base, without causing slippage or flipping out of the base, to incorporate a complementary residue opposite the +1 base, in a mechanism previously termed “dNTP-stabilized incorporation.” The driving force is attributed to be the stacking potential between the templating base and the incoming dNTP base. PMID:19837980

  10. Frameshift deletion by Sulfolobus solfataricus P2 DNA polymerase Dpo4 T239W is selective for purines and involves normal conformational change followed by slow phosphodiester bond formation.

    Science.gov (United States)

    Zhang, Huidong; Beckman, Jeff W; Guengerich, F Peter

    2009-12-11

    The human DNA polymerase kappa homolog Sulfolobus solfataricus DNA polymerase IV (Dpo4) produces "-1" frameshift deletions while copying unmodified DNA and, more frequently, when bypassing DNA adducts. As judged by steady-state kinetics and mass spectrometry, bypass of purine template bases to produce these deletions occurred rarely but with 10-fold higher frequency than with pyrimidines. The DNA adduct 1,N(2)-etheno-2'-deoxyguanosine, with a larger stacking surface than canonical purines, showed the highest frequency of formation of -1 frameshift deletions. Dpo4 T239W, a mutant we had previously shown to produce fluorescence changes attributed to conformational change following dNTP binding opposite cognate bases (Beckman, J. W., Wang, Q., and Guengerich, F. P. (2008) J. Biol. Chem. 283, 36711-36723), reported similar conformational changes when the incoming dNTP complemented the base following a templating purine base or bulky adduct (i.e. the "+1" base). However, in all mispairing cases, phosphodiester bond formation was inefficient. The frequency of -1 frameshift events and the associated conformational changes were not dependent on the context of the remainder of the sequence. Collectively, our results support a mechanism for -1 frameshift deletions by Dpo4 that involves formation of active complexes via a favorable conformational change that skips the templating base, without causing slippage or flipping out of the base, to incorporate a complementary residue opposite the +1 base, in a mechanism previously termed "dNTP-stabilized incorporation." The driving force is attributed to be the stacking potential between the templating base and the incoming dNTP base. PMID:19837980

  11. 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....

  12. Anisotropy of the He+, C+, N+, O+, and Ne+ pickup ion velocity distribution functions

    Science.gov (United States)

    Drews, C.; Berger, L.; Taut, A.; Wimmer-Schweingruber, R. F.

    2016-04-01

    Context. Interstellar and inner-source pickup ions (PUIs) are produced by the ionization of neutral atoms that originate either outside or inside the heliosphere. Just after ionization, the singly charged ions are picked up by the magnetized solar wind plasma and develop strong anisotropic toroidal features in their velocity distribution functions (VDF). As the plasma parcel moves outwards with the solar wind, the pickup ion VDF gets more and more affected by resonant wave-particle interactions, changing heliospheric conditions, and plasma drifts, which lead to a gradual isotropization of the pickup ion VDF. Past investigations of the pickup ion torus distribution were limited to He+ pickup ions at 1 astronomical unit (AU). Aims: The aim of this study is to quantify the state of anisotropy of the He+, C+, N+, O+, and Ne+ pickup ion VDF at 1 AU. Changes between the state of anisotropy between PUIs of different mass-per-charges can be used to estimate the significance of resonant wave-particle interactions for the isotropization of their VDF, and to investigate the numerous simplifications that are generally made for the description of the phase-space transport of PUIs. Methods: Pulse height analysis data by the PLAsma and SupraThermal Ion Composition instrument (PLASTIC) on board the Solar Terrestrial RElations Observatory Ahead (STEREO A) is used to obtain velocity-spectra of He+, C+, N+, O+, and Ne+ relative to the solar wind, f(wsw). The wsw-spectra are sorted by two different configurations of the local magnetic field - one in which the torus distribution lies within the instrument's aperture, φ⊥, and one in which the torus distribution lies exclusively outside the instrument's field of view, φ∥. The ratio of the PUI spectra between φ⊥ and φ∥ is used to determine the degree of anisotropy of the PUI VDF. Results: The data shows that the formation of a torus distribution at 1 AU is significantly more prominent for O+ (and N+) than for He+ (and Ne

  13. 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...

  14. Tree species is the major factor explaining C:N ratios in European forest soils

    DEFF Research Database (Denmark)

    Cools, Nathalie; Vesterdal, Lars; De Vos, Bruno;

    2014-01-01

    The C:N ratio is considered as an indicator of nitrate leaching in response to high atmospheric nitrogen (N) deposition. However, the C:N ratio is influenced by a multitude of other site-related factors. This study aimed to unravel the factors determining C:N ratios of forest floor, mineral soil...... and peat top soils in more than 4000 plots of the ICP Forests large-scale monitoring network. The first objective was to quantify forest floor, mineral and peat soil C:N ratios across European forests. Secondly we determined the main factors explaining this C:N ratio using a boosted regression tree...... analysis (BRT), including fifteen site and environmental variables. Ninety-five percent of the C:N ratios were between 16 and 44 in the forest floor, between 13 and 44 in the peat topsoil and between 10 and 32 in the mineral topsoil. Within the aerated forest floor and the mineral soil, the C:N ratios...

  15. 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...

  16. A cooperative hydrogen bonding system with a Csbnd H⋯O hydrogen bond in ofloxacin

    Science.gov (United States)

    Gao, Xiuxiang; Liu, Yufeng; Li, Huizhen; Bian, Jiang; Zhao, Ying; Cao, Ye; Mao, Yuezhi; Li, Xin; Xu, Yizhuang; Ozaki, Yukihiro; Wu, Jinguang

    2013-05-01

    We have investigated a cooperative hydrogen bonding system with a Csbnd H⋯O hydrogen bond in ofloxacin by using NMR, UV-Vis spectra together with quantum chemistry calculation. Both pH-dependent NMR experiments and DFT calculation indicate that the intra-molecular Csbnd H⋯O hydrogen bond between an aromatic proton and an oxygen atom from the carboxyl group is formed. Notably, the Csbnd H⋯O hydrogen bond forms a cooperative hydrogen bonding system with a neighboring Osbnd H⋯O hydrogen bond between the carboxyl group and the keto oxygen. The cooperative hydrogen bonding system makes the formation and disruption of the Osbnd H⋯O and Csbnd H⋯O hydrogen bonds in a synergistic manner. Comparison on the pKa value of the carboxylic group in different fluoroquinolones compounds indicates that the Csbnd H⋯O hydrogen bond plays a significant role in stabilizing the Osbnd H⋯O hydrogen bond. In addition, the formation and disruption of the cooperative hydrogen bonding system could regulate the conformation of the carboxyl group, which affects the size of the conjugated system and spectral behavior of π-π transition of ofloxacin.

  17. Organomolybdenum (VI) and lithium Organomolybdate (VI) and (V) Complexes with C,N-Chelating Aminoaryl Ligands

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Leur, M. de; Gossage, R.A.; Spek, A.L.

    1999-01-01

    The synthesis and characterization of new, five-coordinate molybdenum bis(imidoaryl) complexes [Mo(NAr)2(C-N)X] (Ar = C6H3i-Pr2-2,6; C-N = [C6H4(CH2NMe2)-2]-; X = Cl (1), Me (2), Et (3), Bu (4), CH2SiMe3 (5), (p-tolyl) (6), (C-N) (7)) is reported. The solid-state structure of 2 has been elucidated b

  18. Reinforcement of precursor-derived Si-(B-)C-N ceramics with carbon nanotubes

    OpenAIRE

    Katsuda, Yuji

    2005-01-01

    Incorporation of carbon nanotubes (CNTs) into the precursor-derived Si-(B-)C-N ceramics has been investigated for the reinforcement of the materials. Different types of CNTs consisting of multi-wall (MW) and single-wall (SW) were examined as the reinforcement of the Si-(B-)C-N ceramics to make a comparison of the effect. Mechanical properties demonstrated in the Si-(B-)C-N/CNT nanocomposites have been discussed in connection with their microstructural features characterized by scanning electr...

  19. Electron conjugation versus π-π repulsion in substituted benzenes: why the carbon-nitrogen bond in nitrobenzene is longer than in aniline.

    Science.gov (United States)

    Zhang, Huaiyu; Jiang, Xiaoyu; Wu, Wei; Mo, Yirong

    2016-04-28

    Gas-phase electron diffraction experiments show that the C-N bond in aniline (1.407 Å) is significantly shorter than in nitrobenzene (1.486 Å). It is known that the amino group is electron-donating and the nitro group is electron-withdrawing, and both substitution groups can effectively conjugate with benzene. Thus, it is puzzling why the C-N bond in nitrobenzene is even longer than the single C-N bond in methylamine (1.472 Å). In this work, we performed computations by strictly localizing the π electrons with the block-localized wavefunction (BLW) method, which is a variant of ab initio valence bond theory. Geometry optimizations of electron-localized states, where the conjugation over the C-N bond is quenched, show that the conjugation in nitrobenzene is only half of the conjugation in aniline. But even in optimal electron-localized states, the C-N bond in nitrobenzene is still 0.074 Å longer than in aniline. As a consequence, it is indeed not the π conjugation which is responsible for the disparity of the C-N bond distances in these systems. Instead, we demonstrated that the π-π repulsion, which is contributed by both Pauli exchange and electrostatic interaction, plays the key role in this "abnormal" behavior. Notably, the π resonance within the nitro group generates a considerable dipole, which repels the π electrons in the benzene ring. The deactivation of the resonance within the nitro group significantly shortens the C-N bond by 0.06 Å. The unfavorable π-π electrostatic repulsion is further exemplified by N2O4. In fact, the destabilizing π-π repulsion is ubiquitous but largely neglected in conjugated systems where only the stabilizing conjugation is the focus. Experimental phenomena such as the C-N bond distances in aniline and nitrobenzene result from the balance of both stabilizing and destabilizing forces. PMID:26852720

  20. On Bond Portfolio Management

    OpenAIRE

    Vladislav Kargin

    2002-01-01

    This paper describes a new method of bond portfolio optimization based on stochastic string models of correlation structure in bond returns. The paper shows how to approximate correlation function of bond returns, compute the optimal portfolio allocation using Wiener-Hopf factorization, and check whether a collection of bonds presents arbitrage opportunities.

  1. Multicenter bonds, bond valence and bond charge apportion

    International Nuclear Information System (INIS)

    In the same way that the valence of an atom issues from the definition of bond index, we shoe here that the three-center bond index lends itself to the definition of a bond valence. Within the charge of a bond, we show that its self-charge (i.e., the amount of electron kept by the atoms involved in the bond) is parted in a such a way that the more electronegative atom tends to allot more electronic charge than the other atom. We give examples of these quantities and discuss the results for different kinds of chemical systems. We also show some results for four-center indices and report six-center indices for hexagonal rings. (author). 54 refs., 4 figs., 8 tabs

  2. Visible light-responded C, N and S co-doped anatase TiO{sub 2} for photocatalytic reduction of Cr(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Lei, X.F., E-mail: leixuefei69@163.com [School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004 (China); Institute of Metallurgical Resource and Environmental Engineering, Northeastern University, Shenyang 110819 (China); Liaoning Key Laboratory of Metallurgical Resource Recycling Science, Shenyang 110819 (China); Liaoning Engineering and Technology Research Center of Boron Resource, Comprehensive, Utilization, Shenyang 110819 (China); Liaoning Provincial Universities Key Laboratory of Boron Resource Ecological, Utilization, Technology and Boron Materials, Shenyang 110819 (China); Xue, X.X.; Yang, H. [Institute of Metallurgical Resource and Environmental Engineering, Northeastern University, Shenyang 110819 (China); Liaoning Key Laboratory of Metallurgical Resource Recycling Science, Shenyang 110819 (China); Liaoning Engineering and Technology Research Center of Boron Resource, Comprehensive, Utilization, Shenyang 110819 (China); Liaoning Provincial Universities Key Laboratory of Boron Resource Ecological, Utilization, Technology and Boron Materials, Shenyang 110819 (China); Chen, C.; Li, X.; Pei, J.X.; Niu, M.C.; Yang, Y.T.; Gao, X.Y. [School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004 (China)

    2015-10-15

    The (C, N and S) co-doped TiO{sub 2} (TH-TiO{sub 2}) samples were synthesized by a sol-gel method calcined at 500 °C, employing butyl titanate as the titanium source and thiourea as the dopant. The structures of TH-TiO{sub 2} samples were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectra (DRS), photoluminescence (PL) spectroscopy, Thermo gravimetry and differential thermal analysis (TG-DTA), Scanning electron microscopy (SEM) and nitrogen adsorption–desorption isotherms. The photocatalytic activities were checked through the photocatalytic reduction of Cr(VI) as a model compound under visible light irradiation. The results showed that the thiourea content played an important role on the microstructure and photocatalytic activity of the samples. According to XPS results, (C, N and S) atoms were successfully co-doped into the nanostructures of TH-TiO{sub 2} samples. TH-TiO{sub 2} samples with thiourea: Ti molar ratio of 1.5 exhibits higher photocatalytic activity than that of the other samples under visible light irradiation, which can be attributed to the synergic effect of the pure anatase structure, the higher light absorption characteristics in visible regions, separation efficiency of electron–hole pairs, the specific surface area and the optimum (C, N and S) content. - Graphical abstract: (C, N and S) co-doped TiO{sub 2} samples show good photocatalytic activity for Cr (VI) reduction under visible light irradiation. - Highlights: • (C, N and S) co-doping in TH-TiO{sub 2} samples can promote the formation of the pure anatase structure. • (C, N and S) atoms were successfully co-doped into the nanostructures of TH-TiO{sub 2} samples. • The band gap energy of TH-TiO{sub 2} samples reduced after (C, N and S) co-doping. • (C, N and S) co-doped TiO{sub 2} samples were effective for the photocatalytic reduction of Cr(VI) under visible light

  3. Organomolybdenum (VI) and lithium Organomolybdate (VI) and (V) Complexes with C,N-Chelating Aminoaryl Ligands

    OpenAIRE

    van Koten, G.; Brandts, J.A.M.; Leur, M. de; Gossage, R. A.; Spek, A.L.

    1999-01-01

    The synthesis and characterization of new, five-coordinate molybdenum bis(imidoaryl) complexes [Mo(NAr)2(C-N)X] (Ar = C6H3i-Pr2-2,6; C-N = [C6H4(CH2NMe2)-2]-; X = Cl (1), Me (2), Et (3), Bu (4), CH2SiMe3 (5), (p-tolyl) (6), (C-N) (7)) is reported. The solid-state structure of 2 has been elucidated by single-crystal X-ray analysis. Compounds 2, 3, 4, 5, and 6 react with alkyl- or aryllithium compounds to form lithium molybdate(VI) derivatives, of which [Li(DME)Mo(NAr)2(C-N)(Me)(p-tolyl)] (10),...

  4. Alanine check points in HNN and HN(C)N spectra

    Science.gov (United States)

    Chatterjee, Amarnath; Kumar, Ashutosh; Hosur, Ramakrishna V.

    2006-07-01

    Rapid resonance assignment is a key requirement in structural genomics research by NMR. In this context we present here two new pulse sequences, namely, HNN-A and HN(C)N-A that have been developed by simple modification of the previously described pulse sequences, HNN and HN(C)N [S.C. Panchal, N.S. Bhavesh, R.V. Hosur, Improved 3D triple resonance experiments, HNN and HN(C)N, for HN and 15N sequential correlations in (13C, 15N) labeled proteins: application to unfolded proteins, J. Biomol. NMR, 20 (2001) 135-147]. These increase the number of start/check points in HNN and/or HN(C)N spectra and hence help in pacing up resonance assignment in proteins.

  5. Bond strengths of New Carbon-nitride-Related material C2N2(CH2)

    International Nuclear Information System (INIS)

    A new carbon-nitride-related material C2N2(CH2) nanopletelet was synthesized by subjecting a precursor C3N4HxOy+Au in a laser-heating diamond anvil cell (LHDAC) to the pressure of 40 GPa and the temperature of 1200-2000 K. The synthesized C2N2(CH2) was accordingly found to be an orthorhombic unit cell of the space group Cmc21 with lattice constants a = 7.625Å, b = 4.490Å, and c = 4.047Å. The bulk modulus B0 was determined to be B0 = 258 ± 3.4 GPa, only the 60 % that of the diamond. C2N2(CH2) consists of the tetrahedrally coordinated C with three C-N single bond and the one C-C single bond, and the bridging carbon with the C-CH2-C bond. The C-N single bond length of the tetrahedron ranges from 1.444 to 1.503 Å. This bond length is close to the C-N single bond of 1.447 to 1.458 Å in the superhard β-C3N4. The compressibility of the C-N and C-C single bond of C2N2(CH2) ranges from 0.976 to 0.982 with the pressure of 30 GPa. These values are very close to the compressibility of the C-N and C-C single bond of 0.978 to 0.982 in β-C3N4, cubic-C3N4, and diamond.

  6. Silicon carbonitride by remote microwave plasma CVD from organosilicon precursor: Physical and mechanical properties of deposited Si:C:N films

    Energy Technology Data Exchange (ETDEWEB)

    Blaszczyk-Lezak, I. [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, PL-90-363 Lodz (Poland); Wrobel, A.M. [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, PL-90-363 Lodz (Poland)]. E-mail: amwrobel@bilbo.cbmm.lodz.pl

    2007-07-15

    Silicon carbonitride (Si:C:N) films produced by the remote microwave hydrogen plasma chemical vapor deposition (RP-CVD) using bis(dimethylamino)methylsilane as single-source precursor and hydrogen as an upstream gas for plasma generation, were examined in terms of their physical (density) and mechanical (hardness, elastic modulus, friction coefficient, and 'plasticity index') properties. The effect of substrate temperature (varied in the range of 30-400 {sup o}C) on the properties of Si:C:N films is presented. A reasonable compositional and structural dependencies of film properties were determined using, respectively, the XPS atomic concentration ratios N/Si and C/Si, as well as the relative integrated intensities of the IR absorption bands from the Si-N and Si-C bonds (controlled by deposition temperature), evaluated in the first part of this work. In view of their good mechanical properties, Si:C:N films seem to be useful coatings for improving surface mechanics of engineering materials.

  7. VB studies on bonding features of HNC(←→)HCN

    Institute of Scientific and Technical Information of China (English)

    廖新丽; 吴玮; 莫亦荣; 张乾二

    2003-01-01

    Within the bonded tableau unitary group approach (BTUGA), a scheme, combined with Pauling's resonance theory to select the predominant valence bond structures for VB calculations, is proposed. This scheme ensures a reliable and illustrative bonding picture in the description of chemical reactions, as exemplified by the isomerization reaction HNCHCN. The computation results account for important bonding features about this isomerization at the ab initio level and explore the mechanism of phenomena such as (i) HCN is more stable than HNC; (ii) the C-N bond first lengthens and then shortens in the vicinity of the transition state; (iii) only H-atom migration is observed in the isomerization process, without the breaking of the CN bond. Our results demonstrate that only a few bonded tableau functions are sufficient enough to provide a visual and reliable bonding picture.

  8. 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

  9. Bond excitations in the pseudogap phase of the Hubbard Model

    OpenAIRE

    Macridin, Alexandru; Jarrell, Mark (Eds. )

    2008-01-01

    Using the dynamical cluster approximation, we calculate the correlation functions associated with the nearest neighbor bond operator which measure the z component of the spin exchange in the two-dimensional Hubbard model with $U$ equal to the bandwidth. We find that in the pseudogap region, the local bond susceptibility diverges at T=0. This shows the existence of degenerate bond spin excitation and implies quantum criticality and bond order formation when long range correlations are consider...

  10. Neural mechanisms of mother-infant bonding and pair bonding: Similarities, differences, and broader implications.

    Science.gov (United States)

    Numan, Michael; Young, Larry J

    2016-01-01

    This article is part of a Special Issue "Parental Care". Mother-infant bonding is a characteristic of virtually all mammals. The maternal neural system may have provided the scaffold upon which other types of social bonds in mammals have been built. For example, most mammals exhibit a polygamous mating system, but monogamy and pair bonding between mating partners occur in ~5% of mammalian species. In mammals, it is plausible that the neural mechanisms that promote mother-infant bonding have been modified by natural selection to establish the capacity to develop a selective bond with a mate during the evolution of monogamous mating strategies. Here we compare the details of the neural mechanisms that promote mother-infant bonding in rats and other mammals with those that underpin pair bond formation in the monogamous prairie vole. Although details remain to be resolved, remarkable similarities and a few differences between the mechanisms underlying these two types of bond formation are revealed. For example, amygdala and nucleus accumbens-ventral pallidum (NA-VP) circuits are involved in both types of bond formation, and dopamine and oxytocin actions within NA appear to promote the synaptic plasticity that allows either infant or mating partner stimuli to persistently activate NA-VP attraction circuits, leading to an enduring social attraction and bonding. Further, although the medial preoptic area is essential for maternal behavior, its role in pair bonding remains to be determined. Our review concludes by examining the broader implications of this comparative analysis, and evidence is provided that the maternal care system may have also provided the basic neural foundation for other types of strong social relationships, beyond pair bonding, in mammals, including humans. PMID:26062432

  11. Binuclear Complexes and Extended Chains Featuring Pt(II)-Tl(I) Bonds: Influence of the Pyridine-2-Thiolate and Cyclometalated Ligands on the Self-Assembly and Luminescent Behavior.

