Ammonium boranes for the selective complexation of cyanide or fluoride ions in water.

Science.gov (United States)

Hudnall, Todd W; Gabbaï, François P

2007-10-03

With the recognition of aqueous fluoride and cyanide ions as an objective, we have investigated the anion binding properties of two isomeric ammonium boranes, namely [p-(Mes2B)C6H4(NMe3)]+ ([1]+) and [o-(Mes2B)C6H4(NMe3)]+ ([2]+). These cationic boranes, which could be obtained by reaction of the known 4- and 2-dimesitylboryl-N,N-dimethylaniline with MeOTf, have been investigated both experimentally and computationally. They both react with fluoride and cyanide ions in organic solvents to afford the corresponding fluoroborate/ or cyanoborate/ammonium zwitterions 1F, 1CN, 2F, and 2CN. In aqueous solution, however, these cationic boranes behave as remarkably selective receptors. Indeed, [1]+ only complexes cyanide ions while [2]+ only complexes fluoride ions. In H2O/DMSO 60:40 vol (HEPES 6 mM, pH 7), the cyanide binding constant of [1]+ and the fluoride binding constant of [2]+ are respectively equal to 3.9 (+/-0.1) x 108 and 910 (+/-50) M-1. Structural and computational studies indicate that both steric and electronic effects contribute to the unusual selectivity displayed by these cationic boranes. Owing to favorable Coulombic effects, the para-derivative [1]+ has a very high affinity for cyanide; yet these effects are not sufficiently intense to allow complexation of the more efficiently hydrated and less basic fluoride anion. In the case of the ortho-derivative [2]+, the proximity of the ammonium moiety leads to an increase in the Lewis acidity of the boron center thus making fluoride binding possible. However, steric effects prevent cyanide coordination to the boron center of [2]+. Finally, cation [1]+ and [2]+ bind their dedicated anions reversibly and show a negligible response in the presence of other common anions including Cl-, Br-, I-, NO3-, OAc-, H2PO4-, and HSO4-.

TD-DFT Insight into Photodissociation of Co-C Bond in Coenzyme B12

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Pawel Michal Kozlowski

2014-02-01

Full Text Available Coenzyme B12 (AdoCbl is one of the most biologically active forms of vitamin B12, and continues to be a topic of active research interest. The mechanism of Co-C bond cleavage in AdoCbl, and the corresponding enzymatic reactions are however, not well understood at the molecular level. In this work, time-dependent density functional theory (TD-DFT has been applied to investigate the photodissociation of coenzyme B12. To reduce computational cost, while retaining the major spectroscopic features of AdoCbl, a truncated model based on ribosylcobalamin (RibCbl was used to simulate Co-C photodissociation. Equilibrium geometries of RibCbl were obtained by optimization at the DFT/BP86/TZVP level of theory, and low-lying excited states were calculated by TD-DFT using the same functional and basis set. The calculated singlet states, and absorption spectra were simulated in both the gas phase, and water, using the polarizable continuum model (PCM. Both spectra were in reasonable agreement with experimental data, and potential energy curves based on vertical excitations were plotted to explore the nature of Co-C bond dissociation. It was found that a repulsive 3(σCo-C → σ*Co-C triplet state became dissociative at large Co-C bond distance, similar to a previous observation for methylcobalamin (MeCbl. Furthermore, potential energy surfaces (PESs obtained as a function of both Co-CRib and Co-NIm distances, identify the S1 state as a key intermediate generated during photoexcitation of RibCbl, attributed to a mixture of a MLCT (metal-to-ligand charge transfer and a σ bonding-ligand charge transfer (SBLCT states.

Regeneration of ammonia borane from polyborazylene

Science.gov (United States)

Sutton, Andrew; Gordon, John C; Ott, Kevin C; Burrell, Anthony K

2013-02-05

Method of producing ammonia borane, comprising providing a reagent comprising a dehydrogenated material in a suitable solvent; and combining the reagent with a reducing agent comprising hydrazine, a hydrazine derivative, or combinations thereof, in a reaction which produces a mixture comprising ammonia borane.

