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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. 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

  5. Achieving C-N bond cleavage in dinuclear metal cyanide complexes.

    Science.gov (United States)

    Cavigliasso, Germán; Christian, Gemma J; Stranger, Robert; Yates, Brian F

    2011-07-28

    Cleavage of cyanide is more difficult to achieve compared to dinitrogen and carbon monoxide, even though these species contain triple bonds of greater strength. In this work, we have used computational methods to investigate thermodynamic and mechanistic aspects of the C-N bond cleavage process in [L(3)M-CN-M'L(3)] systems consisting of a central cyanide unit bound in an end-on fashion to two terminal metal tris-amide complexes. In these systems, [M] is a d(3) transition metal from the 3d, 4d, 5d, or 6d series and groups 4 through 7, and [L] is either [NH(2)], [NMe(2)], [N(i)PrPh], or [N(t)BuAr]. A comparison of various models for the experimentally relevant [L(3)Mo-CN-MoL(3)] system has shown that while the C-N cleavage step appears to be an energetically favourable process, a large barrier exists for the dissociation of [L(3)Mo-CN-MoL(3)]((-)) into [L(3)Mo-C]((-)) and [N-MoL(3)], which possibly explains why C-N bond scission is not observed experimentally. The general structural, bonding, and thermochemical trends across the transition metal series investigated, indicate that the systems exhibiting the greatest degree of C-N activation, and most favourable energetics for C-N cleavage, also possess the most favourable electronic properties, namely, a close match between the relevant π-like orbitals on the metal-based and cyanide fragments. The negative charge on the cyanide fragment leads to significant destabilization of the π* level which needs to be populated through back-donation from the metal centres in order for C-N bond scission to be achieved. Therefore, metal-based systems with high-lying d(π) orbitals are best suited to C-N cleavage. In terms of chemical periodicity, these systems can be identified as the heavier members within a group and the earlier members within a period. As a consequence, Mo complexes are not well suited to cleaving the C-N bond, whereas the Ta analogues are the most favourable systems and should, in principle, be capable of

  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. First-principles analysis of the C-N bond scission of methylamine on Mo-based model catalysts

    Science.gov (United States)

    Lv, Cun-Qin; Li, Jun; Tao, Shu-Xia; Ling, Kai-Cheng; Wang, Gui-Chang

    2010-01-01

    The C-N bond breaking of methylamine on clean, carbon (nitrogen, oxygen)-modified Mo(100) [denoted as Mo(100) and Mo(100)-C(N,O), respectively], Mo2C(100), MoN(100), and Pt(100) surfaces has been investigated by the first-principles density functional theory (DFT) calculations. The results show that the reaction barriers of the C-N bond breaking in CH3NH2 on Mo(100)-C(N,O) are higher than that on clean Mo(100). The calculated energy barrier can be correlated linearly with the density of Mo 4d states at the Fermi level after the adsorption of CH3NH2 for those surfaces. Moreover, the DFT results show that the subsurface atom, e.g., carbon, can reduce the reaction barrier. In addition, We noticed that the activation energies for the C-N bond breaking on Mo2C(100) and MoN(100) are similar to that on Pt(100), suggesting that the catalytic properties of the transition metal carbides and nitrides for C-N bond scission of CH3NH2 might be very similar to the expensive Pt-group metals.

  8. 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.

  9. 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).

  10. Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination.

    Science.gov (United States)

    Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok

    2015-04-21

    Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged as a step- and atom-economical alternative to the conventional C-N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C-H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this context, we were curious to see whether a transition-metal-catalyzed mild C-H amination protocol could be achieved using organic azides as the amino source. We envisaged that a dual role of organic azides as an environmentally benign amino source and also as an internal oxidant via N-N2 bond cleavage would be key to develop efficient C-H amination reactions employing azides. An additional advantage of this approach was anticipated: that a sole byproduct is molecular nitrogen (N2) under the perspective catalytic conditions. This Account mainly describes our research efforts on the development of rhodium- and iridium-catalyzed direct C-H amination reactions with organic azides. Under our initially optimized Rh(III)-catalyzed amination conditions, not only sulfonyl azides but also aryl- and alkyl azides could be utilized as facile amino sources in reaction with various types of C(sp(2))-H bonds bearing such directing groups as pyridine, amide, or ketoxime. More recently, a new

  11. 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...

  12. 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 i...... for redox-active cysteines. In the cytoplasm of Escherichia coli, the protein was a sensitive probe for the redox changes that occur upon disruption of the thioredoxin reductive pathway....

  13. Density Functional Method Studies of X-H (X=C, N, O, Si, P, S) Bond Dissociation Energies

    Institute of Scientific and Technical Information of China (English)

    FU Yao; DONG Xiao-Yu; WANG Yi-Min; LIU Lei; GUO Qing-Xiang

    2005-01-01

    The performances of the density functional theory (DFT) methods in calculating X-H bond dissociation energies (BDE, X=C, N, O, Si, P, S) were evaluated. It was found that most DFT methods including B3LYP, B3PW91,G96LYP, PBE1PBE and BH&HLYP significantly underestimated the X-H BDE by as much as 13-24 kJ/mol.The underestimation is not due to the use of finite basis set, because the DFT methods still significantly underestimate the X-H BDE with the complete basis set. Therefore, these DFT methods can not be used to calculate the BDE directly. Nevertheless, the B3P86 method shows very small underestimation for the X-H BDE. Further analysis suggests that there be no advantage for using the restricted open-shell DFT methods. The unrestricted DFT methods actually perform slightly better than the restricted open-shell DFT methods in most cases. Finally, it was found that the underestimation by the DFT methods was largely systematic. The use of the calibrated UDFT/6-311+ + G(d, p) method was recommended to calculate the X-H BDE.

  14. Substituent-controlled selective synthesis of N-acyl 2-aminothiazoles by intramolecular Zwitterion-mediated C-N bond cleavage.

    Science.gov (United States)

    Wang, Yang; Zhao, Fei; Chi, Yue; Zhang, Wen-Xiong; Xi, Zhenfeng

    2014-11-21

    The cleavage of C-N bonds is an interesting and challenging subject in modern organic synthesis. We have achieved the first zwitterion-controlled C-N bond cleavage in the MCR reaction among lithium alkynethiolates, bulky carbodiimides, and acid chlorides to construct N-acyl 2-aminothiazoles. This is a simple, highly efficient, and general method for the preparation of N-acyl 2-aminothiazoles with a broad range of substituents. The selective synthesis of N-acyl 2-aminothiazoles significantly depends on the steric hindrance of carbodiimides. The result is in striking contrast with our previous convergent reaction giving 5-acyl-2-iminothiazolines via 1,5-acyl migration. It is indeed interesting that the slight change of the substituents on the carbodiimides can completely switch the product structure. Experimental and theoretical results demonstrate the reason why the C-N bond cleavage in the present system is prior to the acyl migration. The intramolecular hydrogen relay via unprecedented Hofmann-type elimination is essential for this totally new zwitterion-controlled C-N bond cleavage.

  15. 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...

  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. 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

  18. 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 ...

  19. 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

  20. 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...

  1. 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.

  2. 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.

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

    Science.gov (United States)

    Makino, T.; Iwadachi, T.

    1998-10-01

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

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

    Science.gov (United States)

    Hatahet, Feras; Boyd, Dana; Beckwith, Jon

    2014-08-01

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

  5. 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...

  6. Macrocycle Synthesis by Chloride-Templated Amide Bond Formation.

    Science.gov (United States)

    Martí-Centelles, Vicente; Burguete, M Isabel; Luis, Santiago V

    2016-03-01

    A new family of pseudopeptidic macrocyclic compounds has been prepared involving an anion-templated amide bond formation reaction at the macrocyclization step. Chloride anion was found to be the most efficient template in the macrocyclization process, producing improved macrocyclization yields with regard to the nontemplated reaction. The data suggest a kinetic effect of the chloride template, providing an appropriate folded conformation of the open-chain precursor and reducing the energy barrier for the formation of the macrocyclic product. PMID:26820908

  7. 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...

  8. 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

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. 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.

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

    DEFF Research Database (Denmark)

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

    2001-01-01

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

  16. 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 ...

  17. 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...

  18. 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.

  19. 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

  20. Formation of H3+ due to Intramolecular Bond Rearrangement in Doubly Charged Methanol

    Science.gov (United States)

    de, Sankar; Rajput, Jyoti; Roy, A.; Ghosh, P. N.; Safvan, C. P.

    2006-11-01

    We report the formation of H3+ by proton coagulation in methanol under the impact of low energy Ar8+ projectiles. Our time-of-flight coincidence measurements with CH3OD establish that the H3+ formation arises from intramolecular bond rearrangement of the methyl group. We have performed ab initio quantum chemical calculations that show the preferred pathway for C-H3 bond cleavage. Fragmentation of organic molecules like methanol under impact of highly charged ions is suggested as an alternative mechanism of H3+ formation in outer space.

  1. 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...

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

    NARCIS (Netherlands)

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

    2001-01-01

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

  3. 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...

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

    Directory of Open Access Journals (Sweden)

    Vijay Kumar Ravi

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

  5. Exploring a Chemical Route for the Formation of Stable Anions of Polyynes [C n H- (n=2,4)] in Molecular Clouds

    Science.gov (United States)

    Gianturco, F. A.; Satta, M.; Mendolicchio, M.; Palazzetti, F.; Piserchia, A.; Barone, V.; Wester, R.

    2016-10-01

    Using quantum chemical methods, we investigate the possible outcomes of {{{H}}}- reactions with acetylene and diacetylene molecules. We find both reactions to be exothermic reactions without barriers, yielding stable anions of the corresponding polyynes: {{{C}}}2{{{H}}}- and {{{C}}}4{{{H}}}-. We show in this work that the computed chemical rates in the case of the formation of the {{{C}}}4{{{H}}}- anion would be larger than those existing for the direct radiative electron attachment (REA) process, the main mechanism generally suggested for their formation. In the case of the {{{C}}}2{{{H}}}- anion, however, the present chemical rates of formation at low T are even lower than those known for its REA process, both mechanisms being inefficient for its formation under astrochemical conditions. The present results are discussed in view of their consequences on the issue of the possible presence of such anions in the ISM environments. They clearly indicate the present chemical route to {{{C}}}2{{{H}}}- formation to be inefficient at the expected temperatures of a dark molecular cloud, whereas this is found not to be the case for the {{{C}}}4{{{H}}}-, in line with the available experimental findings.

  6. Characteristics of C-, N-DBPs formation from algal organic matter: role of molecular weight fractions and impacts of pre-ozonation.

    Science.gov (United States)

    Zhou, Shiqing; Zhu, Shumin; Shao, Yisheng; Gao, Naiyun

    2015-04-01

    Extracellular organic matter (EOM) and intracellular organic matter (IOM) of Microcystis aeruginosa have been reported to contribute to the formation of carbonaceous disinfection by-products (C-DBPs) and nitrogenous disinfection by-products (N-DBPs). Little is known about DBPs formation from different molecular weight (MW) fractions, especially for N-nitrosodimethylamine (NDMA). This study fractionated EOM and IOM into several MW fractions using a series of ultrafiltration membranes and is the first to report on the C-DBPs and N-DBPs formation from chlorination and chloramination of different MW fractions. Results showed that EOM and IOM were mainly distributed in low-MW (100 KDa) fractions. Additionally, the low-MW and high-MW fractions of EOM and IOM generally took an important part in forming C-DBPs and N-DBPs, either in chlorination or in chloramination. Furthermore, the effects of pre-ozonation on the formation of DBPs in subsequent chlorination and chloramination were also investigated. It was found that ozone shifted the high-MW fractions of EOM and IOM into lower MW fractions and increased the C-DBPs and N-DBPs yields to different degrees. As low-MW fractions are more difficult to remove than high-MW fractions by conventional treatment processes, therefore, activated carbon adsorption, nanofiltration (NF) and biological treatment processes can be ideal to remove the low-MW fractions and minimize the formation potential of C-DBPs and N-DBPs. Moreover, the use of ozone should be carefully considered in the treatment of algal-rich water.

  7. 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.

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

    CERN Document Server

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

    2016-01-01

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

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  10. 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)

  11. 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

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

    Science.gov (United States)

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

    2014-03-10

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

  13. 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...

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

    Institute of Scientific and Technical Information of China (English)

    谭越河; 李建晓; 洪文坤; 汪朝阳

    2011-01-01

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

  15. 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)

  16. Formation of H3^+ in methanol : an intramolecular bond rearrangement study

    Science.gov (United States)

    de, Sankar; Rajput, Jyoti; Roy, A.; Safvan, C. P.; Ghosh, P. N.

    2007-06-01

    We report here results of TOF multi-hit coincidence experiment [1] that provide evidence for intramolecular reactions involving proton coagulation in methanol [2] after interaction with 1.2 MeV Ar^8+ projectiles produced from the ECR ion source in the LEIBF laboratory of Inter-University Accelerator Centre, India. Quite remarkably, we have observed the formation of H3^+ due to movement of protons within the multiply charged parent molecular ion through two-body process (CH3OH^2+->H3^+ + COH^+) and such bond formation occurs before the Coulomb repulsion makes the fragment ions to fly apart. Analysis of the fragmentation pattern of CH3OH^2+ has been carried out using ab initio quantum chemical techniques. Structural calculations indicate that the formation of H3^+ is the preferred pathway in the overall fragmentation dynamics of the ground state of this alcohol. The field generated from highly charged ions induces the system to rearrange its structure following a minimum energy pathway and form hydrogen molecular ions. Repeating the experiment with CH3OD confirm our bond rearrangement phenomenon and establish that H3^+ formation occurs only within the methyl group of the alcohol. Ref: [1] S. De et. al. NIMB, 243, 435 (2006) [2] Sankar De et. al. PRL, 97, 213201 (2006)

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

    Indian Academy of Sciences (India)

    RAHUL SHUKLA; DEEPAK CHOPRA

    2016-10-01

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

  18. 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

  19. 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..

  20. 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

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

    Science.gov (United States)

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

    2016-05-17

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

  2. Levoglucosan formation from crystalline cellulose: importance of a hydrogen bonding network in the reaction.

    Science.gov (United States)

    Hosoya, Takashi; Sakaki, Shigeyoshi

    2013-12-01

    Levoglucosan (1,6-anhydro-β-D-glucopyranose) formation by the thermal degradation of native cellulose was investigated by MP4(SDQ)//DFT(B3LYP) and DFT(M06-2X)//DFT(B3LYP) level computations. The computational results of dimer models lead to the conclusion that the degradation occurs by a concerted mechanism similar to the degradation of methyl β-D-glucoside reported in our previous study. One-chain models of glucose hexamer, in which the interchain hydrogen bonds of real cellulose crystals are absent, do not exhibit the correct reaction behavior of levoglucosan formation; for instance, the activation enthalpy (Ea =≈38 kcal mol(-1) ) is considerably underestimated compared to the experimental value (48-60 kcal mol(-1) ). This problem is solved with the use of two-chain models that contain interchain hydrogen bonds. The theoretical study of this model clearly shows that the degradation of the internal glucosyl residue leads to the formation of a levoglucosan precursor at the chain end and levoglucosan is selectively formed from this levoglucosan end. The calculated Ea (56-62 kcal mol(-1) ) agrees well with the experimental value. The computational results of three-chain models indicate that this degradation occurs selectively on the crystalline surface. All these computational results provide a comprehensive understanding of several experimental facts, the mechanisms of which have not yet been elucidated.

  3. 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

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

    Science.gov (United States)

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

    2014-07-15

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

  5. 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.

  6. 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...

  7. 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

  8. 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...

  9. 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

  10. 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

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

    Science.gov (United States)

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

    2011-08-01

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

  12. 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)

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

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi

    2015-01-01

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

  14. 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.

  15. 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

  16. On the formation of equilibrium gels via a macroscopic bond limitation

    Science.gov (United States)

    Lindquist, B. A.; Jadrich, R. B.; Milliron, D. J.; Truskett, T. M.

    2016-08-01

    Restricting the number of attractive physical "bonds" that can form between particles in a fluid suppresses the usual demixing phase transition to very low particle concentrations, allowing for the formation of open, percolated, and homogeneous states, aptly called equilibrium or "empty" gels. Most demonstrations of this concept have directly limited the microscopic particle valence via anisotropic (patchy) attractions; however, an alternative macroscopic valence limitation would be desirable for greater experimental tunability and responsiveness. One possibility, explored in this paper, is to employ primary particles with attractions mediated via a secondary species of linking particles. In such a system, the linker-to-primary particle ratio serves as a macroscopic control parameter for the average microscopic valence. We show that the phase behavior of such a system predicted by Wertheim's first order perturbation theory is consistent with equilibrium gel formation: the primary particle concentrations corresponding to the two-phase demixing transition are significantly suppressed at both low and high linker-to-primary particle ratios. Extensive molecular dynamics simulations validate these theoretical predictions but also reveal the presence of loops of bonded particles, which are neglected in the theory. Such loops cause densification and inhibit percolation, and hence the range of viable empty gel state conditions is somewhat reduced relative to the Wertheim theory predictions.

  17. 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.

  18. 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

  19. 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.

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

    Science.gov (United States)

    Ponec, Robert; Cooper, David L

    2007-01-01

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

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

    Science.gov (United States)

    Limozin, Laurent; Bongrand, Pierre; Robert, Philippe

    2016-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Hatahet Feras

    2010-09-01

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

  3. 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.

  4. Effects of chain length and Au spin-orbit coupling on 3(pi pi*) emission from bridging Cn2- units: theoretical characterization of spin-forbidden radiative transitions in metal-capped one-dimensional carbon chains [H3PAu(C[triple bond]C)nAuPH3].

    Science.gov (United States)

    Cao, Zexing; Zhang, Qianer

    2004-04-19

    Density functional theory and CASSCF calculations have been used to optimize the geometries of binuclear gold(I) complexes [H(3)PAu(C[triple bond]C)(n)AuPH(3)] (n=1-6) in their ground states and selected lowest energy (3)(pi pi*) excited states. Vertical excitation energies obtained by time-dependent density functional calculations for the spin-forbidden singlet-triplet transitions have exponential-decay size dependence. The predicted singlet-triplet splitting limit of [H(3)PAu(C[triple bond]C)(proportional/variant)AuPH(3)] is about 8317 cm(-1). Calculated singlet-triplet transition energies are in reasonable agreement with available experimental observations. The effect of the heavy atom Au spin-orbit coupling on the (3)(pi pi*) emission of these metal-capped one-dimensional carbon allotropes has been investigated by MRCI calculations. The contribution of the spin- and dipole-allowed singlet excited state to the spin-orbit-coupling wave function of the (3)(pi pi*) excited state makes the low-lying acetylenic triplet excited states become sufficiently allowed so as to appear in both electronic absorption and emission.

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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

  10. Plasma-deposited a-C(N) H films

    CERN Document Server

    Franceschini, D E

    2000-01-01

    The growth behaviour, film structure and mechanical properties of plasma-deposited amorphous hydrogenated carbon-nitrogen films are shortly reviewed. The effect of nitrogen-containing gas addition to the deposition to the hydrocarbon atmospheres used is discussed, considering the modifications observed in the chemical composition growth kinetics, carbon atom hybridisation and chemical bonding arrangements of a-C(N):H films. The overall structure behaviour is correlated to the variation of the mechanical properties.

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    In the focus was the question whether metal alkoxide coupling agents – titanium, silane, and zirconium – form covalent bonds to wood and how they improve coating adhesion. In a previous work, a downshift of the lignin infrared (IR) band ∼1600 cm-1 was shown to be consistent with the formation...

  12. 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.

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

    Science.gov (United States)

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

    2012-07-01

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

  14. 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

  15. 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

  16. Intermetallic Compound Formation Mechanisms for Cu-Sn Solid-Liquid Interdiffusion Bonding

    Science.gov (United States)

    Liu, H.; Wang, K.; Aasmundtveit, K. E.; Hoivik, N.

    2012-09-01

    Cu-Sn solid-liquid interdiffusion (SLID) bonding is an evolving technique for wafer-level packaging which features robust, fine pitch and high temperature tolerance. The mechanisms of Cu-Sn SLID bonding for wafer-level bonding and three-dimensional (3-D) packaging applications have been studied by analyzing the microstructure evolution of Cu-Sn intermetallic compounds (IMCs) at elevated temperature up to 400°C. The bonding time required to achieve a single IMC phase (Cu3Sn) in the final interconnects was estimated according to the parabolic growth law with consideration of defect-induced deviation. The effect of predominantly Cu metal grain size on the Cu-Sn interdiffusion rate is discussed. The temperature versus time profile (ramp rate) is critical to control the morphology of scallops in the IMC. A low temperature ramp rate before reaching the bonding temperature is believed to be favorable in a SLID wafer-level bonding process.

  17. 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

  18. 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

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

    Science.gov (United States)

    Murakami, Yasuo; Horiguchi, Seishi; Hamaguchi, Satoshi

    2010-04-01

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

  20. 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

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

    NARCIS (Netherlands)

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

    2013-01-01

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

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

    DEFF Research Database (Denmark)

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

    1998-01-01

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

  3. 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

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

    Science.gov (United States)

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

    2006-12-01

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

  5. 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.

  6. 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

  7. 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...

  8. 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.

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

    Science.gov (United States)

    2013-01-01

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

  10. 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

  11. 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

  12. 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

  13. 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.

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

    Science.gov (United States)

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

    2016-08-10

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

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

    Directory of Open Access Journals (Sweden)

    Hideto Miyabe

    2015-07-01

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

  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. 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.

  18. 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.

  19. 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

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

    Science.gov (United States)

    Abdelhadi, Ousama Mohamed Omer

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

  1. 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 ...

  2. 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 ...

  3. 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.

  4. 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

  5. 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.

  6. 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.

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

    Science.gov (United States)

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

    2013-02-01

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

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

    Science.gov (United States)

    Rouquié, Yann; Jones, Mark I.

    2011-05-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-05-15

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

  10. 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

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

    Science.gov (United States)

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

    2016-09-01

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

  12. 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.

  13. 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.

  14. 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.

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

    Science.gov (United States)

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

    2013-07-29

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

  16. 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.

  17. 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.

  18. 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.

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

    Science.gov (United States)

    Dorofeeva, Olga V; Ryzhova, Oxana N

    2016-04-21

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

  20. 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

  1. 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

  2. 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.

  3. 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.

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

    Science.gov (United States)

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

    2013-11-01

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

  5. Synthesis of mid-dicarboxy polystyrene by ATRP and formation of ionic-bonded supramolecules

    Institute of Scientific and Technical Information of China (English)

    YU Tao; WANG Yun; LU Dairen; BAI Ruke; LU Weiqi

    2007-01-01

    Dimethyl 4,6-bis(bromomethyl) isophthalate was synthesized by bromomethylation,oxidation,esterification and bromination of 1,3-dimethylbenzene.This was used to initiate the atom transfer radical polymerization of styrene successfully.Results showed that the process had some of the good characteristics of controlled/living free radical polymerization.The molecular weight of the obtained polymer increased linearly with monomer conversion,its molecular weight distribution was very narrow,and a linear relationship between ln([M]0/[M]) and polymerization time was found.A well-defined novel structural polystyrene containing two ester groups in the mid-main chain was prepared with controlled molecular weight and narrow polydispersity.The structure of the polymer was confirmed by 1H-NMR spectra.After being hydrolyzed,dicarboxy polystyrene was obtained and used to form ionic-bonded supramolecules with 1-dodecanamine as a model of the star-shaped supramolecules.The supramolecules formed were characterized by Fourier transform infrared (FTIR) spectrum.

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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).

  11. 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.