    Science.gov (United States)

    Berenguer, Jesús R; Lalinde, Elena; Martín, Antonio; Moreno, M Teresa; Sánchez, Sergio; Shahsavari, Hamid R

    2016-08-15

    Platinum solvate complexes [Pt(C6F5)(C^N)(S)] [C^N = phenylpyridinyl (ppy), S = dimethyl sulfoxide (DMSO) (A); C^N = benzoquinolinyl (bzq), S = CH3COCH3 (B)] react with [Tl(Spy)] (Spy = 2-pyridinethiolate) to afford binuclear [{Pt(C6F5)(C^N)}Tl(Spy)] [C^N = ppy (1) and bzq (2)] species containing a Pt-Tl bonding interaction, supported by a μ-Spy-κN,S bridging ligand, as confirmed by X-ray diffraction. However, the related reactions with [Tl(SpyCF3-5)] [SpyCF3-5 = 5-(trifluoromethyl)-2-pyridinethiolate] give neutral extended chains [{Pt(C6F5)(C^N)}Tl(SpyCF3-5)]n [C^N = ppy (3) and bzq (4)]. 3 features a zigzag -Pt-Tl···S-Pt- chain, generated by Pt-Tl and Tl···S bonds, with the SpyCF3 acting as a μ-κN:κ(2)S bridging ligand, whereas 4 displays an unsupported ···Tl-Pt···Tl-Pt··· backbone (angle of ca. 158.7°). The lowest-energy absorption bands in the UV-vis spectra in CH2Cl2, associated with (1)L'LCT transitions with minor (1)LC/(1)MLCT (L' = Spy or SpyCF3-5; L = C^N) character, are similar for all complexes 1-4, demonstrating that for 3 and 4 the chains break down in solution to yield similar bimetallic Pt-Tl units. For 2, two different forms, 2-o (orange) and 2-y (yellow), exhibiting different colors and emissions were found depending on the isolation conditions. Slow crystallization favors formation of the thermodynamically more stable yellow form (2-y), which exhibits a high-energy (HE) structured emission band, whereas fast crystallization gives rise to the orange form (2-o), with a remarkably lower energy structureless emission. Complexes 1 and 3 exhibit dual luminescence in the solid state at 298 K: an unstructured low-energy band associated with (3)ππ* excimeric emission due to π···π (C^N) interactions and a more structured HE band, assigned, with support of density functional theory calculations, to an intraligand (3)LC (C^N) excited state mixed with some ligand (SPy)/platinum-to-ligand (C^N)(3)[(L' + M)LCT] charge transfer. Chain

  12. The importance of chain conformational mobility during 5-exo-cyclizations of C-, N- and O-centred radicals.

    Science.gov (United States)

    Walton, John C

    2014-10-28

    The reaction coordinates of an archetypical set of 5-exo cyclizations of C-, N- and O-centred radicals were investigated by computational methods. G4 theory, and DFT with the um062x functional, were able to rationalise counterintuitive factors such as the 'normal' order of rate constants being: N-centred implied that rigidity at the N-ends of the chains, and the consequent extra energy needed to attain chair-like transition states, might be the reason for slow aminyl cyclizations. A novel linear correlation between cyclization activation energies and the access angles was discovered. The preference for cis-1,2-disubstituted product formation was also accounted for in terms of interaction between the hyperconjugatively delocalized SOMO and the alkene π* orbital. PMID:25179567

  13. Bonding silicones with epoxies

    Energy Technology Data Exchange (ETDEWEB)

    Tira, J.S.

    1980-01-01

    It is shown that silicones, both room temperature vulcanizing (RTV) and millable rubber (press cured) can be successfully bonded to other materials using plasma treatment and epoxy adhesives. The plasma treatment using dry air atmosphere increases the surface energy of the silicone and thus provides a lower water contact angle. This phenomenon allows the epoxy adhesive to wet the silicone surface and ultimately bond. Bond strengths are sufficiently high to result in failures in the silicone materials rather than the adhesive bond.

  14. Australia's Bond Home Bias

    OpenAIRE

    Mishra, Anil V; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  15. METABOLIC ENGINEERING TO DEVELOP A PATHWAY FOR THE SELECTIVE CLEAVAGE OF CARBON-NITROGEN BONDS

    Energy Technology Data Exchange (ETDEWEB)

    John J. Kilbane II

    2004-10-01

    The objective of the project is to develop biochemical pathways for the selective cleavage of C-N bonds in molecules found in petroleum. The initial phase of the project was focused on the isolation or development of an enzyme capable of cleaving the C-N bond in aromatic amides, specifically 2-aminobiphenyl. The objective of the second phase of the research will be to construct a biochemical pathway for the selective removal of nitrogen from carbazole by combining the carA genes from Sphingomonas sp. GTIN11 with the gene(s) encoding an appropriate deaminase. The objective of the final phase of the project will be to develop derivative C-N bond cleaving enzymes that have broader substrate ranges and to demonstrate the use of such strains to selectively remove nitrogen from petroleum. During the first year of the project (October, 2002-September, 2003) enrichment culture experiments resulted in the isolation of microbial cultures that utilize aromatic amides as sole nitrogen sources, several amidase genes were cloned and were included in directed evolution experiments to obtain derivatives that can cleave C-N bonds in aromatic amides, and the carA genes from Sphingomonas sp. GTIN11, and Pseudomonas resinovorans CA10 were cloned in vectors capable of replicating in Escherichia coli. During the second year of the project (October, 2003-September, 2004) enrichment culture experiments succeeded in isolating a mixed bacterial culture that can utilize 2-aminobiphenyl as a sole nitrogen source, directed evolution experiments were focused on the aniline dioxygenase enzyme that is capable of deaminating aniline, and expression vectors were constructed to enable the expression of genes encoding C-N bond cleaving enzymes in Rhodococcus hosts. The construction of a new metabolic pathway to selectively remove nitrogen from carbazole and other molecules typically found in petroleum should lead to the development of a process to improve oil refinery efficiency by reducing the

  16. Malaysia : Bond Market Development

    OpenAIRE

    International Monetary Fund; World Bank

    2013-01-01

    This paper pertains to the bond market development in Malaysia, and provides an overview of the market scenario in the country. Malaysia has been successful in developing the capital markets, particularly bond markets, in the recent past. Now, it faces the challenge of how to improve broader access and efficiency of the bond market. A high degree of investor concentration, dominated by gov...

  17. 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

  18. Credit unions and the common bond

    OpenAIRE

    William R. Emmons; Frank A. Schmid

    1998-01-01

    A distinguishing feature of credit unions is the legal requirement that members share a common bond. This organizing principle recently became the focus of national attention when the Supreme Court and the U.S. Congress took opposite sides in a controversy regarding the number of common bonds (fields of membership) that could coexist within a single credit union. In this article, Emmons and Schmid develop and simulate a model of credit-union formation and consolidation to examine the effects ...

  19. The higher-order C_n dispersion coefficients for hydrogen

    CERN Document Server

    Mitroy, J

    2004-01-01

    The complete set of 2nd, 3rd and 4th order van der Waals coefficients, C_n up to n=32 for the H(1s)-H(1s) dimer are computed using pseudo-states to evaluate the appropriate sum rules. A study of the convergence pattern for n<=16 indicates that all the C_n (n<=16) coefficients are accurate to 13 significant digits. The relative size of the 4th-order C^4_n to the 2nd-order C^2_n coefficients is seen to increase as n increases and at n=32 the 4th-order term is actually larger.

  20. On Levi-fiat hypersurfaces with given boundary in C~n

    Institute of Scientific and Technical Information of China (English)

    Pierre; DOLBEAULT

    2008-01-01

    Let S■C~n be a compact connected 2-codimensional submanifold.If n≥3,essentially local conditions and the assumption:every complex point of S is elliptic imply the existence of a projection in C~n of a Levi-flat(2n-1)-subvariety whose boundary is S(Dolbeault,Tomassini,Zaitsev, 2005).We extend the result when S is homeomorphic to a sphere and has one hyperbolic point. For n=2 many results are known since the 1980’s and a new result with a very technical hypothesis is announced.

  1. 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

  2. Contribution to the study of the (U,Pu)C,N system; Contribution a l'etude du systeme (U,Pu)C,N

    Energy Technology Data Exchange (ETDEWEB)

    Lorenzelli, R. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1968-07-01

    The reactions of UC, PuC, (U,Pu)C, UC{sub 2} and U(C{sub 1-x}O{sub x}) with nitrogen at moderate temperatures (room temperature to 400 C) are described. The influence of the uptake of nitrogen by the powders necessary to sinter the carbides upon the nature of the final product has been investigated; it has been shown that the sintered carbides are hyper-stoichiometric. The reactions of carbon with UN, PuN and (U,Pu)N has also been studied. Under vacuum, carbon reacts on the nitrides at temperatures as low as 1100 C; nitrogen is replaced by carbon and the final product is a carbonitride. The reaction is: MN + x C {yields} MN{sub 1-x}C{sub x} + x/2N{sub 2}. The reaction is limited and the carbonitrides have a fixed composition in presence of M{sub 2}C{sub 3} or MC{sub 2}; hence it is impossible to produce pure MC using the reaction. The ternary diagram U-C-N, Pu-C-N and (U,Pu)C-N have been drawn. They show clearly that it is possible to obtain single phase carbonitrides in a wide domain of compositions. (author) [French] On decrit les reactions avec l'azote de UC, PuC,(U,Pu)C,UC{sub 2} et U(C{sub 1-x}O{sub x}), par action directe de l'azote a temperature moderee (de l'ambiante a 450 C). On a etudie l'influence de la contamination par l'azote des poudres de carbures necessaires au frittage sur la nature des produits frittes; on a montre que les carbures frittes obtenus sont hyperstoechiometriques. On a etudie parallelement les reactions du carbone avec UN, PuN et (U,Pu)N. Sous vide le carbone reagit sur les nitrures des 1100 C: le carbone se substitue a l'azote; l'azote libere est elimine et le produit final est un carbonitrure. La reaction s'ecrit: MN + x C {yields} MN{sub 1-x}C{sub x} + x/2N{sub 2}. La reaction est limitee et les carbonitrures obtenus ont une composition limite fixe en presence des carbures superieurs M{sub 2}C{sub 3} et MC{sub 2}; il est donc impossible d'obtenir MC pur par cette reaction. Les diagrammes

  3. Hydrogen bonds in PC61BM solids

    Directory of Open Access Journals (Sweden)

    Chun-Qi Sheng

    2015-09-01

    Full Text Available 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.

  4. Hydrogen bonds in PC61BM solids

    International Nuclear Information System (INIS)

    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. Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

    Science.gov (United States)

    Schimmelmann, A.; Mastalerz, Maria; Gao, L.; Sauer, P.E.; Topalov, K.

    2009-01-01

    Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ??13Ckerogen vs. ??15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back

  6. Stable isotape ratios of H, C, N an O in Italian citrus juices

    NARCIS (Netherlands)

    Bontempo, L.; Caruso, R.; Fiorillo, M.; Gambino, G.L.; Perini, M.; Simoni, M.; Traulo, P.; Wehrens, H.R.M.J.; Gagliano, G.; Camin, F.

    2014-01-01

    Stable isotope ratios (SIRs) of C, N, H and O have been exensively used in fruit juices quality control (ENV and AOAC methods) to detect added sugar and the watering down of concentrated juice, practices prohibited by European legislation (EU Directive 2012/12). The European Fruit Juice Association

  7. Relationship between C:N/C:O stoichiometry and ecosystem services in managed production systems.

    Science.gov (United States)

    Ghaley, Bhim B; Sandhu, Harpinder S; Porter, John R

    2015-01-01

    Land use and management intensity can influence provision of ecosystem services (ES). We argue that forest/agroforestry production systems are characterized by relatively higher C:O/C:N and ES value compared to arable production systems. Field investigations on C:N/C:O and 15 ES were determined in three diverse production systems: wheat monoculture (Cwheat), a combined food and energy system (CFE) and a beech forest in Denmark. The C:N/C:O ratios were 194.1/1.68, 94.1/1.57 and 59.5/1.45 for beech forest, CFE and Cwheat, respectively. The economic value of the non-marketed ES was also highest in beech forest (US$ 1089 ha(-1) yr(-1)) followed by CFE (US$ 800 ha(-1) yr(-1)) and Cwheat (US$ 339 ha(-1) yr(-1)). The combined economic value was highest in the CFE (US$ 3143 ha(-1) yr(-1)) as compared to the Cwheat (US$ 2767 ha(-1) yr(-1)) and beech forest (US$ 2365 ha(-1) yr(-1)). We argue that C:N/C:O can be used as a proxy of ES, particularly for the non-marketed ES, such as regulating, supporting and cultural services. These ES play a vital role in the sustainable production of food and energy. Therefore, they should be considered in decision making and developing appropriate policy responses for land use management. PMID:25894553

  8. Weak bond screening system

    Science.gov (United States)

    Chuang, S. Y.; Chang, F. H.; Bell, J. R.

    Consideration is given to the development of a weak bond screening system which is based on the utilization of a high power ultrasonic (HPU) technique. The instrumentation of the prototype bond strength screening system is described, and the adhesively bonded specimens used in the system developmental effort are detailed. Test results obtained from these specimens are presented in terms of bond strength and level of high power ultrasound irradiation. The following observations were made: (1) for Al/Al specimens, 2.6 sec of HPU irradiation will screen weak bond conditions due to improper preparation of bonding surfaces; (2) for composite/composite specimens, 2.0 sec of HPU irradiation will disrupt weak bonds due to under-cured conditions; (3) for Al honeycomb core with composite skin structure, 3.5 sec of HPU irradiation will disrupt weak bonds due to bad adhesive or oils contamination of bonding surfaces; and (4) for Nomex honeycomb with Al skin structure, 1.3 sec of HPU irradiation will disrupt weak bonds due to bad adhesive.

  9. Long-term simulation of terrestrial and freshwater C, N and P at the UK scale.

    Science.gov (United States)

    Davies, Jessica; Quinton, John; Tipping, Ed

    2013-04-01

    Understanding C, N and P pools and fluxes throughout the landscape is vital for improving agricultural sustainability, preserving carbon stocks, and reducing the eutrophication of freshwater systems and delivery of nutrients to the sea. Understanding in this area is also instrumental in predicting and mitigating the impacts of climate change and a perturbed C cycle. However, accounting for C, N and P behaviour is challenging as they are determined by highly spatially variable, inter-connected factors such as the underlying substrate, vegetation and soil types, hydrological conditions, topography, and land use. Also, long turnover times in soil organic matter may mean that current C, N and P states have a significant dependency on a site's history of inputs and human perturbations. In addition, the dynamics of C, N and P are highly coupled, increasing the complexity of these processes. This interacting nature of C, N and P and dependency on inter-connected processes makes it important that they are considered simultaneously in an integrated manner, ideally with a long-term perspective. The research presented aims to account for current observable conditions at a UK scale by drawing on expertise in soil science, geochemistry, and hydrology. Ultimately, mechanistic biogeochemical, soil physics and hydrological models are to be integrated and applied at the regional scale over a time scale stretching from the last glaciation up until the present day. This modelling is based on 'terrestrial units', defined as land areas with relatively homogeneous vegetation or land-use (e.g. natural grassland, arable farmland), to which a biogeochemical model (the N14CP model in the case of semi-natural terrestrial units and RothC in agricultural units) is applied to simulate plant-soil C, N and P pools and fluxes. Erosional losses from these pools are then simulated using a mechanistic, energy-based representation, and aquatic loads are calculated by combining these erosion outputs

  10. A Coupled Thermal-Mechanical Analysis of Ultrasonic Bonding Mechanism

    Science.gov (United States)

    Zhang, Chunbo (Sam); Li, Leijun

    2009-04-01

    A three-dimensional (3-D) finite element model has been developed to simulate the coupled thermal-mechanical fields in ultrasonic welding of aluminum foils. Transient distributions and evolution of the in-process variables, including normal stress, shear stress, slide distance, heat generation, temperature, and plastic deformation on the contact interface, and their interactions have been studied in detail. The von Mises plastic strain from the simulation has been correlated with the measured bonded area of ultrasonic joints. A possible mechanism for ultrasonic bond formation is proposed. The severe, localized, plastic deformation at the bond region is believed to be the major phenomenon causing bond formation in ultrasonic welding.

  11. ANALISIS PARAMETER BER DAN C/N DENGAN LNB COMBO PADA TEKNOLOGI DVB-S2

    Directory of Open Access Journals (Sweden)

    Wahyu Pamungkas

    2014-04-01

    Full Text Available Instalasi antena parabola berfungsi untuk memudahkan pada saat pengarahan pointing antena ke satelit yang dituju. Permasalahan yang diketahui yaitu bagaimana perilaku parameter Bit Error Rate (BER dan Carrier to Noise (C/N pada LNB Combo yang menggunakan teknologi DVB-S2. Setelah instalasi antena parabola dilakukan dan sukses, maka langkah selanjutnya yaitu melakukan pointing antena. Pointing antena diarahkan pada posisi satelit yang akan dituju. Satelit yang akan dituju yaitu Palapa D menggunakan frekuensi C-Band sedangkan Ku-Band diarahkan pada satelit NSS 6. Setelah pointing selesai dilakukan maka langkah selanjutnya yaitu menghubungkan dengan Digital Video Broadcasting Satellite Second Generation (DVB-S2. DVB-S2 merupakan receiver. Parameter yang diamati yaitu parameter BER dan C/N. Parameter BER merupakan perbandingan dengan jumlah bit yang diterima secara tidak benar dengan jumlah bit informasi yang ditransmisikan pada selang waktu tertentu. Parameter C/N merupakan perbandingan nilai pada carrier yang diterima dengan nilai sinyal noise yang dihasilkan dalam suatu link. Diperlukan juga Low Noise Block (LNB Combo yang berguna untuk mentransmisikan sinyal ke receiver. LNB yang digunakan merupakan LNB Combo, dimana dua buah frekuensi yakni C-Band dan KU-Band menjadi satu dalam sebuah LNB. Setelah melakukan pengukuran dan melihat hasil pengukuran, dapat disimpulkan bahwa LNB Combo berpengaruh pada sinyal C-Band yang dihasilkan, sinyal C-Band akan mengalami penurunan kualitas, ini dibuktikan dari hasil pengukuran yang telah dilakukan bahwa nilai parameter C/N dan BER pada Ku-Band lebih baik daripada nilai parameter C/N dan BER pada C-Band.

  12. Bond Markets in Africa

    OpenAIRE

    Yibin Mu; Peter Phelps; Janet Gale Stotsky

    2013-01-01

    African bond markets have been steadily growing in recent years, but nonetheless remain undeveloped. African countries would benefit from greater access to financing and deeper financial markets. This paper compiles a unique set of data on corporate bond markets in Africa. It then applies an econometric model to analyze the key determinants of African government securities market and corporate bond market capitalization. Government securities market capitalization is directly related to bette...

  13. Build America Bonds

    OpenAIRE

    Andrew Ang; Vineer Bhansali; Yuhang Xing

    2010-01-01

    Build America Bonds (BABs) are a new form of municipal financing introduced in 2009. Investors in BAB municipal bonds receive interest payments that are taxable, but issuers receive a subsidy from the U.S. Treasury. The BAB program has succeeded in lowering the cost of funding for state and local governments with BAB issuers obtaining finance 54 basis points lower, on average, compared to issuing regular municipal bonds. For institutional investors, BAB issue yields are 116 basis points highe...

  14. Synthesis and characterization of a new material based on porous silica-Chemically immobilized C,N-pyridylpyrazole for heavy metals adsorption

    International Nuclear Information System (INIS)

    The immobilization of C,N-pyridylpyrazole on the surface of epoxy group containing silica gel phase for the formation of a newly synthesized material based on porous silica-bound C,N-pyridylpyrazole (SGPP) is described. The surface modification was characterized by 13C NMR of solid sample, elemental analysis and infrared spectra and was studied and evaluated by determination of the surface area using the BET equation, the adsorption and desorption capability using the isotherm of nitrogen and BJH pore sizes, respectively. The new material exhibits good thermal stability determined by thermogravimetry curves. The synthesized material was utilised in column and batch methods for separation and trace extraction of (Hg2+, Cd2+, Pb2+, Cu2+, Zn2+, K+, Na+ and Li+) and compared to results of classical liquid-liquid extraction with the unbound C,N-pyridylpyrazole compound. The grafting at the surface of silica does not affect complexing properties of the ligand and the material exhibits a high selectivity toward Hg(II)

  15. Synthesis and characterization of a new material based on porous silica-Chemically immobilized C,N-pyridylpyrazole for heavy metals adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Radi, Smaail [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Departement de Chimie, Faculte des Sciences, Universite Mohamed 1er, BP 524, 60 000 Oujda (Morocco)], E-mail: radi_smaail@yahoo.fr; Attayibat, Ahmed [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Departement de Chimie, Faculte des Sciences, Universite Mohamed 1er, BP 524, 60 000 Oujda (Morocco); Lekchiri, Yahya [Laboratoire de Biochimie, Departement de Biologie, Faculte des Sciences, Universite Mohamed 1er, BP 524, 60 000 Oujda (Morocco); Ramdani, Abdelkrim [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Departement de Chimie, Faculte des Sciences, Universite Mohamed 1er, BP 524, 60 000 Oujda (Morocco); Bacquet, Maryse [Laboratoire de Chimie Macromoleculaire, Universite des Sciences et Technologies de Lille, 59655 Villeneuve d' Ascq (France)

    2008-10-15

    The immobilization of C,N-pyridylpyrazole on the surface of epoxy group containing silica gel phase for the formation of a newly synthesized material based on porous silica-bound C,N-pyridylpyrazole (SGPP) is described. The surface modification was characterized by {sup 13}C NMR of solid sample, elemental analysis and infrared spectra and was studied and evaluated by determination of the surface area using the BET equation, the adsorption and desorption capability using the isotherm of nitrogen and BJH pore sizes, respectively. The new material exhibits good thermal stability determined by thermogravimetry curves. The synthesized material was utilised in column and batch methods for separation and trace extraction of (Hg{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, Cu{sup 2+}, Zn{sup 2+}, K{sup +}, Na{sup +} and Li{sup +}) and compared to results of classical liquid-liquid extraction with the unbound C,N-pyridylpyrazole compound. The grafting at the surface of silica does not affect complexing properties of the ligand and the material exhibits a high selectivity toward Hg(II)

  16. The Bond Market's q

    OpenAIRE

    Thomas Philippon

    2006-01-01

    I propose an implementation of the q-theory of investment using bond prices instead of equity prices. Credit risk makes corporate bond prices sensitive to future asset values, and q can be inferred from bond prices. The bond market's q performs much better than the usual measure in standard investment equations. With aggregate data, the fit is three times better, cash flows are driven out and the implied adjustment costs are reduced by more than an order of magnitude. The new measure also imp...

  17. Hydrogen bonding and anaesthesia

    Science.gov (United States)

    Sándorfy, C.

    2004-12-01

    General anaesthetics act by perturbing intermolecular associations without breaking or forming covalent bonds. These associations might be due to a variety of van der Waals interactions or hydrogen bonding. Neurotransmitters all contain OH or NH groups, which are prone to form hydrogen bonds with those of the neurotransmitter receptors. These could be perturbed by anaesthetics. Aromatic rings in amino acids can act as weak hydrogen bond acceptors. On the other hand the acidic hydrogen in halothane type anaesthetics are weak proton donors. These two facts together lead to a probable mechanism of action for all general anaesthetics.

  18. Stepanov-like C^{(n}-pseudo almost automorphy and applications to some nonautonomous higher-order differential equations

    Directory of Open Access Journals (Sweden)

    Toka Diagana

    2012-01-01

    Full Text Available In this paper we introduce and study a new concept called Stepanov-like \\(C^{(n}\\-pseudo almost automorphy, which generalizes in a natural fashion both the notions of \\(C^{(n}\\-pseudo almost periodicity and that of \\(C^{(n}\\-pseudo almost automorphy recently introduced in the literature by the authors. Basic properties of these new functions are investigated. Furthermore, we study and obtain the existence of \\(C^{(N+m}\\-pseudo almost automorphic solutions to some nonautonomous higher-order systems of differential equations with Stepanov-like \\(C^{(m}\\-pseudo almost automorphic coefficients.