Crossbreeding Holstein-Friesian with Ethiopian Boran cattle in a ...

African Journals Online (AJOL)

Unknown

Friesian with Boran (unselected for milk), the epistatic interaction genes might have been lost due to the free recombination process during meiosis. Similar negative recombination effects on milk yield were reported even for crossing between two B.

Application of bonded NdFeB magnet for C-Band circulator component

Science.gov (United States)

Kristiantoro, T.; Idayanti, N.; Sudrajat, N.; Septiani, A.; Dedi

2016-11-01

In this paper bonded NdFeB permanent magnets of the crashed-ribbon type were made as an alternative for circulator magnet to improve their magnetic performance. The fabrication process is also easier than the sintered NdFeB because there had no shrinkage of product (such as sintered barium ferrite magnet), with the others advantages as follows; large freeness of product shapes, high precision of dimension and good corrosion resistance. The dimension of the samples was measured to calculate its bulk densities and the magnetic properties were characterized by Permagraph to obtain values such as; Remanence induction (Br) in kG, Coercivity value (Hcj) in kOe, the Maximum energy product (BH max) in MGOe. Whereas the surface magnetic field strength (B) was observed by the Gauss-meter. The bonded NdFeB permanent magnets revealed 6.39 kG of Br, 6.974 kOe of Hcj and 7.13 MGOe of BHmax. The circulator performance was measured using Vector Network Analyzer (VNA). The optimum values of the circulator measurement at a frequency of 5 GHz show a VSWR value of 1.062 and insertion loss of -0.463 dB. The bonded magnet could be used as component of permanent magnets on the circulator that working on C-Band at a frequency range of 4 GHz - 8 GHz.

Pentaatomic planar tetracoordinate carbon molecules [XCAl(3)](q) [(X,q) = (B,-2), (C,-1), (N,0)] with C-X multiple bonding.

Science.gov (United States)

Cui, Zhong-Hua; Shao, Chang-Bin; Gao, Si-Meng; Ding, Yi-Hong

2010-11-07

Among the fascinating planar tetracoordinate carbon (ptC) species, pentaatomic molecules belong to the smallest class, well-known as "pptC". It has been generally accepted that the planarity of pptC structure is realized via the "delocalization" of the p(z) lone pair at the central carbon and the ligand-ligand bonding interaction. Although "localization" is as key driving force in organic chemistry as "delocalization", the "localization" concept has not been applied to the design of pptC molecules, to the best of our knowledge. In this paper, we apply the "localization" strategy to design computationally a series of new pptC. It is shown that the central carbon atom and one "electronegative" ligand atom X (compared to the Al ligand) effectively form a highly localized C-X multiple bond, converting the lone pair at the central carbon to a two-center two-electron π-bond. At the aug-cc-pVTZ-B3LYP, MP2 and CCSD(T) levels, the designed 18-valence-electron pptC species [XCAl(3)](q); [(X,q) = (B,-2), (C,-1), (N,0)] are found to each possess a stable ptC structure bearing a C-X double bond, indicated by the structural, molecular orbital, Wiberg bonding, potential energy surface and Born-Oppenheimer molecular dynamics (BOMD) analysis. Moreover, our OVGF calculations showed that the presently disclosed (yet previously unconsidered) pptC structure of [C(2)Al(3)](-) could well account for the observed photoelectron spectrum (previously only ascribed to a close-energy fan-like structure). Therefore, [C(2)Al(3)](-) could be the first pptC that bears the highly localized C-X double bond that has been experimentally generated. Notably, the pptC structure is the respective global minimum point for [BCAl(3)](2-) and [NCAl(3)], and the counterion(s) would further stabilize [BCAl(3)](2-) and [C(2)Al(3)](-). Thus, these newly designed pptC species with interesting bonding structure should be viable for future experimental characterization. The presently applied "localization" approach

Cyanide ion complexation by a cationic borane.