  12. 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

  13. Enthalpy of formation of anisole: implications for the controversy on the O-H bond dissociation enthalpy in phenol.

    Science.gov (United States)

    Simões, Ricardo G; Agapito, Filipe; Diogo, Hermínio P; da Piedade, Manuel E Minas

    2014-11-20

    Significant discrepancies in the literature data for the enthalpy of formation of gaseous anisole, ΔfHmo(PhOCH3, g), have fueled an ongoing controversy regarding the most reliable enthalpy of formation of the phenoxy radical and of the gas phase O-H bond dissociation enthalpy, DHo(PhO-H), in phenol. In the present work ΔfHmo(PhOCH3, g) was reassessed using a combination of calorimetric determinations and high-level (W2-F12) ab initio calculations. Static-bomb combustion calorimetry led to the standard molar enthalpy of formation of liquid anisole at 298.15 K, ΔfHmo(PhOCH3, l) = −(117.1 ± 1.4) kJ·mol(-1). The corresponding enthalpy of vaporization was obtained as, ΔvapHmo(PhOCH3) = 46.41 ± 0.26 kJ·mol(-1), by Calvet-drop microcalorimetry. These results give ΔfHmo(PhOCH3, g) = −(70.7 ± 1.4) kJ·mol(-1), in excellent agreement with ΔfHmo(PhOCH3, g) = −(70.8 ± 3.2) kJ·mol(-1), obtained from the W2-F12 calculations. The ΔfHmo(PhOCH3, g) here recommended leads to ΔfHmo(PhO•, g) = 55.5 ± 2.4 kJ·mol(-)1 and DH°(PhO-H) = 368.1 ± 2.6 kJ·mol(-1).

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

    Science.gov (United States)

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

    2016-04-21

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

  15. 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 ...

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. Multidegrees of tame automorphisms of C^n

    CERN Document Server

    Karaś, Marek

    2011-01-01

    Let F=(F_1,...,F_n):C^n --> C^n be a polynomial mapping. By the multidegree of the mapping F we mean mdeg F=(deg F_1,...,deg F_n), an element of N^n. The aim of this paper is to study the following problem (especially for n=3): for which sequence (d_1,...,d_n) in N^n there is a tame automorphism F of C^n such that mdeg F=(d_1,...,d_n). In other words we investigate the set mdeg(Tame(C^n)), where Tame(C^n) denotes the group of tame automorphisms of C^n and mdeg denotes the mapping from the set of polynomial endomorphisms of C^n into the set N^n. Since for all permutation s of {1,...,n} we have (d_1,...,d_n) is in mdeg(Tame(C^n)) if and only if (d_s(1),...,d_s(n)) is in mdeg(Tame(C^n)) we may focus on the set mdeg(Tame(C^n)) intersected with {(d_1,...,d_n) : d_1<=...<=d_n}. In the paper, among other things, we give complete description of the sets: mdeg(Tame(C^n)) intersected with {(3,d_2,d_3):3<=d_2<=d_3}}, mdeg(Tame(C^n)) intersected with {(5,d_2,d_3):5<=d_2<=d_3}}, In the examination of the...

  3. 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

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

    Directory of Open Access Journals (Sweden)

    Kyung Hwan Kim

    2016-07-01

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

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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.

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

    Science.gov (United States)

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

    2012-05-18

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

  11. 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

  12. 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

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

    Science.gov (United States)

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

    2016-09-16

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

  14. 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 ...

  15. 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.

  16. 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

  17. 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

  18. 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

  19. 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)

  20. 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

  1. 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.

  2. 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

  3. 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...

  4. $\\Lambda_c-N$ 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...

  5. 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

  6. Photoelectric properties of n-SiC/n-Si heterojunctions

    Directory of Open Access Journals (Sweden)

    Semenov A. V.

    2012-10-01

    Full Text Available Photovoltaic effect in isotype heterotructure formed by nanocrystalline silicon carbide films on single crystal n-Si substrates (n-SiC/n-Si heterojunction was studied. The films were produced by direct ionic deposition method. The model that takes into account the quantum wells and potential barriers caused by band offsets was proposed to explain the current-voltage characteristics and photovoltaic properties of the heterostructure n-SiC/n-Si.

  7. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-09-20

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

  9. 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.

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

    Science.gov (United States)

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

    1994-05-27

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

  11. 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.

  12. 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.

  13. Effects of extrinsic point defects in phosphorene: B, C, N, O, and F adatoms

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Gaoxue, E-mail: gaoxuew@mtu.edu, E-mail: pandey@mtu.edu, E-mail: shashi.p.karna.civ@mail.mil; Pandey, Ravindra, E-mail: gaoxuew@mtu.edu, E-mail: pandey@mtu.edu, E-mail: shashi.p.karna.civ@mail.mil [Department of Physics, Michigan Technological University, Houghton, Michigan 49931 (United States); Karna, Shashi P., E-mail: gaoxuew@mtu.edu, E-mail: pandey@mtu.edu, E-mail: shashi.p.karna.civ@mail.mil [U.S. Army Research Laboratory, Weapons and Materials Research Directorate, ATTN: RDRL-WM, Aberdeen Proving Ground, Maryland 21005-5069 (United States)

    2015-04-27

    Phosphorene is emerging as a promising 2D semiconducting material with a direct band gap and high carrier mobility. In this paper, we examine the role of the extrinsic point defects including surface adatoms in modifying the electronic properties of phosphorene using density functional theory. The surface adatoms considered are B, C, N, O, and F with a [He] core electronic configuration. Our calculations show that B and C, with electronegativity close to P, prefer to break the sp{sup 3} bonds of phosphorene and reside at the interstitial sites in the 2D lattice by forming sp{sup 2} like bonds with the native atoms. On the other hand, N, O, and F, which are more electronegative than P, prefer the surface sites by attracting the lone pairs of phosphorene. B, N, and F adsorption will also introduce local magnetic moment to the lattice. Moreover, B, C, N, and F adatoms will modify the band gap of phosphorene, yielding metallic transverse tunneling characters. Oxygen does not modify the band gap of phosphorene, and a diode like tunneling behavior is observed. Our results therefore offer a possible route to tailor the electronic and magnetic properties of phosphorene by the adatom functionalization and provide the physical insights of the environmental sensitivity of phosphorene, which will be helpful to experimentalists in evaluating the performance and aging effects of phosphorene-based electronic devices.

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

    Energy Technology Data Exchange (ETDEWEB)

    Vinokur, Anastasiya I.; Fredrickson, Daniel C.

    2016-06-20

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

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

    DEFF Research Database (Denmark)

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

    2010-01-01

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

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

    Science.gov (United States)

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

    2010-01-01

    Proteinase inhibitors are of high pharmaceutical interest and are drug candidates for a variety of indications. Specific kallikrein inhibitors are important for their antitumor activity and their potential application to the treatment of skin diseases. In this study we describe the synthesis of domain 6 of the kallikrein inhibitor Lympho-Epithilial Kazal-Type Inhibitor (LEKTI) by the fragment condensation method and site-directed cystine bridge formation. To obtain the linear LEKTI precursor, the condensation was best performed in solution, coupling the protected fragment 1-22 to 23-68. This method yielded LEKTI domain 6 of high purity and equipotent to the recombinantly produced peptide. PMID:20069636

  18. 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

  19. 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.

  20. 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

  1. 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

  2. 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...

  3. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

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

  4. 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

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

    Science.gov (United States)

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

    2003-03-01

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

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

    Science.gov (United States)

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

    2015-07-29

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

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

    Science.gov (United States)

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

    2012-03-19

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

  8. 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).

  9. 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.

  10. 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.

  11. LAMMPS Framework for Directional Dynamic Bonding

    DEFF Research Database (Denmark)

    2012-01-01

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

  12. 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

  13. 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

  14. Bond Growth under Temperature Gradient.

    Directory of Open Access Journals (Sweden)

    P.K. Satyawali

    1999-12-01

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

  15. 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.

  16. 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.

  17. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

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

  18. 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

  19. 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

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

    Institute of Scientific and Technical Information of China (English)

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

    2005-01-01

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

  1. 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...

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

    Institute of Scientific and Technical Information of China (English)

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

    2016-01-01

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

  3. 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

  4. 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:

  5. 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.

  6. Soil C:N stoichiometry controls carbon sink partitioning between above-ground tree biomass and soil organic matter in high fertility forests

    Directory of Open Access Journals (Sweden)

    Alberti G

    2015-04-01

    Full Text Available The release of organic compounds from roots is a key process influencing soil carbon (C dynamics and nutrient availability in terrestrial ecosystems. Through this process, plants stimulate microbial activity and soil organic matter (SOM mineralization thus releasing nitrogen (N that sustains gross and net primary production (GPP and NPP, respectively. Root inputs also contribute to SOM formation. In this study, we quantified the annual net root-derived C input to soil (Net-Croot across six high fertility forests using an in-growth core isotope technique. On the basis of Net-Croot, wood and coarse root biomass changes, and eddy covariance data, we quantified net belowground C sequestration. Belowground C accumulation and GPP were inversely related to soil C:N, but not to climate or stand age. Soil C content and C:N were also related to soil texture. At these high fertility sites, biomass growth did not change with soil C:N; however, biomass growth-to-GPP ratio significantly increased with increasing soil C:N. This was true for both our six forest sites and for another 23 high fertility sites selected at a global scale. We suggest that, at high fertility sites, plant N demand interacts with soil C:N stoichiometry and microbial activity, resulting in higher allocation of C to above ground tree biomass with increasing soil C:N ratio. When C:N is high, microbes have a low C use efficiency, respire more of the fresh C inputs by roots and prime SOM decomposition, thereby increasing N availability for tree uptake. Soil C sequestration would therefore decrease, whereas the extra N released during SOM decomposition can promote tree growth and ecosystem C sink allocation in aboveground biomass. Conversely, C is sequestered in soil when low soil C:N promotes microbial C use efficiency and new SOM formation and stabilization on clay particles.

  7. 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...

  8. Synthesis and reactivity of silyl ruthenium complexes: the importance of trans effects in C-H activation, Si-C bond formation, and dehydrogenative coupling of silanes.

    Science.gov (United States)

    Dioumaev, Vladimir K; Procopio, Leo J; Carroll, Patrick J; Berry, Donald H

    2003-07-01

    with PMe(3) or PMe(3)-d(9) - is also regioselective (1a-d(9)() is predominantly produced with PMe(3)-d(9) trans to Si), but is very unfavorable. At 70 degrees C, a slower but irreversible SiH elimination also occurs and furnishes (PMe(3))(4)RuH(2). The structure of 4a exhibits a tetrahedral P(3)Si environment around the metal with the three hydrides adjacent to silicon and capping the P(2)Si faces. Although strong Si...HRu interactions are not indicated in the structure or by IR, the HSi distances (2.13-2.23(5) A) suggest some degree of nonclassical SiH bonding in the H(3)SiR(3) fragment. Thermolysis of 1a in C(6)D(6) at 45-55 degrees C leads to an intermolecular CD activation of C(6)D(6). Extensive H/D exchange into the hydride, SiMe(3), and PMe(3) ligands is observed, followed by much slower formation of cis-(PMe(3))(4)Ru(D)(Ph-d(5)). In an even slower intramolecular CH activation process, (PMe(3))(3)Ru(eta(2)-CH(2)PMe(2))H (5) is also produced. The structure of intermediates, mechanisms, and aptitudes for PMe(3) dissociation and addition/elimination of H-H, Si-H, C-Si, and C-H bonds in these systems are discussed with a special emphasis on the trans effect and trans influence of silicon and ramifications for SiC coupling catalysis. PMID:12823028

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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...

  15. 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.

  16. 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

  17. 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

  18. 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

  19. 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...

  20. Redox-controlled hydrogen bonding: turning a superbase into a strong hydrogen-bond donor.

    Science.gov (United States)

    Wild, Ute; Neuhäuser, Christiane; Wiesner, Sven; Kaifer, Elisabeth; Wadepohl, Hubert; Himmel, Hans-Jörg

    2014-05-12

    Herein the synthesis, structures and properties of hydrogen-bonded aggregates involving redox-active guanidine superbases are reported. Reversible hydrogen bonding is switched on by oxidation of the hydrogen-donor unit, and leads to formation of aggregates in which the hydrogen-bond donor unit is sandwiched by two hydrogen-bond acceptor units. Further oxidation (of the acceptor units) leads again to deaggregation. Aggregate formation is associated with a distinct color change, and the electronic situation could be described as a frozen stage on the way to hydrogen transfer. A further increase in the basicity of the hydrogen-bond acceptor leads to deprotonation reactions.

  1. 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.

  2. 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

  3. 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

  4. 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

  5. Soil C:N stoichiometry controls carbon sink partitioning between above-ground tree productivity and soil organic matter in high fertility forests

    Science.gov (United States)

    Cotrufo, M.; Alberti, G.; Vicca, S.; Inglima, I.; Belelli-Marchesini, L.; Genesio, L.; Miglietta, F.; Marjanovic, H.; Martinez, C.; Matteucci, G.; Peressotti, A.; Petrella, L.; Rodeghiero, M.

    2013-12-01

    The release of organic compounds from roots is a key process influencing soil carbon (C) dynamics and nutrient availability in terrestrial ecosystems and is a process by which plants stimulate microbial activity and soil organic matter (SOM) mineralization thus releasing nitrogen (N) to sustain their gross and net primary production (GPP and NPP). Root inputs also contribute to soil organic matter (SOM) formation. In this study, we quantified the annual net root derived C input to soil (Net-Croot) across six high fertile forests using an in-growth core isotope technique. On the basis of Net-Croot, wood and coarse root biomass changes and eddy covariance data, we quantified net belowground C sequestration. This and GPP were inversely related to soil C:N, but not to climate or age. Because, at these high fertile sites, biomass growth did not change with soil C:N ratio, biomass growth-to-GPP ratio significantly increased with increasing soil C:N. This was true for both our six forest sites and for high fertile sites across a set of other 23 sites selected at global scale. We suggest that, at high fertile sites, the interaction between plant demand for nutrients, soil stoichiometry and microbial activity sustain higher ecosystem C-sink allocation to above ground tree biomass with increasing soil C:N ratio and that this clear and strong relationship can be used for modelling forest C sink partitioning between plant biomass and soil. When C:N is high, microbes have a low C use efficiency, respire more of the fresh C inputs by roots and prime SOM decomposition increasing N availability for tree uptake. Soil C sequestration would therefore decrease, whereas the extra N released during SOM decomposition can promote tree growth and ecosystem C sink allocation in aboveground biomass. Conversely, C is sequestered in soil when the low soil C:N promotes microbial C use efficiency and new SOM formation.

  6. Computational study of the enthalpies of formation, DeltafH degrees, and mean bond enthalpies, mBEs, of H4-nEXn0/- and H3-nEXn+/0 (E=C, B; X=F-I).

    Science.gov (United States)

    Raabe, Ines; Himmel, Daniel; Krossing, Ingo

    2007-12-20

    To compensate for lacking experimental standard enthalpies of formation DeltafH degrees of haloboranes/-boranates as well as the isoelectronic halocarbenium ions and halomethanes, high-level quantum chemical calculations up to the ccsd(t)/(SDB-)aug-cc-pVQZ level have been performed to establish these values. Very reliable experimental data (e.g., DeltafH degrees of HCl, F, and CH4) or at the G3 level established values (e.g., DeltafH degrees of CF3+=410 kJ mol(-1)) were used as anchor points to obtain accurate absolute DeltafH degrees and mean bond enthalpy (mBE) values. To further minimize systematic errors of the protocol, all derived quantities were assessed in isodesmic reactions at the G3 and ccsd(t) level using the (SDB-)aug-cc-PVTZ basis set. The obtained DeltafH degrees values are in very good agreement to (scarcely available) accurate experimental and computational data. Almost all B-containing compounds have been assessed for the first time. We derived "best" DeltafH degrees values and used them to determine the mean E-X bond enthalpies in H4-nEXn-/0 and H3-nEXn0/+ (with n=1-3, E=B, C, and X=F-I). In each of the series, the DeltafH degrees values increase from fluorine to iodine, and except for the iodine-containing carbenium ions and the bromo- and iodomethanes, the DeltafH degrees values become lower with the more halogen atoms that are present in the particle. The boron containing species always have a lower DeltafH degrees than the isoelectronic carbenium ions and methanes, and the H4-nEXn-/0 are lower in energy than the parent H3-nEXn+/0. This reflects the greater average B-X bond strengths.

  7. Profile and Character of Atmospheric Structure Constant of Refractive Index C_n~2

    Institute of Scientific and Technical Information of China (English)

    SUN Gang; WENG Ning-Quan; XIAO Li-Ming; WU Yi

    2012-01-01

    Random fluctuations of turbulence bring random fluctuations of the refractive index, making the atmosphere a random fluctuation medium that destroys the coherence of light-waves. Research in atmospheric turbulence is actually the investigation of the atmospheric refractive index. The atmospheric structure constant of refractive index, C n 2 , is an important parameter denoting atmospheric turbulence. In this paper, C n 2 is measured during the day and at night and in all four seasons using a high sensitivity micro-thermal meter QHTP-2. The vertical profile of C n 2 in Hefei (0-30 km) is investigated by the analysis of experimental data. The average profile of C n 2 in Hefei exhibits conspicuous day and night differences with increased altitude. The distribution of log(C n 2 ) is nearly normal and has conspicuous seasonal differences.

  8. 3-Rhoda-1,2-diazacyclopentanes: a series of novel metallacycle complexes derived from C-N functionalization of ethylene.

    Science.gov (United States)

    Drover, Marcus W; Beh, Daniel W; Kennepohl, Pierre; Love, Jennifer A

    2014-10-01

    Rh-containing metallacycles, [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NR)2-]Cl; TPA = N,N,N,N-tris(2-pyridylmethyl)amine have been accessed through treatment of the Rh(I) ethylene complex, [(TPA)Rh(η(2)-CH2CH2)]Cl ([1]Cl) with substituted diazenes. We show this methodology to be tolerant of electron-deficient azo compounds including azo diesters (RCO2N=NCO2R; R = Et [3]Cl, R = iPr [4]Cl, R = tBu [5]Cl, and R = Bn [6]Cl) and a cyclic azo diamide: 4-phenyl-1,2,4-triazole-3,5-dione (PTAD), [7]Cl. The latter complex features two ortho-fused ring systems and constitutes the first 3-rhoda-1,2-diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N-N coordination followed by insertion of ethylene into a [Rh]-N bond. In terms of reactivity, [3]Cl and [4]Cl successfully undergo ring-opening using p-toluenesulfonic acid, affording the Rh chlorides, [(TPA)Rh(III)(Cl)(κ(1)-(C)-CH2CH2(NCO2R)(NHCO2R)]OTs; [13]OTs and [14]OTs. Deprotection of [5]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end-on coordinated diazene [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NH)2-](+) [16]Cl, a hitherto unreported motif. Treatment of [16]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NAc)2-](+), [17]Cl. Treatment of [1]Cl with AcN=NAc did not give the Rh-N insertion product, but instead the N,O-chelated complex [(TPA)Rh(I)(κ(2)-(O,N)-CH3(CO)(NH)(N=C(CH3)(OCH=CH2))]Cl [23]Cl, presumably through insertion of ethylene into a [Rh]-O bond.

  9. 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

  10. Ti(C,N)基硬质合金中的润湿性研究%WETTABILITY OF Ti(C,N)-BASED CERMETS

    Institute of Scientific and Technical Information of China (English)

    刘红卫; 陈康华; 吕海波

    2000-01-01

    主要研究(C,N)基硬质合金中不同粘结相Ni-Co、Ni-Co-Mo和Ni-Co-Mo2C与不同TiN/(TiC+TiN)的硬质相Ti(C,N)之间的润湿性.研究表明,当硬质相中TiN/(TiC+TiN)<0.5时,Ni-Co粘结相是最好的,当TiN/(TiC+TiN)≥0.5时,最适合的粘结相为Ni-Co- Mo2C,而Ni-Co-Mo不宜作为Ti(C,N)基硬质合金的粘结相.

  11. Formation of Self-Templated 2,6-Bis(1,2,3-triazol-4-yl)pyridine [2]Catenanes by Triazolyl Hydrogen Bonding: Selective Anion Hosts for Phosphate.

    Science.gov (United States)

    Byrne, Joseph P; Blasco, Salvador; Aletti, Anna B; Hessman, Gary; Gunnlaugsson, Thorfinnur

    2016-07-25

    We report the remarkable ability of 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) compounds 2 with appended olefin amide arms to self-template the formation of interlocked [2]catenane structures 3 in up to 50 % yield when subjected to olefin ring-closing metathesis in CH2 Cl2 . X-ray diffraction crystallography enabled the structural characterization of both the [2]catenane 3 a and the non-interlocked macrocycle 4 a. These [2]catenanes showed selective triazolyl hydrogen-bonding interactions with the tetrahedral phosphate anion when screened against a range of ions; 3 a,b are the first examples of selective [2]catenane hosts for phosphate. PMID:27295556

  12. 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.

  13. 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

  14. 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)

  15. 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.

  16. 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

  17. 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.

  18. Bonding Character and Formation Energy of Point Defects of He and Vacancy on (001) Surface of bcc Iron by First Principle Calculations

    Institute of Scientific and Technical Information of China (English)

    Jun CAI; Daogang LU

    2013-01-01

    The structure and energy of He impurities and vacancy on (001) surface of bcc iron are investigated by an ab initio method.Three cases for stabilities of a He atom at the surface are found: some of He atoms at surface atomic layers (SAL) relax into vacuum gap; some of surface He atoms at octahedral interstitial site relax into more stable tetrahedral interstitial site; some of surface He atoms still stay at tetrahedral interstitial site.The un-stability of the He atom at the surface system can be explained by deformation mechanism of charge densities and electronic densities of states.It is found that formation energy of the point defects from the topmost SAL to bulk-like atomic layer increase gradually,for example,the formation energies of a monovacancy at the first five topmost SALs are equal to 0.33,1.56,2.04,2.02 and 2.11 eV,respectively.The magnetic moments of Fe atoms in the surface atomic layers are also calculated.

  19. 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

  20. 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.

  1. 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...

  2. 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.

  3. 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.

  4. 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),...

  5. Spark Plasma Sintering Properties of Ultrafine Ti ( C,N)-based Cermet

    Institute of Scientific and Technical Information of China (English)

    FENG Ping; XIONG Wei-hao; ZHENG Yong; YU Li-xin; XIA Yang-hua

    2004-01-01

    Ultrafine Ti( C, N )-based cermet was sintered by SPS from 1050℃ to 1450℃ and its sintering properties, such as porosity, mechanical properties and phase transformation, were investigated by optical mi-croscopy (OM), scanning electron microscopy (SEM), X- ray diffraction (XRD), and differential scanning calo-rimeter (DSC). It is found that the spark plasma sintering properties of Ti( C, N )-based cermet differ from thoseof conventional vacuum sintering. The liquid phase appearance is at least lower by 150℃ than that in vacuum sin-tering. The porosity decreases sharply below 1 200℃ and reaches minimum at 1 200℃ , and afterwards it almostkeeps invariable and no longer increases. SPS remarkably accelerates the phase transformation of Ti( C, N )-basedcermet and it has a powerful ability to remove oxides in Ti( C, N )-based cermets. Above 1 3502 ,denitrificationoccurred. Fresh graphite phase formed above 1 430℃ . Both the porosity and graphite are responsible for the poor TRS.

  6. 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.

  7. [Adenosine- and ethenoadenosine-5'-trimetaphosphates: the effect of covalent bond formation on the state of the affinity label in the complex with phenylalanyl-tRNA-synthetase].

    Science.gov (United States)

    Nevinskiĭ, G A; Podust, V N; Khodyreva, S N; Gorshkova, I I; Lavrik, O I

    1984-01-01

    epsilon ATP is a substrate of phenylalanyl-tRNA synthetase and epsilon Ado is a competitive inhibitor of ATP in the reaction of tRNA aminoacylation (Ki = 1.6 mM). The association of phenylalanyl-tRNA synthetase with ATP or Ado results in synergistic binding of phenylalaninol and phenylalanine, respectively. However neither epsilon ATP nor epsilon Ado exhibit synergism. Adenosine- and ethenoadenosine-5'-trimethaphosphates are shown to be similar affinity reagents of phenylalanyl-tRNA synthetase. ATP being covalently bound to the enzyme shows essentially lower synergistic effect in comparison with free ATP. epsilon ATP-label is practically insensitive to the ligands namely ATP, Phe, phenylalaninol and is highly accessible for I- ions. The scheme of behaviour of affinity labels is assumed to be as follows: a) the formation of specific reagent-enzyme complex, b) the covalent attachment of the reagent to the enzyme, c) the covalent binding induced disruption of the specific complex formed before. PMID:6390177

  8. 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....