  19. Theoretical Study of Geometric Structures for Ground-state Al_nC(n=2-7) Clusters%Theoretical Study of Geometric Structures for Ground-state Al_nC(n=2-7) Clusters

    Institute of Scientific and Technical Information of China (English)

    LI Gui-Fa; LU Shi-Qiang; PENG Ping

    2012-01-01

    With the aid of the molecular orbital DMol3 program,the energetics and electronic structures of several AlnC(n = 2-7) configurations have been searched and calculated by improved minimum energy paths(MEPs) by setting "imaging product".A new high symmetry,supervalence isomer of Al5C cluster,i.e.,D5h-Al5C,at the local minimum in the MEPs is detected.Several parameters,such as binding energy,HOMO-LUMO energy gap,vertical electron detachment energy and electron affinity energy,are calculated to characterize and evaluate the stability of three Al5C configurations,i.e.,D5h-Al5C,Cs-Al5C and C1-Al5C.The results show that the D5h-Al5C cluster is the ground state structure instead of Cs-Al5C.Due to the formation of many central σ bonds after polymerizing for D5h-Al5C,the decrease of the energy for HOMO orbit results in more territory for HOMO electrons of dislocation effect,then the energy difference between HOMO and LUMO is increasing to enhance the stability of molecules to produce such supervalence structure of Al5C cluster.The configuration evolution between D5h-Al5C,Cs-Al5C and C1-Al5C and the synthesis preference in the mode of Al5 + C → Al5C reveals that the Cs-Al5C and C1-Al5C con-figurations are permissive to coexist with D5h-Al5C structure in energetics.

  20. Bonding Description of the Harpoon Mechanism

    CERN Document Server

    Rodriguez-Mayorga, Mauricio; Salvador, Pedro; Sola, Miquel; Matito, Eduard

    2015-01-01

    The lowest-lying states of LiH have been widely used to develop and calibrate many different methods in quantum mechanics. In this paper we show that the charge-transfer processes occurring in these two states are a difficult test for chemical bonding descriptors and can be used to assess new bonding descriptors on its ability to recognize the harpoon mechanism. To this aim, we study the bond formation mechanism in a series of diatomic molecules. In all studied charge-transfer mechanisms, the maximal charge-transfer variation point along the bond formation path occurs when about half electron has been transferred from one atom to another. If the process takes places through a harpoon mechanism, this point of the reaction path coincides with the avoided crossing. The electron sharing indices and one-dimensional plots of the electron localization function and the Laplacian of the electron density along the molecular axis can be used to monitor the bond formation in diatomics and provide a distinction between th...

  1. The synthesis of N-[4-dimethylamino-1-butyl(1-13C)-N-nitrosobenzamide, an inhibitor of trypsin; cyanide does not exchange with acetonitrile

    International Nuclear Information System (INIS)

    The synthesis of N-[4-dimethylamino-1-butyl(1-13C)-N-nitrobenzamide, a powerful active-site-directed inhibitor of trypsin, is reported. An efficient use of 13C-cyanide ion was achieved in the reaction with 1-chloro-3-dimethylaminopropane, the first step of the synthesis. Acetonitrile was used as a co-solvent with water in that step; no evidence was found for cyanide ion exchange with acetonitrile. The earlier report of such an exchange appears to be in error; the formation of hydrocyanic acid under the reaction conditions can account for the observations. (Author)

  2. 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

  3. Negligible Isotopic Effect on Dissociation of Hydrogen Bonds.

    Science.gov (United States)

    Ge, Chuanqi; Shen, Yuneng; Deng, Gang-Hua; Tian, Yuhuan; Yu, Dongqi; Yang, Xueming; Yuan, Kaijun; Zheng, Junrong

    2016-03-31

    Isotopic effects on the formation and dissociation kinetics of hydrogen bonds are studied in real time with ultrafast chemical exchange spectroscopy. The dissociation time of hydrogen bond between phenol-OH and p-xylene (or mesitylene) is found to be identical to that between phenol-OD and p-xylene (or mesitylene) in the same solvents. The experimental results demonstrate that the isotope substitution (D for H) has negligible effects on the hydrogen bond kinetics. DFT calculations show that the isotope substitution does not significantly change the frequencies of vibrational modes that may be along the hydrogen bond formation and dissociation coordinate. The zero point energy differences of these modes between hydrogen bonds with OH and OD are too small to affect the activation energy of the hydrogen bond dissociation in a detectible way at room temperature. PMID:26967376

  4. Coupled valence bond theory

    NARCIS (Netherlands)

    Havenith, R.W.A.

    2005-01-01

    In this Letter, the formulation and implementation of a parallel response property code for non-orthogonal, valence bond wave-functions are described. Test calculations on benzene and cyclobutadiene show that the polarisability and magnetisability tensors obtained using valence bond theory are compa

  5. Bonded labour in Pakistan

    OpenAIRE

    Ercelawn, Aly; Nauman, Muhammad

    2001-01-01

    Examines the continuing prevalence of debt bondage in the 1990s despite the introduction of national legislation banning the practice. Makes recommendations to the Government and the international community for actions to be taken to eliminate bonded labour and provide rehabilitation for freed workers. Includes texts of Land Reforms Regulations, 1972, the Sindh Tenancy Act, 1950 and the Bonded Labour System (Abolition) Act, 1992.

  6. The samurai bond market

    OpenAIRE

    Frank Packer; Elizabeth Reynolds

    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.

  7. Money and Nominal Bonds

    OpenAIRE

    Marchesiani, Alessandro; Senesi, Pietro

    2007-01-01

    This paper studies an economy with trading frictions, ex post heterogeneity and nominal bonds in a model à la Lagos and Wright (2005). It is shown that a strictly positive interest rate is a sufficient condition for the allocation with nominal bonds to be welfare improving. This result comes from the protection against the inflation tax.

  8. Hydrogen bonding in polyanilines

    Energy Technology Data Exchange (ETDEWEB)

    Bahceci, S. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Toppare, L. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Yurtsever, E. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey))

    1994-11-29

    Hydrogen bonding between poly(bisphenol A carbonate) (PC) and polyaniline (PAn) is analyzed using semi-empirical quantum methodology. Fully optimized AM1 molecular orbital calculations are reported for various aniline structures (monomer, dimer and trimer), the monomer of the PC and the hydrogen-bonded model of PAn-PC oligomer. ((orig.))

  9. The main path to C, N, O elements in big bang nucleosynthesis

    International Nuclear Information System (INIS)

    The production of C, N, O elements in a standard big bang nucleosynthesis scenario is investigated. Using the up-to-date data of nuclear reactions in BBN, in particular the 8Li (n, γ) 9Li which has been measured in China Institute of Atomic Energy, a full nucleosynthesis network calculation of BBN is carried out. Our calculation results show that the abundance of 12C is increased for an order of magnitude after addition of the reaction chain 8Li (n, γ) 9Li (α, n) 12B (β) 12C, which was neglected in previous studies. We find that this sequence provides the main channel to convert the light elements into C, N, O in standard BBN. (authors)

  10. Generation of serine/threonine check points in HN(C)N spectra

    Indian Academy of Sciences (India)

    Dinesh Kumar; Jeetender Chugh; Ramakrishna V Hosur

    2009-11-01

    We describe here a simple modification of the HN(C)N experiment for the generation of serine/threonine check points in the three-dimensional experiment. The various `triplet of residue’ specific peak patterns in the spectra are documented for ease of analysis and sequential backbone resonance assignment. The performance of this experiment, referred to as HN(C)N-ST, is demonstrated using two proteins, one properly folded and the other completely denatured. It is noteworthy that, even in the denatured protein, where spectral dispersions are rather poor, about 90% of the sequential connectivities through the chain could be established from this single experiment. This would have great implications for structural genomics efforts.

  11. The development of nano-modified Ti(C,N) cermets.

    Science.gov (United States)

    Rong, Chunlan; Chen, Wenling; Zhang, Xiaobo; Liu, Ning

    2007-01-01

    The unique combination of mechanical properties such as excellent wear resistance and good chemical stability at elevated temperature helps titanium carbonitride based (Ti (C, N)-based) cermets to play an important roles in metal cutting operations. Nowadays, cermets cutting tools are widely used for semi-finishing and finishing works on steel and cast iron. However, their brittleness is still an unavoidable limitation for their utilization. With the development of nano-technology, nano-modified cermets have received more attention due to the high toughening enhancements. In this review, the development of nano-modified Ti(C,N) cermets is discussed including the fabrication, microstructure, mechanical properties, cutting performance and the practical applications in different fields. Many patents having important effect on the development of cermets were noticed, too. PMID:19076029

  12. Shape Bonding method

    Science.gov (United States)

    Pontius, James T. (Inventor)

    2010-01-01

    The present invention is directed to a method of bonding at least two surfaces together. The methods step of the present invention include applying a strip of adhesive to a first surface along a predefined outer boundary of a bond area and thereby defining a remaining open area there within. A second surface, or gusset plate, is affixed onto the adhesive before the adhesive cures. The strip of adhesive is allowed to cure and then a second amount of adhesive is applied to cover the remaining open area and substantially fill a void between said first and second surfaces about said bond area. A stencil may be used to precisely apply the strip of adhesive. When the strip cures, it acts as a dam to prevent overflow of the subsequent application of adhesive to undesired areas. The method results in a precise bond area free of undesired shapes and of a preferred profile which eliminate the drawbacks of the prior art bonds.

  13. Water's Hydrogen Bond Strength

    CERN Document Server

    Chaplin, Martin

    2007-01-01

    Water is necessary both for the evolution of life and its continuance. It possesses particular properties that cannot be found in other materials and that are required for life-giving processes. These properties are brought about by the hydrogen bonded environment particularly evident in liquid water. Each liquid water molecule is involved in about four hydrogen bonds with strengths considerably less than covalent bonds but considerably greater than the natural thermal energy. These hydrogen bonds are roughly tetrahedrally arranged such that when strongly formed the local clustering expands, decreasing the density. Such low density structuring naturally occurs at low and supercooled temperatures and gives rise to many physical and chemical properties that evidence the particular uniqueness of liquid water. If aqueous hydrogen bonds were actually somewhat stronger then water would behave similar to a glass, whereas if they were weaker then water would be a gas and only exist as a liquid at sub-zero temperature...

  14. Effects of Soil C/N Ratio on Apple Growth and Nitrogen Utilization,Residue and Loss

    Institute of Scientific and Technical Information of China (English)

    Shunfeng; GE; Yihua; REN; Ling; PENG; Haigang; XU; Mengmeng; JI; Shaochong; WEI; Yuanmao; JIANG

    2014-01-01

    Soil C /N ratio is an important influencing factor in soil nitrogen cycling. Two-year old apple trees( Borkh. cv. ‘Fuji’/Malus hupehensis) were used to understand the effect of soil C/N ratio [6. 52( CK),10,15,20,25,30,35 and 40]on apple growth and nitrogen utilization and loss by using15N trace technique. The results showed that,with the increasing of soil C/N ratio,apple shoot length and fresh weight increased at first,and then decreased; the higher apple shoot length and fresh weight appeared in C/N = 15,20 and 25 treatments,and there were no significant differences among these three treatments,but significantly higher than the other treatments. Statistical analysis revealed that there was significant difference in nitrogen utilization rate between the different treatments,the highest N utilization rate was occurred in soil C/N = 25 treatment which value was 22. 87%,and there was no significant difference between soil C/N = 25 and C/N = 20 treatments,but both the two treatments were significantly higher than the other treatments; Soil C/N = 40 had the lowest N utilization rate which value was 15. 43%,and this value was less than CK( 16. 65%). The proportion of plant absorption nitrogen from fertilizer was much higher when the value of soil C/N ratio in the range of 15- 25,but the percentage of plant absorption nitrogen from soil was much higher when the soil C/N ratio was too low( < 15) or high( < 25). Amount of residual nitrogen in soil increased gradually with the soil C/N ratio increasing,the amount of residual nitrogen in C/N = 40 treatment was 1. 32 times than that in CK. With the increasing of soil C/N ratio,fertilizer nitrogen loss decreased at first,and then increased,fertilizer nitrogen loss was the minimum in C/N = 25 treatments( 49. 87%) and the maximum were occurred in CK( 61. 54%). Therefore,regarding the apple growth and nitrogen balance situation,the value of soil C/N ratio in the range of 15- 25 would be favorable for apple growth and could

  15. Effect of Potassium and C/N Ratios on Conversion of NH+4 in Soils

    Institute of Scientific and Technical Information of China (English)

    TANG Yan; WANG Xiao-Zhi; ZHAO Hai-Tao; FENG Ke

    2008-01-01

    Two soils, one consisting of 1:1 clay minerals at pH 4.5 and the other containing 2:1 clay minerals at pH 7.0, were used to estimate the conversion of added NH+4 under different C/N ratios (glucose as the C source) and the addition of potassium. Under lower C/N ratios (0:1 and 5:1), a large part of the added NH+4 in the acid soil was held in the forms of either exchangeable or water soluble NH+4 for a relatively long time and under higher C/N ratio (50:1), a large amount of the added NH+4 was directly immobilized by microorganisms. In the second soil containing appreciable 2:1 type clay minerals a large part of the added NH+4 at first quickly entered the interlayer of the minerals under both lower and higher C/N ratios. In second condition, however, owing to microbial assimilation stimulated by glucose the newly fixed NH+4 could be completely released in further incubation because of a large concentration gradicnt between external NH+4 and fixed NH+4 in the mineral interlayer caused by heterotrophic microorganisms, which imply the fixed NH+4 to be available to plants. The results also showed that if a large amount of K+ with carbon source together was added to soil, the higher K+ concentration of soil solution could impede the release of fixed NH+4, even if there was a lot of carbon source.

  16. Höchstfeste nichtrostende austenitische CrMn-Stähle mit (C+N)

    OpenAIRE

    Riedner, Sascha

    2010-01-01

    Nichtrostende austenitische Stähle erzielen in der Regel nur geringe Festigkeiten. Die effektivste Methode zur Festigkeitssteigerung bietet das Legieren mit interstitiellen Atomen. Das gemeinsame Legieren mit (C+N) resultiert in offen erschmelzbaren, hochfesten nichtrostenden Austentiten. Die neuentwickelten Stähle weisen eine sehr hohe Austenitstabilität, Festigkeit, Kaltverfestigung, Zähigkeit und Duktilität auf. Auch unter zyklischer Beanspruchung kann die hohe Festigkeit genut...

  17. Cycloaddition Reactions of C,N-Diphenylnitrone to Methylene-γ-butyrolactones

    Directory of Open Access Journals (Sweden)

    Andrea Goti

    2000-04-01

    Full Text Available Cycloaddition of C,N-diphenylnitrone to α-methylene-γ-butyrolactone afforded two diastereomeric 5-spirosubstituted isoxazolidines with high selectivity. Structural assignment was ascertained by NMR studies and an X-ray diffraction experiment on a single crystal of the major isomer and the diastereoselectivity was rationalized on examination of the alternative transition states leading to the two diastereoisomers.

  18. Cycloaddition Reactions of C,N-Diphenylnitrone to Methylene-γ-butyrolactones

    OpenAIRE

    Andrea Goti; Cristina Faggi; Cordero, Franca M.; Martina Cacciarini

    2000-01-01

    Cycloaddition of C,N-diphenylnitrone to α-methylene-γ-butyrolactone afforded two diastereomeric 5-spirosubstituted isoxazolidines with high selectivity. Structural assignment was ascertained by NMR studies and an X-ray diffraction experiment on a single crystal of the major isomer and the diastereoselectivity was rationalized on examination of the alternative transition states leading to the two diastereoisomers.

  19. Einfluss der Herstellungsparameter auf die mechanischen Eigenschaften von Si-(B-)C-N-Precursorkeramiken

    OpenAIRE

    Bauer, Arndt

    2002-01-01

    Ziel dieser Arbeit ist es, den Herstellungsprozess für Precursorkeramiken zu optimieren und den Einfluss einzelner Herstellungsparameter auf die Eigenschaften und insbesondere auf die Hochtemperaturkriechverformung von Si-(B)-C-N-Precursorkeramiken zu charakterisieren. Am Beispiel eines kommerziell erhältlichen Polysilazans Ceraset werden als wichtigste Parameter die Vernetzungstemperatur der Polymere, die Polymerpartikelgröße nach dem Mahlen und Sieben sowie die Press- und Pyrolysebedingu...

  20. Thermische Entwicklung atomarer freier Volumen und Kristallisation in Si-(B)-C-N-Precursorkeramiken

    OpenAIRE

    Reichle, Klaus Jürgen

    2003-01-01

    Nichtoxidkeramiken auf der Basis von organischen Precursoren weisen günstige Potenziale als zukünftige Hochleistungskeramiken auf. In der vorliegenden Arbeit werden nanoskalige freie Volumen, deren chemische Umgebung sowie deren Entwicklung bei Anlassbehandlungen in Precursorkeramiken des Systems Si-B-C-N mit den spezifischen Methoden der Positronenzerstrahlungsspektroskopie analysiert. Diese freien Volumen sind für Diffusionsprozesse, Festkörperreaktionen oder mechanische Verhalten dieser Ke...

  1. ANALISIS PARAMETER BER DAN C/N DENGAN LNB COMBO PADA TEKNOLOGI DVB-S2

    OpenAIRE

    Wahyu Pamungkas; Eka Wahyudi; Anugrah Ahmad Fauzi

    2014-01-01

    Instalasi antena parabola berfungsi untuk memudahkan pada saat pengarahan pointing antena ke satelit yang dituju. Permasalahan yang diketahui yaitu bagaimana perilaku parameter Bit Error Rate (BER) dan Carrier to Noise (C/N) pada LNB Combo yang menggunakan teknologi DVB-S2. Setelah instalasi antena parabola dilakukan dan sukses, maka langkah selanjutnya yaitu melakukan pointing antena. Pointing antena diarahkan pada posisi satelit yang akan dituju. Satelit yang akan dituju yaitu Palapa D meng...

  2. 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.

  3. Effect of C/N ratio and salinity on power generation in compost microbial fuel cells.

    Science.gov (United States)

    Md Khudzari, Jauharah; Tartakovsky, Boris; Raghavan, G S Vijaya

    2016-02-01

    In this work, compost Microbial Fuel Cells (cMFCs) were used to generate electricity from a mix of fruit and vegetable wastes, and soil with different C/N ratios and salinities. Experiments were carried out in 500mL cMFCs equipped with carbon felt anodes and manganese dioxide cathodes. The cMFCs were loaded with fresh compost and operated at 20-23°C for up to 97days. The low C/N ratio (C/N 24) had a greater power production with a maximum power density of 5.29mW/m(2) (71.43mW/m(3)), indicating a more favorable condition for microbial growth. High-saline cMFCs produced lower power, suggesting that their level of salinity (10g/L of NaCl) inhibited electricigenic microorganisms. The closed-circuit cMFC showed an improved degradation of organic matter by 6% to 8% compared to the control MFC operated in an open circuit mode (no external resistor attached). PMID:26611399

  4. Friction and wear properties of C-N/MeNx nanolayer composites

    International Nuclear Information System (INIS)

    Nanolayer composite coatings enable creation of stable structures with unique properties, and in particular, combination of properties conventionally considered excluding one another, such as high hardness and high toughness. Coatings, typically 1-4 μm thick, were deposited at a total pressure ranging from 0.9 to 3 Pa, at relatively low substrate temperatures not exceeding 200 deg. C. We deposited nanostructured multilayer coatings of the C-N/MeNx type, where Me could be Ti, Nb or Zr. Various substrates such as, highly polished tungsten carbide, steel and silicon were used. This study concentrated on the tribological properties of C-N/MeNx nanostructured multilayers. The friction coefficient, wear and the film transfer in a ball-on-disk tribometer were presented. The samples were measured after the deposition and then thermally treated at a constant temperature in the air. Afterwards, the samples were again measured and then exposed to a higher temperature, until the layer broke down. We also investigated the structure of the coating by means of low-angle X-ray reflection and high-angle X-ray diffraction. The potential application of C-N/MeNx nanolayer composites as hard solid lubricant is discussed

  5. Contribution to the study of the (U,Pu)C,N system

    International Nuclear Information System (INIS)

    The reactions of UC, PuC, (U,Pu)C, UC2 and U(C1-xOx) with nitrogen at moderate temperatures (room temperature to 400 C) are described. The influence of the uptake of nitrogen by the powders necessary to sinter the carbides upon the nature of the final product has been investigated; it has been shown that the sintered carbides are hyper-stoichiometric. The reactions of carbon with UN, PuN and (U,Pu)N has also been studied. Under vacuum, carbon reacts on the nitrides at temperatures as low as 1100 C; nitrogen is replaced by carbon and the final product is a carbonitride. The reaction is: MN + x C → MN1-xCx + x/2N2. The reaction is limited and the carbonitrides have a fixed composition in presence of M2C3 or MC2; hence it is impossible to produce pure MC using the reaction. The ternary diagram U-C-N, Pu-C-N and (U,Pu)C-N have been drawn. They show clearly that it is possible to obtain single phase carbonitrides in a wide domain of compositions. (author)

  6. Interpretation of hydrogen bonding in the weak and strong regions using conceptual DFT descriptors

    OpenAIRE

    Özen, Alimet Sema; Ozen, Alimet Sema; De Proft, Frank; Aviyente , Viktorya; Geerlings, Paul

    2006-01-01

    Hydrogen bonding is among the most fundamental interactions in biology and chemistry, providing an extra stabilization of 1-40 kcal/mol to the molecular systems involved. This wide range of stabilization energy underlines the need for a general and comprehensive theory that will explain the formation of hydrogen bonds. While a simple electrostatic model is adequate to describe the bonding patterns in the weak and moderate hydrogen bond regimes, strong hydrogen bonds, on the other hand, requir...

  7. 77 FR 62510 - C.N. Brown Electricity, LLC; Supplemental Notice That Initial Market-Based Rate Filing Includes...

    Science.gov (United States)

    2012-10-15

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Federal Energy Regulatory Commission C.N. Brown Electricity, LLC; Supplemental Notice That Initial Market-Based... above-referenced proceeding, of C.N. Brown Electricity, LLC's application for market-based...