Science.gov (United States)

Chiu, Ching-Wen; Gabbaï, François P

2008-02-14

While we have previously reported that [1-(Mes2B)-8-(Me3NCH2)-C10H6]+ ([2]+) complexes fluoride ions to form [1-(Mes2FB)-8-(Me3NCH2)-C10H6] (2-F), we now show that this cationic borane also complexes cyanide to form [1-(Mes2(NC)B)-8-(Me3NCH2)-C10H6] (2-CN). This reaction also occurs under biphasic conditions (H2O-CHCl3) and may serve to transport cyanide in organic phases. The zwitterionic cyanoborate 2-CN has been fully characterized and its crystal structure determined. UV-vis titration experiments carried out in THF indicate that [2]+ has a higher affinity for fluoride (K > 10(8) M(-1)) than cyanide (K = 8.0 (+/-0.5) x 10(5) M(-1)). Steric effects which impede cyanide binding to the sterically congested boron center of [2]+ are most likely at the origin of this selectivity. Finally, electrochemical studies indicate that [2]+ is significantly more electrophilic than its neutral precursor 1-(Mes2B)-8-(Me2NCH2)-(C10H6) (1). These studies also show that reduction of [2]+ is irreversible, possibly because of elimination of the NMe3 moiety under reductive conditions. In fact, [2]OTf reacts with NaBH4 to afford 1-(Mes2B)-8-(CH3)-(C10H6) (4) which has also been fully characterized.

Borata-Wittig olefination reactions of ketones, carboxylic esters and amides with bis(pentafluorophenyl)borata-alkene reagents.

Science.gov (United States)

Wang, Tongdao; Kohrt, Sonja; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

2017-08-07

The strongly electrophilic borane derivative amino-CH 2 CH 2 CH 2 -B(C 6 F 5 ) 2 6 was α-CH deprotonated with LiTMP to give the borata-alkene {[amino-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ][Li + ]} 2 9 which underwent facile [2 + 2] cycloaddition reactions with benzophenone or fluorenone to yield the respective 1,2-oxaboretanides 11a,b. Compounds 9 and 11 were characterized by the X-ray diffraction. Thermolysis or hydrolysis of compounds 11a,b gave the corresponding borata-Wittig olefination products 12a,b. A variety of R-CH 2 -CH 2 -B(C 6 F 5 ) 2 boranes (conveniently generated by hydroboration of terminal alkenes R-CH[double bond, length as m-dash]CH 2 with Piers' borane [HB(C 6 F 5 ) 2 ]) were analogously deprotonated to give the respective borata-alkenes 16a-e (R: Ph-CH 2 -, n C 4 H 9 , t Bu, Cy, PhCH 2 CH 2 -). They underwent "non-classical" borata-Wittig olefination reactions with ethylformate to give the respective enolether carbonylation products, or their C 1 -elongated aldehydes (after hydrolysis). The borata-alkene [Ph-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ] [Li + HTMP] (16a) gave the respective "non-classical" borata-Wittig olefination products, the enolethers 25a,b and 27, respectively, upon treatment with methyl- or ethyl acetate or γ-butyrolactone.

In Situ Formation of AgCo Stabilized on Graphitic Carbon Nitride and Concomitant Hydrolysis of Ammonia Borane to Hydrogen

Directory of Open Access Journals (Sweden)

Qi Wang

2018-04-01

Full Text Available The development of highly-efficient heterogeneous supported catalysts for catalytic hydrolysis of ammonia borane to yield hydrogen is of significant importance considering the versatile usages of hydrogen. Herein, we reported the in situ synthesis of AgCo bimetallic nanoparticles supported on g-C3N4 and concomitant hydrolysis of ammonia borane for hydrogen evolution at room temperature. The as-synthesized Ag0.1Co0.9/g-C3N4 catalysts displayed the highest turnover frequency (TOF value of 249.02 mol H2·(molAg·min−1 for hydrogen evolution from the hydrolysis of ammonia borane, which was higher than many other reported values. Furthermore, the Ag0.1Co0.9/g-C3N4 catalyst could be recycled during five consecutive runs. The study proves that Ag0.1Co0.9/g-C3N4 is a potential catalytic material toward the hydrolysis of ammonia borane for hydrogen production.