  9. 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

  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

    2009-01-01

    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

  11. 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

  12. 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

  13. 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...

  14. 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.

  15. The Role of Ice Compositions for Snowlines and the C/N/O Ratios in Active Disks

    CERN Document Server

    Piso, Ana-Maria A; Oberg, Karin I

    2016-01-01

    The elemental compositions of planets define their chemistry, and could potentially be used as beacons for their formation location if the elemental gas and grain ratios of planet birth environments, i.e. protoplanetary disks, are well understood. In disks, the ratios of volatile elements, such as C/O and N/O, are regulated by the abundance of the main C, N, O carriers, their ice binding environment, and the presence of snowlines of major volatiles at different distances from the central star. We explore the effects of disk dynamical processes, molecular compositions and abundances, and ice compositions on the snowline locations of the main C, O and N carriers, and the C/N/O ratios in gas and dust throughout the disk. The gas-phase N/O ratio enhancement in the outer disk (exterior to the H2O snowline) exceeds the C/O ratio enhancement for all reasonable volatile compositions. Ice compositions and disk dynamics individually change the snowline location of N2, the main nitrogen carrier, by a factor of 2-3, and ...

  16. 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

  17. 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.

  18. High temperature strength and ductility of the (C+N) strengthening Fe-Cr-Mn(W,V) steels

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Fe-Cr-Mn(W, V) austenite steels used as low radioactive structural materials in fusion reactor have been investigated. The resultsshow that the high temperature strength and the creep fracture life of Fe-Cr-Mn(W, V) steels can be effectively improved through (C+N) complex-strengthening, so can be the high temperature ductility. The strength and ductility of the steels are superior to that of SUS316 steels and JPCAS below 673K. The relationship between strength, ductility andthe formation temperature is related to the evolution of deformation microstructure. The fracture and microstructure observation above 673Kindicates that the main way to further improve ductility at high temperature is the control of carbide coarsening at the grain boundaries.

  19. Formation, structure, and properties of "welded" h-BN/graphene compounds

    Science.gov (United States)

    Chernozatonskii, L. A.; Demin, V. A.; Artyukh, A. A.

    2016-07-01

    Structures of h-BN/graphene with holes where atoms at the edges are bonded to each other by sp 2 hybridized C-B and C-N bonds and form continuous junctions from layer to layer with topological defects inside holes have been considered. Their formation, as well as the moiré-type stable atomic structure of such compounds (with different rotation angles of graphene with respect to the hexagonal boron nitride monolayer) with closed hexagonal holes in the AA centers of packing of the moiré superlattice, has been studied. The stability, as well as the electronic and mechanical properties, of such bilayer BN/graphene nanomeshes has been analyzed within electron density functional theory. It has been shown that they have semiconducting properties. Their electronic band structures and mechanical characteristics differ from the respective properties of separate monolayer nanomeshes with the same geometry and arrangement of holes.

  20. 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.

  1. 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

  2. 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.

  3. Nanoparticles of Si C N from low temperature RF plasmas: selective size, composition and structure

    Science.gov (United States)

    Viera, G.; García-Caurel, E.; Costa, J.; Andújar, J. L.; Bertran, E.

    1999-04-01

    Silane-based rf plasma CVD is used to produce nanostructured materials. Depending on the discharge conditions, either ultrafine powder of alloys (Si-C-N), with potential applications for advanced ceramics, or nanostructured thin films grown in the presence of nanoparticles, can be obtained. The present study deals with the synthesis of nanoparticles based on the Si-C-N system in plasmas of SiH 4, CH 4, NH 3 and Ar. Ultrafine quasi-monodisperse powder particles of controlled mean size were produced in conditions of fast particle development. Before the onset of particle coagulation, non-agglomerated amorphous clusters smaller than 10 nm were obtained.

  4. 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

  5. Differential hepatoprotective mechanisms of rutin and quercetin in CCl4-intoxicated BALB/cN mice

    Institute of Scientific and Technical Information of China (English)

    Robert DOMITROVI(C); Hrvoje JAKOVAC; Vanja VASILJEV MARCHESI; Sanda VLADIMIR-KNE(Z)EVI(C); Olga CVIJANOVI(C); (Z)arko TADI(C); (Z)eljko ROMI(C); Dario RAHELI(C)

    2012-01-01

    Aim:To investigate the mechanisms underlying the protective effects of quercetin-rutinoside (rutin) and its aglycone quercetin against CCl4-induced liver damage in mice.Methods:BALB/cN mice were intraperitoneally administered rutin (10,50,and 150 mg/kg) or quercetin (50 mg/kg) once daily for 5 consecutive days,followed by the intraperitoneal injection of CCl4 in olive oil (2 mL/kg,10% v/v).The animals were sacrificed 24 h later.Blood was collected for measuring the activities of ALT and AST,and the liver was excised for assessing Cu/Zn superoxide dismutase (SOD) activity,GSH and protein concentrations and also for immunoblotting.Portions of the livers were used for histology and immunohistochemistry. Results:Pretreatment with rutin and,to a lesser extent,with quercetin significantly reduced the activity of plasma transaminases and improved the histological signs of acute liver damage in CCl4-intoxicated mice.Quercetin prevented the decrease in Cu/Zn SOD activity in CCl4-intoxicated mice more potently than rutin.However,it was less effective in the suppression of nitrotyrosine formation.Quercetin and,to a lesser extent,rutin attenuated the inflammation in the liver by down-regulating the CCl4-induced activation of nuclear factor-kappa B (NF-κB),tumor necrosis factor-α (TNF-α) and cyclooxygenase (COX-2).The expression of inducible nitric oxide synthase (iNOS) was more potently suppressed by rutin than by quercetin.Treatment with both flavonoids significantly increased NF-E2-related factor 2 (Nrf2) and heme oxygenase (HO-1) expression in injured livers,although quercetin was less effective than rutin at an equivalent dose.Quercetin more potently suppressed the expression of transforming growth factor-β1 (TGF-β1) than rutin.Conclusion:Rutin exerts stronger protection against nitrosative stress and hepatocellular damage but has weaker antioxidant and antiinflammatory activities and antifibrotic potential than quercetin,which may be attributed to the presence of a

  6. 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

  7. A first principles analysis of the effect of hydrogen concentration in hydrogenated amorphous silicon on the formation of strained Si-Si bonds and the optical and mobility gaps

    Energy Technology Data Exchange (ETDEWEB)

    Legesse, Merid; Nolan, Michael, E-mail: Michael.nolan@tyndall.ie; Fagas, Giorgos, E-mail: Georgios.fagas@tyndall.ie [Tyndall National Institute, University College Cork, Lee Maltings, Dyke Parade, Cork (Ireland)

    2014-05-28

    In this paper, we use a model of hydrogenated amorphous silicon generated from molecular dynamics with density functional theory calculations to examine how the atomic geometry and the optical and mobility gaps are influenced by mild hydrogen oversaturation. The optical and mobility gaps show a volcano curve as the hydrogen content varies from undersaturation to mild oversaturation, with largest gaps obtained at the saturation hydrogen concentration. At the same time, mid-gap states associated with dangling bonds and strained Si-Si bonds disappear at saturation but reappear at mild oversaturation, which is consistent with the evolution of optical gap. The distribution of Si-Si bond distances provides the key to the change in electronic properties. In the undersaturation regime, the new electronic states in the gap arise from the presence of dangling bonds and strained Si-Si bonds, which are longer than the equilibrium Si-Si distance. Increasing hydrogen concentration up to saturation reduces the strained bonds and removes dangling bonds. In the case of mild oversaturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structure shows that the extra hydrogen atoms form a bridge between neighbouring silicon atoms, thus increasing the Si-Si distance and increasing disorder in the sample.

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

    Directory of Open Access Journals (Sweden)

    Bhim B Ghaley

    Full Text Available 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.

  9. Voltage-Induced Effect on Resistance of C:N/Si Heterojunctions

    Institute of Scientific and Technical Information of China (English)

    GAO Xi-Li; ZHANG Xiao-Zhong; WAN Cai-Hua; WANG Ji-Min

    2012-01-01

    Nitrogen doped a-C/Silicon (a-C:N/Si) heterojunctions have been fabricated by using the pulsed laser deposition (PLD) technique and their current-voltage characteristics at various temperatures are investigated.For reverse applied voltages,a-C:N/Si heterojunctions exhibit metal-insulator transition characteristics and the transition temperature can be controlled by the applied voltages.After the excitation of repeated high reverse applied voltages,the current-voltage curves show obvious hysteresis behaviors at low temperatures.These hysteresis behaviors are reproducible and the ratio of the high/low resistance can be greater than 104.%Nitrogen doped a-C/Silicon (a-C:N/Si) heterojunctions have been fabricated by using the pulsed laser deposition (PLD) technique and their current-voltage characteristics at various temperatures are investigated. For reverse applied voltages, a-C.N/Si heterojunctions exhibit metal-insulator transition characteristics and the transition temperature can be controlled by the applied voltages. After the excitation of repeated high reverse applied voltages, the current-voltage curves show obvious hysteresis behaviors at low temperatures. These hysteresis behaviors are reproducible and the ratio of the high/low resistance can be greater than 104.

  10. 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

  11. 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

    mineral soil layers it was the humus type. Deposition and climatic variables were of minor importance at the European scale. Further analysis for eight main forest tree species individually, showed that the influence of environmental variables on C:N ratios was tree species dependent. For Aleppo pine...

  12. 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 ...

  13. 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

  14. Bond percolation in films

    Science.gov (United States)

    Korneta, W.; Pytel, Z.

    1988-04-01

    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  15. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    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...

  16. 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

  17. Structural and Spectral Studies on the Ni(Ⅱ) Complexes of 1,5-Diazacyclooctane (DACO) Bearing Heterocyclic Pendants: Formation of a Two-dimensional Network Via Hydrogen Bonds and π-π Stacking Interactions

    Institute of Scientific and Technical Information of China (English)

    DU,Miao(杜淼); DU,Miao; XU,Qiang(徐强); XU,Qiang; GUO,Ya-Mei (郭亚梅); GUO,Ya-Mei; WENG,Lin-Hong(翁林红); WENG,Lin-Hong; BU,Xian-He (卜显和); BU,Xian-He

    2001-01-01

    A penta-coordinated Ni(II) complex with a 1,5-diazacyclooctane (DACO) ligand functionazed by two imidazole donor pendants, [NiiL1Cl] (ClO4)'HH2O (1) (where L1 = 1,5-bis (imidazol-4-ylmethyl)-1,S-diazacyclooctane) has been synthesized and characterized by X-ray diffraction, infrared spectra, elemental analyses, conductance, thermal analyses and UV-Vis techniques. Complex 1 crystallizes in triclinic crystal system, P-1 space group with a = 0.74782(7), b = 1.15082(10), c = 1.237s1(11) nm, a=82.090(2), β=73.011(2), γ=83.462(2)°, V= 1.00603(16) nn3, Mr = 486.00, Z=2,Dc=1.604 g/cm3, final R=0.0435, and wR=0.1244. The structures of 1 and its related complexes show that in all the three mononuclear complexes, each Ni(Ⅱ) center is penta-coordinated with a near regular square pyranid (RSP) to distorted square-pyramidal (DSP) coordination environment due to the boat/chair configuration of DACO ring in these complexes, and the degree of distortion increases with the augment of the size of the heterocyclic pendants. In addition, the most striking feature of complex 1 resides in the formation of a two-dimensional network structure through hydrogen bonds and stabilized by π-π stacking. The solution behaviors of the Ni(ⅡI) complexes are also discussed in detail.

  18. 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

  19. 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 ...

  20. Bonding thermoplastic polymers

    Science.gov (United States)

    Wallow, Thomas I.; Hunter, Marion C.; Krafcik, Karen Lee; Morales, Alfredo M.; Simmons, Blake A.; Domeier, Linda A.

    2008-06-24

    We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

  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. 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)

  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. 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.

  5. 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.

  6. The 14C(n,γ) cross section between 10 keV and 1 M

    CERN Document Server

    Reifarth, R; Forssén, C; Besserer, U; Couture, A; Dababneh, S; Dörr, L; Görres, J; Haight, R C; Käppeler, F; Mengoni, A; O'Brien, S; Patronis, N; Plag, R; Rundberg, R S; Wiescher, M; Wilhelmy, J B

    2008-01-01

    The neutron capture cross section of 14C is of relevance for several nucleosynthesis scenarios such as inhomogeneous Big Bang models, neutron induced CNO cycles, and neutrino driven wind models for the r process. The 14C(n,γ) reaction is also important for the validation of the Coulomb dissociation method, where the (n,γ) cross section can be indirectly obtained via the time-reversed process. So far, the example of 14C is the only case with neutrons where both, direct measurement and indirect Coulomb dissociation, have been applied. Unfortunately, the interpretation is obscured by discrepancies between several experiments and theory. Therefore, we report on new direct measurements of the 14C(n,γ) reaction with neutron energies ranging from 20 to 800 keV.

  7. Study on Valent Electron Structure of(Ti、W)(C、N)%(Ti,W)(C,N)的价电子结构研究

    Institute of Scientific and Technical Information of China (English)

    章桥新

    2001-01-01

    The valent electron structute of (Ti、W)(C、N)solid solution hasbeen analyzed according to the classical electron theory of solid and molecule.The result shows that the covalent electron number nA in the strongest bond of (Ti、W)(C、N)solid solution decreases with the increase of W or N.Some properties of (Ti、W)(C、N)has been analyzed based on this result.%根据固体与分子经验电子理论,对(Ti,W)(C,N)固溶体的价电子结构进行了分析,结果表明:(Ti,W)(C,N)固溶体的最强键上的共价电子数nA随W或N的增加而减小,并借此对(Ti,W)(C,N)的一些性能进行了分析。

  8. 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.

  9. 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...

  10. Ti(C,N) and (Ti,Al)N hard wear resistant coatings

    OpenAIRE

    K. Gołombek; J. Mikuła; W. Kwaśny; L.W. Żukowska; L.A. Dobrzański

    2010-01-01

    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 coa...

  11. 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.

  12. 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.

  13. 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).

  14. Uranium nitride as LWR TRISO fuel: Thermodynamic modeling of U-C-N

    Science.gov (United States)

    Besmann, Theodore M.; Shin, Dongwon; Lindemer, Terrence B.

    2012-08-01

    TRISO coated particle fuel is envisioned as a next generation replacement for current urania pellet fuel in LWR applications. To obtain adequate fissile loading the kernel of the TRISO particle will likely need to be UN instead of UO2. In support of the necessary development effort for this new fuel system, an assessment of phase regions of interest in the U-C-N system was undertaken as the fuel will be prepared by the carbothermic reduction of the oxide followed by nitriding, will be in equilibrium with carbon within the TRISO particle, and will react with minor actinides and fission products. The phase equilibria and thermochemistry of the U-C-N system is reviewed, including nitrogen pressure measurements above various phase fields. Measurements were used to confirm an ideal solution model of UN and UC adequately represents the UC1-xNx phase. Agreement with the data was significantly improved by effectively adjusting the Gibbs free energy of UN by +12 kJ/mol. This also required adjustment of the value for the sesquinitride by +17 kJ/mol to obtain agreement with phase equilibria. The resultant model together with reported values for other phases in the system was used to generate isothermal sections of the U-C-N phase diagram. Nitrogen partial pressures were also computed for regions of interest.

  15. Flexible C : N ratio enhances metabolism of large phytoplankton when resource supply is intermittent

    Science.gov (United States)

    Talmy, D.; Blackford, J.; Hardman-Mountford, N. J.; Polimene, L.; Follows, M. J.; Geider, R. J.

    2014-09-01

    Phytoplankton cell size influences particle sinking rate, food web interactions and biogeographical distributions. We present a model in which the uptake, storage and assimilation of nitrogen and carbon are explicitly resolved in different-sized phytoplankton cells. In the model, metabolism and cellular C : N ratio are influenced by the accumulation of carbon polymers such as carbohydrate and lipid, which is greatest when cells are nutrient starved, or exposed to high light. Allometric relations and empirical data sets are used to constrain the range of possible C : N, and indicate that larger cells can accumulate significantly more carbon storage compounds than smaller cells. When forced with extended periods of darkness combined with brief exposure to saturating irradiance, the model predicts organisms large enough to accumulate significant carbon reserves may on average synthesize protein and other functional apparatus up to five times faster than smaller organisms. The advantage of storage in terms of average daily protein synthesis rate is greatest when modeled organisms were previously nutrient starved, and carbon storage reservoirs saturated. Small organisms may therefore be at a disadvantage in terms of average daily growth rate in environments that involve prolonged periods of darkness and intermittent nutrient limitation. We suggest this mechanism is a significant constraint on phytoplankton C : N variability and cell size distribution in different oceanic regimes.

  16. 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

  17. 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

  18. Equilibrium CO bond lengths

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  19. 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...

  20. C/N ratio control and substrate addition for periphyton development jointly enhance freshwater prawn Macrobrachium rosenbergii production in ponds

    NARCIS (Netherlands)

    Asaduzzaman, M.; Wahab, M.A.; Verdegem, M.C.J.; Huque, S.; Salam, M.A.; Azim, M.E.

    2008-01-01

    The present research investigated the effect of carbon/nitrogen ratio (C/N ratio) control in ponds with or without substrate addition for periphyton development on production of giant freshwater prawn. C/N ratios of 10, 15 and 20 were investigated in 40 m¿ 2 ponds stocked with 2 prawn juveniles (5.0

  1. 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...

  2. T47D Cells Expressing Myeloperoxidase Are Able to Process, Traffic and Store the Mature Protein in Lysosomes: Studies in T47D Cells Reveal a Role for Cys319 in MPO Biosynthesis that Precedes Its Known Role in Inter-Molecular Disulfide Bond Formation.

    Science.gov (United States)

    Laura, Richard P; Dong, David; Reynolds, Wanda F; Maki, Richard A

    2016-01-01

    Among the human heme-peroxidase family, myeloperoxidase (MPO) has a unique disulfide-linked oligomeric structure resulting from multi-step processing of the pro-protein monomer (proMPO) after it exits the endoplasmic reticulum (ER). Related family members undergo some, but not all, of the processing steps involved with formation of mature MPO. Lactoperoxidase has its pro-domain proteolytically removed and is a monomer in its mature form. Eosinophil peroxidase undergoes proteolytic removal of its pro-domain followed by proteolytic separation into heavy and light chains and is a heterodimer. However, only MPO undergoes both these proteolytic modifications and then is further oligomerized into a heterotetramer by a single inter-molecular disulfide bond. The details of how and where the post-ER processing steps of MPO occur are incompletely understood. We report here that T47D breast cancer cells stably transfected with an MPO expression plasmid are able to efficiently replicate all of the processing steps that lead to formation of the mature MPO heterotetramer. MPO also traffics to the lysosome granules of T47D cells where it accumulates, allowing in-depth immunofluorescent microscopy studies of MPO trafficking and storage for the first time. Using this novel cell model we show that formation of MPO's single inter-molecular disulfide bond can occur normally in the absence of the proteolytic events that lead to separation of the MPO heavy and light chains. We further demonstrate that Cys319, which forms MPO's unique inter-molecular disulfide bond, is important for events that precede this step. Mutation of this residue alters the glycosylation and catalytic activity of MPO and blocks its entry into the endocytic pathway where proteolytic processing and disulfide bonding occur. Finally, using the endocytic trafficking of lysosomal hydrolases as a guide, we investigate the role of candidate receptors in the endocytic trafficking of MPO.

  3. T47D Cells Expressing Myeloperoxidase Are Able to Process, Traffic and Store the Mature Protein in Lysosomes: Studies in T47D Cells Reveal a Role for Cys319 in MPO Biosynthesis that Precedes Its Known Role in Inter-Molecular Disulfide Bond Formation.

    Directory of Open Access Journals (Sweden)

    Richard P Laura

    Full Text Available Among the human heme-peroxidase family, myeloperoxidase (MPO has a unique disulfide-linked oligomeric structure resulting from multi-step processing of the pro-protein monomer (proMPO after it exits the endoplasmic reticulum (ER. Related family members undergo some, but not all, of the processing steps involved with formation of mature MPO. Lactoperoxidase has its pro-domain proteolytically removed and is a monomer in its mature form. Eosinophil peroxidase undergoes proteolytic removal of its pro-domain followed by proteolytic separation into heavy and light chains and is a heterodimer. However, only MPO undergoes both these proteolytic modifications and then is further oligomerized into a heterotetramer by a single inter-molecular disulfide bond. The details of how and where the post-ER processing steps of MPO occur are incompletely understood. We report here that T47D breast cancer cells stably transfected with an MPO expression plasmid are able to efficiently replicate all of the processing steps that lead to formation of the mature MPO heterotetramer. MPO also traffics to the lysosome granules of T47D cells where it accumulates, allowing in-depth immunofluorescent microscopy studies of MPO trafficking and storage for the first time. Using this novel cell model we show that formation of MPO's single inter-molecular disulfide bond can occur normally in the absence of the proteolytic events that lead to separation of the MPO heavy and light chains. We further demonstrate that Cys319, which forms MPO's unique inter-molecular disulfide bond, is important for events that precede this step. Mutation of this residue alters the glycosylation and catalytic activity of MPO and blocks its entry into the endocytic pathway where proteolytic processing and disulfide bonding occur. Finally, using the endocytic trafficking of lysosomal hydrolases as a guide, we investigate the role of candidate receptors in the endocytic trafficking of MPO.

  4. T47D Cells Expressing Myeloperoxidase Are Able to Process, Traffic and Store the Mature Protein in Lysosomes: Studies in T47D Cells Reveal a Role for Cys319 in MPO Biosynthesis that Precedes Its Known Role in Inter-Molecular Disulfide Bond Formation

    Science.gov (United States)

    Laura, Richard P.; Dong, David; Reynolds, Wanda F.; Maki, Richard A.

    2016-01-01

    Among the human heme-peroxidase family, myeloperoxidase (MPO) has a unique disulfide-linked oligomeric structure resulting from multi-step processing of the pro-protein monomer (proMPO) after it exits the endoplasmic reticulum (ER). Related family members undergo some, but not all, of the processing steps involved with formation of mature MPO. Lactoperoxidase has its pro-domain proteolytically removed and is a monomer in its mature form. Eosinophil peroxidase undergoes proteolytic removal of its pro-domain followed by proteolytic separation into heavy and light chains and is a heterodimer. However, only MPO undergoes both these proteolytic modifications and then is further oligomerized into a heterotetramer by a single inter-molecular disulfide bond. The details of how and where the post-ER processing steps of MPO occur are incompletely understood. We report here that T47D breast cancer cells stably transfected with an MPO expression plasmid are able to efficiently replicate all of the processing steps that lead to formation of the mature MPO heterotetramer. MPO also traffics to the lysosome granules of T47D cells where it accumulates, allowing in-depth immunofluorescent microscopy studies of MPO trafficking and storage for the first time. Using this novel cell model we show that formation of MPO’s single inter-molecular disulfide bond can occur normally in the absence of the proteolytic events that lead to separation of the MPO heavy and light chains. We further demonstrate that Cys319, which forms MPO’s unique inter-molecular disulfide bond, is important for events that precede this step. Mutation of this residue alters the glycosylation and catalytic activity of MPO and blocks its entry into the endocytic pathway where proteolytic processing and disulfide bonding occur. Finally, using the endocytic trafficking of lysosomal hydrolases as a guide, we investigate the role of candidate receptors in the endocytic trafficking of MPO. PMID:26890638

  5. 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

  6. 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

  7. 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.

  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 dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  10. 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.

  11. 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.

  12. Wood Bond Testing

    Science.gov (United States)

    1989-01-01

    A joint development program between Hartford Steam Boiler Inspection Technologies and The Weyerhaeuser Company resulted in an internal bond analyzer (IBA), a device which combines ultrasonics with acoustic emission testing techniques. It is actually a spinoff from a spinoff, stemming from a NASA Lewis invented acousto-ultrasonic technique that became a system for testing bond strength of composite materials. Hartford's parent company, Acoustic Emission Technology Corporation (AET) refined and commercialized the technology. The IBA builds on the original system and incorporates on-line process control systems. The IBA determines bond strength by measuring changes in pulsar ultrasonic waves injected into a board. Analysis of the wave determines the average internal bond strength for the panel. Results are displayed immediately. Using the system, a mill operator can adjust resin/wood proportion, reduce setup time and waste, produce internal bonds of a consistent quality and automatically mark deficient products.