  8. Chemical bonding modifications of tetrahedral amorphous carbon and nitrogenated tetrahedral amorphous carbon films induced by rapid thermal annealing

    Energy Technology Data Exchange (ETDEWEB)

    McCann, R. [NIBEC, School of Electrical and Mechanical Engineering, University of Ulster at Jordanstown, Newtownabbey, Co. Antrim, BT37 OQB, N. Ireland (United Kingdom); Roy, S.S. [NIBEC, School of Electrical and Mechanical Engineering, University of Ulster at Jordanstown, Newtownabbey, Co. Antrim, BT37 OQB, N. Ireland (United Kingdom)]. E-mail: s.sinha-roy@ulster.ac.uk; Papakonstantinou, P. [NIBEC, School of Electrical and Mechanical Engineering, University of Ulster at Jordanstown, Newtownabbey, Co. Antrim, BT37 OQB, N. Ireland (United Kingdom); Bain, M.F. [Queens University of Belfast, School of Elect and Elect Engineering, Belfast, Antrim, N. Ireland (United Kingdom); Gamble, H.S. [Queens University of Belfast, School of Elect and Elect Engineering, Belfast, Antrim, N. Ireland (United Kingdom); McLaughlin, J.A. [NIBEC, School of Electrical and Mechanical Engineering, University of Ulster at Jordanstown, Newtownabbey, Co. Antrim, BT37 OQB, N. Ireland (United Kingdom)

    2005-06-22

    Tetrahedral amorphous carbon (ta-C) and nitrogenated tetrahedral amorphous carbon films (ta-CN {sub x}), deposited by double bend off plane Filtered Vacuum Cathodic Arc were annealed up to 1000 deg. C in flowing argon for 2 min. Modifications on the chemical bonding structure of the rapidly annealed films, as a function of temperature, were investigated by NEXAFS, X-ray photoelectron and Raman spectroscopies. The interpretation of these spectra is discussed. The results demonstrate that the structure of undoped ta-C films prepared at floating potential with an arc current of 80 A remains stable up to 900 deg. C, whereas that of ta-CN {sub x} containing 12 at.% nitrogen is stable up to 700 deg. C. At higher temperatures, all the spectra indicated the predominant formation of graphitic carbon. Through NEXAFS studies, we clearly observed three {pi}* resonance peaks at the {sup '}N K edge structure. The origin of these three peaks is not well established in the literature. However our temperature-dependant study ascertained that the first peak originates from C=N bonds and the third peak originates from the incorporation of nitrogen into the graphite like domains.

  9. 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.

  10. 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...... to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...

  11. 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....

  12. The Halogen Bond

    Science.gov (United States)

    2016-01-01

    The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design. PMID:26812185

  13. METABOLIC ENGINEERING TO DEVELOP A PATHWAY FOR THE SELECTIVE CLEAVAGE OF CARBON-NITROGEN BONDS

    Energy Technology Data Exchange (ETDEWEB)

    John J. Kilbane III

    2003-12-01

    The objective of the project is to develop biochemical pathways for the selective cleavage of C-N bonds in molecules found in petroleum. The initial phase of the project will focus on the isolation or development of an enzyme capable of cleaving the C-N bond in aromatic amides, specifically 2-aminobiphenyl. The objective of the second phase of the research will be to construct a biochemical pathway for the selective removal of nitrogen from carbazole by combining the carA genes from Sphingomonas sp. GTIN11 with the gene(s) encoding an appropriate amidase. The objective of the final phase of the project will be to develop derivative CN bond cleaving enzymes that have broader substrate ranges and to demonstrate the use of such strains to selectively remove nitrogen from petroleum. The project is on schedule and no major difficulties have been encountered. During the first year of the project (October, 2002-September, 2003) enrichment culture experiments have resulted in the isolation of promising cultures that may be capable of cleaving C-N bonds in aromatic amides, several amidase genes have been cloned and are currently undergoing directed evolution to obtain derivatives that can cleave C-N bonds in aromatic amides, and the carA genes from Sphingomonas sp. GTIN11, and Pseudomonas resinovorans CA10 were cloned in vectors capable of replicating in Escherichia coli. Future research will address expression of these genes in Rhodococcus erythropolis. Enrichment culture experiments and directed evolution experiments continue to be a main focus of research activity and further work is required to obtain an appropriate amidase that will selectively cleave C-N bonds in aromatic substrates. Once an appropriate amidase gene is obtained it must be combined with genes encoding an enzyme capable of converting carbazole to 2'aminobiphenyl-2,3-diol: specifically carA genes. The carA genes from two sources have been cloned and are ready for construction of C-N bond cleavage

  14. Microstructure and cutting performance of Ti(C, N)-based cermets heat-treated in nitrogen

    Institute of Scientific and Technical Information of China (English)

    LIU Wenjun; XIONG Weihao; ZHENG Yong; SHI Zengmin; YE Jiajian

    2007-01-01

    Ti(C, N)-based cermets were treated using hot isostatic pressing (HIP) at 1423 K in nitrogen. The microstructures compared with the as-sintered cermets were investigated using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray analysis, and electron microprobe analysis. It was found that high nitrogen activity in the surface zone resulted in the formation of gradient structure. Approximately 20-μm-deep, nitrogen-rich and titanium-rich hard surface zone was introduced by the beat treatment. The nitrogen activity was the driving force that caused the transportation of the atoms through the binder, titanium towards the surface, and tungsten and molybdenum inwards. In the surface zone, the particle size became fine, the inner rim disappeared, and the volume fraction of the outer rim and the binder phase considerably reduced. Small grains of TiN, WC, Mo2C, and nitrogen-rich carbonitride phases formed in the surface zone during the heat treatment, improving the tribological property of the heat-treated cermet.

  15. Formation of Benzimidazoisoquinolinium and Benzimidazoisoindolinum Cyclic Systems by the Reaction of 2-(2-Alkynylphenyl)benzimidazoles with Iodine and Iodine-Iodine Interaction Including Halogen Bonding in Their Crystal Structures.

    Science.gov (United States)

    Matsumoto, Shoji; Kikuchi, Shu; Norita, Naoto; Masu, Hyuma; Akazome, Motohiro

    2016-07-01

    The reaction of 2-(2-alkynylphenyl)benz[d]imidazoles with molecular iodine constructed 5- and 6-membered rings as novel organic salts in high yield. The constituted number of ring systems was influenced by the substituent at the triple bond: 6-membered rings were formed from compounds bearing aryl substituents, whereas 5-membered ones were obtained from compounds with hydrogen or alkyl substituents. The products were obtained with triiodide as a counteranion; however, compounds with iodide were also obtainable under certain conditions. We also revealed that they had an iodine-iodine interaction included in halogen bonding between an iodo moiety of the cation and a triiodide or iodide of the counteranion. The iodine-iodine interaction was formed with greater preference than the electrostatic interaction between the cationic atom and triiodide or iodide. PMID:27258839

  16. Bond dissociation & electronegativity equalization

    OpenAIRE

    Verstraelen, Toon; Ayers, Paul W.; Van Speybroeck, Veronique; Waroquier, Michel

    2012-01-01

    It is well known that the Electrongativity Equalization Mtehod (EEM) fails to describe the charge distribution upon bond dissocation. In this presentation, the bond dissocation is studied with the Atom-Condensed Kohn-Sham DFT approximated to second order (ACKS2). After reviewing the basic equations, a two-fragment system is studied in the dissociation limit. The limiting behavior of the Coulomb interaction (1/r) and the Kohn-Sham matrix elements (exponentially decaying) are plugged into the e...

  17. Anodic bonded graphene

    OpenAIRE

    Balan, Adrian; Kumar, Rakesh; Boukhicha, Mohamed; Beyssac, Olivier; Bouillard, Jean-Claude; Taverna, Dario; Sacks, William; Marangolo, Massimiliano; Lacaze, Emmanuelle; Escoffier, Walter; Poumirol, Jean-Marie; Shukla, Abhay

    2010-01-01

    Abstract We show how to prepare graphene samples on a glass substrate with the anodic bonding method. In this method, a graphite precursor in flake form is bonded to a glass substrate with the help of an electrostatic field and then cleaved off to leave few layer graphene on the substrate. Now that several methods are available for producing graphene, the relevance of our method is in its simplicity and practicality for producing graphene samples of about 100 ?m lateral dimensions. This me...

  18. 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.

  19. Some new members of MAX family including light-elements: Nanolayered Hf2XY (X= Al, Si, P and Y=B, C, N)

    Science.gov (United States)

    Aydin, Sezgin; Tatar, Aynur; Ciftci, Yasemin Oztekin

    2016-03-01

    The structural, electronic, mechanical and dynamical properties of new members of MAX family (Hf2XY, X=Al, Si, P and Y= B, C, N compounds) with Cr2AlC-type structure have been investigated by first-principles density functional plane-wave pseudopotential calculations within generalized gradient approximation. From calculated cohesive energies, all compounds are energetically stable. And, from calculated elastic constants and phonon dispersion curves, it is shown that all compounds are mechanically stable, while the boron including ones are dynamically unstable except for Hf2PB. At the same time, related mechanical properties such as bulk and shear moduli are calculated. For further mechanical characterization, hardnesses of the compounds are determined theoretically. It is observed from electronic structure calculations including band structure and partial density of states, all stable compounds are metallic. Additionally, bonding nature of the compounds are analyzed by using 3D and 2D electron density maps, Mulliken atomic charges and bond overlap populations.

  20. Occult cervical lymph node metastases in 100 consecutive patients with cN0 tongue cancer

    Institute of Scientific and Technical Information of China (English)

    JIN Wu-long; YE Wei-min; ZHENG Jia-wei; ZHOU Liang; ZHU Han-guang; ZHANG Zhi-yuan; TIAN Jie

    2008-01-01

    Background Squamous cell carcinoma (SCC) of the tongue is one of the most common cancers in the oral and maxillofacial region. To provide clinical evidence for selective neck dissection in management of cN0 patients by analyzing the characteristics and correlation of factors of occult cervical lymph node metastases (OCLNM) in patients with SCC of the tongue.Methods From 2002 to 2006, 100 consecutive patients with SCC of the tongue were reviewed by analyzing the characteristics of OCLNM, diameter of the tumor, T classifications, depth of invasion, forms of growth, pathological grade and degree of differentiation.Results The rate of OCLNM in 100 patients with SCC of the tongue was 22%. The most common region with OCLNM was level Ⅱ in the ipsilateral neck, followed by levels Ⅰ and Ⅲ. There were 51.61% (16/31) of OCLNM in level Ⅱ and 87.10% (27/31) of OCLNM in levels Ⅰ-Ⅲ. There was no significant correlation between the diameter of tumor and OCLNM (P >0.05). OCLNM was statistically significantly correlated with the depth of invasion, forms of growth, pathological grade and degree of differentiation (P <0.05). The rate of occult metastases increased with the increased pathological grade,the decreased degree of differentiation and the increased depth of invasion.Conclusions The most common regions with OCLNM in cN0 patients with SCC of the tongue were levels Ⅰ-Ⅲ in the ipsilateral neck. Supraomohyoid neck dissection should be the elective treatment to the neck in patients with cN0 SCC of the tongue by consideration of the clinical and pathological factors for the depth of invasion, forms of growth, pathological grade, and degree of differentiation.

  1. Bond Length and Bond Order in One of the Shortest Cr-Cr Bonds

    OpenAIRE

    La Macchia, Giovanni; Aquilante, Francesco; Veryazov, Valera; Roos, Bjorn O.; Gagliardi, Laura

    2008-01-01

    Multiconfigurational quantum chemical calculations on the R-diimines dichromium compound confirm that the Cr-Cr bond, 1.80 A, is among the shortest Cr (I)-Cr (I) bonds. However, the bond between the two Cr atoms is only a quadruple bond rather than a quintuple bond. The reason why the bond is so short has to be attributed to the strain in the NCCN ligand moieties.

  2. 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...

  3. 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.

  4. Individual alpha elements, C, N, and Ba in early-type galaxies

    International Nuclear Information System (INIS)

    Spectral data on early-type galaxies are analyzed for chemical abundance with an emphasis on obtaining detailed abundances for the elements O and Si in addition to C, N, Na, Mg, Ca, Fe, and Ba. The abundance trends with velocity dispersion fit preconceptions based upon previous Mg conclusions, namely, that larger galaxies have a higher alpha element to iron peak ratio indicative of a higher ratio of Type II to Type Ia supernova products. The heaviest alpha elements, Ca and Ti, do not participate in this trend, although this fact does not necessarily alter the basic picture given the uncertainties in nucleosynthetic yields. Elements that likely have significant contributions from intermediate-mass stars, namely, C, N, and Ba, also gain ground relative to Fe in massive galaxies at a modest level, with the Ba conclusion uncertain from our data alone. After the velocity dispersion trend is subtracted, [M/H], [N/Fe], [Na/Fe], [Mg/Fe], and [Ca/Fe] probably have cosmic scatter, and no quantity can be shown to not have cosmic scatter.

  5. Effect of annealing on EPR spectra of Ti-Si-C-N samples

    Science.gov (United States)

    Guskos, N.; Anagnostakis, E. A.; Zolnierkiewicz, G.; Typek, J.; Biedunkiewicz, A.; Guskos, A.; Berczynski, P.

    2012-03-01

    Two nanocrystalline samples of TiC+SiC+20%C (sample 1) and Si3N4+Si(C,N)+Ti(C,N)+1%C (sample 2) were prepared by non-hydrolytic sol-gel method. The latter sample was produced from sample 1, by subjecting it to additional annealing at high temperature. XRD measurements showed the presence of aggregates of cubic SiC+TiC nanoparticles (10 to 30 nm in size). In both samples, a very narrow electron paramagnetic resonance (EPR) line originating from localized magnetic centers was centered at g eff˜2. At T = 130 K, we registered the linewidths Δ H pp = 1.41(2) G and Δ H pp = 2.92(2) G for the sample without and with thermal annealing, respectively. For the non-annealed sample, the resonance line was fitted by a Lorentzian line in the low temperature range, and by a Dysonian line above 70 K, which indicates a significant change in electrical conductivity. Therefore, thermal annealing can significantly improve the transport properties of samples. An analysis of the temperature dependence of the EPR parameters ( g-factor, linewidth, integrated intensity) showed that thermal annealing has a significant impact on the reorientation processes of localized magnetic centers.

  6. Efficiency Calibration for Measuring the 12C(n, 2n)11C Cross Section

    Science.gov (United States)

    Eckert, Thomas; Gula, August; Vincett, Laurel; Yuly, Mark; Padalino, Stephen; Russ, Megan; Bienstock, Mollie; Simone, Angela; Ellison, Drew; Desmitt, Holly; Sangster, Craig; Regan, Sean; Fitzgerald, Ryan

    2015-11-01

    One possible inertial confinement fusion diagnostic involves tertiary neutron activation via the 12C(n, 2n)11C reaction. A recent experiment to measure this reaction cross-section involved coincidence counting the annihilation gamma rays produced by the positron decay of 11C. This requires an accurate value for the full-peak coincidence efficiency of the NaI detector system. The GEANT 4 toolkit was used to develop a Monte Carlo simulation of the detector system which can be used to calculate the required efficiencies. For validation, simulation predictions have been compared with the results of two experiments. In the first, full-peak coincidence positron annihilation efficiencies were measured for 22Na decay positrons that annihilate in a small plastic scintillator. In the second, a NIST-calibrated 68Ge source was used. A comparison of calculated with measured efficiencies, as well as 12C(n, 2n)11C cross sections are presented. Funded in part by a grant from the DOE through the Laboratory for Laser Energetics.

  7. Preparation of state purified beams of He, Ne, C, N, and O atoms

    Science.gov (United States)

    Jankunas, Justin; Reisyan, Kevin S.; Osterwalder, Andreas

    2015-03-01

    The production and guiding of ground state and metastable C, N, and O atoms in a two-meter-long, bent magnetic guide are described. Pure beams of metastable He(3S1) and Ne(3P2), and of ground state N(4S3/2) and O(3P2) are obtained using an Even-Lavie valve paired with a dielectric barrier discharge or electron bombardment source. Under these conditions no electronically excited C, N, or O atoms are observed at the exit of the guide. A general valve with electron impact excitation creates, in addition to ground state atoms, electronically excited C(3P2; 1D2) and N(2D5/2; 2P3/2) species. The two experimental conditions are complimentary, demonstrating the usefulness of a magnetic guide in crossed or merged beam experiments such as those described in Henson et al. [Science 338, 234 (2012)] and Jankunas et al. [J. Chem. Phys. 140, 244302 (2014)].

  8. Preparation of state purified beams of He, Ne, C, N, and O atoms

    Energy Technology Data Exchange (ETDEWEB)

    Jankunas, Justin; Reisyan, Kevin S.; Osterwalder, Andreas, E-mail: andreas.osterwalder@epfl.ch [Institute for Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland)

    2015-03-14

    The production and guiding of ground state and metastable C, N, and O atoms in a two-meter-long, bent magnetic guide are described. Pure beams of metastable He({sup 3}S{sub 1}) and Ne({sup 3}P{sub 2}), and of ground state N({sup 4}S{sub 3/2}) and O({sup 3}P{sub 2}) are obtained using an Even-Lavie valve paired with a dielectric barrier discharge or electron bombardment source. Under these conditions no electronically excited C, N, or O atoms are observed at the exit of the guide. A general valve with electron impact excitation creates, in addition to ground state atoms, electronically excited C({sup 3}P{sub 2}; {sup 1}D{sub 2}) and N({sup 2}D{sub 5/2}; {sup 2}P{sub 3/2}) species. The two experimental conditions are complimentary, demonstrating the usefulness of a magnetic guide in crossed or merged beam experiments such as those described in Henson et al. [Science 338, 234 (2012)] and Jankunas et al. [J. Chem. Phys. 140, 244302 (2014)].

  9. The corrosion behavior of Cr-(C,N) PVD hard coatings deposited on various substrates

    International Nuclear Information System (INIS)

    A comparison was made between the electrochemical corrosion behavior of chromium carbonitride (Cr-(C,N)) and chromium nitride (Cr-N) coatings produced by evaporation in a thermionic-arc ion-plating apparatus at 450 deg. C. These coatings were deposited on substrates in the form of discs of mild-steel (CK 45) and stainless-steel (SS 304). Potentiodynamic polarization tests, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) were the techniques used to characterize the corrosion behavior. The potentiodynamic tests revealed the current density versus potential for the coated and uncoated substrates and the difference in their corrosion potentials (Ecorr). In all cases the Ecorr shifted to a more positive potential after the coatings were applied. The electrochemical impedance spectroscopy measurements as a function of immersion time were carried out in a 0.5 M NaCl solution at the Ecorr. The corrosion properties, lower current density, and higher polarization resistance were found to be two to six times better than the uncoated substrate for the Cr-(C,N) coatings and two orders of magnitude better for the Cr-N coatings

  10. DFT investigation on dihydrogen-bonded amine-borane complexes.

    Science.gov (United States)

    Yan, Shihai; Zou, Hongmei; Kang, Wukui; Sun, Lixiang

    2016-01-01

    The DFT method has been employed in the exploration on dihydrogen-bonded amine-borane complexes, with a special emphasis on the dimerization and substituent group effect. Stable dihydrogen bonded complexes can be generated from these amine-borane monomers with the appearance of NH(δ+)…H(δ-)B interactions. The binding energy decreases gradually with the increase of the steric effect of the substituents. The substituent group number mainly varies the C-N bond length. The dimerization generates close H…H and influences predominantly the N-B distance. The effect of dimerization on IR and vibrational circular dichroism (VCD) spectra is stronger than that of the number of substituent groups, which leads to distinct NBO charge variation on α-C. Both the substituent group number and dimerization enhance the chemical shift difference between hydrogen atoms covalently bonded to N and B, Δδ H-H, which can be hired as an index for structural determination. It is proposed that amine-borane complexes with more substituent groups in higher degree of polymerization are potentially interesting materials for hydrogen storage. Graphical Abstract Both the number of substituent group and dimerization enhance the chemical shift difference of hydrogen atoms covalently bonded on N and B, Δδ H-H, which can be employed as an index for the structural determination. PMID:26696542

  11. 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.

  12. TEXT tf coil bonding system

    International Nuclear Information System (INIS)

    An extensive bond test program was conducted prior to manufacturing and bonding the toroidal field (TF) coils for the Texas Experimental Tokamak (TEXT). The bonding materials consisted of fiberglass cloth with pre-impregnated, 'B' staged Hexcel F-159 resin. Approximately 100 double lap bond samples were constructed to test quality, strength, and repeatability of the bonds. The variables investigated included surface machining methods, surface preparations, bond sample size (planform area), bonding pressure, bonding temperature, and the number of laminations bonded simultaneously. Double lap shear tests conducted at room temperature resulted in ultimate shear strengths for all variables in the range of 3000 to 7000 psi with an average value of 5650 psi. Fatigue tests were also conducted to demonstrate bond integrity over the anticipated cycle lifetime of the TEXT machine (10/sup 6/ cycles) under simulated worst case conditions. 2 refs

  13. Insulation bonding test system

    Science.gov (United States)

    Beggs, J. M.; Johnston, G. D.; Coleman, A. D.; Portwood, J. N.; Saunders, J. M.; Redmon, J. W.; Porter, A. C. (Inventor)

    1984-01-01

    A method and a system for testing the bonding of foam insulation attached to metal is described. The system involves the use of an impacter which has a calibrated load cell mounted on a plunger and a hammer head mounted on the end of the plunger. When the impacter strikes the insulation at a point to be tested, the load cell measures the force of the impact and the precise time interval during which the hammer head is in contact with the insulation. This information is transmitted as an electrical signal to a load cell amplifier where the signal is conditioned and then transmitted to a fast Fourier transform (FFT) analyzer. The FFT analyzer produces energy spectral density curves which are displayed on a video screen. The termination frequency of the energy spectral density curve may be compared with a predetermined empirical scale to determine whether a igh quality bond, good bond, or debond is present at the point of impact.

  14. The Illiquidity of Corporate Bonds

    OpenAIRE

    Bao, Jack; Pan, Jun; Wang, Jiang

    2011-01-01

    This paper examines the illiquidity of corporate bonds and its asset-pricing implications. Using transactions data from 2003 to 2009, we show that the illiquidity in corporate bonds is substantial, significantly greater than what can be explained by bid–ask spreads. We establish a strong link between bond illiquidity and bond prices. In aggregate, changes in market-level illiquidity explain a substantial part of the time variation in yield spreads of high-rated (AAA through A) bonds, overshad...