Distribution of sulfhydryl boranes in mice and rats

International Nuclear Information System (INIS)

Slatkin, D.N.; Micca, P.L.; Laster, B.H.; Fairchild, R.G.

1986-01-01

The results of experiments on the distribution of boranes in rat and mice tissues and melanomas are reported. Comparisons are made between the behavior of borane monomers and dimers under different dose rates and cummulative doses

Final Report for the DOE-BES Program Mechanistic Studies of Activated Hydrogen Release from Amine-Boranes

Energy Technology Data Exchange (ETDEWEB)

Larry G. Sneddon; R. Thomas Baker

2013-01-13

Effective storage of hydrogen presents one of the most significant technical gaps to successful implementation of the hydrogen economy, particularly for transportation applications. Amine boranes, such as ammonia borane H3NBH3 and ammonia triborane H3NB3H7, have been identified as promising, high-capacity chemical hydrogen storage media containing potentially readily released protic (N-H) and hydridic (B-H) hydrogens. At the outset of our studies, dehydrogenation of ammonia borane had been studied primarily in the solid state, but our DOE sponsored work clearly demonstrated that ionic liquids, base-initiators and/or metal-catalysts can each significantly increase both the rate and extent of hydrogen release from amine boranes under moderate conditions. Our studies also showed that depending upon the activation method, hydrogen release from amine boranes can occur by very different mechanistic steps and yield different types of spent-fuel materials. The fundamental understanding that was developed during this grant of the pathways and controlling factors for each of these hydrogen-release mechanisms is now enabling continuing discovery and optimization of new chemical-hydride based hydrogen storage systems.

Synthesis and characterization of borane-terminated poly(silole-co-germole) for the evaluation of luminescent PLED.

Science.gov (United States)

Kim, Myoung-Hee; Lee, Jun; Kim, Jong-Hyun; Woo, Hee-Gweon; Kim, Bo-Hye; Yang, Kap Seung; Sohn, Honglae

2012-05-01

Codehydrocoupling (in the presence of various inorganic B, Al-hydrides) followed by borane-capping (with Ph2BCl) of 1,1-dihydrotetraphenylsilole (1) and 1,1-dihydrotetraphenylgermole (2) (9:1 mole ratio) gave electroluminescent poly(silole-co-germole)s containing borane-ends (3) in high yield. The polymerization yield and molecular weight with Selectrides increase in the order L-Selectride L-Selectride < Red-Al borane-terminated copolymer 3 emits at 522 nm and are electroluminescent at 521 nm. The fluorescence quantum yield of 3 in toluene is (1.60 +/- 0.30) x 10(-2). The emission color is green and the maximum brightness of the device is 2,753 cd/m2 with a luminous efficiency of 0.66 Im/W. The borane end group exhibited no appreciable effect on the luminescent properties of 3. The electroluminescent copolymer 3 with boranyl end group is hence a good candidate for PLED fabrication.

Phospholyl(borane) Amino Acids and Peptides: Stereoselective Synthesis and Fluorescent Properties with Large Stokes Shift.