  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. 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.

  15. 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.

  16. Efficient Room-Temperature Activation of Methane by TaN(+) under C-N Coupling.

    Science.gov (United States)

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2016-09-12

    The thermal reaction of diatomic tantalum nitride cation [TaN](+) with methane has been explored using FT-ICR mass spectrometry complemented by high-level quantum chemical calculation; based on this combined experimental/computational approach, mechanistic aspects of this novel, highly efficient C-N coupling process have been uncovered. In distinct contrast to [TaN](+) , its lighter congeners [VN](+) and [NbN](+) are inert towards methane under ambient conditions, and the origins of the remarkably variable efficiencies of the three metal nitrides are uncovered by CCSD(T) calculations. PMID:27510819

  17. Effect of Ti(C, N) on Properties of Low-carbon MgO-C Bricks

    Institute of Scientific and Technical Information of China (English)

    QIN Xianpeng; LI Yuanbing; YANG Zhenghong; LI Yawei

    2008-01-01

    The effect of Ti(C, N) on properties of low-carbon MgO-C bricks was investigated. The phase composition and the microstructure of the matrix of low-carbon MgO-C brick containing Ti(C, N) were studied by XRD and SEM analysis together with EDS. The results showed that Ti(C, N) distributed in the matrix of lowcarbon MgO-C brick uniformly after being treated at 1600℃ for 3h in coke powder bed, and Ti(C, N) and MgO formed a solid solution. After the treatment at 1600℃ for 3h in coke powder bed, the bulk density and cold crushing strength of low-carbon MgO-C brick with Ti(C, N) decreased, and the apparent porosity and linear change rate of specimens increased. The oxidation resistance of low-carbon MgO-C brick with Ti(C, N) was superior to that of low-carbon MgO-C brick with no additives, but inferior to that of low-carbon MgO-C brick with Al powder. The slag resistance of the specimen with Ti(C, N) was excellent as well.

  18. High-level ab initio predictions for the ionization energy, bond dissociation energies, and heats of formation of nickel carbide (NiC) and its cation (NiC+).

    Science.gov (United States)

    Lau, Kai-Chung; Chang, Yih Chung; Shi, Xiaoyu; Ng, C Y

    2010-09-21

    The ionization energy (IE) of NiC and the 0 K bond dissociation energies (D(0)) and heats of formation at 0 K (ΔH(o)(f0)) and 298 K (ΔH(o)(f298)) for NiC and NiC(+) are predicted by the wavefunction based CCSDTQ(Full)/CBS approach and the multireference configuration interaction (MRCI) method with Davidson correction (MRCI+Q). The CCSDTQ(Full)/CBS calculations presented here involve the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations along with the zero-point vibrational energy (ZPVE), high-order correlation, core-valence electronic (CV), spin-orbit coupling (SO), and scalar relativistic effect (SR) corrections. The present calculations provide the correct symmetry predictions for the ground states of NiC and NiC(+) to be (1)∑(+) and (2)∑(+), respectively. The CCSDTQ(Full)/CBS IE(NiC)=8.356 eV is found to compare favorably with the experimental IE value of 8.372 05±0.000 06 eV. The predicted IE(NiC) value at the MRCI+Q/cc-pwCV5Z level, including the ZPVE, SO, and SR effects is 8.00 eV, which is 0.37 eV lower than the experimental value. This work together with the previous experimental and theoretical investigations supports the conclusion that the CCSDTQ(Full)/CBS method is capable of providing reliable IE predictions for 3d-transition metal carbides, such as FeC and NiC. Furthermore, the CCSDTQ(Full)/CBS calculations give the prediction of D(0)(Ni-C)-D(0)(Ni(+)-C)=0.688 eV, which is also consistent with the experimental determination of 0.732 21±0.000 06 eV, whereas the MRCI+Q calculations (with relativistic and CV effects) predict a significantly lower value of 0.39 eV for D(0)(Ni-C)-D(0)(Ni(+)-C). The analysis of the correction terms shows that the CV and valence-valence electronic correlations beyond CCSD(T) wavefunction and the relativistic effect make significant contributions to the calculated thermochemical properties of NiC/NiC(+). For the experimental D(0) and ΔH(o)(f0) values of

  19. 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.

  20. Experimental Investigation of Second Interface Cement Bond Evaluation

    Institute of Scientific and Technical Information of China (English)

    Che Xiaohua; Qiao Wenxiao

    2007-01-01

    Cement bond model wells (1:10 scaled-down) were made with a gradually degrading cement annulus for cement bond evaluation of the first interface (between the casing and the cement annulus) and the second interface (between the cement annulus and the formation).Experimental simulation on cement bond logging was carried out with these model wells.The correlation of acoustic waveforms,casing wave energy and free casing area before and after cement bonding of the second interface was established.The experimental results showed that the arrival of the casing waves had no relationship with the cement bonding of the second interface,but the amplitude of the casing head wave decreased obviously after the second interface was bonded.So,cement bonding of the second interface had little effect on the evaluation of the cement bond quality of the first interface by using casing head wave arrivals.Strong cement annulus waves with early arrivals were observed before the second interface was bonded,while obvious "formation waves" instead of cement annulus waves were observed after the second interface was bonded.

  1. 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....

  2. Growth of marine bacteria and ammonium regeneration from substrates in different C:N ratios

    Institute of Scientific and Technical Information of China (English)

    WANG Jiangtao; YIN Xiaonan

    2009-01-01

    Natural assemblages of marine bacteria were chosen in a batch culture experiments. The impact of varying nitrogen substrate concentrations and the substrate C:N ratios (C:Ns) on the bacterial C:N ratio (C:NB), the bacterial growth efficiency (BGE) and ammonium regeneration was mainly examined. The C:Ns ratios varied from 5:1 (carbon limitation) to 40:1 (nitrogen limitation) with varying combinations of glucose and NO3. The C:NB ratio had positive relationship with the C:Ns ratio (r=0.93, n=8), whose value was 3.77 when the C:Ns ratio was 5:1 but increased to 6.47 when the C:Ns ratio was 40:1. These results indicate that the C:NB ratio is a potential diagnostic tool for determining the bacterial growth in natural waters controlled by either, carbon or nitrogen. BGE decreased with the declining nitrate concentration and negatively related to C:Ns (r=-0.51,n=8). The average value of BGE was 0.20. This value was a little lower than other reports, which could be induced by the nitrogen source used in our experiments. Finally, regeneration time of ammonium delayed with the increasing C:Ns ratio, which indicates that there were different metabolism mechanisms when bacterial growth was limited by carbon source and nitrogen source.

  3. 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)].

  4. 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.

  5. Global biodiversity, stoichiometry and ecosystem function responses to human-induced C-N-P imbalances.

    Science.gov (United States)

    Carnicer, Jofre; Sardans, Jordi; Stefanescu, Constantí; Ubach, Andreu; Bartrons, Mireia; Asensio, Dolores; Peñuelas, Josep

    2015-01-01

    Global change analyses usually consider biodiversity as a global asset that needs to be preserved. Biodiversity is frequently analysed mainly as a response variable affected by diverse environmental drivers. However, recent studies highlight that gradients of biodiversity are associated with gradual changes in the distribution of key dominant functional groups characterized by distinctive traits and stoichiometry, which in turn often define the rates of ecosystem processes and nutrient cycling. Moreover, pervasive links have been reported between biodiversity, food web structure, ecosystem function and species stoichiometry. Here we review current global stoichiometric gradients and how future distributional shifts in key functional groups may in turn influence basic ecosystem functions (production, nutrient cycling, decomposition) and therefore could exert a feedback effect on stoichiometric gradients. The C-N-P stoichiometry of most primary producers (phytoplankton, algae, plants) has been linked to functional trait continua (i.e. to major axes of phenotypic variation observed in inter-specific analyses of multiple traits). In contrast, the C-N-P stoichiometry of higher-level consumers remains less precisely quantified in many taxonomic groups. We show that significant links are observed between trait continua across trophic levels. In spite of recent advances, the future reciprocal feedbacks between key functional groups, biodiversity and ecosystem functions remain largely uncertain. The reported evidence, however, highlights the key role of stoichiometric traits and suggests the need of a progressive shift towards an ecosystemic and stoichiometric perspective in global biodiversity analyses.

  6. The first direct measurement of 12C(12C,n)23Mg at stellar energies

    CERN Document Server

    Bucher, B; Fang, X; Heger, A; Almaraz-Calderon, S; Alongi, A; Ayangeakaa, A D; Beard, M; Best, A; Browne, J; Cahillane, C; Couder, M; deBoer, R J; Kontos, A; Lamm, L; Li, Y J; Long, A; Lu, W; Lyons, S; Notani, M; Patel, D; Paul, N; Pignatari, M; Roberts, A; Robertson, D; Smith, K; Stech, E; Talwar, R; Tan, W P; Wiescher, M; Woosley, S E

    2015-01-01

    Neutrons produced by the carbon fusion reaction 12C(12C,n)23Mg play an important role in stellar nucleosynthesis. However, past studies have shown large discrepancies between experimental data and theory, leading to an uncertain cross section extrapolation at astrophysical energies. We present the first direct measurement that extends deep into the astrophysical energy range along with a new and improved extrapolation technique based on experimental data from the mirror reaction 12C(12C,p)23Na. The new reaction rate has been determined with a well-defined uncertainty that exceeds the precision required by astrophysics models. Using our constrained rate, we find that 12C(12C,n)23Mg is crucial to the production of Na and Al in Pop-III Pair Instability Supernovae. It also plays a non-negligible role in the production of weak s-process elements as well as in the production of the important galactic gamma-ray emitter 60Fe.

  7. 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.

  8. The reactivity of [PhP(Se)(mu-Se)]2 and (PhP)3Se2 towards acetylenes and cyanamides: X-ray crystal structures of some P-Se-C and P-Se-C-N heterocycles.

    Science.gov (United States)

    Bhattacharyya, Pravat; Slawin, Alexandra M Z; Woollins, J Derek

    2002-06-17

    Several unusual P-Se-C and P-Se-C-N heterocycles are formed by the reaction of [PhP(Se)(mu-Se)]2 or (PhP)3Se2 with alkynes or cyanamides, generated by the fragmentation of the organophosphorus-selenium compound and addition across the C identical to C or C identical to N triple bond of the organic substrate. X-ray crystallographic analysis reveals an unexpected diversity of structural motifs within these heterocyclic systems, including P2SeCN, P2C2Se and PC2Se2 rings.

  9. 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

  10. The influence of Mo Content on the Microstructure and Properties of Ti(C,N)-based Ceramets%Mo含量对Ti(C,N)基金属陶瓷组织和性能的影响

    Institute of Scientific and Technical Information of China (English)

    章晓波; 刘宁

    2006-01-01

    Ti(C,N)基金属陶瓷是一种新型工具材料,在高速切削刀具中得到广泛应用.本文介绍了金属陶瓷中Mo或Mo2C的作用,并综述了国内外关于Mo或Mo2C对Ti(C,N)基金属陶瓷显微组织和性能的影响.

  11. Search for Theta(1540)^+ in exclusive proton-induced reaction p+C(N) \\to Theta^+ \\bar{K}^0 + C(N) at the energy of 70 GeV

    CERN Document Server

    Antipov, Y M; Batarin, V A; Eroshin, O V; Kolganov, V Z; Konstantinov, A S; Kozhevnikov, A P; Kurshetsov, V F; Kushnirenko, A E; Landsberg, L G; Leontiev, V M; Lomkatsi, G S; Mukhin, V A; Molchanov, V V; Nilov, A P; Patalakha, D I; Petrenko, S V; Petrukhin, A I; Smolyankin, V T; Vavilov, D V; Victorov, V A; Antipov, Yu. M.

    2004-01-01

    A search for narrow Theta(1540)^+, a candidate for pentaquark baryon with positive strangeness, has been performed in an exclusive proton-induced reaction p+C(N) \\to Theta^+ \\bar{K}^0 + C(N) on carbon nuclei or quasifree nucleons at E_{beam}=70 GeV (sqrt{s} = 11.5 GeV) studying nK^+, pK_S and pK_L decay channels of Theta(1540)^+ in four different final states of the Theta^+ \\bar{K}^0 system. In order to assess the quality of the identification of the final states with neutron or K_L we reconstructed Lambda(1520)\\to nK_S and phi\\to K_LK_S decays in the calibration reactions p+C(N)\\to Lambda(1520)K^+ + C(N) and p+C(N)\\to p\\phi + C(N). We found no evidence for narrow pentaquark peak in any of the studied final states and decay channels. Assuming that the production characteristics of the Theta^+ \\bar{K^0} system are not drastically different from those of the Lambda(1520)K^+ and p\\phi systems, we established upper limits on the cross section ratios sigma(Theta^+\\bar{K}^0)/sigma(Lambda(1520)K^+) < 0.02 and sig...

  12. Reactivity of the uranium(IV) carbene complex [U(BIPM(TMS))(Cl)(μ-Cl)₂Li(THF)₂] (BIPM(TMS) = {C(PPh₂NSiMe₃)₂}) towards carbonyl and heteroallene substrates: metallo-Wittig, adduct formation, C-F bond activation, and [2 + 2]-cycloaddition reactions.

    Science.gov (United States)

    Cooper, Oliver J; Mills, David P; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2014-10-14

    The reactivity of the uranium(IV) carbene complex [U(BIPM(TMS))(Cl)(μ-Cl)2Li(THF)2] (1, BIPM(TMS) = {C(PPh2NSiMe3)2}) towards carbonyl and heteroallene substrates is reported. Reaction of 1 with benzophenone proceeds to give the metallo-Wittig terminal alkene product Ph2C=C(PPh2NSiMe3)2 (2); the likely "UOCl2" byproduct could not be isolated. Addition of the bulky ketone PhCOBu(t) to 1 resulted in loss of LiCl, coordination of the ketone, and dimerisation to give [U(BIPM(TMS))(Cl)(μ-Cl){OC(Ph)(Bu(t))}]2 (3). The reaction of 1 with coumarin resulted in ring opening of the cyclic ester and a metallo-Wittig-type reaction to afford [U{BIPM(TMS)[C(O)(CHCHC6H4O-2)]-κ(3)-N,O,O'}(Cl)2(THF)] (4) where the enolate product remains coordinated to uranium. The reaction of PhCOF with 1 resulted in C-F bond activation and oxidation resulting in isolation of [U(O)2(Cl)2(μ-Cl)2{(μ-LiDME)OC(Ph)=C(PPh2NSiMe3)(PPh2NHSiMe3)}2] (5) along with [U(Cl)2(F)2(py)4] (6). The reactions of 1 with tert-butylisocyanate or dicyclohexylcarbodiimide resulted in the isolation of the [2 + 2]-cycloaddition products [U{BIPM(TMS)[C(NBu(t)){OLi(THF)2(μ-Cl)Li(THF)3}]-κ(4)-C,N,N',N''}(Cl)3] (7) and [U{BIPM(TMS)[C(NCy)2]-κ(4)-C,N,N',N''}(Cl)(μ-Cl)2Li(THF)2] (8). Complexes 2-8 have been variously characterised by single crystal X-ray diffraction, multi-nuclear NMR and FTIR spectroscopies, Evans method solution magnetic moments, variable temperature SQUID magnetometry, and elemental analyses.

  13. 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.

  14. 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

  15. Microstructure and wear behavior of laser cladding Ni-based alloy composite coating reinforced by Ti(C,N) particulates

    Institute of Scientific and Technical Information of China (English)

    Qi Yongtian; Shi Hanchao; Zou Zengda; Hu Liping

    2008-01-01

    In this paper, Ni-based alloy composite coating reinforced by Ti (C,N) particles was fabricated on the mild steel through laser cladding technology. The microstructure of laser cladding layer was analyzed by means of optical microscopy (OM),X-ray diffraction (XRD) and scanning electron microscopy (SEM).The wear resistance test of the coating was evaluated using an M-2000 tester. The results showed that the Ni-based composite coating had an ability of rapid solidification to form dendritic crystals microstructure consisting of Ti (C,N) particulates uniformly distributed in the matrix. It was found that some Ti(C,N) particles are similar to be round in shape, and the others are irregular. Laser cladding layer reinforced by Ti(C,N) particulates was found to possess good wear resistance property.

  16. Carbon content and C:N ratio of transparent exopolymeric particles (TEP) produced by bubbling exudates of diatoms

    DEFF Research Database (Denmark)

    Mari, Xavier

    1999-01-01

    a coastal area (Kattegat, Denmark), TEP carbon concentration in the surface mixed layer was on the order of 230 ± 150 µg C l-1. This is high relative to other sources of particulate organic carbon (e.g. phytoplankton) and depending on TEP turnover rates, suggests that TEP is an important pathway......-non-limited to N-limited conditions. While the C:N ratio of the diatom cells grown under N-limited conditions was high (C:N >= 14), the TEP aggregates formed by coagulation of the extracellular release produced by these cells exhibited a C:N ratio relatively constant (C:N = 7.3 ± 2.6) and apparently independent...

  17. 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)

  18. Diffusion bonding of titanium alloy to tin-bronze

    Institute of Scientific and Technical Information of China (English)

    李卓然; 冯吉才; 刘会杰

    2002-01-01

    The vacuum diffusion bonding of titanium alloy to tin-bronze has been studied and the feasibility and appropriate processing parameters have been investigated. The maximum tensile strength of the joints is bonded joint has been observed by SEM, X-ray and EPMA, and the main factors affecting diffusion bonding have been analyzed. The intermetallic compounds Ti2Cu and TiCu were formed near the interface. The width and quantity of the intermetallic compound increases with the increase of the bonding time. The formation of the intermetallic compounds results in embrittlement of the joint and the poor joint properties.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  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. [C, N, P, K Stoichiometric Characteristic of Leaves, Root and Soil in Different Abandoned Years in Loess Plateau].

    Science.gov (United States)

    Zhang, Hai-dong; Ru, Hai-li; Jiao, Feng; Xue, Chao-yu; Guo, Mei-li

    2016-03-15

    The research of plant ecological stoichiometry characteristics, nutrients distribution and their changes is of great significance to explain the response and adaptation of plants to environmental change. Leaves, root and soil from eight different abandoned years in Yanhe River basin were selected to study the content, characteristic ratio and distribution of carbon ( C) , nitrogen (N) , phosphorus (P), potassium (K). The results showed that the C, N, P, K contents of plant leaves were 444.21, 22.34, 1.49, 14.66 mg · g⁻¹ respectively, the C/N, C/P, C/K, N/P ratios of plant leaves were 21.86, 424.72, 39.82, 20.27 respectively; the C, N, P, K contents of root were 285.16, 5.79, 0.27, 6.07 mg · g⁻¹ respectively, the C/N, C/P, C/K, N/P ratios of root were .60. 56, 1019.33, 46.55, 21.36 respectively; the C, N, P, K contents of soil were 2.28, 0.18, 0.28, 4.33 mg · g⁻¹ respectively, the C/N, C/P, C/K, N/P ratios of soil were 16.43, 8.40, 0.54, 0.66 respectively. During the abandoned year of 1-35, C content of leaves increased, N content increased and then declined, P content declined overall, K content declined and then increased. The C/N, C/P, C/K, N/P ratios of plant leaves showed a rising trend overall. The changing pattern of root was different from that of leaves. Along with the increasing rehabilitation age, C and N contents of soil increased, P content changed as arc-sin function, K content changed as parabola, C/N decreased, C/P, C/K, N/P increased. With the increase of Abandoned Years, the ratio of C, P, K contents in leaves and root decreased, the ratio of C, N, P contents in leaves and soil decreased, the ratio of C, N contents in root and soil decreased. Corresponding relationship and its intension between different abandoned years and plant nutrient limit status and its allocation pattern were different.

  5. 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.

  6. 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.

  7. Validity of bond strength tests: A critical review: Part I.

    Science.gov (United States)

    Sirisha, Kantheti; Rambabu, Tankonda; Shankar, Yalavarthi Ravi; Ravikumar, Pabbati

    2014-07-01

    Adhesive systems are selected based on their bond strengths achieved while testing in laboratories. These bond strengths can predict the longevity of a restoration to some extent. There were several discrepancies in the reported bond strengths. To critically review the reliability of macro-bond strength tests used to evaluate resin-tooth interface. Relevant literature published between January 1983 and May 2013 was collected from PubMed database, Google scholar, and hand-searched journals of Conservative Dentistry, Endodontics and Dental materials. Variables that influence the test outcome are categorized into substrate-related factors, factors related to specimen properties, preparation of specimens, and test methodology. Impact of these variables on the test outcome is critically analyzed. There is lack of a standard format for reporting the bond strength tests, which could lead to misinterpretation of the data and bonding abilities of adhesives. PMID:25125840

  8. Formation and reactivity of a porphyrin iridium hydride in water: acid dissociation constants and equilibrium thermodynamics relevant to Ir-H, Ir-OH, and Ir-CH2- bond dissociation energetics.

    Science.gov (United States)

    Bhagan, Salome; Wayland, Bradford B

    2011-11-01

    Aqueous solutions of group nine metal(III) (M = Co, Rh, Ir) complexes of tetra(3,5-disulfonatomesityl)porphyrin [(TMPS)M(III)] form an equilibrium distribution of aquo and hydroxo complexes ([(TMPS)M(III)(D(2)O)(2-n)(OD)(n)]((7+n)-)). Evaluation of acid dissociation constants for coordinated water show that the extent of proton dissociation from water increases regularly on moving down the group from cobalt to iridium, which is consistent with the expected order of increasing metal-ligand bond strengths. Aqueous (D(2)O) solutions of [(TMPS)Ir(III)(D(2)O)(2)](7-) react with dihydrogen to form an iridium hydride complex ([(TMPS)Ir-D(D(2)O)](8-)) with an acid dissociation constant of 1.8(0.5) × 10(-12) (298 K), which is much smaller than the Rh-D derivative (4.3 (0.4) × 10(-8)), reflecting a stronger Ir-D bond. The iridium hydride complex adds with ethene and acetaldehyde to form organometallic derivatives [(TMPS)Ir-CH(2)CH(2)D(D(2)O)](8-) and [(TMPS)Ir-CH(OD)CH(3)(D(2)O)](8-). Only a six-coordinate carbonyl complex [(TMPS)Ir-D(CO)](8-) is observed for reaction of the Ir-D with CO (P(CO) = 0.2-2.0 atm), which contrasts with the (TMPS)Rh-D analog which reacts with CO to produce an equilibrium with a rhodium formyl complex ([(TMPS)Rh-CDO(D(2)O)](8-)). Reactivity studies and equilibrium thermodynamic measurements were used to discuss the relative M-X bond energetics (M = Rh, Ir; X = H, OH, and CH(2)-) and the thermodynamically favorable oxidative addition of water with the (TMPS)Ir(II) derivatives.

  9. Rotational spectra and properties of complexes B···ICF3 (B = Kr or CO) and a comparison of the efficacy of ICl and ICF3 as iodine donors in halogen bond formation.

    Science.gov (United States)

    Stephens, Susanna L; Walker, Nicholas R; Legon, Anthony C

    2011-12-14

    The ground-state rotational spectra of two weakly bound complexes B···ICF(3) (B = Kr or CO) formed by trifluoroiodomethane have been observed in pulsed jets by using two types of Fourier-transform microwave spectroscopy (chirped-pulse and Fabry-Perot cavity). Both complexes exhibit symmetric-top type spectra, thus indicating that the Kr atom in Kr···ICF(3) and both the C and O atoms in OC···ICF(3) lie along the C(3) axis of ICF(3). The rotational constant B(0), the centrifugal distortion constants D(J) and D(JK), and the iodine nuclear quadrupole coupling constant χ(aa)(I) were determined for each of the isotopologues (84)Kr···ICF(3), (86)Kr···ICF(3), (16)O(12)C···ICF(3), (16)O(13)C···ICF(3), and (18)O(12)C···ICF(3). Interpretation of the spectroscopic constants reveals that the carbon atom of CO is adjacent to I and participates in the weak bond in OC···ICF(3). Simple models based on unperturbed component geometries lead to the distances r(Kr···I) = 3.830(1) Å and r(C···I) = 3.428(1) Å in Kr···ICF(3) and OC···ICF(3), respectively, and to the quadratic force constants for stretching of the weak bond k(σ) = 2.80 N m(-1) and 3.96 N m(-1), respectively. The distances r(Z···I) (Z is the acceptor atom in B), the k(σ) values, and the angular geometries of the pair of complexes B···ICF(3) and B···ICl for a given B are compared when B = Kr, CO, H(2)O, H(2)S, or NH(3). The comparison reveals that the iodine bond in B···ICF(3) is systematically longer and weaker than that of B···ICl, while the angular geometry of the B···I moiety is isomorphic in B···ICF(3) and B···ICl for a given B. It is concluded that -CF(3) is less effective than -Cl as an electron-withdrawing group when attached to an I atom and that the angular geometries of the B···ICF(3) can be predicted by means of a simple rule that holds for many hydrogen- and halogen-bonded complexes.