  15. Flexible C, N and P allocation in maize plants and soil microbial biomass under recurrent and long-term drought

    Science.gov (United States)

    Larionova, Alla; Semenov, Vyacheslav; Yevdokimov, Ilya; Blagodatskaya, Evgenia

    2016-04-01

    One of the negative effects of the global warming is increasing aridity worldwide. Alterations in plant and microbial C, N and P in response to drought events can differ considerably in magnitude and direction. Therefore, synchronization between C, N and P in plants, dissolved forms and microbial biomass in soil is of great interest. Our objective was to evaluate C:N:P stoichiometry relations in plants and soil as affected by moderate water shortage and severe drought with subsequent rewetting. We tested the sensitivity of stoichiometry ratios in plants, dissolved compounds and soil microbial biomass in greenhouse experiment with maize. Three treatments were used: i) control with constant soil moisture (CTL); ii) soil with constantly low wetness of 25% WHC (DRY) and iii) soil exposed to drying-rewetting events (DRW). N dynamics was the most sensitive to water stress in maize plants and soil, while P dynamics was almost unaffected by drought and rewetting. As a result, C:N and N:P ratios were also sensitive to water treatment indicating that C, N and P cycles were decoupled by the water stresses. High C:N ratios in CTL and low C:N ratios in DRY and DRW treatments indicate stoichiometric flexibility in plants and soil microbes. N allocation was found to respond to N shortage in CTL and increased salt concentrations in soil solution in DRY and DRW treatments. C:N:P stoichiometry in soil microbes was found flexible during active plant growth, while that at the end of growth season turned to almost homeostatic ratio. The research was supported by Russian Science Foundation (project 14-14-00625)

  16. Anodic bonded graphene

    Energy Technology Data Exchange (ETDEWEB)

    Balan, Adrian; Kumar, Rakesh; Boukhicha, Mohamed; Beyssac, Olivier; Bouillard, Jean-Claude; Taverna, Dario; Sacks, William; Shukla, Abhay [Universite Pierre et Marie Curie-Paris 6, CNRS-UMR7590, Institut de Mineralogie et de Physique des Milieux Condenses, 140 rue de Lourmel, Paris, F-75015 France (France); Marangolo, Massimiliano; Lacaze, Emanuelle; Gohler, Roger [Universite Pierre et Marie Curie-Paris 6, CNRS-UMR7588, Institut des Nanosciences de Paris, 140 rue de Lourmel, Paris, F-75015 France (France); Escoffier, Walter; Poumirol, Jean-Marie, E-mail: abhay.shukla@upmc.f [Laboratoire National des Champs Magnetiques Intenses, INSA UPS CNRS, UPR 3228, Universite de Toulouse, 143 avenue de Rangueil, 31400 Toulouse (France)

    2010-09-22

    We show how to prepare graphene samples on a glass substrate with the anodic bonding method. In this method, a graphite precursor in flake form is bonded to a glass substrate with the help of an electrostatic field and then cleaved off to leave few layer graphene on the substrate. Now that several methods are available for producing graphene, the relevance of our method is in its simplicity and practicality for producing graphene samples of about 100 {mu}m lateral dimensions. This method is also extensible to other layered materials. We discuss some detailed aspects of the fabrication and results from Raman spectroscopy, local probe microscopy and transport measurements on these samples.

  17. 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.

  18. Intramolecular hydrogen bonds in sulfur-containing aminophenols

    Science.gov (United States)

    Belkov, M. V.; Harbachova, A. N.; Ksendzova, G. A.; Polozov, G. I.; Skornyakov, I. V.; Sorokin, V. L.; Tolstorozhev, G. B.; Shadyro, O. I.

    2010-07-01

    IR Fourier spectroscopy methods have been adopted to study intramolecular interactions that occur in CCl4 solutions of antiviral derivatives of aminophenol. Analysis of the IR spectra showed that intramolecular bonds O-H···N, O-H···O=C, N-H···O=S=O, and O-H···O=S=O can occur in these compounds depending on the substituent on the amino group. Not only the presence of intramolecular O-H···N, O-H···O=S=O, and N- H···O=S=O hydrogen bonds in 2-amino-4,6-di-tert-butylphenol derivatives containing a sulfonamide fragment but also conformational equilibrium among these types of intramolecular interactions are essential for the manifestation of high efficiency in suppressing HIV-infection in cell culture.

  19. Effect of the C:N:P ratio on the denitrifying dephosphatation in a sequencing batch biofilm reactor (SBBR).

    Science.gov (United States)

    Mielcarek, Artur; Rodziewicz, Joanna; Janczukowicz, Wojciech; Thornton, Arthur J; Jóźwiak, Tomasz; Szymczyk, Paula

    2015-12-01

    A series of investigations were conducted using sequencing batch biofilm reactor (SBBR) to explore the influence of C:N:P ratio on biological dephosphatation including the denitrifying dephosphatation and the denitrification process. Biomass in the reactor occurred mainly in the form of a biofilm attached to completely submerged disks. Acetic acid was used as the source of organic carbon. C:N:P ratios have had a significant effect on the profiles of phosphate release and phosphate uptake and nitrogen removal. The highest rates of phosphate release and phosphate uptake were recorded at the C:N:P ratio of 140:70:7. The C:N ratio of 2.5:1 ensured complete denitrification. The highest rate of denitrification was achieved at the C:N:P ratio of 140:35:7. The increase of nitrogen load caused an increase in phosphates removal until a ratio C:N:P of 140:140:7. Bacteria of the biofilm exposed to alternate conditions of mixing and aeration exhibited enhanced intracellular accumulation of polyphosphates. Also, the structure of the biofilm encouraged anaerobic-aerobic as well as anoxic-anaerobic and absolutely anaerobic conditions in a SBBR. These heterogeneous conditions in the presence of nitrates may be a significant factor determining the promotion of denitrifying polyphosphate accumulating organism (DNPAO) development. PMID:26702975

  20. Nature of large (Ti, Nb)(C, N) particles precipitated during the solidification of Ti, Nb HSLA steel

    Institute of Scientific and Technical Information of China (English)

    Xiaojun Zhuo; Xinhua Wang; Wanjun Wang; Hae-Geon Lee

    2007-01-01

    To investigate the microsegregation phenomena and complex (Ti, Nb)(C, N) precipitation behavior during continuous casting, a unidirectional solidification unit was employed to simulate the solidification process. The samples of Ti, Nb-addition steels after unidirectional solidification were examined using field emission scanning electron microscope (FE-SEM) and electron probe X-ray microanalyzer (EPMA). In such specimens, dendrite structure and mushy zone can be detected along the solidification direction. It shows that the addition of titanium, niobium to high-strength low-alloyed (HSLA) steel results in undesirable (Ti, Nb)(C, N) precipitation because of microsegregation. The effect of cooling rate on (Ti, Nb)(C, N) precipitation was investigated. The composition of large precipitates was determined using FE-SEM with EDS. Large (Ti, Nb)(C, N) precipitates could be divided into three kinds according to the composition and morphology. With the cooling rate increasing, Ti-rich (Ti, Nb)(C, N) precipitates are transformed to Nb-rich (Ti, Nb)(C, N) precipitates.

  1. Dopamine receptors in pituitary adenomas: PET visualization with 11C-N-methylspiperone

    Energy Technology Data Exchange (ETDEWEB)

    Muhr, C.; Bergstroem, M.L.; Lundberg, P.O.; Bergstroem, K.H.; Hartvig, P.; Lundqvist, H.; Antoni, G.; Langstroem B2

    1986-03-01

    Two patients with pituitary tumors were examined with positron emission tomography (PET) after intravenous administration of 11C-N-methylspiperone. In repeat studies the patients were given 1 mg of intravenous haloperidol prior to the administration of the radioligand to block the dopamine receptors. High uptakes of the radiolabeled ligand were seen in one of the tumors. With haloperidol pretreatment the uptake was lower, probably mainly showing the remaining unspecific binding. The most marked uptake and the largest effect of haloperidol pretreatment was seen in a patient with a hormonally active prolactinoma. Dopamine receptor binding in pituitary tumors can be demonstrated in vivo with PET, and quantification of this binding is possible using a compartmental model. This technique may be useful in improving our understanding of the variable response to medical treatment of prolactinomas with dopamine agonists as well as in the prediction of the effect of such treatment.

  2. Novel Rhodate and Iridate Complexes containing C,N Chelating Arylamine Ligand Systems

    OpenAIRE

    van Koten, G; Wehman - Ooyevaar, I.C.M.; Vedral, J.A.; Jastrzebski, J.T.B.H.; Grove, D.M.

    1993-01-01

    The synthesis is described of a series of new iridate and rhodate complexes Li(L-C, N){2}M(cod) (M = Rh, Ir; cod = cycloocta-1,5-diene) containing the ortho-chelating, mono-anionic, arylamine ligands L = C{6}H{4}CH{2}NR{2}-2 (R = Me, Et), C{6}H{3}CH{2}NMe{2}- 2-Me-5, C{6}H{4}CH(Me)NMe{2}-(R)-2 or C{6}H{4}CH{2}NMe(}t{Bu)-2. The synthetic procedure for the -ate complexes from [MCl(cod)] {2} depends on the solubility of the starting aryllithium compound in benzene-an indirect effect of the bulky...

  3. Chemical footprints of anthropogenic nitrogen deposition on recent soil C : N ratios in Europe

    Directory of Open Access Journals (Sweden)

    C. Mulder

    2015-03-01

    Full Text Available Long-term human interactions with landscape and nature produced a plethora of trends and patterns of environmental disturbances in time and space. Nitrogen deposition, closely tracking energy and land use, is known to be among the main pollution drivers, affecting both freshwater as terrestrial ecosystems. We investigated the geographical distribution of nitrogen deposition and the impacts of accumulation on recent soil carbon to nitrogen ratios over Europe. After the Second Industrial Revolution (1880–2010, large landscape stretches characterized by different atmospheric deposition caused either by industrialized areas or by intensive agriculture emerged. Nitrogen deposition affects in a still recognizable way recent soil C : N ratios despite the emission abatement of oxidized and reduced nitrogen during the last two decades. Given the seemingly disparate land-use history, we focused on ~ 10 000 unmanaged ecosystems, providing evidence for a rapid response of nature to chronic nitrogen supply by atmospheric deposition.

  4. UV spectra of iron-doped carbon clusters FeC_n n = 3-6

    CERN Document Server

    Steglich, Mathias; Johnson, Anatoly; Maier, John P

    2015-01-01

    Electronic transitions of jet-cooled FeC$_n$ clusters ($n = 3 - 6$) were measured between 230 and 300 nm by a mass-resolved 1+1 resonant two-photon ionization technique. Rotational profiles were simulated based on previous calculations of ground state geometries and compared to experimental observations. Reasonable agreement is found for the planar fan-like structure of FeC$_3$. The FeC$_4$ data indicate a shorter distance between the Fe atom and the bent C$_4$ unit of the fan. The transitions are suggested to be $^{3}$A$_{2} \\leftarrow ^{3}$B$_{1}$ for FeC$_3$ and $^{5}$A$_{1} \\leftarrow ^{5}$A$_{1}$ for FeC$_4$. In contrast to the predicted C$_{\\infty \\text{v}}$ geometry, non-linear FeC$_5$ is apparently observed. Line width broadening prevents analysis of the FeC$_6$ spectrum.

  5. Dopamine receptors in pituitary adenomas: PET visualization with 11C-N-methylspiperone

    International Nuclear Information System (INIS)

    Two patients with pituitary tumors were examined with positron emission tomography (PET) after intravenous administration of 11C-N-methylspiperone. In repeat studies the patients were given 1 mg of intravenous haloperidol prior to the administration of the radioligand to block the dopamine receptors. High uptakes of the radiolabeled ligand were seen in one of the tumors. With haloperidol pretreatment the uptake was lower, probably mainly showing the remaining unspecific binding. The most marked uptake and the largest effect of haloperidol pretreatment was seen in a patient with a hormonally active prolactinoma. Dopamine receptor binding in pituitary tumors can be demonstrated in vivo with PET, and quantification of this binding is possible using a compartmental model. This technique may be useful in improving our understanding of the variable response to medical treatment of prolactinomas with dopamine agonists as well as in the prediction of the effect of such treatment

  6. Chemical footprints of anthropogenic nitrogen deposition on recent soil C : N ratios in Europe

    Science.gov (United States)

    Mulder, C.; Hettelingh, J.-P.; Montanarella, L.; Pasimeni, M. R.; Posch, M.; Voigt, W.; Zurlini, G.

    2015-07-01

    Long-term human interactions with the natural landscape have produced a plethora of trends and patterns of environmental disturbances across time and space. Nitrogen deposition, closely tracking energy and land use, is known to be among the main drivers of pollution, affecting both freshwater and terrestrial ecosystems. We present a statistical approach for investigating the historical and geographical distribution of nitrogen deposition and the impacts of accumulation on recent soil carbon-to-nitrogen ratios in Europe. After the second Industrial Revolution, large swaths of land emerged characterized by different atmospheric deposition patterns caused by industrial activities or intensive agriculture. Nitrogen deposition affects soil C : N ratios in a still recognizable way despite the abatement of oxidized and reduced nitrogen emissions during the last 2 decades. Given a seemingly disparate land-use history, we focused on ~ 10 000 unmanaged ecosystems, providing statistical evidence for a rapid response of nature to the chronic nitrogen supply through atmospheric deposition.

  7. Flax Fiber - Interfacial Bonding

    Science.gov (United States)

    Measured flax fiber physical and chemical properties potentially impact bonding and thus stress transfer between the matrix and fiber within composites. These first attempts at correlating flax fiber quality and biofiber composites contain the initial steps towards identifying key flax fiber charac...

  8. Bonds Between Atoms.

    Science.gov (United States)

    Holden, Alan

    The field of inquiry into how atoms are bonded together to form molecules and solids crosses the borderlines between physics and chemistry encompassing methods characteristic of both sciences. At one extreme, the inquiry is pursued with care and rigor into the simplest cases; at the other extreme, suggestions derived from the more careful inquiry…

  9. Metallic Re-Re bond formation in different MRe2O6 (M=Fe, Co, Ni) rutile-like polymorphs: The role of temperature in high-pressure synthesis

    International Nuclear Information System (INIS)

    Different polymorphs of MRe2O6 (M=Fe, Co, Ni) with rutile-like structures were prepared using high-pressure high-temperature synthesis. For syntheses temperatures higher than ∼1573 K, tetragonal rutile-type structures (P42/mnm) with a statistical distribution of M- and Re-atoms on the metal position in the structure were observed for all three compounds, whereas rutile-like structures with orthorhombic or monoclinic symmetry, partially ordered M- and Re-ions on different sites and metallic Re-Re-bonds within Re2O10-pairs were found for CoRe2O6 and NiRe2O6 at a synthesis temperature of 1473 K. According to the XPS measurements, a mixture of Re+4/Re+6 and M2+/M3+ is present in both structural modifications of CoRe2O6 and NiRe2O6. The low-temperature forms contain more Re+4 and M3+ than the high-temperature forms. Tetragonal and monoclinic modifications of NiRe2O6 order with a ferromagnetic component at ∼24 K, whereas tetragonal and orthorhombic CoRe2O6 show two magnetic transitions: below ∼17.5 and 27 K for the tetragonal and below 18 and 67 K for the orthorhombic phase. Tetragonal FeRe2O6 is antiferromagnetic below 123 K. - Graphical abstract: Complex rhenium oxides MRe2O6 crystallize in different rutile-like polymorphs depending on synthesis temperature. Low temperature modifications contain chains of edge-sharing ReO6-octahedra with Re-Re bonds

  10. Rising flux of nutrients (C, N, P and Si) in the lower Mekong River

    Science.gov (United States)

    Li, Siyue; Bush, Richard T.

    2015-11-01

    Changing human land use is accelerating global element cycling and appreciably altering ecosystems in the riverine-estuarine systems. This is evident by dramatic shifts in the supply of nutrients (C, N, P, Si). However, very little is known about the magnitude and rates of these changes. We examine the Mekong, one of the world largest rivers, to assess on a whole-of-system scale, the spatial, monthly and inter-annual flux of nutrients and stoichiometric ratios using a huge data-set (1985-2011). Seasonal and spatial patterns are apparent and linked to hydrology. The estimated mean flux (×109 mol/y) of elements from the Mekong at Pakse are 414.5 for DIC, 4.1 for DIN (3.3 for NO3--N and 0.8 for NH4+-N), 10.2 for TN, 0.32 for DIP, 0.46 for TP and 62.8 for DSi, respectively, which are intermediate relative to other large rivers. However, compared to the river reach at Pakse, the total river fluxes are two-fold greater for C, N, P and DSi. Annual flux increases significantly for DIC, NO3--N, DIN, TN and DSi, and is especially pronounced for all N and P species during the recent decade (1998 onward). Distinct shifts of nutrient stoichiometry, with far-reaching changes for phytoplankton productivity in the Mekong estuary are also evident, as the system shifts from potentially N limited to P limited. These notable changes to the exports and ratios of nutrient variables and anthropogenically-driven nutrient concerns are becoming a defining feature of the Mekong Plume to the South China Sea.

  11. Wear resistance of PM composite materials reinforced with the Ti(C,N ceramic particles

    Directory of Open Access Journals (Sweden)

    A. Włodarczyk-Fligier

    2008-10-01

    Full Text Available Purpose: of the project was evaluation of the effect of heat treatment and of the reinforcing Ti(C,N particles in the EN AW-AlCu4Mg1(A aluminium alloy on the mechanical properties, wear resistance.Design/methodology/approach: some of the composite materials were hyperquenched for 0.5 h at the temperature of 495ºC with the subsequent cooling in water, and were quench aged next for 6 h at 200°C. Hardness tests were made on HAUSER hardness tester with the Vickers method at 10 N. Abrasion resistance wear tests were carried out with the constant number of cycles of 5000 (120 m at various loads: 4, 5, 6, 7, and 8 N. Test pieces were rinsed in the ultrasonic washer to clean them and next were weighed on the analytical balance with the accuracy of 0.0001 g to check the mass loss.Findings: Besides visible improvement of mechanical properties and wear resistance there were also observed the influence of heat treatment.Practical implications: Tested composite materials can be applied among others in automotive industry but it requires additional researches.Originality/value: It was demonstrated that the mechanical properties, as well as the wear resistance of the investigated composite materials with the EN AW-Al Cu4Mg1(A alloy matrix may be formed by the dispersion hardening with the Ti(C,N particles in various portions and by the precipitation hardening of the matrix.

  12. Oxytocin and mutual communication in mother-infant bonding

    Directory of Open Access Journals (Sweden)

    Miho eNagasawa

    2012-02-01

    Full Text Available Mother-infant bonding is universal to all mammalian species. In this review, we describe the manner in which reciprocal communication between the mother and infant leads to mother-infant bonding in rodents. In rats and mice, mother-infant bond formation is reinforced by various social stimuli, such as tactile stimuli and ultrasonic vocalizations from the pups to the mother, and feeding and tactile stimulation from the mother to the pups. Some evidence suggests that mother and infant can develop a cross-modal sensory recognition of their counterpart during this bonding process. Neurochemically, oxytocin in the neural system plays a pivotal role in each side of the mother-infant bonding process, although the mechanisms underlying bond formation in the brains of infants has not yet been clarified. Impairment of mother-infant bonding, that is, deprivation of social stimuli from the mother, strongly influences offspring sociality, including maternal behavior toward their own offspring in their adulthood, implying a non-genomic transmission of maternal environment, even in rodents. The comparative understanding of cognitive functions between mother and infants, and the biological mechanisms involved in mother-infant bonding may help us understand psychiatric disorders associated with mother-infant relationships.

  13. The mechanism of the formation of the hemiaminal and Schiff base from the benzaldehyde and triazole studied by means of the topological analysis of electron localisation function and catastrophe theory

    Science.gov (United States)

    Berski, Slawomir; Zbigniew Ciunik, Leszek

    2015-04-01

    The mechanisms of reaction of benzaldehyde (ald) with 4-amine-4H-1,2,4-triazole (4at), leading to Schiff base (Sch) and water, were investigated using topological analysis of the electron localisation function and catastrophe theory. Two reactions (synthesis of hemiaminal and synthesis of Schiff base) are represented by one catastrophe sequence: ald+4at: 1-14-[FF†F†FFTS1FF†F†FF†F†CF†]-2-9-[C†FFTS3F†F†FFF]-0:Sch+H2O with only fold (F) and cusp (C) catastrophes. The first reaction, in which a molecule of the hemiaminal is formed, consists of 14 steps separated by 13 catastrophes. The mechanism is non-concerted. The covalent bond C-N is formed after the formation of the O-H bond is terminated. The Schiff base formation through the water molecule elimination in the second reaction requires nine steps with eight catastrophes. The mechanism is non-concerted because first the C-O bond is broken and then the proton transfer occurs that results in the O-H bond creation.

  14. C-H bond halogenation catalyzed or mediated by copper: an overview.

    Science.gov (United States)

    Hao, Wenyan; Liu, Yunyun

    2015-01-01

    Carbon-halogen (C-X) bonds are amongst the most fundamental groups in organic synthesis, they are frequently and widely employed in the synthesis of numerous organic products. The generation of a C-X bond, therefore, constitutes an issue of universal interest. Herein, the research advances on the copper-catalyzed and mediated C-X (X = F, Cl, Br, I) bond formation via direct C-H bond transformation is reviewed. PMID:26664634

  15. Development of HIP bonding procedure and mechanical properties of HIP bonded joints for reduced activation ferritic steel F-82H

    International Nuclear Information System (INIS)

    Structural materials of blanket components in fusion DEMO reactors will receive a neutron wall load more than 3-5MW/m2 as well as exposed by surface heat flux more than 0.5MW/m2. A reduced activation ferritic steel F-82H has been developed by JAERI in collaboration with NKK from viewpoints of resistance for high temperature and neutron loads and lower radioactivity. This study intends to obtain basic performance of F-82H to establish the fabrication procedure of the first wall and blanket box by using Hot Isostatic Pressing (HIP) bonding. Before HIP bonding tests, effects of heat treatment temperature and surface roughness on mechanical properties of joints were investigated in the heat treatment tests and diffusion bonding tests, respectively. From these results, the optimum HIP bonding conditions and the post heat treatment were selected. Using these conditions, the HIP bonding tests were carried out to evaluate HIP bondability and to obtain mechanical properties of the joints. Sufficient HIP bonding performance was obtained under the temperature of 1040degC, the compressive stress of 150MPa, the holding time of 2h, and the surface roughness ∼μ m. Mechanical properties of HIP bonded joints with these conditions were similar to those of as-received base metal. An oxide formation on the surface to be bonded would need to be avoided for sufficient bonding. The bonding ratio, Charpy impact value and fatigue performance of the joints strongly depended on the HIP conditions, especially temperature, while micro-structure, Vickers hardness and tensile properties had little dependence on the HIP temperature. The surface roughness strongly affected the bonding ratio and would be required to be in the level of a few μ m. In the HIP bonding test of the welded material, the once-melted surface could be jointed by the HIP bonding under the above-mentioned procedure. (J.P.N.)

  16. Convertible bond valuation focusing on Chinese convertible bond market

    OpenAIRE

    Yang, Ke

    2010-01-01

    This paper mainly discusses the methods of valuation of convertible bonds in Chinese market. Different from common convertible bonds in European market, considering the complicate features of Chinese convertible bond, this paper represents specific pricing approaches for pricing convertible bonds with different provisions along with the increment of complexity of these provisions. More specifically, this paper represents the decomposing method and binomial tree method for pricing both of Non-...