Science.gov (United States)

Arribat, Mathieu; Rémond, Emmanuelle; Clément, Sébastien; Lee, Arie Van Der; Cavelier, Florine

2018-01-24

The synthesis of phospholyl(borane) amino acids was stereoselectively achieved by reaction of phospholide anion with iodo α-amino ester derived from l-aspartic acid or l-serine, followed by in situ complexation with borane. Phospholyl(borane) amino acids are easy to store and can be subjected to direct transformation into the corresponding free phospholyl, gold complex, oxide or sulfur derivatives as well as phospholinium salts, thus offering a variety of side chains. After selective deprotection of carboxylic function or amine, C- or N- peptide coupling with an alanine moiety proved the possible incorporation into peptides. Such phospholyl amino acid and peptide derivatives exhibit fluorescent properties with a large Stokes shift (160 nm) and fluorescence up to 535 nm, depending on the phosphole aromaticity and the chemical environment. These phospholyl(borane) amino acids constitute a new class of unnatural amino acids useful for structure-activities relationship studies and appear to be promising fluorophores for the development of labeled peptides.

Base metal dehydrogenation of amine-boranes

Science.gov (United States)

Blacquiere, Johanna Marie [Ottawa, CA; Keaton, Richard Jeffrey [Pearland, TX; Baker, Ralph Thomas [Los Alamos, NM

2009-06-09

A method of dehydrogenating an amine-borane having the formula R.sup.1H.sub.2N--BH.sub.2R.sup.2 using base metal catalyst. The method generates hydrogen and produces at least one of a [R.sup.1HN--BHR.sup.2].sub.m oligomer and a [R.sup.1N--BR.sup.2].sub.n oligomer. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources, such as, but not limited to, fuel cells.

Electronic structure, chemical bonding, phase stability, and ground-state properties of YNi2-x(Co/Cu)xB2C

International Nuclear Information System (INIS)

Ravindran, P.; Johansson, B.; Eriksson, O.

1998-01-01

In order to understand the role of Ni site substitution on the electronic structure and chemical bonding in YNi 2 B 2 C, we have made systematic electronic-structure studies on YNi 2 B 2 C as a function of Co and Cu substitution using the supercell approach within the local density approximation. The equilibrium volume, bulk modulus (B 0 ) and its pressure derivative (B 0 ' ), Grueneisen constant (γ G ), Debye temperature (Θ D ), cohesive energy (E c ), and heat of formation (ΔH) are calculated for YNi 2-x (Co/Cu) x B 2 C (x=0,0.5,1.0,1.5,2). From the total energy, electron-energy band structure, site decomposed density of states, and charge-density contour we have analyzed the structural stability and chemical bonding behavior of YNi 2 B 2 C as a function of Co/Cu substitution. We find that the simple rigid band model successfully explains the electronic structure and structural stability of Co/Cu substitution for Ni. In addition to studying the chemical bonding and electronic structure we present a somewhat speculative analysis of the general trends in the behavior of critical temperature for superconductivity as a function of alloying. copyright 1998 The American Physical Society

Asymmetric Reduction of tert-Butanesulfinyl Ketimines by N-Heterocyclic Carbene Boranes.

Science.gov (United States)

Liu, Tao; Chen, Ling-yan; Sun, Zhihua

2015-11-20

N-heterocyclic carbene borane (NHC-borane) based on a triazole core is demonstrated for the first time to be efficient for reduction of a variety of tert-butanesulfinyl ketimines. Up to 95% yield and up to >99% diastereomeric excess were achieved. NHC-borane exhibited excellent activities that are more efficient than or comparable to commonly used reductive reagents such as NaBH4, NaBH3CN, l-selectride, Ru catalyst, or BH3-THF.

Photoelectron spectroscopy of B4O4−: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

International Nuclear Information System (INIS)

Tian, Wen-Juan; Chen, Qiang; Ou, Ting; Li, Si-Dian; Zhao, Li-Juan; Xu, Hong-Guang; Zheng, Wei-Jun; Zhai, Hua-Jin

2015-01-01

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B 4 O 4 0/− clusters. The measured PES spectra of B 4 O 4 − exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of C s B 4 O 4 − ( 2 A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D 2h B 4 O 4 − ( 2 B 2g ) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B 2 O 2 core bonded with terminal BO and/or BO 2 groups. The same Y-shaped and rhombic structures are also located for the B 4 O 4 neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B 4 O 4 0/− clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B 4 O 4 0/− clusters. This work is the first experimental study on a molecular system with an o-bond

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

Energy Technology Data Exchange (ETDEWEB)

Colby, Denise; Bergman, Robert; Ellman, Jonathan

2010-05-13

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

Hydrolysis of ammonia borane as a hydrogen source: fundamental issues and potential solutions towards implementation.