  10. 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.

  11. 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...

  12. 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.

  13. Functionalization of methyl (R)-phenylglycinate through orthopalladation: C-Hal, C-O, C-N, and C-C bond coupling.

    Science.gov (United States)

    Nieto, Sonia; Arnau, Palmira; Serrano, Elena; Navarro, Rafael; Soler, Tatiana; Cativiela, Carlos; Urriolabeitia, Esteban P

    2009-12-21

    The ortho functionalization of methyl R-phenylglycinate has been easily achieved using the known orthopalladated complex [Pd(mu-Cl){R-C(6)H(4)(CH(CO(2)Me)NH(2))-2}](2) (1) as synthetic tool. Different functional groups have been introduced at the ortho position of the aryl ring. The reaction of (R)-1 with X(2) or PhI(OAc)(2) gives XC(6)H(4)(CH(CO(2)Me)NH(2))-2 (X = I, Br, OMe, OEt) through oxidative coupling, while the reaction with CO gives an isoindolone. (R)-1 also reacts with one, two, or three alkyne molecules to give different metal-containing or metal-free heterocycles. The resulting functionalized amino esters or heterocycles retain the chirality of (R)-1, according with the values of the optical rotation and the obtained ee values ranging from 22%-87%. The X-ray structures of six representative compounds have also been determined.

  14. 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

  15. 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.

  16. 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

  17. Effects of Different Carbon Sources and NaBr-KCI on Synthesis of Ti(C,N)

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Ti(C,N) was synthesized with the starting materi-als of 76.9% titania white and 23.1% carbon black (graphite or activated carbon),or 40% titania white and 60% amylum,with or without 10% NaBr-KCI,dry moulding and carbon embedded firing at 1 300 ℃ and 1 400 ℃ for 3 h,respectively.Phase composition and microstructure of the synthesized Ti (C,N) were analyzed by XRD,SEM and EPMA.Effects of different carbon sources and NaBr-KCl on the synthesis of Ti (C,N) were investigated.The results show that:(1) Ti (C,N) can be synthesized by using carbon black,graphite,activated carbon or amylum as carbon source separately;(2) Additive NaBr-KCI is more fa-vorable for accelerating the carbothdrmal reduction reac-tion using carbon black or amylum as carbon source;(3) In the presence of NaBr-KCl,particle size of the synthesized Ti (C,N) is 5-8 μm using carbon black as carbon source fired at 1 300 ℃ for 3 h,while that is only 1-3 μm using graphite,activated carbon or amy-lum fired at 1 400 ℃ for 3 h.

  18. Photochemical tissue bonding

    Science.gov (United States)

    Redmond, Robert W.; Kochevar, Irene E.

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  19. 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…

  20. C, N and P Behavior in Bhitarkanika Mangroves, East coast of India

    Science.gov (United States)

    Alagappan, Dr

    2009-04-01

    In the east coast of India is relatively rich in mangroves has varied physiography and fluctuating freshwater input which modify their nutrient dynamics within this ecosystem The Bhitarkanika mangrove ecosystem is fed by two main rivers and are undergoing anthropogenic stress due to agriculture and as prawn culture and petrol boats from a fishing harbor . Hence the biogeochemistry of this pristine ecosystem is being altered significantly. . An attempt has here been made to elucidate the existing variation and role of anthropogenic variability on the nutrient variations and enrichment from mangroves. The flux estimates C, N and P have been quantified from Bhitarkanika mangrove accounting for spatial and temporal (seasonal) variation. The annual rates were estimated and compared with other mangroves in india and other parts of the world. The influence of elevated nutrient inputs through anthropogenic influence enhances their fluxes. The flux data were analyzed for net biogeochemical performance using LOICZ approach as well. The surface water samples were collected in pre-monsoon, monsoon and post monsoon season and were quantified for dissolve nutrients. The residence time of the water was found to be low with positive salinity. An attempt has also been made to distinguish the natural and anthropogenic fluxes. Overall, the mangrove ecosystem act as a source for N and P during the pre-monsoon and post-monsoon season while in monsoon it acts as sink for these nutrients.

  1. 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

  2. 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...

  3. 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.

  4. 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.

  5. [C, N, P stoichiometric characteristics of tree, shrub, herb leaves and litter in forest community of Shaanxi Province, China].

    Science.gov (United States)

    Jiang, Pei-pei; Cao, Yang; Chen, Yun-ming

    2016-02-01

    A total of 121 sampling sites were selected to study the C, N, P stoichiometric characteristics among the leaves of tree, shrub, herb and the litter of the majority forest community of Shaanxi Province, China. We also studied their relationships with geographical factors. The results showed that C, N concentrations were highest in tree leaf, P concentration was highest in herb leaf, and the C, N, P concentrations were lowest in litter. Leaf C: N: P ratios of tree, shrub, herb leaves and litter were 439.4:14.2:1, 599.2:13.5:1, 416.5:13.3:1, 504.8:15.5:1, respectively. The N:P ratios of tree, shrub and herb leaves were not significantly different, but they were all significantly higher than that of litter layer, indicating N:P ratio of different living life forms' leaves was stable. Compared with N, C and P had better relationships in each layer, and the relationships of leaf C, N, P stoichiometry between tree and herb leaves were better than those between tree and shrub leaves. The correlations of C, N, P stoichiometry between litter and the tree or herb leaves were highly significantly positive, and the correlations of P stoichiometry between litter and shrub leaves were highly significantly positive. Shrub leaf N, P concentration increased with the increasing latitude, and herb leaf N, P concentrations decreased with the increasing longitude. Compared with the longitude and latitude, the effect of altitude was smaller, and only tree leaf N:P decreased with the increasing latitude. Multivariate linear regression analysis results showed that the influence of geographical factors on herb leaf was longitude > latitude > altitude, while was latitude > longitude > altitude for tree, shrub leaves and litter. PMID:27396106

  6. 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.)

  7. 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).

  8. 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.

  9. 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

  10. 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.

  11. 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-...

  12. 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.

  13. Indirect bonding technique in orthodontics

    Directory of Open Access Journals (Sweden)

    Kübra Yıldırım

    2016-08-01

    Full Text Available ‘Direct Bonding Technique’ which allows the fixed orthodontic appliances to be directly bonded to teeth without using bands decreased the clinic time for bracket bonding and increased esthetics and oral hygiene during orthodontic treatment. However, mistakes in bracket positioning were observed due to decreased direct visual sight and access to posterior teeth. ‘Indirect Bonding Technique’ was developed for eliminating these problems. Initially, decreased bond strength, higher bond failure rate, periodontal tissue irritation, compromised oral hygiene and increased laboratory time were the main disadvantages of this technique when compared to direct bonding. The newly developed materials and modified techniques help to eliminate these negative consequences. Today, the brackets bonded with indirect technique have similar bond strength with brackets bonded directly. Moreover, indirect and direct bonding techniques have similar effects on periodontal tissues. However, indirect bonding technique requires more attention and precision in laboratory and clinical stage, and has higher cost. Orthodontist's preference between these two bonding techniques may differ according to time spent in laboratory and clinic, cost, patient comfort and personal opinion.

  14. 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.

  15. 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

  16. 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

  17. A 19F NMR study of C-I....pi- halogen bonding

    DEFF Research Database (Denmark)

    Hauchecorne, Dieter; vand er Veken, Benjamin J.; Herrebout, Wouter A.;

    2011-01-01

    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...

  18. Mo2C对Ti(C,N)基金属陶瓷腐蚀性能的影响%Effect of Mo2C on Corrosion Behavior of Ti(C,N)-based Cermets

    Institute of Scientific and Technical Information of China (English)

    董广彪; 熊计; 郭智兴; 万维财; 易成红

    2012-01-01

    通过静态浸泡腐蚀和动电位极化两种方法,研究了Mo2C对Ti(C,N)基金属陶瓷在NaOH溶液中腐蚀性能的影响.实验结果表明:Ti(C,N)基金属陶瓷的耐蚀性明显优于WC-Co硬质合金;添加Mo2C可以大幅度提高Ti(C,N)基金属陶瓷的机械性能,硬度从91.2到94.0 HRA和抗弯强度从930到1350 MPa,但会降低金属陶瓷的耐蚀性能;由于Mo2C的加入,会使金属陶瓷的动电位极化曲线出现两个钝化区,但是两个钝化区域的电流均未达到真正的钝化电流(10-5 A/cm2),因而这些钝化现象均为伪钝化;在经动电位极化后的试样表面,粘结相Ni和白色的内环相均会被腐蚀,其中内环相为富Mo的(Mo,Ti)(C,N)固溶体,其耐腐蚀性较未溶的Ti(C,N)芯更差.随着Mo2C添加量的提高,内环形相的厚度随之会增加,从而降低了Ti(C,N)基金属陶瓷的耐蚀性能.%The effect of M02C on corrosion behavior of Ti (C,N)-based cermets in NaOH alkali solution was studied by static corrosion and electrochemical corrosion. The results show that the corrosion resistance of Ti(C,N)-based cermets is obviously better than that of cemented carbides. The M02C addition could improve mechanical properties of cermets greatly, as the hardness increases from 91.2 to 94.0 HRA and transverse rupture strength increases from 930 to 1 350 MPa, but it also decreases the corrosion resistance of cermets. As the MojC addition added, there are two passive regions for the polarization curves. But those passive regions are all pseudopassivation which could not reach the real passivation current(10-5 A/cm2). It could be found on electrochemical corrosion surface that the binder Ni and the inner rims are all corroded. The inner rims is (Mo,Ti)(C,N) solid solution which is poor in corrosion resistance. With the increase of Mo2C addition, the thickness of inner rims increases. So the corrosion resistance of Ti(C,N)-based cermets decreases with the Mo2C addition.

  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. 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.

  1. Stable isotope ratios of H, C, N and O in Italian citrus juices.

    Science.gov (United States)

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

    2014-09-01

    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 (AIJN) set some reference guidelines in order to allow the judging of the genuiness of a juice. Moreover, various studies have been carried out to determine the natural variability of SIRs in fruit juices, but none of these has investigated SIRs extensively in authentic citrus juices from Italy. In this work, about 500 citrus juice samples were officially collected in Italy by the Italian Ministry of Agricultural and Forestry Policies from 1998 onwards. (D/H)(I) and (D/H)(II) in ethanol and δ(13) C(ethanol), δ(13) C(pulp), δ(13) C(sugars), δ(18) O(vegetalwater), δ(15) N(pulp), and δ(18) O(pulp) were determined using Site-Specific Natural Isotope Fractionation-Nuclear Magnetic Resonance and Isotope Ratio Mass Spectrometry, respectively. The characteristic ranges of variability in SIRs in genuine Italian citrus juice samples are here presented as well as their relationships and compliance with the limits indicated by the AIJN and others proposed in the literature. In particular, the Italian range of values was found to be not completely in agreement with AIJN guidelines, with the risk that genuine juices could be judged as not genuine. Variety seems not to influence SIRs, whereas harvest year and region of origin have some influence on the different ratios, although their data distribution shows overlapping when principal component analysis is applied.

  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. Stable isotope ratios of H, C, N and O in Italian citrus juices.

    Science.gov (United States)

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

    2014-09-01

    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 (AIJN) set some reference guidelines in order to allow the judging of the genuiness of a juice. Moreover, various studies have been carried out to determine the natural variability of SIRs in fruit juices, but none of these has investigated SIRs extensively in authentic citrus juices from Italy. In this work, about 500 citrus juice samples were officially collected in Italy by the Italian Ministry of Agricultural and Forestry Policies from 1998 onwards. (D/H)(I) and (D/H)(II) in ethanol and δ(13) C(ethanol), δ(13) C(pulp), δ(13) C(sugars), δ(18) O(vegetalwater), δ(15) N(pulp), and δ(18) O(pulp) were determined using Site-Specific Natural Isotope Fractionation-Nuclear Magnetic Resonance and Isotope Ratio Mass Spectrometry, respectively. The characteristic ranges of variability in SIRs in genuine Italian citrus juice samples are here presented as well as their relationships and compliance with the limits indicated by the AIJN and others proposed in the literature. In particular, the Italian range of values was found to be not completely in agreement with AIJN guidelines, with the risk that genuine juices could be judged as not genuine. Variety seems not to influence SIRs, whereas harvest year and region of origin have some influence on the different ratios, although their data distribution shows overlapping when principal component analysis is applied. PMID:25230174

  4. 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...

  5. 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...

  6. 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.

  7. China-Russia Bond

    Institute of Scientific and Technical Information of China (English)

    Ji Zhiye; Ma Zongshi

    2007-01-01

    @@ Thanks to China's successful launching of the Year of Russia, 2006 will surely go down as a milestone in the history of the China-Russia bond. Furthermore, a still-warmer climate will continue to prevail in 2007 when Moscow, in its turn, hosts the Year of China, trying to outshine its next-door neighbor in this regard, as Russian President Vladimir Putin promised in the exchange of new year greetings with his Chinese counterpart, President Hu Jintao.

  8. 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.

  9. Direct bonded space maintainers.

    Science.gov (United States)

    Santos, V L; Almeida, M A; Mello, H S; Keith, O

    1993-01-01

    The aim of this study was to evaluate clinically a bonded space maintainer, which would reduce chair-side time and cost. Sixty appliances were fabricated from 0.7 mm stainless steel round wire and bonded using light-cured composite to the two teeth adjacent to the site of extraction of a posterior primary tooth. Twenty males and sixteen females (age range 5-9-years-old) were selected from the Pedodontic clinic of the State University of Rio de Janeiro. The sixty space maintainers were divided into two groups according to the site in which they were placed: a) absent first primary molar and b) absent second primary molar. Impressions and study models were obtained prior to and 6 months after bonding the appliances. During this period only 8.3% of failures were observed, most of them from occlusal or facial trauma. Student t-test did not show statistically significant alterations in the sizes of the maintained spaces during the trial period.

  10. Tetra-ammine-2κ(4) C-μ-cyanido-1:2κ(2) C:N-tricyanido-1κ(3) C-copper(II)palladium(II).

    Science.gov (United States)

    Suchá, Veronika; Kuchár, Juraj; Harms, Klaus

    2013-05-01

    The title compound, [Cu(NH3)4-(μ2-NC)-Pd(CN)3], is a binuclear copper(II)palladium(II) complex, in which the Cu(II) coordination is defined by four ammine ligands and one bridging cyanide ligand. The Cu-N bond lengths in the base of the resulting CuN5 pyramid are in the range 2.016 (3)-2.024 (3) Å and the apical Cu-N( C) distance is 2.385 (4) Å. Based on the τ parameter, the shape of the coordination polyhedron is tetra-gonal-pyramidal (τ = 0). All atoms of the square-planar tetracyanidopalladate(II) moiety and the Cu(II) ion are located on a mirror plane. The electroneutral mol-ecules inter-act by N-H⋯N hydrogen bonds, resulting in the formation of a three-dimensional network. PMID:23723754

  11. New results for the formation of a muoniated radical in the Mu + Br2 system: a van der Waals complex or evidence for vibrational bonding in Br-Mu-Br?

    Science.gov (United States)

    Fleming, Donald G; Cottrell, Stephen P; McKenzie, Iain; Macrae, Roderick M

    2012-08-21

    New evidence is presented for the observation of a muoniated radical in the Mu + Br(2) system, from μSR longitudinal field (LF) repolarisation studies in the gas phase, at Br(2) concentrations of 0.1 bar in a Br(2)/N(2) mixture at 300 K and at 10 bar total pressure. The LF repolarisation curve, up to a field of 4.5 kG, reveals two paramagnetic components, one for the Mu atom, formed promptly during the slowing-down process of the positive muon, with a known Mu hyperfine coupling constant (hfcc) of 4463 MHz, and one for a muoniated radical formed by fast Mu addition. From model fits to the Br(2)/N(2) data, the radical component is found to have an unusually high muon hfcc, assessed to be ∼3300 MHz with an overall error due to systematics expected to exceed 10%. This high muon hfcc is taken as evidence for the observation of either the Br-Mu-Br radical, and hence of vibrational bonding in this H[combining low line]-L[combining low line]-H[combining low line] system, or of a MuBr(2) van der Waals complex formed in the entrance channel. Preliminary ab initio electronic structure calculations suggest the latter is more likely but fully rigorous calculations of the effect of dynamics on the hfcc for either system have yet to be carried out.

  12. Coulombic Models in Chemical Bonding.

    Science.gov (United States)

    Sacks, Lawrence J.

    1986-01-01

    Compares the coulumbic point charge model for hydrogen chloride with the valence bond model. It is not possible to assign either a nonpolar or ionic canonical form of the valence bond model, while the covalent-ionic bond distribution does conform to the point charge model. (JM)

  13. Mittal bonded tongue thrusting appliance

    Directory of Open Access Journals (Sweden)

    Rekha Mittal

    2014-01-01

    Full Text Available These days majority of orthodontist includes bonded molar attachment in their inventory to eliminate the discomfort of molar separation during initial appointment and band spaces left at the end of treatment. This article describes a innovative and economical method of attachment of bonded tongue crib if required during the initial or later stages of treatment along with bonded molar tubes.

  14. 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

  15. 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

  16. 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.

  17. 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.

  18. Effects of C/N ratio and substrate addition on natural food communities in freshwater prawn monoculture ponds

    NARCIS (Netherlands)

    Asaduzzaman, M.; Rahman, M.M.; Azim, M.E.; Islam, M.A.; Wahab, M.A.; Verdegem, M.C.J.; Verreth, J.A.J.

    2010-01-01

    An on-station trial was conducted to investigate the effects of three C/N ratios (10/1, 15/1 and 20/1) along with substrate presence or absence on natural food communities in freshwater prawn culture ponds. An experiment was carried out in 40 m2 ponds stocked with a stocking density of 2 prawn juven

  19. C/N-controlled periphyton-based freshwater prawn farming system: a sustainable approach to increase pond productivity

    NARCIS (Netherlands)

    Asaduzzaman, M.

    2012-01-01

    Three technologies showed to improve productivity and sustainability of pond production: (1) C/N ratio control, (2) providing substrates for periphyton development, and (3) fish driven re-suspension. The novelty of this PhD research is to combine these technologies, with the goal to raise pond produ

  20. Effects of C/N controlled periphyton based organic farming of freshwater prawn on water quality parameters and biotic factors

    Directory of Open Access Journals (Sweden)

    Md. Rezoanul Haque

    2014-08-01

    Full Text Available The effects of C:N controlled periphyton based organic farming of freshwater prawn on water quality parameters and biotic factors were investigated. The experiment had two treatments: T1 and T2 each with three replications. Stocking density was maintained at 20,000 juveniles ha-1. In T1, only commercially available prawn feed was applied and in T2, a locally formulated and prepared feed containing 24% crude protein with C:N ratio close to 20 was used, and maize flour and bamboo side shoots were provided for maintaining C:N ratio 20.Mean values of water quality parameters did not vary significantly (P>0.05 between treatments. Periphytic biomass in terms of dry matter, ash free dry matter (AFDM and chlorophyll a showed significant difference (P<0.05 among different sampling months. Individual harvesting weight, individual weight gain, specific growth rates, gross and net yields of prawn were significantly higher (P<0.05 in T2 than T1. Therefore, it was concluded that freshwater prawn might consume periphyton biomass in C:N controlled periphyton based organic farming practices resulted a significantly (P<0.05 higher production of freshwater prawn than traditional farming.

  1. Analyses of antibacterial activity and cell compatibility of titanium coated with a Zr-C-N film.

    Directory of Open Access Journals (Sweden)

    Yin-Yu Chang

    Full Text Available OBJECTIVE: The purpose of this study was to verify the antibacterial performance and cell proliferation activity of zirconium (Zr-carbon (C-nitride (N coatings on commercially pure titanium (Ti with different C contents. MATERIALS AND METHODS: Reactive nitrogen gas (N(2 with and without acetylene (C(2H(2 was activated by Zr plasma in a cathodic-arc evaporation system to deposit either a zirconium nitride (ZrN or a Zr-C-N coating onto Ti plates. The bacterial activity of the coatings was evaluated against Staphylococcus aureus with the aid of SYTO9 nucleic acid staining and scanning electron microscopy (SEM. Cell compatibility, mRNA expression, and morphology related to human gingival fibroblasts (HGFs on the coated samples were also determined by using the MTT assay, reverse transcriptase-polymerase chain reaction, and SEM. RESULTS: The Zr-C-N coating with the highest C content (21.7 at% exhibited the lowest bacterial preservation (P<0.001. Biological responses including proliferation, gene expression, and attachment of HGF cells to ZrN and Zr-C-N coatings were comparable to those of the uncoated Ti plate. CONCLUSIONS: High-C-content Zr-C-N coatings not only provide short-term antibacterial activity against S. aureus but are also biocompatible with HGF cells.

  2. 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

  3. Characterization of phase transformation and microstructure of nano hard phase Ti(C,N)-based cermet by spark plasma sintering

    Institute of Scientific and Technical Information of China (English)

    丰平; 熊惟皓; 李鹏; 余新; 夏阳华

    2004-01-01

    By means of optical microscope (OM), scanning electron microscope (SEM) and transmission electron microscope (TEM), the process of densification, the characterization of phase transformation and the microstructure for spark plasma sintering (SPS) nano hard phase Ti(C,N)-based cermet were investigated. It is found that the spark plasma sintering (SPS) enables the nano hard phase Ti(C,N)-based cermet to densify rapidly, however, the full densification of the sintered samples can not be obtained. The rate of phase transformation is significantly quick.When being sintered at 1 200 ℃ for 8 min, Mo2C is completely dissolved, and TiN dissolves into TiC entirely and disappears. Above 1 200 ℃, Ti(C,N) begins to decompose and the atoms of C and N separate from Ti(C,N) resulting in the generation of N2 and the graphite. Due to the denitrification and the graphitization, the density and the hardness of sintered samples are rather low. The distribution of grain size of the sample sintered at 1 350 ℃ covers a wide range of 90 - 500 nm, and most of the grain size are about 200 nm. The hard phase is not of typical core-rim structure. Oxides on the surface of particles can not be fully removed and present in sample as titanium oxide TiO2.Graphite exists in band-like shape.

  4. 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

  5. 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

  6. EFFECT OF Mo AND Mo2C ON THE MICROSTRUCTURE AND PROPERTIES OF THE CERMETS BASED ON Ti(C,N)

    Institute of Scientific and Technical Information of China (English)

    S.Q.Zhou; W.Zhao; W.H.Xiong; Y.N.Zhou

    2008-01-01

    Effect of Mo and Mo2 C on the microstructure and properties of Ti(C,N)-based cermets was investigated in this article. The results have indicated that the weight percentage of Mo from 5 to 10 can reduce Ti(C,N) grain diameter and thickness of the rim,and Ti(C,N) grain can be wetted by Ni-Cu-Mo liquid so as to get small contiguity of Ti(C,N) grain. In that way, the transverse rupture strength of Ti(C,N)-based cermets has reached 1800-1900 MPa; the fracture toughness has been due to 16-18 MPa.m1/2.But 15 wt pct Mo was not more effective on Ti(C,N)-based cermets, because the thickness of the rim becomes larger. In the circumstance of Mo2C, 5 wt pct Mo2C was good for microstructure and properties of Ti(C,N)-based cermets, but 11 wt pct Mo2C has resulted in larger contiguity of Ti(C,N) grain and big Ti(C,N) grain diameter so as to reduce transverse rupture strength and fracture toughness. So that, the effect of Mo on Ti(C,N)-based cermets is better than Mo2C.