  17. Void-free wafer-level adhesive bonding utilizing modified poly (diallyl phthalate)

    Science.gov (United States)

    Zhong, Fang; Dong, Tao; Yong, He; Yan, Su; Wang, Kaiying

    2013-12-01

    A new thermosetting polymer, modified poly (diallyl phthalate) (PDAP), is used as intermediate layer to realize a void-free wafer-level transfer bonding, in which the bonding interface contains patterned metal. Through glass-silicon bonding experiments, bonding defects are easily recognized with light microscopy. Three typical defect types are identified as: uneven flow defect, particle defect and bubble defect. The processing parameters, such as bonding pressure, pre-baking temperature, polymer thickness and coating conditions, have been optimized based on analysis of the defect formation. The optimized conditions have yielded a void-free wafer-level adhesive bonding. Then, the die shearing test indicates a good bonding strength. Additionally, the transfer bonding process is applied in SOI-silicon bonding as a practical example of MEMS fabrication.

  18. Is There a Quadruple Bond in C2?

    Science.gov (United States)

    de Sousa, David Wilian Oliveira; Nascimento, Marco Antonio Chaer

    2016-05-10

    The chemical structure of the ground state of C2 has been the subject of intense debate after the suggestion that the molecule could exhibit a "fourth" covalent bond. In this paper, we investigate this problem explicitly avoiding all the points of conflict from the previous papers to show that there is no quadruple bond in C2. The generalized product function energy partitioning (GPF-EP) method has been applied to calculate the interference energy (IE) that accounts for the formation of covalent bonds for each bond of the molecule. The IE analysis shows that for the standard σ and π bonds interference exhibits the expected behavior, while for the "fourth" bond interference is a destabilizing factor. To make sure this could not be attributed to a new kind of bond, we performed an equivalent analysis for the (3)Σ(-) excited state of C3 molecule in which similar "bonding" occurs between the two ending carbon atoms. We also show that the difference in force constants of C2 and acetylene can be rationalized in terms of the amount of charge density in the internuclear region by looking at the changes in the overlaps between orbitals along the bond axis. PMID:27045682

  19. Localized CO2 laser bonding process for MEMS packaging

    Institute of Scientific and Technical Information of China (English)

    SUN Li; A. P. MALSHE; S. CUNNINGHAM; A. MORRIS

    2006-01-01

    The packaging poses a critical challenge for commercialization of MEMS products. Major problems with the packaging process include degraded reliability caused by the excess stress due to thermal mismatch and altered performance of the MEMS device after packaging caused by thermal exposure. The localized laser bonding technique for ceramic MEMS packaging to address above-mentioned challenges was investigated. A continuous wave CO2 laser was used to locally heat sealing material for ceramic MEMS package lid to substrate bonding. To determine the laser power density and scanning speed,finite element analysis thermal models were constructed to simulate the localized laser bonding process. Further,the effect of external pressure at sealing ring on the bonding formation was studied. Pull testing results show that the scanning speed and external pressure have significant influence on the pull strength at the bonding interface. Cross-sectional microscopy of the bonding interface indicates that the packages bonded with relatively low scanning speed and external pressure conditions have higher bonding quality. This research demonstrates the potential of localized laser bonding process for ceramic MEMS packaging.

  20. A 19F NMR study of C-I....pi- halogen bonding

    DEFF Research Database (Denmark)

    Hauchecorne, Dieter; vand er Veken, Benjamin J.; Herrebout, Wouter A.; Hansen, Poul Erik

    The formation of halogen bonded complexes between toluene-d8 and the perfluoroiodopropanes 1-C3F7I and 2-C3F7I has been investigated using 19F NMR spectroscopy. For both Lewis acids, evidence was found for the formation of a C–I⋯π halogen bonded complex. The complex formed is a 1:1 type. Using...

  1. Isotope effects on chemical shifts in the study of intramolecular hydrogen bonds

    DEFF Research Database (Denmark)

    Hansen, Poul Erik

    2015-01-01

    The paper deals with the use of isotope effects on chemical shifts in characterizing intramolecular hydrogen bonds. Both so-called resonance-assisted (RAHB) and non-RAHB systems are treated. The importance of RAHB will be discussed. Another very important issue is the borderline between “static......” and tautomeric systems. Isotope effects on chemical shifts are particularly useful in such studies. All kinds of intramolecular hydrogen bonded systems will be treated, typical hydrogen bond donors: OH, NH, SH and NH+, typical acceptors C=O, C=N, C=S C=N−. The paper will be deal with both secondary...... and primary isotope effects on chemical shifts. These two types of isotope effects monitor the same hydrogen bond, but from different angles...

  2. NEXAFS Chemical State and Bond Lengths of p-Aminobenzoic Acid in Solution and Solid State

    Science.gov (United States)

    Stevens, J. S.; Gainar, A.; Suljoti, E.; Xiao, J.; Golnak, R.; Aziz, E. F.; Schroeder, S. L. M.

    2016-05-01

    Solid-state and solution pH-dependent NEXAFS studies allow direct observation of the electronic state of para-aminobenzoic acid (PABA) as a function of its chemical environment, revealing the chemical state and bonding of the chemical species. Variations in the ionization potential (IP) and 1s→π* resonances unequivocally identify the chemical species (neutral, cationic, or anionic) present and the varying local environment. Shifts in σ* shape resonances relative to the IP in the NEXAFS spectra vary with C-N bond length, and the important effect of minor alterations in bond length is confirmed with nitrogen FEFF calculations, leading to the possibility of bond length determination in solution.

  3. Changes in the Coupling of C, N and P Cycles During River Transport from Source to Sea.

    Science.gov (United States)

    Cosby, B. J., Jr.; Withers, P.; Thompson, J.; Evans, C.; Fovet, O.; Bowes, M.; Gozzard, E.; Demars, B.; Stutter, M.

    2015-12-01

    The UK Turf2Surf project asks when, where and how coupling between C, N & P cycles occurs within terrestrial, freshwater and estuarine ecosystems. C-N-P cycling and fluxes are followed through two UK catchments, the Conwy and Ribble, which are Centre for Ecology and Hydrology catchment observatories for landscape scale research from source to sea. The Conwy is typical of non-industrialised areas with few discrete agricultural and industrial sources while the Ribble has a mixed urban and agricultural landscape. Both have areas of upland and moor with peats in the Conwy. Field and laboratory experiments track the incorporation of terrestrial C, N & P into the riverine ecosystems of the catchments and measure changes in C-N-P stoichiometry and cycling along the stream networks from uplands to the river-estuary transition zone (RETZ). We present results focussed on the riverine systems. Flume mesocosms at 18 sites investigated in-stream nutrient processing and algal response to increased C, N & P concentrations (singly and combined). River reach experiments at 14 sites across land use and DOC gradients examined whole ecosystem metabolic response to C, N & P additions. Pore-water sampling with DET (diffusive equilibrium in thin films) gel probes at 5 sites quantified N & P fluxes and distributions across the sediment-water interface. Laboratory mesocosm experiments with streamwater from a variety of land uses (and DOC levels) studied the fate and cycling of stream organic matter subjected to controlled light/dark treatments, and the addition of N & P and a biocide. Results indicate that the study streams are N limited in the headwaters, but become progressively N & P co-limited near the RETZ. DOC processing in streams transitions from primarily photochemical degradation in headwaters (releasing N & P) to biotic aquatic DOC production (consuming N & P) downstream. Increasing C supply leads to increasing average ecosystem respiration irrespective of N & P status

  4. Bond cleavages of adenosine 5'-triphosphate induced by monochromatic soft X-rays

    International Nuclear Information System (INIS)

    To investigate which type of bond is likely to be cleaved by soft X-ray exposure to an adenosine 5'-triphosphate (ATP), we observed spectral changes in X-ray absorption near edge structure (XANES) around nitrogen and oxygen K-edge of an ATP film by soft X-ray irradiation. Experiments were performed at a synchrotron soft X-ray beamline at SPring-8, Japan. The XANES spectra around the nitrogen and oxygen .K-edge slightly varied by exposure to 560 eV soft X-rays. These changes are originated from the cleavage of C-N bonds between a sugar and a nucleobase site and of C-O, P-O or O-H bond of sugar and phosphate site. From the comparison between the change in XANES intensity of σ* peak at nitrogen and that at oxygen K-edges, it is inferred that the C-O, P-O or O-H bond of sugar and phosphate is much efficiently cleaved than the C-N of N-glycoside bond by the exposure of 560 eV soft X-ray to ATP film.

  5. N-H∙∙∙O, O-H∙∙∙O hydrogen-bonded supramolecular sheet formation in the bis(2-aminoanilinium) fumarate, 3-methylanilinium hydrogen fumarate and 4-chloroanilinium hydrogen fumarate salts.

    Science.gov (United States)

    Sathya, D; Jagan, R; Padmavathy, R; Kumar, R Mohan; Sivakumar, K

    2013-08-01

    In bis(2-aminoanilinum) fumarate, 2C₆H₉N₂⁺·C₄H₂O₄²⁻, (I), the asymmetric unit consists of two aminoanilinium cations and one fumarate dianion, whereas in 3-methylanilinium hydrogen fumarate, C₇H₁₀N⁺·C₄H3O₄⁻, (II), and 4-chloroanilinium hydrogen fumarate, C₆H₇ClN⁺·C₄H3O₄⁻, (III), the asymmetric unit contains two symmetry-independent hydrogen fumate anions and anilinium cations with a slight difference in their geometric parameters; the two salts are isostructural. In (II) and (III), the carboxylic acid H atoms of the anions are disordered across both ends of the anion, with equal site occupancies of 0.50. Both the 4-chloroanilinium cations of (III) are disordered over two orientations with major occupancies fixed at 0.60 in each case. The hydrogen fumarate anions of (II) and (III) form one-dimensional anionic chains linked through O-H∙∙∙O hydrogen bonds. Salts (II) and (III) form two-dimensional supramolecular sheets built from R₄⁴16), R₄⁴(18), R₅⁵(25) and C₂²(14) motifs extending parallel to the (010) plane, whereas in (I), an (010) sheet is formed built from two R₄³(13) motifs, two R₂²(9) motifs and an R₄⁴(18) motif. PMID:23907887

  6. Domestic Bond Market Development

    OpenAIRE

    Jonathan A. Batten; Szilagyi, Peter G.

    2007-01-01

    A two-tiered approach to financial market development aimed at both bank and bond market reform would also be complementary to longer term economic development, provided services could be delivered through efficient financial and legal institutions (Chakraborty and Ray 2006) and there was strong protection for investors and sound fiscal and monetary policy management by government (Burger and Warnock 2006b). Historically, local issuers tend to issue in the major currencies (U.S. dollars, yen,...

  7. Effects of wildfires on ash Carbon, Nitrogen and C/N ratio in Mediterranean forests

    Science.gov (United States)

    Pereira, P.; Ubeda, X.; Martin, D. A.

    2009-04-01

    Carbon (C) and Nitrogen(N) are key nutrients in ecosystems health and the more affected by fire temperatures, because of their low temperatures of volatilization. After a wildfire, due higher temperatures reached, a great amount of C and N can be evacuated from the ecosystems and the percentage of C and N not vaporized is concentrated in ashes. Hence, the study of ash C and N is of major importance because will be linked with the capacity of ecosystem recuperation. The aim of this work is study the C, and C/N of three wildfires occurred in Mediterranean forests dominated by Quercus suber and Pinus pinea in Portugal. In the first wildfire, named "Quinta do Conde", we collected 30 samples, in the second, "Quinta da Areia", 32 samples and the third, "Casal do Sapo" 40 samples To estimate the consequences of wildfires in the parameters in study, we collected several samples of unburned litter near burned areas, composed by the same vegetation. The results showed that wildfires induced in % of Total Carbon (%TC) ashes content a non significantly reduction in Quinta do Conde plot (at a pSapo plot (pSapo plot (pSapo plot. In all parameters in study, wilfires induced a greater spatial variability, by the analysis of the Coefficient of Variation. Our tests effectuated in laboratory with samples collected near wildfires occurrence and exposed to the temperature gradient (150°, 200°, 250°, 300°, 350°, 400°, 450°, 500°, 550°C) fit with the results obtained. With temperature gradient, we identified a decrease of %TC ash content of Quercus suber samples and a rise until the 300°C in Pinus pinaster samples decreasing thereafter especially after the 400°C. In %TN we identified a rise in both species reducing abruptly at 450°C. C/N ratio decrease importantly after the 150°C. Theses results showed us that wildfires can have different effects C and N litter resources, depending on the severity and temperature reached. Crossing the results obtained in laboratory

  8. Effect of RF power and annealing on chemical bonding and morphology of a-CNx thin films as humidity sensor

    International Nuclear Information System (INIS)

    Amorphous carbon nitride (a-CNx) thin films were deposited using radio frequency plasma enhanced chemical vapor deposition (rf-PECVD) technique. A set of a-CNx thin films were prepared using pure methane (CH4) gas diluted with nitrogen (N2) gas. The rf power was varied at 50, 60, 70, 80, 90 and 100 W. These films were then annealed at 400 °C in a quartz tube furnace in argon (Ar) gas. The effects of rf power and thermal annealing on the chemical bonding and morphology of these samples were studied. Surface profilometer was used to measure film thickness. Fourier transform infra-red spectroscopy (FTIR) and Field emission scanning electron microscopy (FESEM) measurements were used to determine their chemical bonding and morphology respectively. The deposition rate of the films increased constantly with increasing rf power up to 80W, before decreasing with further increase in rf power. Fourier transform infra-red spectroscopy (FTIR) studies showed a systematic change in the spectra and revealed three main peaks included C-N, C=N, C=C and C≡N triple bond. C=N and C≡N bonds decreased with increased C-N bonds after thermal annealing process. The FESEM images showed that the structure is porous for as-deposited and covered by granule-like grain structure after thermal annealing process was done. The resistance of the a-CNx thin film changed from 23.765 kΩ to 5.845 kΩ in the relative humidity range of 5 to 92 % and the film shows a good response and repeatability as a humidity sensing materials. This work showed that rf power and thermal annealing has significant effects on the chemical bonding and surface morphology of the a-CNx films and but yield films which are potential candidate as humidity sensor device

  9. Disulfide bonds of acetylcholinesterase

    International Nuclear Information System (INIS)

    The positions of the inter- and intrasubunit disulfide bridges were established for the 11S form of acetylcholinesterase (AChE) isolated from Torpedo californica. A major form of AChE localized within the basal lamina of the synapse is a dimensionally asymmetric molecule which contains either two (13S) or three (17S) sets of catalytic subunits linked to collagenous and non-collagenous structural subunits. Limited proteolysis yields a tetramer of catalytic subunits which sediments at 11S. Each catalytic subunit contains 8 cysteine residues. Initially, these Cys residues were identified following trypsin digestion of the reduced protein alkylated with [14C]-iodoacetate. Peptides were resolved by gel filtration followed by reverse phase HPLC. To determine the disulfide bonding profile, native non-reduced 11S AChE was treated with a fluorescent, sulfhydryl-specific reagent, monobromobimane, prior to proteolytic digestion. One fluorescent Cys peptide was identified indicating that a single sulfhydryl residue was present in its reduced form. Three pairs of disulfide bonded peptides were identified, sequenced, and localized in the polypeptide chain. The Cys residue that is located in the C-terminal tryptic peptide was disulfide bonded to an identical peptide and thus forms the intersubunit crosslink. Finally, the cysteine positions have been compared with the sequence of the homologous protein, thyroglobulin. Both likely share a common pattern of folding

  10. Integration of European Bond Markets

    OpenAIRE

    Christiansen, Charlotte

    2012-01-01

    I investigate the time variation in the integration of EU government bond markets. The integration is measured by the explanatory power of European factor portfolios for the individual bond markets for each year. The integration of the government bond markets is stronger for EMU than non-EMU members and stronger for old than new EU members. The integration is weaker for the sovereign debt crisis countries than for other countries. The integration of the EU bond markets is decreasing over time...

  11. Doseringsutrustningen SafeBond Electronic

    OpenAIRE

    Bodegren, Patrik

    2003-01-01

    This thesis for the Master of Science degree was performed at Oppunda Electronics AB. The assignment was to further develop an existing prototype of a dispensing equipment. The dispensing equipment doses a kind of glue, bonding which dentist use to mend teeth. The dispensing equipment is adjusted to dose 12 micro litres of bonding. With the dispensing equipment SafeBond Electronic the user can reduce the bonding consumption with approximately 50 percent. Furthermore will the handling of the b...

  12. Chemical bonding and electronic structure of fullerene-based compounds

    International Nuclear Information System (INIS)

    This talk will focus on the nature of bonding of fullerenes with other materials as demonstrated by synchrotron radiation and x-ray photoemission. Adsorption of C60 on metallic and semiconducting substrates occurs via charge transfer from the substrate to a LUMO-derived resonance, resulting in Fermi level alignment and dipole formation. Bonding of metal atoms to C60 depends on the metal work function and bulk cohesive energy. Evaporation of high cohesive energy materials onto a fullerene substrate results in metal cluster nucleation and limited C60 disruption for transition metals. Low cohesive energy metals form compounds with a degree of ionic character related to the metal work function. Photoemission results show the formation of ionic K-fulleride compounds while greater hybridization is observed for Ca-rich fullerides. Finally the electronic structure of fluorinated and hydrogenated fullerenes demonstrate changes in states derived from C60 π bonds due to reaction of dangling bonds

  13. Changes in organic matter (C, N and P) of soils under subsistence agriculture; Mudancas na materia organica (C, N e P) de solos sob agricultura de subsistencia

    Energy Technology Data Exchange (ETDEWEB)

    Fraga, Vania da Silva

    2002-10-01

    Productivities under low input or subsistence agriculture are strongly dependent on nutrient supply from soil organic matter mineralization (SOM). Few results are available and they indicate declines in soil fertility under this agricultural system, particularly in SOM levels. In an attempt to understand the nature and extent of these declines we selected ten sites having cultivated areas adjacent with areas under native vegetation at the same slope position, in the states of Pernambuco and Paraiba. Based on the management history, in situ observations and {sup 137} Cs concentrations to evaluate soil erosion, the areas were divided in four groups having different levels of soil use intensity: Undisturbed Dry Forest (UDF), Disturbed Dry Forest (DDF), Preserved-Cultivated (PC) and Degraded-Cultivated (DC). In the first part of this work we quantified total organic C, N and P, in addition to {sup 137} Cs concentrations, under the assumption that changes in organic nutrient contents among land use groups would be greater than the within group variability, thus enabling inferences at a regional scale. Concentrations of C and N in DC were 50% smaller (P<0.05) than those in UDF. Of these losses, 43% were attributed to erosion processes while 57% were related to SOM mineralization. The Po/Pi ratio under UDF was 1.47 and decreased to o.82 in PC and DC (P<0.05). The effects of changes in land use were greater when considering the 0-7.5 cm layer rather than the 0-15 cm layer. Interrelationships between C and P in the dry forest areas suggested that P availability and water controlled C accumulation in these soils. In the second part of this work two experiments were conducted. The first one included a preliminary phase, comparing four methods in their capacity to detect changes in soil organic matter quality. Eighty samples that maximized the variability in C content of the whole set (n=160), were analyzed for: C in the light SOM fraction (density < 1 kg dm{sup -3}) (C-lf); C

  14. Diffusion Bonding of Silicon Carbide for MEMS-LDI Applications

    Science.gov (United States)

    Halbig, Michael C.; Singh, Mrityunjay; Shpargel, Tarah P.; Kiser, J. Douglas

    2007-01-01

    A robust joining approach is critically needed for a Micro-Electro-Mechanical Systems-Lean Direct Injector (MEMS-LDI) application which requires leak free joints with high temperature mechanical capability. Diffusion bonding is well suited for the MEMS-LDI application. Diffusion bonds were fabricated using titanium interlayers between silicon carbide substrates during hot pressing. The interlayers consisted of either alloyed titanium foil or physically vapor deposited (PVD) titanium coatings. Microscopy shows that well adhered, crack free diffusion bonds are formed under optimal conditions. Under less than optimal conditions, microcracks are present in the bond layer due to the formation of intermetallic phases. Electron microprobe analysis was used to identify the reaction formed phases in the diffusion bond. Various compatibility issues among the phases in the interlayer and substrate are discussed. Also, the effects of temperature, pressure, time, silicon carbide substrate type, and type of titanium interlayer and thickness on the microstructure and composition of joints are discussed.

  15. Bonding in Molecular Crystals from the Local Electronic Pressure Viewpoint

    CERN Document Server

    Tsirelson, Vladimir G; Tokatly, Ilya V

    2015-01-01

    The spatial distribution of the internal pressure of an electron fluid, which spontaneously arises at the formation of a molecule or a crystal, is linked to the main features of chemical bonding in molecular crystals. The local pressure is approximately expressed in terms of the experimental electron density and its derivatives using the density functional formalism and is applied to identify the bonding features in benzene, formamide and chromium hexacarbonyl. We established how the spatial regions of compression and stretching of the electron fluid in these solids reflect the typical features of chemical bonds of different types. Thus, the internal electronic pressure can serve as a bonding descriptor, which has a clear physical meaning and reveals the specific features of variety of the chemical bonds expressing them in terms of the electron density.

  16. Hamiltonian formulation of bond graphs

    NARCIS (Netherlands)

    Golo, Goran; Schaft, van der Arjan; Breedveld, Peter C.; Maschke, Bernhard M.; Johansson, R.; Rantzer, A.

    2003-01-01

    This paper deals with the mathematical formulation of bond graphs. It is proven that the power continuous part of bond graphs, the junction structure, can be associated with a Dirac structure and that the equations describing a bond graph model correspond to a port Hamiltonian system. The conditions

  17. Electron impact total (elastic + inelastic) cross-sections of C, N and O atoms amd their simple molecules

    International Nuclear Information System (INIS)

    Total (elastic + inelastic) cross-sections for electron scattering from C, N, O atoms and their simple molecules are studied theoretically. The e--C, N, O atomic calculations are done in the complex optical potential approach. To study the electron scattering from O2, N2, CO, NO, CN, C2 as well as CO2, N2O, NO2 and O3 targets, we have adopted an additivity rule, wherein the molecular cross-section is an incoherent sum of the cross-sections of the constituent atoms. The cross-sections of C, N and O atoms are presented at incident energies Ei = 10-1000 eV, the molecular cross-sections are presented at Ei = 100-1000 eV. The reliability of the additivity rule is discussed against the background of experimental data. (orig.)