Science.gov (United States)

Sanyal, Udishnu; Demirci, Umit B; Jagirdar, Balaji R; Miele, Philippe

2011-12-16

In today's era of energy crisis and global warming, hydrogen has been projected as a sustainable alternative to depleting CO(2)-emitting fossil fuels. However, its deployment as an energy source is impeded by many issues, one of the most important being storage. Chemical hydrogen storage materials, in particular B-N compounds such as ammonia borane, with a potential storage capacity of 19.6 wt % H(2) and 0.145 kg(H2)L(-1), have been intensively studied from the standpoint of addressing the storage issues. Ammonia borane undergoes dehydrogenation through hydrolysis at room temperature in the presence of a catalyst, but its practical implementation is hindered by several problems affecting all of the chemical compounds in the reaction scheme, including ammonia borane, water, borate byproducts, and hydrogen. In this Minireview, we exhaustively survey the state of the art, discuss the fundamental problems, and, where applicable, propose solutions with the prospect of technological applications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoelectron spectroscopy of B4O4-: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

Science.gov (United States)

Tian, Wen-Juan; Zhao, Li-Juan; Chen, Qiang; Ou, Ting; Xu, Hong-Guang; Zheng, Wei-Jun; Zhai, Hua-Jin; Li, Si-Dian

2015-04-01

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B4O40/- clusters. The measured PES spectra of B4O4- exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of Cs B4O4- (2A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D2h B4O4- (2B2g) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B2O2 core bonded with terminal BO and/or BO2 groups. The same Y-shaped and rhombic structures are also located for the B4O4 neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B4O40/- clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B4O40/- clusters. This work is the first experimental study on a molecular system with an o-bond.

Photoelectron spectroscopy of B4O4 (-): Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters.

Science.gov (United States)

Tian, Wen-Juan; Zhao, Li-Juan; Chen, Qiang; Ou, Ting; Xu, Hong-Guang; Zheng, Wei-Jun; Zhai, Hua-Jin; Li, Si-Dian

2015-04-07

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B4O4 (0/-) clusters. The measured PES spectra of B4O4 (-) exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of Cs B4O4 (-) ((2)A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D2h B4O4 (-) ((2)B2g) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B2O2 core bonded with terminal BO and/or BO2 groups. The same Y-shaped and rhombic structures are also located for the B4O4 neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B4O4 (0/-) clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B4O4 (0/-) clusters. This work is the first experimental study on a molecular system with an o-bond.

Zinc and resin bonded NdFeB magnets

International Nuclear Information System (INIS)

Leonowicz, M.; Kaszuwara, W.

2002-01-01

Zinc and resin bonded NdFeB magnets were processed. Basic magnetic parameters as well as compressive strength were evaluated versus annealing temperature and volume fraction of the bonding agent. For the zinc bonded magnets phase composition was investigated. The additional NdZn 5 phase was found in the Zn bonded magnets after annealing. Comparison of the Zn and resin bonded magnets reveals higher remanence for the former and higher coercivity for the latter. For the Zn and resin bonded magnets, 15 wt.% Zn / 370 o C and 7-10 wt.% resin were chosen as the optimal processing parameters. (author)

Regeneration of ammonia borane from spent fuel materials.

Science.gov (United States)

Summerscales, Owen T; Gordon, John C

2013-07-28

A shift to the hydrogen economy requires the development of an effective hydrogen fuel carrier with high volumetric and gravimetric storage capacity. Ammonia borane (AB) has emerged as a leading candidate due to its light weight and multiple protic (N-H) and hydridic (B-H) hydrogens. As a consequence, much work has been directed towards fine tuning the release of H2 from AB, in addition to its regeneration from the dehydrogenated "spent fuel" materials. This review summarizes the development of these regeneration methodologies.