  7. 水对二氧化碳插入TpRu(PPh3)(CH3CN)H生成甲酸根配合物的影响%Water Effect on CO2 Insertion into Ruthenium Hydride Bond of TpRu(PPh3) (CH3CN)H to Form Formate Complexes

    Institute of Scientific and Technical Information of China (English)

    尹传奇; 吴莉; 付晓滨; 许志涛; 吴少文

    2003-01-01

    A promoting effect of water on CO2 insertion into TpRu (PPh3)(CH3CN)H (Tp = Hydrotris(pyrazolyl)borate) is observed. In situ high-pressure NMR monitoring shows that CO2 readily inserts into Ru-H to form the hydrated metal formate TpRu(PPh3)(CH3CN)(η1-OCHO) · H2O, in which the formate ligand is intermolecularly H-bonded to a water molecule. Theoretical calculations carried out at the B3LYP level show that reaction barrier of the CO2 insertion is significantly reduced in the presence of water. In the transition state of the process, elec trophilicity of the carbon center of CO2 is enhanced by the formation of H-bonds between its oxygen atoms and H2O. The hydrated formate species TpRu(PPh3)(CH3CN)(η1-OCHO) · H2O comes into equilibrium rapidly with another metal formate species TpRu(PPh3)(H2O)(η1-OCHO), in which the coordinated H2O is intramolecularly H-bonded with the formate ligand.%分别研究了在干燥THF及H2O/THF条件下CO2与TpRu(PPh3)(CH3CN)H(Tp=Hydrotris(pyrazolyl)borate)的反应, 发现水对CO2插入TpRu(PPh3)(CH3CN)H的反应具有显著促进作用. 原位高压NMR研究显示, 在水存在下, CO2插入Ru-H键形成水合甲酸根配合物TpRu(PPh3)(CH3CN)(η1-OCHO)H2O, 其中甲酸根配体与溶剂中水分子形成分子间氢键. B3LYP水平的理论计算表明, CO2插入TpRu(PPh3)(CH3CN)H 中Ru-H键的能垒由于水的存在而显著降低; 在过渡态, CO2分子中碳原子的亲电性由于其氧原子与水分子形成氢键而得到增强. TpRu(PPh3)(CH3CN)(η1-OCHO)*H2O很快转化为另一甲酸根配合物TpRu(PPh3)(H2O)(η1-OCHO), 并与之达成平衡. 后者由于甲酸根配体与水分子配体间形成分子内氢键而稳定.

  8. 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.

  9. 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

  10. 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

  11. Molecular orbital analysis of the hydrogen bonded water dimer

    Science.gov (United States)

    Wang, Bo; Jiang, Wanrun; Dai, Xin; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin

    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 hydrogen bonding in ice, liquid water, functional materials and biological systems. PMID:26905305

  12. 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 ...

  13. 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...

  14. Hydrogen bonding in ionic liquids.

    Science.gov (United States)

    Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

    2015-03-01

    Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak

  15. Preparation, properties, and application characteristics of metastable layers of the Ti-Si-C-N system

    International Nuclear Information System (INIS)

    In the Ti-Si-C and Ti-Si-C-N systems, metastable layers were precipitated by means of non-reactive magnetron sputtering of hot-pressed two-phase TiC/SiC and TiN/SiC targets with 20 mole% and 50 mole% SiC. The preparation parameters were varied as follows: ion bombardment during precipitation (bias sputtering), substrate temperature, and annealing times when annealing amorphous 50%:50% TiC/SiC and 50%:50% TiN/SiC layers. Sputtering of targets containing 20% SiC was found to result in monophase fcc layers (NaCl structure). This was documented on the basis of X-ray and electron diffraction patterns. Direct precipitation of targets with 50 mole% SiC resulted in amorphous layers. Increasing the ion bombardment during accretion, raising the substrate temperature, and annealing amorphous 50%:50% TiC/SiC and 50%:50% TiN/SiC (layers precipitated directly) resulted in the crystallization of TiC and TiN nanocrystallites, respectively, imbedded in an amorphous SiC matrix. These crystallites were detected both by X-ray and by electron diffractions and by XPS studies. The XPS measurements of crystalline TiC and amorphous SiC reference layers demonstrated the existence of new kinds of carbon interface phases ('pseudocarbide layers') around TiC and amorphous SiC regions, respectively, which have a positive impact on the mechanical properties of the layers. The hardness of the layers can be correlated with the degrees of crystallization and texture. Adhesion and toughness are worse in SiC-bearing layers than PVD TiC and TiN layers, respectively. The application characteristics of the layers were determined by model wear tests relative to 100Cr6 by means of a pin/disk tribometer. N-bearing layers were found to have clearly higher friction coefficients and greater wear than layers without N. (orig.)

  16. Solar Wind C, N, and O Abundances and the Solar Metallicity

    Science.gov (United States)

    von Steiger, R.; Zurbuchen, T.; Shearer, P.; Gilbert, J. A.

    2014-12-01

    Solar wind composition provides important constraints to solar composition and to the processes that modify such compositional patterns in the atmospheres of the Sun and of active stars. There are a number of ways that composition can be observed, including spectroscopy, helioseismology, and the collection of solar samples either in the form of solar wind or energetic particles. In either case, models are needed to infer compositional constraints from observations. For example, models are needed to interpret solar spectroscopy results, and the evolution of these has recently led to significant changes to the previously accepted solar composition. The collection of solar samples requires a different type of consideration. Most solar wind and energetic particle samples are fractionated according to first ionization potential (FIP) as first pointed out by Hovestadt et al. in the seventies - elements with FIP below 10 eV are enhanced relative to elements at higher FIP, and He and possibly Ne are further depleted. Besides FIP fractionation there are indications from both isotopic and elemental data that mass fractionation, either through gravitational and/or collisional processes, may also play a role. Based on comparisons of in situ data with coronal spectroscopy it is evident that most of these processes occur at the interface between the photosphere and the corona. However, the high-latitude corona near solar minimum appears to undergo much less fractionation, if any at all. Thus it provides a heliospheric sample that is - to within our observational constraints - photospheric in nature. The low-latitude heliosphere further provides direct access to plasmas that have the fractionation pattern qualitatively and quantitatively similar to the one observed in the corona. We present a recent reanalysis of the SWICS observations on both Ulysses and ACE using modern statistical tools. Concentrating on C, N, and O, which together with the recently published Ne (Shearer et al

  17. Straightforward synthesis of novel cyclic metallasiloxanes supported by an N,C,N-chelating ligand.

    Science.gov (United States)

    Fridrichová, Adéla; Mairychová, Barbora; Padělková, Zdeňka; Lyčka, Antonín; Jurkschat, Klaus; Jambor, Roman; Dostál, Libor

    2013-12-14

    The reaction of an N,C,N-intramolecularly coordinated tin(IV) carbonate LSn(Ph)(CO3) (1) and antimony(III) and bismuth(III) oxides (LMO)2 (where M = Sb (2), Bi (3) and L = C6H3-2,6-(CH2NMe2)2) with (HO)SiPh2(O)SiPh2(OH) in 1 : 1 (in the case of 1) or 1 : 2 molar ratio (in the cases of 2 and 3) gave the metallasiloxanes cyclo-LSn(Ph)(OSiPh2)2O (4) and cyclo-LM(OSiPh2)2O (where M = Sb (6) and Bi (7)) containing six-membered MSi2O3 rings. Alternatively, the compounds 4, 6 and 7 can be also prepared reacting Ph2Si(OH)2 and compounds 1, 2 and 3, respectively, in the molar ratio of either 2 : 1 (for 4) or 4 : 1 (for 6 and 7). The reaction of Ph2Si(OH)2 with 1 in 1 : 1 molar ratio gave cyclo-Ph2Si(OSnL(Ph)O)2SiPh2 (5) containing an eight-membered Sn2Si2O4 stannasiloxane ring. The analogous eight-membered stibasiloxane derivative cyclo-Ph2Si(OSbLO)2SiPh2 (8) was obtained as well, while attempts to synthesize the bismuth analogue failed. Compounds 1-3 react with the siloxane cyclo-(Me2SiO)3 providing either eight-membered metallasiloxanes cyclo-LSn(Ph)(OSiMe2O)2SiMe2 (9) and cyclo-LSb(OSiMe2O)2SiMe2 (10) or the six-membered bismutasiloxane cyclo-LBi(OSiMe2)2O (11). All compounds were characterized with the help of elemental analysis, (1)H, (13)C, (29)Si and (119)Sn NMR spectroscopy, and single crystal X-ray diffraction analyses (except 9 and 10). PMID:24068043

  18. Residual stresses in chemically vapor deposited coatings in the Ti-C-N system

    International Nuclear Information System (INIS)

    Residual stresses in chemically vapor deposited monolithic and graded coatings in the Ti-C-N system were investigated as a function of substrate material and coating composition by X-ray diffraction Sin2 Ψ method. The thermal expansion coefficients (CTEs) of the graphite substrates ranged from 2.5x10-6 K-1 to 8.6x10-6 K-1. Titanium nitride (CTE 9.35x10-6 K-1) and titanium carbide (CTE 7.5x10-6 K-1) coatings deposited on the low-expansion substrates (CTEs 2.5-3.5x10-6 K-1) exhibited crack networks which accounted for low stress levels measured in the coatings. A phenomenalogical explanation of the crack patterns was given. The coatings grown on the substrates with high coefficients of thermal expansion (CTEs 7.8-8.6x10-6 K-1) had no cracks. Residual stresses in the TiN coatings on these substrates were measured to be tensile. Whereas TiC coatings always exhibited compressive stresses ranging from -54±10 MPa to -288±18 MPa. The TiCxNy coatings deposited on the substrate with a thermal expansion coefficient of 8.6x10-6 K-1 also had compressive stresses increased with increasing TiC mole fraction in the TiCxNy up to about 0.9 above which stresses decreased. The residual stresses in the top TiC layers of the graded TiN/TiC coatings with linear, parabolic and exponentional composition profiles grown on the the same substrate (CTE 8.6x10-6 K-1) were measured to be compressive and about 475 MPa. Stresses in the coatings were calculated and attributed to the thermal expansion mismatch between the coating and the substrate. It was shown that the measured stresses were, in general, found to be in good agreement with the calculated ones. (orig.)

  19. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

    Vinther, Tine N; Pettersson, Ingrid; Huus, Kasper;

    2015-01-01

    The structure of insulin, a glucose homeostasis-controlling hormone, is highly conserved in all vertebrates and stabilized by three disulfide bonds. Recently, we designed a novel insulin analogue containing a fourth disulfide bond located between positions A10-B4. The N-terminus of insulin's B......-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...... 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 affinities. Thus...

  20. Infrared Spectra and Hydrogen Bonds of Biologically Active Benzaldehydes

    Science.gov (United States)

    Tolstorozhev, G. B.; Skornyakov, I. V.; Belkov, M. V.; Shimko, A. N.; Shadyro, O. I.; Brinkevich, S. D.; Samovich, S. N.

    2013-09-01

    IR-Fourier spectra of solutions and crystals of biologically active benzaldehyde derivatives were studied. Specific features of the formation of intra- and intermolecular hydrogen bonds were analyzed. Spectral signatures that characterized participation of the hydroxyl OH group and also the OCH3 and C=O groups in the formation of intramolecular hydrogen bonds of the three different types O-H···O-H, O-H···O-CH3, and O-H···O=C were revealed. Intramolecular hydrogen bonds of the types O-H···O-H and O-H···O-CH3 were absent for benzaldehyde derivatives in the crystal phase. Only hydroxyl and carbonyl groups participated in intermolecular interactions. This resulted in the formation of linear intermolecular dimers. Seven various configurations of the linear dimers were identified in solutions and crystals.

  1. 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.

  2. A systematic investigation and insight into the formation mechanism of bilayers of fatty acid/soap mixtures in aqueous solutions.

    Science.gov (United States)

    Xu, Wenlong; Song, Aixin; Dong, Shuli; Chen, Jingfei; Hao, Jingcheng

    2013-10-01

    Vesicles are the most common form of bilayer structures in fatty acid/soap mixtures in aqueous solutions; however, a peculiar bilayer structure called a "planar sheet" was found for the first time in the mixtures. In the past few decades, considerable research has focused on the formation theory of bilayers in fatty acid/soap mixtures. The hydrogen bond theory has been widely accepted by scientists to explain the formation of bilayers. However, except for the hydrogen bond, no other driving forces were proposed systematically. In this work, three kinds of weak interactions were investigated in detail, which could perfectly demonstrate the formation mechanism of bilayer structures in the fatty acid/soap mixtures in aqueous solutions. (i) The influence of hydrophobic interaction was detected by changing the chain length of fatty acid (C(n)H(2n+1)COOH), in which n = 10 to 18, the phase behavior was investigated, and the phase region was presented. With the help of cryogenic transmission electron microscopy (cryo-TEM) observations, deuterium nuclear magnetic resonance ((2)H NMR), and X-ray diffraction (XRD) measurements, the vesicles and planar sheets were determined. The chain length of C(n)H(2n+1)COOH has an important effect on the physical state of the hydrophobic chain, resulting in an obvious difference in the viscoelasticity of the solution samples. (ii) The existence of hydrogen bonds between fatty acids and their soaps in aqueous solutions was demonstrated by Fourier transform infrared (FT-IR) spectroscopy and molecule dynamical simulation. From the pH measurements, the pH ranges of the bilayer formation were at the pKa values of fatty acids, respectively. (iii) Counterions can be embedded in the stern layer of the bilayers and screen the electrostatic repulsion between the COO(-) anionic headgroups. FT-IR characterization demonstrated a bidentate bridging coordination mode between counterions and carboxylates. The conductivity measurements provided the degree

  3. Prof C. N. Yang (Physics Nobel Prize 1957) from Tsinghua University (Beijing) during his CERN Colloquium: "Thematic Melodies of Twentieth Century Theoretical Physics: Quantization, Symmetry and Phase Factor".

    CERN Multimedia

    Maximilien Brice

    2006-01-01

    Prof C. N. Yang (Physics Nobel Prize 1957) from Tsinghua University (Beijing) during his CERN Colloquium: "Thematic Melodies of Twentieth Century Theoretical Physics: Quantization, Symmetry and Phase Factor".

  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. 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...

  6. 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.

  7. 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.

  8. 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....... They can effectively be used for nitrogen removal from low C/N domestic wastewater without external carbon addition. In addition, conventional and alternative carbon sources for enhanced biological nitrogen removal were also reviewed. We conclude that alternative carbon sources such as wine distillery...

  9. End-of-pipe denitrification using RAS effluent waste streams: Effect of C/N-ratio and hydraulic retention time

    DEFF Research Database (Denmark)

    Suhr, Karin Isabel; Pedersen, Per Bovbjerg; Arvin, Erik

    2013-01-01

    the on-farm study revealed as a rough estimate that potentially 17–24% of the generated VFA was lost due to the current sludge management. Inlet water to the denitrification reactors ranged in NO3-N concentration from 8.3 to 11.7 g m−3 and CODS from 52.9 to 113.4 g m−3 (10.0 ± 1.2 ◦C). The highest NO3-N...... removal rate obtained was at the intermediate treatments; 91.5–124.8 g N m−3 reactor d−1. The effect of the C/N ratio depended on the HRT. At low HRT, the variation in C/N ratio had no significant effect on NO3-N removal rate, contrary to the effect at the high HRT. The stoichiometric ratio of CODS/NO3-N...

  10. 电弧离子镀法制备高硬度Cr-Si-C-N薄膜%Cr-Si-C-N HARD FILMS PREPARED BY ARC ION DEPOSITION METHOD

    Institute of Scientific and Technical Information of China (English)

    聂朝胤; Akiro Ando; 卢春灿; 贾晓芳

    2009-01-01

    采用电弧离子反应沉积技术在SCM415渗碳淬火钢基片上沉积了Cr-Si-C-N薄膜,三甲基硅烷(TMS)反应气体作为Si和C掺杂源,通过改变TMS流量实现了薄膜中si和C含量的调节.利用XPS,XRD,HRTEM和显微硬度计研究了Cr-Si-C-N薄膜的化学状态、显微组织和显微硬度.Cr-Si-C-N薄膜中的Si和C含量随TMS流量的增加而单调增加.在TMS流鼍小于:90 mL/min时,薄膜中Si和C含量较少,薄膜由Cr(C,N)纳米晶与Si_3N_4非品(nc-Cr(C,N)/a-Si_3N_4)组成,薄膜硬度随流量的增加而单调增大,最大至4500 HK.硬度的增加源于固溶强化及薄膜中纳米晶/非晶复合结构的形成;当TMS流量大于90 mL/min时,薄膜中Si和C含量较多,多余的C以游离态形式存在,且随TMS流量的增加而增多,薄膜硬度下降.%PVD or CVD Me-Si N nanocomposite films synthesized by doping Si element in metallic nitride matrix have exhibited good oxidation resistance and wear resistance. As melting the alloy target containing Si is not easy, it is difficulty to dope much more Si in the fihns by PVD techniques. In addition, the Me-Si-N films do not have enough lubrication. In this paper, Cr-Si-C-N films were prepared by cathode arc ion deposition technique, in which tetramethylsilane (TMS) was used as Si and C sources, and their concentrations in the Cr-Si-C-N fihns can be controlled by TMS flow. The state of chemical bonding, microstructure and microhardncss were investigated by XPS, XRD, HRTEM and microindentation hardness tester. Results show that the Si and C contents increase monotonicly with the increase of TMS flow. When the TMS flow is lower than 90 mL/min, the Cr-Si-C-N fihn has a composite structure of Cr(C, N) nanocrystals dispersing in the amorphous Si_3N_4 (nc-Cr(C, N)/a-Si_3N_4), and the microhardness increases to 4500 HK with increas-ing TMS flow. Such high hardness originates from the solid solution hardening of the doping fewer element and the Veprek nanocompositc structure

  11. Effect of C/N ratio, aeration rate and moisture content on ammonia and greenhouse gas emission during the composting

    Institute of Scientific and Technical Information of China (English)

    Tao Jiang; Frank Schuchardt; Guoxue Li; Rui Guo; Yuanqiu Zhao

    2011-01-01

    Gaseous emission (N2O,CH4 and NH3) from composting can be an important source of anthropogenic greenhouse gas and air pollution.A laboratory scale orthogonal experiment was conducted to estimate the effects of C/N ratio,aeration rate and initial moisture content on gaseous emission during the composting of pig faeces from Chinese Ganqinfen system.The resnits showed that about 23.9%to 45.6% of total organic carbon (TOC) was lost in the form of CO2 and 0.8% to 7.5% of TOC emitted as CH4.Most of the nitrogen was lost in the form of NH3,which account for 9.6% to 32.4% of initial nitrogen.N2O was also an important way of nitrogen losses and 1.5% to 7.3% of initial total nitrogen was lost as it.Statistic analysis showed that the aeration rate is the most important factor which could affect the NH3 (p =0.0189),CH4 (p =0.0113) and N2O (p =0.0493) emissions significantly.Higher aeration rates reduce the CH4 emission but increase the NH3 and N2O losses.C/N ratio could affect the NH3 (p =0.0442) and CH4 (p =0.0246) emissions significantly,but not the N2O.Lower C/N ratio caused higher NH3 and CH4 emissions.The initial moisture content can not influence the gaseous emission significantly.Most treatments were matured after 37 days,except a trial with high moisture content and a low C/N ratio.

  12. Nitrogen pools and C:N ratios in well-drained Nordic forest soils related to climate and soil texture

    Energy Technology Data Exchange (ETDEWEB)

    Callesen, I.; Raulund-Rasmussen, K.; Westman, C. J.; Tau-Strand, L. (Dept. of Forest Ecology, Helsinki Univ. (FI))

    2007-07-01

    Relationships between soil nitrogen (N) pools, climate, and soil-texture class in well-drained Nordic forest soils may be used for upscaling of regional N budgets. Total soil N pools and C:N ratios were studied in forest soils in Fennoscandia and Denmark (55-70 deg N, 5-27 deg E) in boreal pine and spruce forest, boreal mixed forest, and nemoral forest types (beech, oak, mixed). Total N pools in 198 forest soil profiles were calculated from horizon thickness, bulk density, stone content and nitrogen concentration and related to climate and soil texture through multiple linear regressions. The top 100 cm of the mineral soil and the organic layer were included. C:N ratios were calculated from C and N concentrations in 10-cm depth sections. Total soil N pools ranged from 0.05 to 1.65 kg N m-2 and were positively correlated with mean annual temperature (MAT) and mean annual precipitation (MAP). The range of mean annual temperatures was -2 deg C to 8.4 deg C, and the range of mean annual precipitations was 282 to 2270 mm y-1. Soil N pools were highly variable and related to climate and soil texture class. The total soil N pools in coarse textured soils changed more with changing MAT and MAP than those in medium textured soils due to lower N pools in coarse soils in the northern part of the study area. C:N ratios were negatively correlated with temperature and precipitation in the uppermost mineral soil layers and the organic layer. C:N ratios of soil organic matter in the organic layer or top mineral soil are indicators of litter quality and degree of humification, but also reflect ecosystem N status in high N deposition areas.

  13. Humidity contribution to C_n^2 over a 600m pathlength in a tropical marine environment

    CERN Document Server

    Chang, M P J L; Gilbreath, G C; Oh, E; Chang, Mark P. J. L.; Font, Carlos O.; Oh, Eun

    2007-01-01

    We present new optical turbulence structure parameter measurements, C_n^2, over sea water between La Parguera and Magueyes Island (17.6N 67W) on the southwest coast of Puerto Rico. The 600 meter horizontal paths were located approximately 1.5 m and 10 m above sea level. No data of this type has ever been made available in the literature. Based on the data, we show that the C_n^2 measurements are about 7 times less compared to equivalent land data. This strong evidence reinforces our previous argument that humidity must be accounted for to better ascertain the near surface atmospheric turbulence effects, which current visible / near infrared C_n^2 bulk models fail to do. We also explore the generalised fractal dimension of this littoral data and compare it to our reference land data. We find cases that exhibit monofractal characteristics, that is to say, the effect of rising temperatures during the daylight hours upon turbulence are counterbalanced by humidity, leading to a single characteristic scale for the ...

  14. Biomass and nutrient productivities of Tetraselmis chuii under mixotrophic culture conditions with various C:N ratios

    Science.gov (United States)

    Lu, Lin; Wang, Jun; Yang, Guanpin; Zhu, Baohua; Pan, Kehou

    2016-05-01

    Mass microalgal culture plays an irreplaceable role in aquaculture, but microalgal productivity is restricted by traditional autotrophic culture conditions. In the present study, a Tetraselmis chuii strain belonging to the phylum Chlorophyta was isolated from south Yellow Sea. The growth rate and biomass productivity of this strain was higher under mixotrophic conditions with different carbon:nitrogen (C:N) ratios than those under autotrophic conditions. When the C:N ratio was 16, the optical density and biomass productivity were 3.7- and 5-fold higher than their corresponding values under autotrophic culture conditions, respectively. Moreover, T. chuii synthesized more polysaccharides and total lipids under mixotrophic conditions. In addition, T. chuii cultured under mixotrophic conditions synthesized more types of fatty acids than autotrophic culture conditions. At a C:N ratio of 16, the percentage of C16:0 and C18:1 reached 30.08% and 24.65% of the total fatty acid (TFA) content, respectively. These findings may provide a basis for largescale mixotrophic culture of T. chuii, as a potential bait-microalga.