  18. Molecular orbital analysis of the hydrogen bonded water dimer

    OpenAIRE

    Bo Wang; Wanrun Jiang; Xin Dai; Yang Gao; Zhigang Wang; Rui-Qin Zhang

    2016-01-01

    As an essential interaction in nature, hydrogen bonding plays a crucial role in many material formations and biological processes, requiring deeper understanding. Here, using density functional theory and post-Hartree-Fock methods, we reveal two hydrogen bonding molecular orbitals crossing the hydrogen-bond’s O and H atoms in the water dimer. Energy decomposition analysis also shows a non-negligible contribution of the induction term. Our finding sheds light on the essential understanding of ...

  19. From an insulating to a superfluid pair-bond liquid

    OpenAIRE

    Cuoco, Mario; Ranninger, Julius

    2006-01-01

    We study an exchange coupled system of itinerant electrons and localized fermion pairs resulting in a resonant pairing formation. This system inherently contains resonating fermion pairs on bonds which lead to a superconducting phase provided that long range phase coherence between their constituents can be established. The prerequisite is that the resonating fermion pairs can become itinerant. This is rendered possible through the emergence of two kinds of bond-fermions: individual and compo...

  20. FTIR adsorption studies of H2O and CH3OH in the isostructural H-SSZ-13 and H-SAPO-34: formation of H-bonded adducts and protonated clusters.

    Science.gov (United States)

    Bordiga, Silvia; Regli, Laura; Lamberti, Carlo; Zecchina, Adriano; Bjørgen, Morten; Lillerud, Karl Petter

    2005-04-28

    The acidity of the isostructural H-SSZ-13 and H-SAPO-34 has been investigated by transmission FTIR spectroscopy using H2O and CH3OH as molecular probes. Interactions between the zeolitic samples and the probe molecules led to perturbations and proton transfers directly related to the acidity of the materials. The entire set of acidic sites in H-SSZ-13 interacts with H2O and CH3OH to give H-bonded adducts or protonated species. H3O+ is not formed in appreciable amounts upon H2O adsorption on H-SSZ-13, but at high coverages H2O generates clusters that have a proton affinity sufficiently high to abstract protons from the zeolite framework. Parallel experiments carried out for H-SAPO-34 showed that the H2O clusters abstract protons from Brønsted sites only to a minor extent. Moving to CH3OH, even if it has a higher proton affinity than H2O and should expectingly experience an easier protonation, proton transfer is totally absent in H-SAPO-34 under our set of conditions. The clear evidence of methanol protonation in H-SSZ-13 definitely states the strong acidic character of this material. When irreversibly adsorbed CH3OH is present in H-SSZ-13, an appreciable amount of (CH3)2O is formed upon heating to 573 K. Compared to its SAPO analogue, the present set of data indisputably points to H-SSZ-13 as the strongest Brønsted acidic material. PMID:16851897

  1. Conference on Yang-Mills Gauge Field Theories : C. N. Yang's Contributions to Physics

    CERN Document Server

    Phua, K K

    2016-01-01

    During the last six decades, Yang–Mills theory has increasingly become the cornerstone of theoretical physics. It is seemingly the only fully consistent relativistic quantum many-body theory in four space-time dimensions. As such it is the underlying theoretical framework for the Standard Model of Particle Physics, which has been shown to be the correct theory at the energies we now can measure. It has been investigated also from many other perspectives, and many new and unexpected features have been uncovered from this theory. In recent decades, apart from high energy physics, the theory has been actively applied in other branches of physics, such as statistical physics, condensed matter physics, nonlinear systems, etc. This makes the theory an indispensable topic for all who are involved in physics.The conference celebrated the exceptional achievements using Yang–Mills theory over the years but also many other truly remarkable contributions to different branches of physics from Prof C N Yang. This volum...

  2. High conductivity a-C:N thin films prepared by electron gun evaporation

    International Nuclear Information System (INIS)

    By employing electron beam evaporation, amorphous carbon nitride (a-C:N) thin films, with a low nitrogen content (∼ 1%), were prepared on Si(110) and glass substrates at about 150 deg. C. The source was a graphite target and an ambient of N2 was introduced into the growing chamber. The source-substrate distance (SSD) was the main parameter that was intentionally varied. Electron dispersion spectroscopy measurements indicate the nitrogen concentration in the layer as ∼ 1%. The dark electrical conductivity (σ) of layers was very sensitive to SSD variation, changing up to six orders of magnitude when this parameter was varied from 10.5 to 23.5 cm. A maximum value of σ = 1 x 103 Ω-1 cm-1 at room temperature was obtained when the SSD was equal to 15.5 cm. We have deduced that, in accordance with the Ferrari-Robertson model (FRM), our samples are localized in the second stage of the amorphization trajectory of FRM. When the SSD increases the C atoms have more probability to collide with N2 molecules, and the content of nitrogen in the a-C film increases. The amorphization trajectory followed by the films with an SSD increase is from nanocrystalline graphite to amorphous carbon. The changes in the amorphization are due to the nitrogen content in the layers

  3. The C-N-cycle additional channels through the combinative resonances phenomenon (CIRs)

    International Nuclear Information System (INIS)

    The Combinative Isobar Resonances are shown as new channels of the C-N-cycle. In 1994 we had firstly used our new developed approach - the Method of Spectra Superpositionproviding measurement of d σ (E) /d ω at every accelerator (including colliders ) with highest energy-resolution depending (for thin targets) only on energy-resolution of detectors [1-5]. Rarely one can read about this[6].That time the Excitation Function (EF) of the l2C(p,po) elastic scattering with energy-resolution ∼10 keV for Ep=16 ∼ 19.5 MeV of cyclotron protons by using the multi angular magnetic spectrograph as detector was measured.It was wonderful when after data processing so surprised curve with a saturated structure of overlapped resonances - fluctuations of cross-section (Fig.1) was obtained (in contrary to EF obtained by M.J. LeVine and P.D.Parker in 60 Th at the tandem generator [7]). The precise agreement between well known thresholds and nuclear levels with the brightest anomalies in our curve and not disappearing fine structures in full-events curve (stat.err. 3%) - all this, only, had satisfied me that these structures are not just a joke of statistics. Fig.l shows a comparison of our obtained EF with thresholds and levels of well known product-nuclei

  4. Moessbauer study and thermodynamic modeling of Fe-C-N alloy

    Energy Technology Data Exchange (ETDEWEB)

    Balanyuk, A.G.; Gavriljuk, V.G.; Shivanyuk, V.N.; Tyshchenko, A.I.; Rawers, J.C.

    2000-09-01

    Moessbauer spectroscopy and Monte Carlo computer simulation have been combined to understand the reason for the solid-solution stability of Fe-0.93 C-0.91 N alloy (mass%). Interstitial concentrations in austenite and ferrite were determined on the basis of X-ray diffraction measurements of the lattice dilatation. The hyperfine structure of Moessbauer spectra was analyzed to identify different atomic configurations in solid solutions and determine their fractions. Thereafter Monte Carlo simulation of the interstitial distribution in ferritic and austenitic solid solutions was performed, and values of the interstitial-interstitial interaction energies were obtained for the first and second coordination spheres in austenite and the first to the fourth coordination spheres in ferrite. Simulation shows that in both austenitic and ferritic phases the interaction of interstitial atoms is characterized by a strong repulsion within the first two coordination spheres. Experimental data and simulated interstitial distributions are consistent and complementary. It is concluded that the absence of interstitial clusters prevents carbide and nitride precipitates and causes the higher thermodynamic stability of Fe-C-N solid solutions as compared with Fe-C and Fe-N ones.

  5. The higher order C_n dispersion coefficients for the alkali atoms

    CERN Document Server

    Mitroy, J

    2004-01-01

    The van der Waals coefficients, from C_11 through to C_16 resulting from 2nd, 3rd and 4th order perturbation theory are estimated for the alkali (Li, Na, K and Rb) atoms. The dispersion coefficients are also computed for all possible combinations of the alkali atoms and hydrogen. The parameters are determined from sum-rules after diagonalizing the fixed core Hamiltonian in a large basis. Comparisons of the radial dependence of the C_n/r^n potentials give guidance as to the radial regions in which the various higher-order terms can be neglected. It is seen that including terms up to C_10/r^10 results in a dispersion interaction that is accurate to better than 1 percent whenever the inter-nuclear spacing is larger than 20 a_0. This level of accuracy is mainly achieved due to the fortuitous cancellation between the repulsive (C_11, C_13, C_15) and attractive (C_12, C_14, C_16) dispersion forces.

  6. Quantitative effects of composting state variables on C/N ratio through GA-aided multivariate analysis

    International Nuclear Information System (INIS)

    It is widely known that variation of the C/N ratio is dependent on many state variables during composting processes. This study attempted to develop a genetic algorithm aided stepwise cluster analysis (GASCA) method to describe the nonlinear relationships between the selected state variables and the C/N ratio in food waste composting. The experimental data from six bench-scale composting reactors were used to demonstrate the applicability of GASCA. Within the GASCA framework, GA searched optimal sets of both specified state variables and SCA's internal parameters; SCA established statistical nonlinear relationships between state variables and the C/N ratio; to avoid unnecessary and time-consuming calculation, a proxy table was introduced to save around 70% computational efforts. The obtained GASCA cluster trees had smaller sizes and higher prediction accuracy than the conventional SCA trees. Based on the optimal GASCA tree, the effects of the GA-selected state variables on the C/N ratio were ranged in a descending order as: NH4+-N concentration > Moisture content > Ash Content > Mean Temperature > Mesophilic bacteria biomass. Such a rank implied that the variation of ammonium nitrogen concentration, the associated temperature and the moisture conditions, the total loss of both organic matters and available mineral constituents, and the mesophilic bacteria activity, were critical factors affecting the C/N ratio during the investigated food waste composting. This first application of GASCA to composting modelling indicated that more direct search algorithms could be coupled with SCA or other multivariate analysis methods to analyze complicated relationships during composting and many other environmental processes. - Research Highlights: → A genetic algorithm aided stepwise cluster analysis method in food waste composting. → Nonlinear relationships between the selected state variables and the C/N ratio. → Introduced proxy tables save around 70% computational

  7. Effect of nitrogen surrounding gas and plasma assistance on nitrogen incorporation in a-C:N films by femtosecond pulsed laser deposition

    Science.gov (United States)

    Bourquard, F.; Maddi, C.; Donnet, C.; Loir, A.-S.; Barnier, V.; Wolski, K.; Garrelie, F.

    2016-06-01

    In the context of nitrogen-rich amorphous carbon thin films ultrafast pulsed laser deposition from graphite targets in inert nitrogen or nitrogen plasma ambient, this study assesses the correlation between the ablation plume composition and dynamics and the thin films contents and structures. The use of both optical emission spectroscopy and spectrally resolved 2D imaging, coupled with intensified CCD temporal resolution, allows to precisely follow such species of the plume as CN and C2 molecules, from their apparition to their deposition on the substrate. The results show that carbon-nitrogen bonding arises at the early time of expansion with little changes in quantity thereafter. The key role of the DC-bias is in lowering the molecular weight of the ambient gas, thus easing molecules way toward the target and interfering with the chemical reaction for CN generation. Depending on the ambient pressure, these processes will have drastically different effects on the thin films properties and contents. This work thus explains the origin of high nitrogen contents in a-C:N thin films obtained using DC-bias, and proposes an easy in situ optical observation-based way to predict and look for the best conditions to maximize those contents in future work.

  8. Terahertz Vibrations and Hydrogen-Bonded Networks in Crystals

    Directory of Open Access Journals (Sweden)

    Masae Takahashi

    2014-03-01

    Full Text Available The development of terahertz technology in the last few decades has made it possible to obtain a clear terahertz (THz spectrum. THz vibrations clearly show the formation of weak bonds in crystals. The simultaneous progress in the code of first-principles calculations treating noncovalent interactions has established the position of THz spectroscopy as a powerful tool for detecting the weak bonding in crystals. In this review, we are going to introduce, briefly, the contribution of weak bonds in the construction of molecular crystals first, and then, we will review THz spectroscopy as a powerful tool for detecting the formation of weak bonds and will show the significant contribution of advanced computational codes in treating noncovalent interactions. From the second section, following the Introduction, to the seventh section, before the conclusions, we describe: (1 the crystal packing forces, the hydrogen-bonded networks and their contribution to the construction of organic crystals; (2 the THz vibrations observed in hydrogen-bonded molecules; (3 the computational methods for analyzing the THz vibrations of hydrogen-bonded molecules; (4 the dispersion correction and anharmonicity incorporated into the first-principles calculations and their effect on the peak assignment of the THz spectrum (5 the temperature dependence; and (6 the polarization dependence of the THz spectrum.

  9. ASEAN+3 Bond Market Guides

    OpenAIRE

    Asian Development Bank (ADB)

    2012-01-01

    The ASEAN+3 Bond Market Guide contains the comprehensive reports of the ASEAN+3 Bond Market Forum Sub-Forum 1 (SF1) and Sub-Forum 2 (SF2). The SF1 report (Volume 1) analyzes the harmonization and standardization of the existing bond markets in the ASEAN+3. It also contains the individual market guides of 11 economies under the ASEAN+3 Bond Market Forum (ABMF). The SF2 report (Volume 2) provides an overview of the ASEAN+3 bond markets and their infrastructures, as well as issues confronted by ...

  10. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    The paper examines the role of structured bonds in the optimal portfolio of a small retail investor. We consider the typical structured bond essentially repacking an exotic option and a zero coupon bond, i.e. an investment with portfolio insurance. The optimal portfolio is found when the investment...... opportunities consist of a risky reference fund, a risk-free asset and a structured bond. Key model elements are the trading strategy and utility function of the investor. Our numerical results indicate structured bonds do have basis for consideration in the optimal portfolio. The product holdings are...

  11. Mechanical and Corrosion Properties of Fe-Cr-Mn-C-N Austenitic Stainless Steels for Drill Collars

    Science.gov (United States)

    Lee, Eunkyung; Ryu, Jiseung; Jeon, Seol; Mishra, Brajendra; Palmer, Bruce R.

    2016-06-01

    The mechanical and corrosion properties of air/water-quenched CN66 (0.28/0.38 wt pct, C/N) and CN71 (0.27/0.44 wt pct, C/N) steels after heat treatment were investigated. The carbon condensed area of the water-quenched alloys decreased compared with the air-cooled alloys, and lattice expansions occurred, resulting in a strained region. The values of UTS and elongation of water-quenched CN71 were increased as 105 MPa and 25.2 pct compared with the air-cooled CN71, and decreased sour corrosion resistance (1.8 × 10-4 mm/year).

  12. Room temperature strain rate sensitivity in precursor derived HfO2/Si-C-N(O ceramic nanocomposites

    Directory of Open Access Journals (Sweden)

    Ravindran Sujith

    2014-01-01

    Full Text Available Investigation on the room temperature strain rate sensitivity using depth sensing nanoindentation is carried out on precursor derived HfO2/Si-C-N(O ceramic nanocomposite sintered using pulsed electric current sintering. Using constant load method the strain rate sensitivity values are estimated. Lower strain rate sensitivity of ∼ 3.7 × 10−3 is observed and the limited strain rate sensitivity of these ceramic nanocomposites is explained in terms of cluster model. It is concluded that presence of amorphous Si-C-N(O clusters are responsible for the limited flowability in these ceramics.

  13. Long-Term Impact of Soil Management on Microbial Biomass C, N and P in Rice-Based Cropping System

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A 12-year field experiment was conducted to investigate the effect of different tillage methods and fertilization systems on microbial biomass C, N and P of a gray fluvo-aguic soil in rice-based cropping system. Five fertilization treatments were designed under conventional tillage (CT) or no tillage (NT) system: no fertilizer (CK); chemical fertilizer only (CF); combining chemical fertilizer with pig manure (PM); combining chemical fertilizer with crop straw (CS) and fallow (F). The results showed that biomass C, N and P were enriched in the surface layer of no-tilled soil, whereas they distributed relatively evenly in the tilled soil, which might result from enrichment of crop residue, organic manure and mineral fertilizer, and surficial development of root systems under NT. Under the cultivation system, NT had slightly greater biomass C, N and P at 0~5 cm depth, significantly less biomass C, N and P at 5~15 cm depth, less microbial biomass C, N and equivalent biomass P at 15~30 cm depth as compared to CT, indicating that tillage was beneficial for the multiplication of organisms in the plowed layer of soil. Under the fallow system, biomass C, N and P in the surface layer were significantly greater for NT than CT while their differences between the two tillage methods were negligible in the deeper layers. In the surface layer, biomass C, N and P in the soils amended with organic manure combined with mineral fertilizers were significantly greater than those of the treatments only with mineral fertilizers and the control. Soils without fertilizer had the least biomass nutrient contents among the five fertilization treatments. Obviously, the long-term application of organic manure could maintain the higher activity of microorganisms in soils. The amounts of biomass C, N and P in the fallowed soils varied with the tillage methods; they were much greater under NT than under CT, especially in the surface layer, suggesting that the frequent plowing could decrease

  14. The use of image analysis to investigate C:N ratio in the mixture of chicken manure and straw

    Science.gov (United States)

    Czekała, W.; Dach, J.; Ludwiczak, A.; Przybylak, A.; Boniecki, P.; Koszela, K.; Zaborowicz, M.; Przybył, K.; Wojcieszak, D.; Witaszek, K.

    2015-07-01

    The aim of the study was to determine the possibility of analysis of C:N ratio in the chicken manure and wheat straw mixture. This paper presents preliminary assumptions and parameters of extraction characteristics process. It also presents an introduction of digital image analysis of chicken manure and wheat straw mixture. This work is an introduction to the study on develop computer system that could replace chemical analysis. Good understanding the value of dependence C:N on the basis of image analysis will help in selection of optimal conditions for biological waste treatment.

  15. Effective Biological Nitrogen Removal Treatment Processes for Domestic Wastewaters with Low C/N Ratios: A Review

    DEFF Research Database (Denmark)

    Sun, Sheng-Peng; Pellicer i Nàcher, Carles; Merkey, Brian;

    2010-01-01

    Discharge of nitrogenous components to water bodies can cause eutrophication, deterioration of water quality, toxicity to aquatic life, and pose a potential hazard to human and animal health. Biological nitrogen removal can remove nitrogenous components via conversion to harmless nitrogen gas...... with high efficiency and relative low costs. However, the removal of nitrogen from domestic wastewater with a low carbon/nitrogen (C/N) ratio can often be limited in municipal wastewater plants (WWTPs) because organic carbon is a limiting factor for denitrification. The present work reviews innovative......-effective nitrogen removal from low C/N ratio domestic wastewater can be obtained in the near future....

  16. Mechanical and Corrosion Properties of Fe-Cr-Mn-C-N Austenitic Stainless Steels for Drill Collars

    Science.gov (United States)

    Lee, Eunkyung; Ryu, Jiseung; Jeon, Seol; Mishra, Brajendra; Palmer, Bruce R.

    2016-04-01

    The mechanical and corrosion properties of air/water-quenched CN66 (0.28/0.38 wt pct, C/N) and CN71 (0.27/0.44 wt pct, C/N) steels after heat treatment were investigated. The carbon condensed area of the water-quenched alloys decreased compared with the air-cooled alloys, and lattice expansions occurred, resulting in a strained region. The values of UTS and elongation of water-quenched CN71 were increased as 105 MPa and 25.2 pct compared with the air-cooled CN71, and decreased sour corrosion resistance (1.8 × 10-4 mm/year).

  17. Hydrogen bonds in PC{sub 61}BM solids

    Energy Technology Data Exchange (ETDEWEB)

    Sheng, Chun-Qi [Department of Physics, Zhejiang University, Hangzhou 310027 (China); Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121 (China); Li, Wen-Jie; Du, Ying-Ying; Chen, Guang-Hua; Chen, Zheng; Li, Hai-Yang; Li, Hong-Nian, E-mail: phylihn@mail.zju.edu.cn [Department of Physics, Zhejiang University, Hangzhou 310027 (China)

    2015-09-15

    We have studied the hydrogen bonds in PC{sub 61}BM solids. Inter-molecular interaction is analyzed theoretically for the well-defined monoclinic (P2{sub 1}/n) structure. The results indicate that PC{sub 61}BM combines into C–H⋯O{sub d} bonded molecular chains, where O{sub d} denotes the doubly-bonded O atom of PC{sub 61}BM. The molecular chains are linked together by C–H⋯O{sub s} bonds, where O{sub s} denotes the singly-bonded O atom of PC{sub 61}BM. To reveal the consequences of hydrogen bond formation on the structural properties of PC{sub 61}BM solids (not limited to the monoclinic structure), we design and perform some experiments for annealed samples with the monoclinic (P2{sub 1}/n) PC{sub 61}BM 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⋯O{sub d} bonds seem persisting in the altered structures. The inter-molecular hydrogen bonds can help to understand the phase separation in polymer/PC{sub 61}BM blends and may be responsible for the existence of liquid PC{sub 61}BM.

  18. Integrated survey of elemental stoichiometry (C, N, P from the Western to Eastern Mediterranean Sea

    Directory of Open Access Journals (Sweden)

    M. Pujo-Pay

    2010-10-01

    Full Text Available This paper provides an extensive vertical and longitudinal description of the biogeochemistry in the whole Mediterranean Sea during the summer 2008. During this strong stratified period, the distribution of nutrients, particulate and dissolved organic carbon (DOC, nitrogen (DON and phosphorus (DOP were investigated along a 3000 km transect (BOUM cruise crossing the Western and Eastern Mediterranean basins. The partitioning of chemical C, N and P species among all these mineral and organic pools has been analysed to produce a detailed spatial and vertical extended examination of the elemental stoichiometry. Surface Mediterranean waters were depleted in nutrients and the thickness of this depleted layer increased towards the East from about 10 m in the Gulf of Lion to more than 100 m in the Levantine basin, concomitantly to the gradual deepening of the thermocline and nutriclines. We used threshold in oxygen concentration to discriminate the water column in three layers; surface (Biogenic Layer BL, intermediate (Mineralization Layer ML, and deep layer (DL and to propose a schematic representation of biogeochemical fluxes between the different compartments and to compare the functioning of the two basins. The stoichiometry revealed a clear longitudinal and vertical gradient in the mineral fraction with a P-depletion evidenced on both dimension. As a consequence of the severe deficiency in phosphorus, the C:N:P ratios in all pools within the BL largely exceed the Redfield ratios. Despite these gradients, the deep estimated fluxes in the mineral compartment tend towards the canonical Redfield values in both basins. A change in particulate matter composition has been evidenced by a C increase relative to N and P along the whole water column in the western basin and between BL and ML in the eastern one. More surprisingly, a decrease in N relative to P with depth was encountered in the whole Mediterranean Sea. We suggest that there was a more rapid

  19. Effects of Land Use Change on C-N cycling: Microbes Matter.

    Science.gov (United States)

    Hofmockel, K.