  15. Microstructural characterization of Ti-C-N thin films prepared by reactive crossed beam pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Escobar-Alarcon, L., E-mail: luis.escobar@inin.gob.mx [Departamento de Fisica, Instituto Nacional de Investigaciones Nucleares, Apdo. Postal 18-1027, Mexico DF 11801 (Mexico); Medina, V.; Camps, Enrique; Romero, S. [Departamento de Fisica, Instituto Nacional de Investigaciones Nucleares, Apdo. Postal 18-1027, Mexico DF 11801 (Mexico); Fernandez, M. [Departamento de Aceleradores, Instituto Nacional de Investigaciones Nucleares, Apdo. Postal 18-1027, Mexico DF 11801 (Mexico); Solis-Casados, D. [Centro Conjunto de Investigacion en Quimica Sustentable, Facultad de Quimica UAEMex, km. 14.5 carr. Toluca-Atlacomulco (Mexico)

    2011-08-15

    In this work, Raman spectroscopy has been used to characterize Ti-C-N thin films in order to obtain information about the microstructure of the deposited materials, and in particular to study the effects due to the carbon incorporation into the TiN lattice. Ti-C-N thin films were prepared using a crossed plasma configuration in which the ablation of two different targets, titanium and carbon, in a reactive atmosphere was performed. With this configuration, the carbon content in the films was varied in an easy way from 5.0 at% to 40.0 at%. Thin film composition was determined from Non-Rutherford Backscattering Spectroscopy (NRBS) measurements. X-ray photoelectron spectroscopy and X-Ray diffraction measurements were also carried out in order to characterize the films in more detail, with this being used to give support to the interpretation of the Raman spectra. The Raman results revealed that at lower carbon concentrations a solid solution Ti(C, N) is formed, whilst at higher carbon concentrations a nanocomposite, consisting of nanocrystalline TiCN and TiC immersed in an amorphous carbon matrix is obtained.

  16. Domestication and defence: Foliar tannins and C/N ratios in cassava and a close wild relative

    Science.gov (United States)

    Mondolot, Laurence; Marlas, Amandine; Barbeau, Damien; Gargadennec, Annick; Pujol, Benoît; McKey, Doyle

    2008-09-01

    Plant domestication is accompanied by shifts in resource allocation, as a result of farmer selection for genotypes that give high yields in agricultural habitats. Relaxed natural selection for chemical and physical defences in these habitats could facilitate resource allocation to yield. We compared the concentrations of tannins, and C/N ratios, which are often correlated with investment in cell-wall compounds, in leaves of landraces of domesticated cassava ( Manihot esculenta) and a close wild relative in French Guiana. Foliar concentrations of tannins were about 1.9 times higher in the wild relative than in domesticated cassava. Histochemical analyses showed that tannins were present in nearly all palisade and spongy parenchyma cells of the wild taxon, but in only some cells of these tissues in M. esculenta. C/N ratios were also 1.9 times higher in leaves of the wild relative than in those of domesticated cassava. Tannins accounted for only a small proportion of total carbon, and the higher C/N ratio in wild than in domesticated cassava may reflect higher investment in carbon-containing compounds additional to tannins, such as cell-wall compounds. The divergence in these traits between cassava and this close wild relative mirrors a broad pattern observed in wild plant species across habitats varying in resource availability. One explanation for our results is that domestication in cassava may have favoured a shift from a resource conservation strategy to a resource acquisition strategy.

  17. Atom probe tomography of a Ti-Si-Al-C-N coating grown on a cemented carbide substrate.

    Science.gov (United States)

    Thuvander, M; Östberg, G; Ahlgren, M; Falk, L K L

    2015-12-01

    The elemental distribution within a Ti-Si-Al-C-N coating grown by physical vapour deposition on a Cr-doped WC-Co cemented carbide substrate has been investigated by atom probe tomography. Special attention was paid to the coating/substrate interface region. The results indicated a diffusion of substrate binder phase elements into the Ti-N adhesion layer. The composition of this layer, and the Ti-Al-N interlayer present between the adhesion layer and the main Ti-Si-Al-C-N layer, appeared to be sub-stoichiometric. The analysis of the interlayer showed the presence of internal surfaces, possibly grain boundaries, depleted in Al. The composition of the main Ti-Al-Si-C-N layer varied periodically in the growth direction; layers enriched in Ti appeared with a periodicity of around 30 nm. Laser pulsing resulted in a good mass resolution that made it possible to distinguish between N(+) and Si(2+) at 14 Da.

  18. 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...

  19. 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...

  20. Hydrogen Bonds Involving Metal Centers

    OpenAIRE

    Pavlović, G.; Raos, N.

    2006-01-01

    Hydrogen bonds involving metal center as a hydrogen donor or hydrogen acceptor are only a specific type of metal-hydrogen interactions; it is therefore not easy to differentiate hydrogen bond from other metal-hydrogen interactions, especially agostic ones. The first part of the review is therefore devoted to the results of structural chemistry and molecular spectroscopy (NMR, IR), as a tool for differentiating hydrogen bondings from other hydrogen interactions. The classical examples of Pt···...

  1. Bond failure patterns in vivo.

    Science.gov (United States)

    Linklater, Rognvald A; Gordon, Peter H

    2003-05-01

    The aim of this study was to identify the presence and pattern of differences in bond failure between tooth types in vivo when bonding orthodontic brackets with the no-mix orthodontic composite adhesive Right-On. In vivo bond failure for a single operator was recorded for 108 consecutive patients undergoing fixed-appliance orthodontic treatment. The bond failure data were analyzed by survival analysis. Time to first failure or censorship was recorded for each bonded attachment. Overall failure in the sample matched previous clinical studies but conflicted with previous ex vivo bond strength data. Mandibular and posterior teeth had significantly higher rates of failure than did maxillary and anterior teeth. The type of attachment used had a significant effect on bond survival. The results of this study confirm that in vivo bond survival is not uniform for all teeth. Comparisons between the findings of this study and those of a previous ex vivo study by the same authors failed to validate ex vivo bond strength testing as clinically relevant.

  2. Wafer bonding applications and technology

    CERN Document Server

    Gösele, Ulrich

    2004-01-01

    During the past decade direct wafer bonding has developed into a mature materials integration technology. This book presents state-of-the-art reviews of the most important applications of wafer bonding written by experts from industry and academia. The topics include bonding-based fabrication methods of silicon-on-insulator, photonic crystals, VCSELs, SiGe-based FETs, MEMS together with hybrid integration and laser lift-off. The non-specialist will learn about the basics of wafer bonding and its various application areas, while the researcher in the field will find up-to-date information about this fast-moving area, including relevant patent information.

  3. Photoinduced hydrogen-bonding dynamics.

    Science.gov (United States)

    Chu, Tian-Shu; Xu, Jinmei

    2016-09-01

    Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bonding formed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water. PMID:27491849

  4. A simplified indirect bonding technique

    Directory of Open Access Journals (Sweden)

    Radha Katiyar

    2014-01-01

    Full Text Available With the advent of lingual orthodontics, indirect bonding technique has become an integral part of practice. It involves placement of brackets initially on the models and then their transfer to teeth with the help of transfer trays. Problems encountered with current indirect bonding techniques used are (1 the possibility of adhesive flash remaining around the base of the brackets which requires removal (2 longer time required for the adhesive to gain enough bond strength for secure tray removal. The new simplified indirect bonding technique presented here overcomes both these problems.

  5. Characterization of Dentine to Assess Bond Strength of Dental Composites

    Directory of Open Access Journals (Sweden)

    Saad Liaqat

    2015-04-01

    Full Text Available This study was performed to develop alternating dentine adhesion models that could help in the evaluation of a self-bonding dental composite. For this purpose dentine from human and ivory was characterized chemically and microscopically before and after acid etching using Raman and SEM. Mechanical properties of dentine were determined using 3 point bend test. Composite bonding to dentine, with and without use of acid pre-treatment and/or the adhesive, were assessed using a shear bond test. Furthermore, micro gap formation after restoration of 3 mm diameter cavities in dentine was assessed by SEM. Initial hydroxyapatite level in ivory was half that in human dentine. Surface hydroxyapatites decreased by approximately half with every 23 s of acid etch. The human dentine strength (56 MPa was approximately double that of ivory, while the modulus was almost comparable to that of ivory. With adhesive use, average shear bond strengths were 30 and 26 MPa with and without acid etching. With no adhesive, average bond strength was 6 MPa for conventional composites. This, however, increased to 14 MPa with a commercial flowable “self–bonding” composite or upon addition of low levels of an acidic monomer to the experimental composite. The acidic monomer additionally reduced micro-gap formation with the experimental composite. Improved bonding and mechanical properties should reduce composite failures due to recurrent caries or fracture respectively.

  6. Reactive Bonding Film for Bonding Carbon Foam Through Metal Extrusion

    CERN Document Server

    Chertok, Maxwell; Irving, Michael; Neher, Christian; Tripathi, Mani; Wang, Ruby; Zheng, Gayle

    2016-01-01

    Future tracking detectors, such as those under development for the High Luminosity LHC, will require mechanical structures employing novel materials to reduce mass while providing excellent strength, thermal conductivity, and radiation tolerance. Adhesion methods for such materials are under study at present. This paper demonstrates the use of reactive bonding film as an adhesion method for bonding carbon foam.

  7. Digital Control of Bonding Force for Gold Wire Bonding Machine

    Directory of Open Access Journals (Sweden)

    Xiaochu Wang

    2013-01-01

    Full Text Available In order to digitally control the bonding force of a wire bonder precisely, this paper uses a DC solenoid as a force source, and by controlling the solenoid’s current, which causes the electromagnetic force, we can control the bonding force that capillary applies. The bonding force control system in this paper is composed of PC (Personal Computer and hypogyny MCU (Micro Controller Unit, which communicate using a RS485 interface. The digital value of a given bonding force is given by the PC to the MCU. By comparing the sampling current of the solenoid, and through PID regulation, D/A converter of the digital potentiometer and the solenoid driver circuit, the half-closed loop control system of bonding force is accomplished. Tuning of the PID parameters is accomplished with fuzzy adaptive control theory and simulated by Matlab simulink. The control system is tested by comparing the desired bonding force and the force actually applied and examming the relationship between bonding quality and bonding force.

  8. [Effective nitrogen removal in low C/N wastewater with combined aerobic-low DO biofilm treatment process].

    Science.gov (United States)

    Chen, Xiu-Rong; Ai, Qi-Feng; Xu, Wen-Lu; Wu, Min-Lin

    2011-10-01

    The municipal wastewater in China is characterized by low ratio of carbon to nitrogen, which is the key restrictive factor for effective biological removal of nitrogen. In this study, the aerobic-low DO biofilm process was used for the nitrogen removal of municipal wastewater. By means of adjusting inflow ratios of aerobic section to low-DO section, hydraulic retention time (HRT) and inflow ratio of carbon to nitrogen (C/N), the performances of nitrification in aerobic biofilm section and denitrification in low-DO section could be improved, the good performance of nitrogen removal was achieved. In order to insure the good effluent quality, especially for ammonia nitrogen and total nitrogen indexes, the nitrification and denitrification could be made up in aerobic and low-DO biofilm section respectively due to the coexistence of aerobic and anoxic zone in biofilm. There were 3 stages for the research process. In the first stage, the original C/N, inflow ratios of aerobic section to low-DO section were chosen as 3:1 and 1:1 respectively, then the effects of various HRT (aerobic section + low DO section) values such as (10 + 5) h, (8 + 4) h, (6 + 3) h, (4 + 2) h to nitrogen removal were analyzed. According to the conclusion in the first stage, the original C/N was kept at 3:1, HRT (aerobic section + low DO section) was (10 + 5) h. Then, the effects of various inflow ratios to nitrogen removal were studied in the second stage. In the third stage, when HRT(aerobic section + low DO section) was (10 + 5) h and inflow ratio was 1:1, the original C/N were adjusted from 2:1, 3:1, 5:1 to 10:1. To conclude, the optimal parameters for nitrogen removal in the biofilm system were as follows: original C/N = 5:1, inflow ratio of aerobic to low-DO section = 1:1, HRT of aerobic and low-DO sections were 10 h and 5 h respectively. As a result, COD, ammonia nitrogen and total nitrogen could be removed from 254 mg/L to 48 mg/L, 37.2 mg/L to 9.3 mg/L and 48.2 mg/L to 14.8 mg

  9. 29 CFR 2580.412-19 - Term of the bond, discovery period, other bond clauses.

    Science.gov (United States)

    2010-07-01

    ... SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules § 2580.412-19 Term of the bond, discovery... 29 Labor 9 2010-07-01 2010-07-01 false Term of the bond, discovery period, other bond clauses... new bond must be obtained each year. There is nothing in the Act that prohibits a bond for a...

  10. Are hydrogen bonds responsible for glycine conformational preferences?

    Energy Technology Data Exchange (ETDEWEB)

    Cormanich, Rodrigo A.; Ducati, Lucas C. [Chemistry Institute, State University of Campinas, P.O. Box 6154, 13083-970 Campinas, SP (Brazil); Rittner, Roberto, E-mail: rittner@iqm.unicamp.br [Chemistry Institute, State University of Campinas, P.O. Box 6154, 13083-970 Campinas, SP (Brazil)

    2011-08-25

    Highlights: {yields} Glycine conformational preferences in the isolated state were fully investigated. {yields} The lowest energy conformation is not stabilized by hydrogen bonding. {yields} Steric and hyperconjugative effects were analyzed for all conformers. {yields} Several theoretical methods were used to explain the conformational preferences. - Abstract: Glycine conformational preferences have mostly been explained as due to the formation of intramolecular hydrogen bonding, despite other possible relevant intramolecular interactions that may be present in this molecular system. This paper, within the framework of the quantum theory of atoms in molecules and natural bond orbital analysis, at the B3LYP/aug-cc-pVDZ level, shows that hydrogen bonding formally stabilizes just one of the glycine conformers. Indeed, these theoretical calculations suggest that both steric hindrance and hyperconjugative effects rule conformational preferences of this model compound and may not be ignored in discussions of amino acid conformational analyses.

  11. Theoretical insights into the cycloaddition reaction mechanism between ketenimine and methyleneimine: An alternative approach to the formation of pyrazole and imidazole

    Indian Academy of Sciences (India)

    Nana Wang; Xiaojun Tan; Weihua Wang; Fangfang Wang; Ping Li

    2016-02-01

    The cycloaddition reaction mechanism between interstellar molecules, ketenimine and methyleneimine, has been systematically investigated employing the second-order Møller-Plesset perturbation theory (MP2) method in order to better understand the reactivity of nitrogenous cumulene ketenimine with the C=N double bond compound methyleneimine. Geometry optimizations and vibrational analyses have been performed for the stationary points on the potential energy surfaces of the system. Calculations show that five-membered cyclic carbene intermediates could be produced through pericyclic reaction processes between ketenimine and methyleneimine. Through the subsequent hydrogen transfer processes, carbene intermediates can be isomerized to the pyrazole and imidazole compounds, respectively. The present study is helpful to understand the formation of prebiotic species in interstellar space.

  12. /sup 14/C isotope effects in /sup 1/H and /sup 13/C N. M. R. spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Funke, C.W.; Kaspersen, F.M.; Sperling, E.M.G.; Wagenaars, G.N.

    1986-03-15

    Replacement of /sup 12/C by /sup 14/C induces small upfield shifts of the directly bonded /sup 1/H and /sup 13/C nuclei; these shift differences can be used to measure the extent of /sup 14/C labelling.

  13. First principle study of magnetic and electronic properties of single X (X = Al, Si) atom added to small carbon clusters (C n X, n = 2-10)

    Science.gov (United States)

    Afshar, M.; Hoseini, S. S.; Sargolzaei, M.

    2016-07-01

    In this paper, the magnetic and electronic properties of single aluminum and silicon atom added to small carbon clusters (C n X; X = Al, Si; n = 2-10) are studied in the framework of generalized-gradient approximation using density functional theory. The calculations were performed for linear, two dimensional and three dimensional clusters based on full-potential local-orbital (FPLO) method. The total energies, HOMO-LUMO energy gap and total magnetic moments of the most stable structures are presented in this work. The calculations show that C n Si clusters have more stability compared to C n Al clusters. In addition, our magnetic calculations were shown that the C n Al isomers are magnetic objects whereas C n Si clusters are nonmagnetic objects.

  14. Computational Chemistry of Adhesive Bonds

    Science.gov (United States)

    Phillips, Donald H.

    1999-01-01

    This investigation is intended to determine the electrical mechanical, and chemical properties of adhesive bonds at the molecular level. The initial determinations will be followed by investigations of the effects of environmental effects on the chemistry and properties of the bond layer.

  15. How to bond to root canal dentin

    Science.gov (United States)

    Nica, Luminita; Todea, Carmen; Furtos, Gabriel; Baldea, Bogdan

    2014-01-01

    Bonding to root canal dentin may be difficult due to various factors: the structural characteristic of the root canal dentin, which is different from that of the coronal dentin; the presence of the organic tissue of the dental pulp inside the root canal, which has to be removed during the cleaning-shaping of the root canal system; the smear-layer resulted after mechanical instrumentation, which may interfere with the adhesion of the filling materials; the type of the irrigants used in the cleaning protocol; the type of the sealer and core material used in the obturation of the endodontic space; the type of the materials used for the restoration of the endodontically treated teeth. The influence of the cleaning protocol, of the root canal filling material, of the type of the adhesive system used in the restoration of the treated teeth and of the region of the root canal, on the adhesion of several filling and restorative materials to root canal dentin was evaluated in the push-out bond strength test on 1-mm thick slices of endodontically treated human teeth. The results showed that all these factors have a statistically significant influence on the push-out bond strength. Formation of resin tags between radicular dentin and the investigated materials was observed in some of the samples at SEM analysis.

  16. Effects of single bond-ion and single bond-diradical form on the stretching vibration of Cdbnd N bridging bond in 4,4‧-disubstituted benzylidene anilines

    Science.gov (United States)

    Cao, Chao-Tun; Bi, Yakun; Cao, Chenzhong

    2016-06-01

    Fifty-seven samples of model compounds, 4,4‧-disubstituted benzylidene anilines, p-X-ArCH = NAr-p-Y were synthesized. Their infrared absorption spectra were recorded, and the stretching vibration frequencies νCdbnd N of the Cdbnd N bridging bond were determined. New stretching vibration mode was proposed by means of the analysis of the factors affecting νCdbnd N, that is there are mainly three modes in the stretching vibration of Cdbnd N bond: (I) polar double bond form Cdbnd N, (II) single bond-ion form C+-N- and (III) single bond-diradical form Crad -Nrad . The contributions of the forms (I) and (II) to the change of νCdbnd N can be quantified by using Hammett substituent constant (including substituent cross-interaction effects between X and Y groups), whereas the contribution of the form (III) can be quantified by employing the excited-state substituent constant. The most contribution of these three forms is the form (III), the next is the form (II), whose contribution difference was discussed with the viewpoint of energy requirements in vibration with the form (III) and form (II).

  17. Effects of influent C/N ratios on CO2 and CH4 emissions from vertical subsurface flow constructed wetlands treating synthetic municipal wastewater

    International Nuclear Information System (INIS)

    Highlights: ► The effects of influent C/N ratios on GHG fluxes from VSSF CWs were investigated. ► The GHG fluxes at different influent C/N ratios were estimated by the CMB model. ► The measured GHG fluxes agreed with the predicted ones in the range C/N = 2.5:1–5:1. ► C/N ratios in the range of 2.5:1–5:1 range generated relatively low GHG fluxes. ► An influent of C/N = 5:1 achieved the greatest BNR efficiency with the lowest GHG flux. - Abstract: Greenhouse gases (GHG) emissions from constructed wetlands (CWs) can mitigate the environmental benefits of nutrient removal because reduced water pollution could be replaced by emission of GHG. Therefore, the GHG (CO2 and CH4) fluxes of vertical subsurface flow constructed wetlands (VSSF CWs) under different influent C/N ratios of synthetic municipal wastewater were analyzed directly by GHG flux measurements, and estimated by carbon mass balance (CMB) over a 12 month period. The VSSF CWs system achieved the highest biological nutrient removal (BNR) efficiency between C/N ratios of 5:1 and 10:1 across all kinds of pollutants. Variation in influent C/N ratios dramatically influenced GHG fluxes from the VSSF CWs system. The GHG flux measured in situ agreed with those predicted by the CMB model and represented relatively low GHG fluxes when C/N ratios were between 2.5:1 and 5:1. It was determined that the optimum C/N ratio is 5:1, at which VSSF CWs can achieve a relatively high BNR efficiency and a low level of GHG flux.

  18. Quantum Confinement in Hydrogen Bond

    CERN Document Server

    Santos, Carlos da Silva dos; Ricotta, Regina Maria

    2015-01-01

    In this work, the quantum confinement effect is proposed as the cause of the displacement of the vibrational spectrum of molecular groups that involve hydrogen bonds. In this approach the hydrogen bond imposes a space barrier to hydrogen and constrains its oscillatory motion. We studied the vibrational transitions through the Morse potential, for the NH and OH molecular groups inside macromolecules in situation of confinement (when hydrogen bonding is formed) and non-confinement (when there is no hydrogen bonding). The energies were obtained through the variational method with the trial wave functions obtained from Supersymmetric Quantum Mechanics (SQM) formalism. The results indicate that it is possible to distinguish the emission peaks related to the existence of the hydrogen bonds. These analytical results were satisfactorily compared with experimental results obtained from infrared spectroscopy.

  19. Bonded Excimer in Stacked Cytosines: A Semiclassical Simulation Study

    Directory of Open Access Journals (Sweden)

    Weifeng Wu

    2015-01-01

    Full Text Available The formation of a covalent bond between two stacked cytosines, one of which is excited by an ultrafast laser pulse, was studied by semiclassical dynamics simulations. The results show that a bonded excimer is created, which sharply lowers the energy gap between the LUMO and HOMO and consequently facilitates the deactivation of the electronically excited molecule. This is different from the case of two stacked adenines, where the formation of a covalent bond alters the nonadiabatic deactivation mechanism in two opposite ways. It lowers the energy gap and consequently leads to the coupling between the HOMO and LUMO levels, thus enhancing the deactivation of the electronically excited molecule. On the other hand, it leads to restriction of the deformation vibration of the pyrimidine in the excited molecule, because of a steric effect, and this delays the deactivation process of the excited adenine molecule with return to the electronic ground state.

  20. The Significance of Multivalent Bonding Motifs and “Bond Order” in DNA-Directed Nanoparticle Crystallization

    Energy Technology Data Exchange (ETDEWEB)

    Thaner, Ryan V.; Eryazici, Ibrahim; Macfarlane, Robert J.; Brown, Keith A.; Lee, Byeongdu; Nguyen, SonBinh T.; Mirkin, Chad A.

    2016-05-18

    Multivalent oligonucleotide-based bonding elements have been synthesized and studied for the assembly and crystallization of gold nanoparticles. Through the use of organic branching points, divalent and trivalent DNA linkers were readily incorporated into the oligonucleotide shells that define DNA-nanoparticles and compared to monovalent linker systems. These multivalent bonding motifs enable the change of "bond strength" between particles and therefore modulate the effective "bond order." In addition, the improved accessibility of strands between neighboring particles, either due to multivalency or modifications to increase strand flexibility, gives rise to superlattices with less strain in the crystallites compared to traditional designs. Furthermore, the increased availability and number of binding modes also provide a new variable that allows previously unobserved crystal structures to be synthesized, as evidenced by the formation of a thorium phosphide superlattice.

  1. Dentin-bonding agents

    Directory of Open Access Journals (Sweden)

    João Carlos Gomes

    2008-01-01

    Full Text Available New dental restorative materials have been developed to meet not only the functional demands, but esthetics as well, and in the last few years an enormous range of new materials has appeared for use in dentistry. Among them, several adhesive systems, and different operative techniques for each group materials. Therefore, is indispensable for the professional to know about the properties, characteristics, and association of these materials with the dental structures, in order to select and use them correctly. Should conventional self-etching adhesive systems be used? This question encouraged this literature review to be conducted, with the aim of comparing the conventional adhesive systems with the self-etching systems and to look for scientific data that would help professionals to choose which adhesive system to use. When compared to conventional systems, it was noted that the self-etching systems show less sensitivity to technique, especially as regards errors the operator could commit. The self-etching systems, particularly the 2-step type, have shown equivalent values of bond strength, marginal microleakage and performance, therefore, will be an option for direct composite resin restorations in posterior teeth.

  2. Mechanical and electronic properties of antiperovskite Ti-based compounds AXTi{sub 3} (X = C, N): A first-principles investigation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ni-Na; Lu, Hong-Yan, E-mail: luhongyan2006@gmail.com [School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000 (China); Shao, Ding-Fu, E-mail: dfshao@issp.ac.cn; Lu, Wen-Jian [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China)

    2016-01-28

    In this paper, we systematically studied the mechanical and electronic properties of a series of antiperovskite-type Ti-based ternary carbides and nitrides AXTi{sub 3} (A = Ba, Ca, In, Sn, Sr, Zn, Cu, Al, Ga, Cd, and La; X = C, N) from first-principles calculations. By calculating the formation energies, elastic constants, and other mechanical parameters, we predicted that 7 carbides ACTi{sub 3} and 7 nitrides ANTi{sub 3} compounds are stable among the 22 compounds. The predicted large Young's modulus and high hardness imply a good mechanical application prospect of AXTi{sub 3}. Particularly, SnNTi{sub 3} was found to show ferromagnetic ground state. For the electronic structure, our results confirm that the compounds are metallic in nature, and the density of states near the Fermi energy is predominately contributed by Ti-3d states. The effect of A- and X-site atom doping on AXTi{sub 3} can be evaluated by rigid band approximation. Our prediction will be useful for the experimental exploration of the new antiperovskite compounds.

  3. Synthesis of (B-C-N) Nanomaterials by Arc Discharge Using Heterogeneous Anodes

    Institute of Scientific and Technical Information of China (English)

    Djamel Eddine GOURARI; Manitra RAZAFINIMANANA; Marc MONTHIOUX; Raul ARENAL; Flavien VALENSI; Sébastien JOULIE; Virginie SERIN

    2016-01-01

    In spite of the current prevalence of the CVD-based processes,the electric arc remains an interesting process for the synthesis of carbon nanoforms,thanks to its versatility,robustness and easiness.It also allows performing in-situ substitution of carbon atoms by hetero-elements in the graphene lattice.Our work aims to establish a correlation between the plasma properties,type and chemical composition (and the substitution rate) of the obtained single-wall carbon nanotubes.The plasma was characterized by optical emission spectroscopy and the products were analyzed by high resolution transmission electron microscopy and core level Electron Energy-Loss Spectroscopy (EELS).Results show that a high boron content leads to a plasma temperature decrease and hinders the formation of nanotubes.This effect can be compensated by increasing the arc current and/or yttrium content.The optimal conditions for the synthesis of boron-and/or nitrogen-substituted nanotubes correspond to a high axial plasma temperature associated to a strong radial gradient.EELS analysis confirmed that the boron incorporates into the graphenic lattice.

  4. Synthesis of (B-C-N) Nanomaterials by Arc Discharge Using Heterogeneous Anodes

    Science.gov (United States)

    Djamel Eddine, Gourari; Manitra, Razafinimanana; Marc, Monthioux; Raul, Arenal; Flavien, Valensi; Sébastien, Joulie; Virginie, Serin

    2016-05-01

    In spite of the current prevalence of the CVD-based processes, the electric arc remains an interesting process for the synthesis of carbon nanoforms, thanks to its versatility, robustness and easiness. It also allows performing in-situ substitution of carbon atoms by hetero-elements in the graphene lattice. Our work aims to establish a correlation between the plasma properties, type and chemical composition (and the substitution rate) of the obtained single-wall carbon nanotubes. The plasma was characterized by optical emission spectroscopy and the products were analyzed by high resolution transmission electron microscopy and core level Electron Energy-Loss Spectroscopy (EELS). Results show that a high boron content leads to a plasma temperature decrease and hinders the formation of nanotubes. This effect can be compensated by increasing the arc current and/or yttrium content. The optimal conditions for the synthesis of boron- and/or nitrogen-substituted nanotubes correspond to a high axial plasma temperature associated to a strong radial gradient. EELS analysis confirmed that the boron incorporates into the graphenic lattice.

  5. Effect of density of hydrogen-bonding donor on hydrogen-bonded multilayer buildup

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hongyu; MA Ning; WANG Zhiqiang

    2005-01-01

    The effect of density of hydrogen-bonding donor (HBD) on the formation of layer-by-layer assemblies of poly(4-vinylpyridine) and poly(4-vinylphenol) was investigated. For this purpose, a series of ethyl-substituted poly(4-vinylphenol) (EsPVPhf) with variable ethyl substitute percentage was synthesized by grafting the phenol moiety along the poly(4-vinylphenol) backbone with 1-bromoethane. UV-vis spectroscopy revealed a uniform deposition process of the hydrogen-bonded multilayer consisting of poly(4- vinylpyridine) (PVPy) and EsPVPhf with variable density of HBD. Notably, it was found that increasing the HBD density of EsPVPhf resulted in a marked decrease of both amount of polymers adsorbed and film thickness, which should be related to the EsPVPhf conformation change from coiled state to extended conformation in ethanol solution. Compared with the effect of charge density in polyelectrolyte multilayer, however, there does not exist a critical density of HBD in our case of hydrogen-bonded multilayer assembly. In addition, surface structures of PVPy/EsPVPhf multilayer films also can be tailored controllably by adjusting HBD density of EsPVPhf. As a result, a new method for tuning the structure of hydrogen-bonding-directed multilayer films was developed.

  6. Self-Healing of Unentangled Polymer Networks with Reversible Bonds

    Science.gov (United States)

    Stukalin, Evgeny B.; Cai, Li-Heng; Kumar, N. Arun; Leibler, Ludwik; Rubinstein, Michael

    2013-01-01

    Self-healing polymeric materials are systems that after damage can revert to their original state with full or partial recovery of mechanical strength. Using scaling theory we study a simple model of autonomic self-healing of unentangled polymer networks. In this model one of the two end monomers of each polymer chain is fixed in space mimicking dangling chains attachment to a polymer network, while the sticky monomer at the other end of each chain can form pairwise reversible bond with the sticky end of another chain. We study the reaction kinetics of reversible bonds in this simple model and analyze the different stages in the self-repair process. The formation of bridges and the recovery of the material strength across the fractured interface during the healing period occur appreciably faster after shorter waiting time, during which the fractured surfaces are kept apart. We observe the slowest formation of bridges for self-adhesion after bringing into contact two bare surfaces with equilibrium (very low) density of open stickers in comparison with self-healing. The primary role of anomalous diffusion in material self-repair for short waiting times is established, while at long waiting times the recovery of bonds across fractured interface is due to hopping diffusion of stickers between different bonded partners. Acceleration in bridge formation for self-healing compared to self-adhesion is due to excess non-equilibrium concentration of open stickers. Full recovery of reversible bonds across fractured interface (formation of bridges) occurs after appreciably longer time than the equilibration time of the concentration of reversible bonds in the bulk. PMID:24347684

  7. Positively charged phosphorus as a hydrogen bond acceptor

    DEFF Research Database (Denmark)

    Hansen, Anne Schou; Du, Lin; Kjærgaard, Henrik Grum

    2014-01-01

    Phosphorus (P) is an element that is essential to the life of all organisms, and the atmospheric detection of phosphine suggests the existence of a volatile biogeochemical P cycle. Here, we investigate the ability of P to participate in the formation of OH···P hydrogen bonds. Three bimolecular...

  8. The Chemical Bond and Solid-state Physics

    Science.gov (United States)

    Phillips, James C.

    1970-01-01

    Proposes a new scale of ionicity, with which the ionic character of bonding in crystals can be predicted and measured. This new scale of ionicity has led to improved understanding of such crystalline properties as lattice structure, heats of formation, elastic constants, and nonlinear optical properties. Bibliography. (LC)

  9. Hydrogen bonding in oxalic acid and its complexes: A database study of neutron structures

    Indian Academy of Sciences (India)

    R Chitra; Amit Das; R R Choudhury; M Ramanadham; R Chidambaram

    2004-08-01

    The basic result of carboxylic group that the oxygen atom of the –OH never seems to be a hydrogen bond acceptor is violated in the cases, namely urea oxalic acid and bis urea oxalic acid complexes, where the hydroxyl oxygen atom is an acceptor of a weak N–H... O hydrogen bond. The parameters of this hydrogen bond, respectively in these structures are: hydrogen acceptor distance 2.110 Å and 2.127 Å and the bending angle at hydrogen, 165.6° and 165.8°. The bond strength around the hydroxyl oxygen is close to 1.91 valence units, indicating that it has hardly any strength left to form hydrogen bonds. These two structures being highly planar, force the formation of this hydrogen bond. As oxalic acid is the common moiety, the structures of the two polymorphs, -oxalic acid and -oxalic acid, also were looked into in terms of hydrogen bonding and packing.

  10. Evaluating the potential for halogen bonding in ketosteroid isomerase’s oxyanion hole using unnatural amino acid mutagenesis

    Science.gov (United States)

    Kraut, Daniel A; Churchil, Michael J; Dawson, Phillip E

    2009-01-01

    There has recently been an increasing interest in controlling macromolecular conformations and interactions through halogen bonding. Halogen bonds are favorable electrostatic interactions between polarized, electropositive chlorine, bromine or iodine atoms and electronegative atoms such as oxygen or nitrogen. These interactions have been likened to hydrogen bonds both in terms of their favored acceptor molecules, their geometries, and their energetics. We asked whether a halogen bond could replace a hydrogen bond in the oxyanion hole of ketosteroid isomerase, using semi-synthetic enzyme containing para-halogenated phenylalanine derivatives to replace the tyrosine hydrogen bond donor. Formation of a halogen bond to the oxyanion in the transition state would be expected to rescue the effects of mutation to phenylalanine, but all of the halogenated enzymes were comparable in activity to the phenylalanine mutant. We conclude that, at least in this active site, a halogen bond cannot functionally replace a hydrogen bond. PMID:19260691

  11. C:N:P Molar Ratios, Sources and 14C Dating of Surficial Sediments from the NW Slope of Cuba.

    Science.gov (United States)

    de la Lanza Espino, Guadalupe; Soto, Luis A

    2015-01-01

    The surficial sediments recovered from 12 sites located near the channel axis of the Florida Straits and the lower slope off NW Cuba were analyzed for total organic carbon (TOC), nitrogen (TN), phosphorus (TP), elemental C:N:P ratios, C and N isotopic values, and 14C dating. The depth profiles of TOC, TN, and TP (0-18 cm) displayed a downcore trend and a significant variation. The TOC values were low (0.15 to 0.62%; 66 to 516 µmol g(-1)). Sites near the island's lower slope had lower TOC average concentrations (158-333 µmol g(-1)) than those closer to the channel axis (averaging 341-516 µmol g(-1); p <0.05). The TN concentrations near the lower slope attained 0.11% (80 µmol g(-1)), whereas, towards the channel axis, they decreased to 0.07% (55 µmol g(-1); p<0.05). The C:N ratios ranged from 1.9 to 10.2. The mean molar C:N ratio (5.4) indicated a marine hemipelagic deposition. The TP was lower at sites near the lower slope (38.4 to 50.0 µmol gv; 0.12% to 0.16%) than those near the channel axis (50.0 to 66 µmol g(-1); 0.15 to 0.21%). C:P fluctuated from 7.7 to 14.1 in the surficial sediment layer. The bulk organic δ13Corg and δ15N values confirmed pelagic organic sources, and the 14C dating revealed that the sediments were deposited during the Holocene (1000-5000 yr BP). We suggest that the hydrodynamic conditions in the Straits influence vertical and advective fluxes of particulate organic material trapped in the mixed-layer, which reduces the particulate matter flux to the seabed.

  12. C:N:P Molar Ratios, Sources and 14C Dating of Surficial Sediments from the NW Slope of Cuba.

    Directory of Open Access Journals (Sweden)

    Guadalupe de la Lanza Espino

    Full Text Available The surficial sediments recovered from 12 sites located near the channel axis of the Florida Straits and the lower slope off NW Cuba were analyzed for total organic carbon (TOC, nitrogen (TN, phosphorus (TP, elemental C:N:P ratios, C and N isotopic values, and 14C dating. The depth profiles of TOC, TN, and TP (0-18 cm displayed a downcore trend and a significant variation. The TOC values were low (0.15 to 0.62%; 66 to 516 µmol g(-1. Sites near the island's lower slope had lower TOC average concentrations (158-333 µmol g(-1 than those closer to the channel axis (averaging 341-516 µmol g(-1; p <0.05. The TN concentrations near the lower slope attained 0.11% (80 µmol g(-1, whereas, towards the channel axis, they decreased to 0.07% (55 µmol g(-1; p<0.05. The C:N ratios ranged from 1.9 to 10.2. The mean molar C:N ratio (5.4 indicated a marine hemipelagic deposition. The TP was lower at sites near the lower slope (38.4 to 50.0 µmol gv; 0.12% to 0.16% than those near the channel axis (50.0 to 66 µmol g(-1; 0.15 to 0.21%. C:P fluctuated from 7.7 to 14.1 in the surficial sediment layer. The bulk organic δ13Corg and δ15N values confirmed pelagic organic sources, and the 14C dating revealed that the sediments were deposited during the Holocene (1000-5000 yr BP. We suggest that the hydrodynamic conditions in the Straits influence vertical and advective fluxes of particulate organic material trapped in the mixed-layer, which reduces the particulate matter flux to the seabed.

  13. Long-term P weathering and recent N deposition control contemporary plant-soil C, N and P

    Science.gov (United States)

    Davies, Jessica; Tipping, Edward; Rowe, Edwin; Boyle, John; Graf Pannatier, Elisabeth; Martinsen, Vegard

    2016-04-01

    Models are needed to understand how plant-soil nutrient stores and fluxes have responded to the last two centuries of widespread anthropogenic nutrient pollution and predict future change. These models need to integrate across carbon, nitrogen and phosphorus (C, N, & P) cycles and simulate changes over suitable timescales using available driving data. It is also vital that they are constrainable against observed data to provide confidence in their outputs. To date, no models address all of these requirements. To meet this need, a new model, N14CP, is introduced, which is initially applied to Northern hemisphere temperate and boreal ecosystems over the Holocene. N14CP is parameterized and tested using 88 northern Europe plot-scale studies, providing the most robust test of such a model to date. The model simulates long-term P weathering, based on the assumption of a starting pool of weatherable P (Pweath0, g m-2), which is gradually transformed into organic and sorbed pools. Nitrogen fixation (and consequently primary production) is made dependent on available P. In the absence of knowledge about the spatial variability of Pweath0, N14CP produces good average soil and plant variables, but cannot simulate variations among sites. Allowing Pweath0 to vary between sites improves soil C, N and P results greatly, suggesting contemporary soil C, N and P are sensitive to long-term P weathering. Most sites were found to be N limited. Anthropogenic N deposition since 1800 was calculated to have increased plant biomass substantially, in agreement with observations, and consequently increased soil carbon pools.

  14. Unfolding Ubiquitin by force: water mediated H-bond destabilization

    Directory of Open Access Journals (Sweden)

    Germán Pabón

    2012-12-01

    Full Text Available Using the “pull and wait” (PNW simulation protocol at 300 K, we studied the unfolding by force of an ubiquitin molecule. PNW was implemented in the CHARMM program using an integration time step of 1 fs and a uniform dielectric constant of 1. The ubiquitin molecule, initially solvated, was put under mechanical stress, exerting forces from different directions. The rupture of five hydrogen bonds between parallel strands β1 and β5 takes place during the extension from 13 to 15 Å, defines a mechanical barrier for unfolding and dominates the point of maximum unfolding force. The simulations described here show that given adequate time, a small applied force can destabilize those five H-bonds relative to the bonds that can be created to water molecules; allowing the formation of stable H-bonds between a single water molecule and the donor and acceptor groups of the interstrand H-bonds. Thus, simulations run with PNW show that the force is not responsible for “ripping apart” the backbone H-bonds; it merely destabilizes them making them less stable than the H-bonds they can make with water. Additional simulations show that the force necessary to destabilize the H-bonds and allow them to be replaced by H-bonds to water molecules depends strongly on the pulling direction. By using a simulation protocol that allows equilibration at each extension we have been able to observe the details of the events leading to the unfolding of ubiquitin by mechanical force.

  15. H-Bonded Liquid Crystalline Polymer Network Materials

    Institute of Scientific and Technical Information of China (English)

    LIN Hong-Cheu; HENDRIANTO Jemmy

    2001-01-01

    @@Side-chain copolymers, poly(mOBA-co-mStilb)s, composed of proton acceptors (stilbazoles) and proton donors (benzoic acids) connected to polyacrylate backbone with different methylene spacer lengths (m = 6 and 10) were prepared in different donor/acceptor molar ratios. The H-bonded copolymeric networks were formed once they were synthesized, and showed more homogenous phase than the physical-blended supramolecular networks consisting of donor and acceptor homopolymers, i.e.H-bonded blends of PmOBA and PmStilb. In order to compare the effects of the backbone connection of these H-bonded copolymers and blends, we also built monomer-monomer and polymer-monomer H-bonded complexes of similar structures (shown in Fig. 1). DSC, POM, and powder XRD studies reveal that the copolymers (m = 10)with mole fractions of benzoic acids between 0.33-0.83 show the smectic A (SMA) phase with layer spacing values between 42.22A-50.47A (increases with higher H-bonded crosslinking density between benzoic acids and stilbazoles), while for m = 6, liquid crystalline behavior still can be observed at 0.89 molar fraction of benzoic acids. However, on the basis of powder XRD study it is found that the d spacing values of H-bonded copolymers with m = 6 in the SmA phase increase with higher molar ratios of benzoic acids, which is agreed with the formation of microphase separation due to the hydrogen bonds of benzoic acids connected themselves from the same backbone. The isotropization temperatures of the H-bonded copolymers and blends increase as the molar ratios of benzoic acids increase, while the higher crosslinking density of the H-bonded copolymeric networks and blends can stabilize the liquid crystalline phase.

  16. H-Bonded Liquid Crystalline Polymer Network Materials

    Institute of Scientific and Technical Information of China (English)

    LIN; Hong-Cheu

    2001-01-01

    Side-chain copolymers, poly(mOBA-co-mStilb)s, composed of proton acceptors (stilbazoles) and proton donors (benzoic acids) connected to polyacrylate backbone with different methylene spacer lengths (m = 6 and 10) were prepared in different donor/acceptor molar ratios. The H-bonded copolymeric networks were formed once they were synthesized, and showed more homogenous phase than the physical-blended supramolecular networks consisting of donor and acceptor homopolymers, i.e.H-bonded blends of PmOBA and PmStilb. In order to compare the effects of the backbone connection of these H-bonded copolymers and blends, we also built monomer-monomer and polymer-monomer H-bonded complexes of similar structures (shown in Fig. 1). DSC, POM, and powder XRD studies reveal that the copolymers (m = 10)with mole fractions of benzoic acids between 0.33-0.83 show the smectic A (SMA) phase with layer spacing values between 42.22A-50.47A (increases with higher H-bonded crosslinking density between benzoic acids and stilbazoles), while for m = 6, liquid crystalline behavior still can be observed at 0.89 molar fraction of benzoic acids. However, on the basis of powder XRD study it is found that the d spacing values of H-bonded copolymers with m = 6 in the SmA phase increase with higher molar ratios of benzoic acids, which is agreed with the formation of microphase separation due to the hydrogen bonds of benzoic acids connected themselves from the same backbone. The isotropization temperatures of the H-bonded copolymers and blends increase as the molar ratios of benzoic acids increase, while the higher crosslinking density of the H-bonded copolymeric networks and blends can stabilize the liquid crystalline phase.……

  17. Vertical Profile of C, N, P, K and Radionuclides in Soil Collected from Highland Tea Plantation Areas

    Directory of Open Access Journals (Sweden)

    Zaini Hamzah

    2011-01-01

    Full Text Available Problem statement: Cameron Highlands is a well known agricultural area in Peninsular Malaysia. Long term usage of fertilizer has caused accumulation of major elemental component in the soil. This accumulation will cause enrichment of the nutrient in the catchment located at downstream of the river through runoff. Approach: Two tea plantations on the upstream with hilly condition plantation were selected as the location for monitoring the accumulation of the major nutrient component N, P and K. C was also determined to estimate the total organic content in the soil. Natural radionuclides i.e., 226Ra, 228Ra and 40K were also determined and anthropogenic radionuclides 137Cs were detectable. The samples were measured using Elemental Analyzer, Energy Dispersive X-rays Fluorescence (EDXRF and gamma spectrometer. The data set were analyzed using Principle Component Analysis (PCA and Cluster Analysis (CA to check the distribution and elemental sources. Results: The trend for all depth profile measurement results shown monotonically trend through the depth where it shown no observable trend except for C, N, P and 137Cs decreasing through the depth. PCA results indicate that there are two sources for plantation A and three sources for plantation B that led to the accumulation of these elements. Three clusters of group element were found for both tea plantation area and the major sources are from fertilizer, natural occurring and atmospheric natural process. The model for C, N and P was found to be exponentially proportional to the depth with removing mixing layer. Conclusion: The range of concentrations for measured elements shows that the concentrations of elements in tea plantation B are higher than in tea plantation A. All depth profile gives monotonically trend except for C, N, P and 137Cs since these elements were added to the soil. C, N and P are decreasing exponentially with depth. The amount of 137Cs was found to be detectable for both study

  18. Ti+C+N FILM PREPARATION AND ITS PROPERTIES BY LOW ENERGY CO-DEPOSITION ON STEEL

    Institute of Scientific and Technical Information of China (English)

    Z.Z.Yi; X.Zhang; T.H.Zhang; Z.S.Xiao

    2002-01-01

    The Ti+C+N film was co-deposited on H13 steel by Filtered Vacuum Arc PlasmaDeposition (FVAPD) operated with a modified cathode. The co-deposited layer waseffective for the improvement of surface hardness and corrosion resistance. The nano-hardness value of the co-deposited film is 1.3 times more than that of undepositedsample. The corrosion behavior measurement shows that the corrosion resistance foracid corrosion and pitting corrosion was improved greatly. It is owing to the formationof the new ternary ceramic phase TiCo.7 No.3 in the co-deposited layer. The mechanismof property improvement is discussed.

  19. Theoretical Study on the Structure and Stability of Si4X (X = Li, Be, B, C, N, O, F) Clusters

    Institute of Scientific and Technical Information of China (English)

    孙仁安; 李钠; 张旭

    2004-01-01

    The density functional theory B3LYP/6-311g* method is used in the geometry optimization and frequency calculation on Si4X (X = Li, Be, B, C, N, O, F) clusters. The equilibrium structures of these clusters are quasi-trigonal bipyramidal structures with C2v symmetry. The periodicity of their thermal stabilities and vibration spectra has been discussed. The influence of the inserted second period element impurities for the structures and stabilities of the Si5 clusters have also been investigated.

  20. Slip-rolling resistance of novel Zr(C,N) thin film coatings under high Hertzian contact pressures

    Energy Technology Data Exchange (ETDEWEB)

    Manier, Charles-Alix

    2010-08-24

    Today, coatings are used in many applications ranging from the decoration purposes to the improvement of efficiency such as in machining tools, medical tools, computer devices (hard disks) and many more. Especially the automotive industry anticipates a benefit in using coatings for example in powertrains and gears where the mechanical components are stressed under slip-rolling motion. A cost effective option to increase efficiency is based on the increase of the load carrying capacity by thin film coatings. It would also represent a way towards downsizing. In the work presented here, a small review concerning rolling contact fatigue of coatings was performed. Experimentally it is then shown, that crystalline Zr(C,N) coatings can be slip-rolling resistant at 120 C in factory fill engine oil up to ten million cycles under average Hertzian contact pressures up to P{sub 0mean} = 1.94 GPa (P{sub 0max} = 2.91 GPa). Basically, it represents here the doubling of the normal force acting on the surface compared to uncoated steel traditionally lubricated with fully formulated oil. Typically, the coated substrates are made of the quenched and tempered bearing steel Cronidur 30. The Zr(C,N) coatings were fully characterized using different characterisation techniques in order to understand the difference in slip-rolling resistance under those high tribological demands. Effectively, the slip-rolling resistance of different batches of the Zr(C,N) coatings is evaluated using a defined and powerful testing procedure. Different results of lifetime were achieved without fundamental changes of the deposition procedure. The characterisation achieved permits the identification of microstructural disparities which should affect the load carrying capacity of the coating. Moreover, the efficiency of the high slip-rolling resistant Zr(C,N) coating was considered not only with respect to the improvement of the load carrying capacity of the substrate but also in terms of tribological