    2012-12-01

    Large swaths of the terrestrial landscape have been altered by human actions on Earth's biophysical systems, resulting in the homogenization of Earth's biota, while simultaneously increasing greenhouse gases and reactive nitrogen (N). This is especially poignant in grasslands that have been largely replaced by managed agricultural systems with substantial N inputs, or by unmanaged grasslands that are dominated by exotic species. Impacted ecosystems may be important for global C models, because they comprise a major portion of the global land area, terrestrial NPP and the world's soil C stocks. This research investigates how anthropogenic changes in plant community composition and agricultural management systems influence the composition and function of microbial communities that mediate key aspects of belowground C and N cycling and storage. Data from agroecology and grassland climate change experiments are used to illustrate how microbial responses can have important implications for large scale coupling of C and N cycles. In this study exotic plant species significantly decreased root inputs, causing shifts in microbial community composition, including both specific taxa and functional guilds of bacteria. By contrast, climate change (precipitation manipulation) caused functional responses (increased carbon and phosphorus cycling) that were not detected in the microbial community composition. Mycorrhizal fungi in managed systems were responsive to both root biomass and nitrogen inputs, significantly altering hydrolytic enzyme activity and aggregate turnover. Collectively small-scale processes can alter the ecosystem biogeochemical cycles. Together theses results suggest that linking microbial communities to coupled C-N cycles may have important implications for terrestrial C cycling feedbacks that are an integral part of the anthropocene era.

  20. Measurement of kinetics of Nb(C,N) precipitation using hot torsion testing

    International Nuclear Information System (INIS)

    Precipitation of Nb(C,N) in austenite of microalloyed steels is a well studied subject. Strain induced precipitates play a critical part in retarding recrystallization of austenite in the finishing passes of hot rolling. Hence, knowledge of how precipitation takes place is of major industrial significance. Measurements of fraction precipitated as a function of time at constant temperature (PTT curves) have been obtained through several experimental methods. One of them uses the principle of stress relaxation in axial compression for measurements of kinetics of TiC precipitation in austenite of Ti microalloyed steels. However, the total true deformation that can be applied in compression is usually limited to about 0.8. On the other hand, deformation of austenite in industrial processes is executed in several passes under continuous cooling before precipitation takes place. Successive cycles of deformation followed by recrystallization leads to substantial grain refinement which in turn may effect the process of precipitation. Therefore, the capability of axial compression to reproduce a more realistic hot rolling scenario seems to be very limited as far as austenite conditioning is concerned. A viable alternative may be torsion testing. Hot torsion can be used, for instance, to apply several passes with strains, strain rates, delay times and temperatures similar to those found in an industrial process. It would be then desirable to combine the ability of torsion to simulate industrial schedules with the stress relaxation technique to obtain PTT curves. But before building up PTT curves from simulated 'as hot rolled' austenite, it is necessary to investigate if torsion experiments are able to detect precipitation. This paper describes an application of torsion testing and the stress relaxation techniques to measure kinetics of precipitation

  1. Microbial Biomass C,N and P in Disturbed Dry Tropical Forest Soils, India

    Institute of Scientific and Technical Information of China (English)

    J.S.SINGH; D.P.SINGH; A.K.KASHYAP

    2010-01-01

    Variations in microbial biomass C(MB-C),N(MB-N)and P(MB-P)along a gradient of different dominant vegetation covers(natural forest,mixed deciduous forest,disturbed savanna and grassland ecosystems)in dry tropical soils of Vindhyan Plateau,India were studied from January 2005 to December 2005.The water holding capacity,organic C,total N,total P and soil moisture content were comparatively higher in forest soils than in the savanna and grassland sites.Across different study sites the mean annual MB-C,MB-N and MB-P at 0-15 cm soil depth varied from 312.05 ± 4.22to 653.40 ± 3.17,32.16 ± 6.25 to 75.66 ± 7.21 and 18.94 ± 2.94 to 30.83 ± 23.08 μg g-1 dry soil,respectively.At all the investigated sites,the maximum MB-C,MB-N and MB-P occurred during the dry period(summer season)and the minimum in wet period(rainy season).In the present study,soil MB-C,MB-N and MB-P were higher at the forest sites compared to savanna and grassland sites.The differences in MB-C,MB-N and MB-P were significant(P mixed deciduous forest > savanna > grassland.The results suggested that deforestation and land use practices(conversion of forest into savanna and grassland)caused the alterations in soil properties,which as a consequence,led to reduction in soil nutrients and MB-C,MB-N and MB-P in the soil of disturbed sites(grassland and savanna)compared to undisturbed forest ecosystems.

  2. Ti(C,N and (Ti,AlN hard wear resistant coatings

    Directory of Open Access Journals (Sweden)

    K. Gołombek

    2010-04-01

    Full Text Available Purpose: Investigation the influence of kind of PVD coatings structure (homogenous or gradient on properties of deposited tool materials: cemented carbides and cermets.Design/methodology/approach: Analysis of the structure, analysis of the mechanical and functional properties: surface roughness, microhardness tests, scratch tests, cutting tests. The Ti(C,N gradient coating was investigated by XPS method with multifunctional PHI 5700/660 spectrometer. The characteristic of surface region coating were determined from XPS depth profile. X-ray qualitative phase analysis and the grazing incidence X-ray diffraction method (GIXRD was employed to collect the detailed information about phase composition of investigated material’s surface layer. Microstructural of investigations substrates and coatings by transmission electron miocroscopy (TEM were done.Findings: Results of the investigation the influence of PVD coatings structure (homogenous or gradient and kind on properties of coated tool materials: cemented carbides and cermets are given in the paper. Coatings are characterized by dense, compact structure, there have been identified no pores, fractures and discontinuities. The coatings were deposited uniformly onto the investigated substrate materials and show a characteristic columnar, fine-graded structure. The results of roughness, microhardness and cutting tests confirm the advantages of the PVD coatings. The coatings deposited onto the investigated substrates are characterised by good adhesion and causes increasing of wear resistance. The grazing incidence X-ray diffraction method (GIXRD in the investigated coatings were used to describe the structure and gradient character of the coatings.Practical implications: Deposition of hard, thin, gradient coatings on materials surface by PVD method features one of the most intensely developed directions of improvement of the working properties of materials.Originality/value: New techniques of gradient

  3. Silicon carbide wafer bonding by modified surface activated bonding method

    Science.gov (United States)

    Suga, Tadatomo; Mu, Fengwen; Fujino, Masahisa; Takahashi, Yoshikazu; Nakazawa, Haruo; Iguchi, Kenichi

    2015-03-01

    4H-SiC wafer bonding has been achieved by the modified surface activated bonding (SAB) method without any chemical-clean treatment and high temperature annealing. Strong bonding between the SiC wafers with tensile strength greater than 32 MPa was demonstrated at room temperature under 5 kN force for 300 s. Almost the entire wafer has been bonded very well except a small peripheral region and few voids. The interface structure was analyzed to verify the bonding mechanism. It was found an amorphous layer existed as an intermediate layer at the interface. After annealing at 1273 K in vacuum for 1 h, the bonding tensile strength was still higher than 32 MPa. The interface changes after annealing were also studied. The results show that the thickness of the amorphous layer was reduced to half after annealing.

  4. Fluxless eutectic bonding of GaAs-on-Si by using Ag/Sn solder

    Science.gov (United States)

    Eo, Sung-Hwa; Kim, Dae-Seon; Jeong, Ho-Jung; Jang, Jae-Hyung

    2013-11-01

    Fluxless GaAs-on-Si wafer bonding using Ag/Sn solder was investigated to realize uniform and void-free heterogeneous material integration. The effects of the diffusion barrier, Ag/Sn thickness, and Ar plasma treatment were studied to achieve the optimal fluxless bonding process. Pt on a GaAs wafer and Mo on a Si wafer act as diffusion barriers by preventing the flow of Ag/Sn solder into both the wafers. The bonding strength is closely related to the Ag/Sn thickness and Ar plasma treatment. A shear strength test was carried out to investigate the bonding strength. Under identical bonding conditions, the Ag/Sn thickness was optimized to achieve higher bonding strength and to avoid the formation of voids due to thermal stress. An Ar plasma pretreatment process improved the bonding strength because the Ar plasma removed carbon contaminants and metal-oxide bonds from the metal surface.

  5. A normal form for a real 2-codimensional submanifold in \\mathbb{C}^{N+1} near a CR singularity

    OpenAIRE

    Burcea, Valentin

    2011-01-01

    We construct a formal normal form for a real 2-codimensional submanifold M\\subset\\mathbb{C}^{N+1} near a CR singularity approximating the sphere. This result gives a higher dimensional extension of Huang-Yin's normal form in \\mathbb{C}^{2}.

  6. Franklin Medal and Bower prize awarded to C.N. Yang. On the Yang-Mills gauge field theory

    International Nuclear Information System (INIS)

    C.N. Yang was awarded the Benjamin Franklin Medal and 1995 Bower Prize mainly for his fundamental work on nonabelian gauge field theory. A brief introduction to this theory and its important role in the development of physics is given

  7. Processing of carbon fiber reinforced composites with particulate-filled precursor-derived Si-C-N matrix phases

    OpenAIRE

    Lee, Sea-Hoon

    2004-01-01

    Die Arbeit widmet sich Faktoren, die bei der Herstellung von keramischen Faser-Matrix-Verbundwerkstoffen (FRC, fiber-reinforced composites) deren mechanische und thermische Eigenschaften beeinflussen. Insbesondere wurden der Einfluss von Fuellstoffen und die Optimierung des PIP-Verfahrens (Precursor Impregnation and Pyrolysis) zur Herstellung kohlenstofffaserverstaerkter Si-C-N-Precursorkeramiken untersucht. Dabei wurden fuenf Bereiche betrachtet, die jeweils in einem Kapitel dargelegt wurden...

  8. Stand heterogeneity of total carbon and nitrogen, and C/N ratio in soil of mountain meadows

    Czech Academy of Sciences Publication Activity Database

    Vranová, V.; Formánek, P.; Rejšek, K.; Janouš, Dalibor

    2007-01-01

    Roč. 4, č. 2 (2007), s. 149-155. ISSN 1801-5395 R&D Projects: GA MŽP SM/640/18/03; GA MŽP SM/630/2/03 Institutional research plan: CEZ:AV0Z60870520 Keywords : carbon * nitrogen * C/N ratio * mountain meadow Subject RIV: EF - Botanics

  9. Credit default swaps, bond spreads and the bond market

    OpenAIRE

    Zhu, Meicheng

    2014-01-01

    With the rapid development of the credit default swap (CDS) market, the issue of how the introduction of CDSs affects the corporate bond market has been of particular interest to researchers and policy makers. This has been investigated in the literature from two perspectives. One is to examine the relationship between the CDS and the bond markets in price discovery, and the other is concerned with researching the CDS trading effects on bond spreads. Referring to the former approach, most rel...

  10. C : N : P stoichiometry at the Bermuda Atlantic Time-series Study station in the North Atlantic Ocean

    Directory of Open Access Journals (Sweden)

    A. Singh

    2015-06-01

    Full Text Available Nitrogen (N and phosphorus (P availability determine the strength of the ocean's carbon (C uptake, and variation in the N : P ratio in inorganic nutrients is key to phytoplankton growth. A similarity between C : N : P ratios in the plankton biomass and deep-water nutrients was observed by Alfred C. Redfield around 80 years ago and suggested that biological processes in the surface ocean controlled deep ocean chemistry. Recent studies have emphasized the role of inorganic N : P ratios in governing biogeochemical processes, particularly the C : N : P ratio in suspended particulate organic matter (POM, with somewhat less attention given to exported POM and dissolved organic matter (DOM. Herein, we extend the discussion on ecosystem C : N : P stoichiometry but also examine temporal variation of stoichiometric relationships. We have analysed elemental stoichiometry in the suspended POM and total (POM + DOM organic matter (TOM pools in the upper 100 m, and in the exported POM and sub-euphotic zone (100–500 m inorganic nutrient pools from the monthly data collected at the Bermuda Atlantic Time-series Study (BATS site located in the western part of the North Atlantic Ocean. C : N : P ratios in the TOM pool were more than twice that in the POM pool. Observed C : N ratios in suspended POM were approximately equal to the canonical Redfield Ratio (C : N : P = 106 : 16 : 1, while N : P and C : P ratios in the same pool were more than twice the Redfield Ratio. Average N : P ratios in the subsurface inorganic nutrient pool were ~ 26 : 1, squarely between the suspended POM ratio and the Redfield ratio. We have further linked variation in elemental stoichiometry with that of phytoplankton cell abundance observed at the BATS site. Findings from this study suggest that the variation elemental ratios with depth in the euphotic zone was mainly due to different growth rates of cyanobacterial cells. These time-series data have also allowed us to examine the

  11. C : N : P stoichiometry at the Bermuda Atlantic Time-series Study station in the North Atlantic Ocean

    Science.gov (United States)

    Singh, A.; Baer, S. E.; Riebesell, U.; Martiny, A. C.; Lomas, M. W.

    2015-11-01

    Nitrogen (N) and phosphorus (P) availability, in addition to other macro- and micronutrients, determine the strength of the ocean's carbon (C) uptake, and variation in the N : P ratio of inorganic nutrient pools is key to phytoplankton growth. A similarity between C : N : P ratios in the plankton biomass and deep-water nutrients was observed by Alfred C. Redfield around 80 years ago and suggested that biological processes in the surface ocean controlled deep-ocean chemistry. Recent studies have emphasized the role of inorganic N : P ratios in governing biogeochemical processes, particularly the C : N : P ratio in suspended particulate organic matter (POM), with somewhat less attention given to exported POM and dissolved organic matter (DOM). Herein, we extend the discussion on ecosystem C : N : P stoichiometry but also examine temporal variation in stoichiometric relationships. We have analyzed elemental stoichiometry in the suspended POM and total (POM + DOM) organic-matter (TOM) pools in the upper 100 m and in the exported POM and subeuphotic zone (100-500 m) inorganic nutrient pools from the monthly data collected at the Bermuda Atlantic Time-series Study (BATS) site located in the western part of the North Atlantic Ocean. C : N and N : P ratios in TOM were at least twice those in the POM, while C : P ratios were up to 5 times higher in TOM compared to those in the POM. Observed C : N ratios in suspended POM were approximately equal to the canonical Redfield ratio (C : N : P = 106 : 16 : 1), while N : P and C : P ratios in the same pool were more than twice the Redfield ratio. Average N : P ratios in the subsurface inorganic nutrient pool were ~ 26 : 1, squarely between the suspended POM ratio and the Redfield ratio. We have further linked variation in elemental stoichiometry to that of phytoplankton cell abundance observed at the BATS site. Findings from this study suggest that elemental ratios vary with depth in the euphotic zone, mainly due to different

  12. Solder extrusion pressure bonding process and bonded products produced thereby

    Science.gov (United States)

    Beavis, Leonard C.; Karnowsky, Maurice M.; Yost, Frederick G.

    1992-01-01

    Production of soldered joints which are highly reliable and capable of surviving 10,000 thermal cycles between about -40.degree. C. and 110.degree. C. Process involves interposing a thin layer of a metal solder composition between the metal surfaces of members to be bonded and applying heat and up to about 1000 psi compression pressure to the superposed members, in the presence of a reducing atmosphere, to extrude the major amount of the solder composition, contaminants including fluxing gases and air, from between the members being bonded, to form a very thin, strong intermetallic bonding layer having a thermal expansion tolerant with that of the bonded members.

  13. Avoiding silicon/glass bonding damage with fusion bonding method

    Institute of Scientific and Technical Information of China (English)

    Daohong Yang(杨道虹); Chen Xu(徐晨); Guangdi Shen(沈光地)

    2004-01-01

    A novel fusion bonding method between silicon and glass with Nd:YAG laser is described.This method overcomes the movable mechanical parts damage caused by the electrostatics force in micro-electronic machine-system(MEMS)device during the anodic bonding. The diameter of laser spot is 300 μm,the power of laser is 100 W,the laser velocity for bonding is 0.05 m/s,the average bonding tension is 6.3 MPa.It could distinctly reduce and eliminate the defects and damage,especially in movable sensitive mechanical parts of MEMS device.

  14. 19 CFR 113.12 - Bond application.

    Science.gov (United States)

    2010-04-01

    ... 19 Customs Duties 1 2010-04-01 2010-04-01 false Bond application. 113.12 Section 113.12 Customs... CUSTOMS BONDS Bond Application and Approval of Bond § 113.12 Bond application. (a) Single entry bond application. In order to insure that the revenue is adequately protected the port director may require...

  15. Microhardness study of Ti(C, N films deposited on stainless steel 316 by the hallow cathode discharge gun

    Directory of Open Access Journals (Sweden)

    A.J. Novinrooz

    2005-12-01

    Full Text Available Purpose: The micro hardness properties of Titanium Carbonitride composite coated on SS-316 substrates were studied to achieve a desired harden surfaces.Design/methodology/approach: Hollow Cathode Discharge gun (HCD–gun was employed for deposition of the Ti(C, N on SS-316. The evaporated and ionized metal (Ti was coated as an under layer with 0.5 ampere beam current and 100 volt bias voltage. The reactant nitrogen and methane gasses were fed through inlet in to the chamber containing Ti element to form Ti (C, N matrix with an optimized ratio.Findings: In this work, Glow Discharge Optical emission Spectroscopy (GDOS used for compositional analysis of the content elements. On the bases of this operation it was revealed the existence of Ti, C, N elements, X-ray diffraction (XRD technique was utilized to investigate films crystalline structure. The investigation showed that samples with different stoichiometry have a fcc structure with (111 plan of reflection. The atomic ratio of carbon and nitrogen were measured using energy dispersive X-ray (EDX analysis. The optimized value was funned to be TiC0.87 N0.13. The atomic force microscopy (AFM and scanning electron microscopy (SEM were employed to study the films microstructure. A hardness of 3250 HV was obtained in the carbon content C/C+ N atomic ratio of 9 to 1 using a Vickers microhardness tester.Research limitations/implications: As the study was carried out on a limited surfaces, we shall endeavor further attempt on large area deposition.Practical implications: The tools coated in titanium accompanied by nitride and carbide has shown significant improvement. Good compatibility of Ti (C, N compound makes these composite suitable in various technical and industrial applications.Originality/value: It may be remarked that, the hardness obtained in this work is very encouraging and therefore, it is convenient to regard this as a privileged step taken in tool manufacturing aspect.

  16. Effects of Nitrogen Sources and C/N Ratios on the Lipid-Producing Potential of Chlorella sp. HQ.

    Science.gov (United States)

    Zhan, Jingjing; Hong, Yu; Hu, Hongying

    2016-07-28

    Microalgae are being researched for their potential as attractive biofuel feedstock, particularly for their lipid production. For maximizing biofuel production, it is necessary to explore the effects of environmental factors on algal lipid-producing potential. In this study, the effects of nitrogen (N) sources (NO2-N, NO3-N, urea-N, NH4-N, and N-deficiency) and carbon-to-nitrogen ratios (C/N= 0, 1.0, 3.0, and 5.0) on algal lipid-producing potential of Chlorella sp. HQ were investigated. The results showed that for Chlorella growth and lipid accumulation potential, NO2-N was the best amongst the nitrogen sources, and NO3-N and urea-N also contributed to algal growth and lipid accumulation potential, but NH4-N and N-deficiency instead caused inhibitory effects. Moreover, the results indicated that algal lipid-producing potential was related to C/N ratios. With NO2-N treatment and carbon addition (C/N = 1.0, 3.0, and 5.0), total lipid yield was enhanced by 12.96-20.37%, but triacylglycerol (TAG) yields decreased by 25.52-94.31%. As for NO3-N treatment, carbon addition led to a 17.82-57.43%/ 25.86-82.67% reduction of total lipid/TAG yields. When NH4-N was used as the nitrogen source, total lipid/TAG yields were increased by 46.67-113.33%/28.99-74.76% with carbon addition. The total lipid/TAG yields of urea-N treatment varied with C/N ratios. Overall, the highest TAG yield (TAG yield: 38.75 ± 5.21 mg/l; TAG content: 44.16 ± 4.35%) was achieved under NO2-N treatment without carbon addition (C/N = 0), the condition that had merit for biofuel production. PMID:27090186

  17. Integration of European Bond Markets

    DEFF Research Database (Denmark)

    Christiansen, Charlotte

    2014-01-01

    I investigate the time variation in the integration of EU government bond markets. The integration is measured by the explanatory power of European factor portfolios for the individual bond markets for each year. The integration of the government bond markets is stronger for EMU than non-EMU memb......I investigate the time variation in the integration of EU government bond markets. The integration is measured by the explanatory power of European factor portfolios for the individual bond markets for each year. The integration of the government bond markets is stronger for EMU than non......-EMU members and stronger for old than new EU members. For EMU countries, the integration is weaker the lower the credit rating is. During the recent crisis periods, the integration is weaker, particularly for EMU countries....

  18. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

    Vinther, Tine N; Pettersson, Ingrid; Huus, Kasper;

    2015-01-01

    -chain is flexible and can adapt multiple conformations. We examined how well disulfide bond predictions algorithms could identify disulfide bonds in this region of insulin. In order to identify stable insulin analogues with additional disulfide bonds, which could be expressed, the Cβ cut-off distance had...... higher yields in comparison to analogues with additional disulfide bonds that were more difficult to predict. In contrast, addition of the fourth disulfide bond rendered all analogues resistant to fibrillation under stress conditions and all stable analogues bound to the insulin receptor with picomolar...... predicts four additional four disulfide insulin analogues which could be expressed. Although the location of the additional disulfide bonds is only slightly shifted, this shift impacts both stability and activity of the resulting insulin analogues....

  19. Supersymmetric Valence Bond Solid States

    OpenAIRE

    Arovas, Daniel P.; Hasebe, Kazuki; Qi, Xiao-Liang; Zhang, Shou-Cheng

    2009-01-01

    In this work we investigate the supersymmetric version of the valence bond solid (SVBS) state. In one dimension, the SVBS states continuously interpolate between the valence bond states for integer and half-integer spin chains, and they generally describe superconducting valence bond liquid states. Spin and superconducting correlation functions can be computed exactly for these states, and their correlation lengths are equal at the supersymmetric point. In higher dimensions, the wave function...

  20. Mezzanine finance and corporate bonds

    OpenAIRE

    Libena TETREVOVA

    2009-01-01

    The article deals with the problems of mezzanine finance in relation to corporate bonds. Firstly, attention is paid to definition of mezzanine finance. The term mezzanine finance is used as a term for hybrid forms of financing that combine elements of debt and equity financing. Mezzanine finance represents an alternative form of financing corporate activities. Secondly, possible forms of mezzanine finance are characterized. We can say that special types of corporate bonds (convertible bonds a...