26 CFR 11.412(c)-11 - Election with respect to bonds.

Science.gov (United States)

2010-04-01

... amount payable at maturity (or, in the case of a bond which is callable prior to maturity, the earliest... 26 Internal Revenue 14 2010-04-01 2010-04-01 false Election with respect to bonds. 11.412(c)-11... OF 1974 § 11.412(c)-11 Election with respect to bonds. (a) In general. Section 412(c)(2)(B) provides...

Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds

Directory of Open Access Journals (Sweden)

Ibon Alkorta

2017-10-01

Full Text Available It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N2, CO, HC≡CH, CH2=CH2, C3H6, PH3, H2S, HCN, H2O, H2CO and NH3 and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H2O, F2, Cl2, Br2, ClF, BrCl, H3SiF, H3GeF, F2CO, CO2, N2O, NO2F, PH2F, AsH2F, SO2, SeO2, SF2, and SeF2 can be represented to good approximation by means of the equation D e = c ′ N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ′ is a constant, conveniently chosen to have the value 1.00 kJ mol−1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1 the hydrogen bond; (2 the halogen bond; (3 the tetrel bond; (4 the pnictogen bond; and (5 the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III Acetylacetonate

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Ebru Ünel Barın

2015-06-01

Full Text Available The catalytic activity of ruthenium(III acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II species is formed in situ from the reduction of ruthenium(III and characterized using UV-Visible, Fourier transform infrared (FTIR, 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II species is mer-[Ru(N2Me43(acacH]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II catalyst formed from the reduction of ruthenium(III acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds.

Science.gov (United States)

Alkorta, Ibon; Legon, Anthony C

2017-10-23

It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N₂, CO, HC≡CH, CH₂=CH₂, C₃H₆, PH₃, H₂S, HCN, H₂O, H₂CO and NH₃) and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H₂O, F₂, Cl₂, Br₂, ClF, BrCl, H₃SiF, H₃GeF, F₂CO, CO₂, N₂O, NO₂F, PH₂F, AsH₂F, SO₂, SeO₂, SF₂, and SeF₂) can be represented to good approximation by means of the equation D e = c ' N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ' is a constant, conveniently chosen to have the value 1.00 kJ mol -1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1) the hydrogen bond; (2) the halogen bond; (3) the tetrel bond; (4) the pnictogen bond; and (5) the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

Preparation and properties of isotropic Nd-Fe-B bonded magnets with sodium silicate binder

Energy Technology Data Exchange (ETDEWEB)

Liu, W.Q.; Hu, R.J.; Yue, M., E-mail: yueming@bjut.edu.cn; Yin, Y.X.; Zhang, D.T.

2017-08-01

Graphical abstract: To improve the working temperature of bonded Nd-Fe-B magnets, the heat-resistant binder, sodium silicate, was used to prepare new type bonded Nd-Fe-B magnets. The three-dimensional Si-O-Si structure formed in the curing process has excellent strength; it can ensure that the bonded magnets have a certain shape and usable magnetic properties when working at 200 °C. - Highlights: • Sodium silicate enables bonded Nd-Fe-B magnets to be used for higher operation temperatures. • The sodium silicate bonded magnets exhibit usable maximum energy product of 4.057 MGOe at 200 °C. • The compressive strength of sodium silicate bonded magnets is twice bigger than that of epoxy resin bonded magnets. - Abstract: In present study, sodium silicate, a kind of heat-resistant binder, was used to prepare bonded Nd-Fe-B magnets with improved thermal stability and mechanical strength. Effect of curing temperature and curing time of the new binder to the magnetic properties, microstructure, and mechanical strength of the magnets was systematically investigated. Fracture surface morphology observation show that sodium silicate in bonded magnets could completely be cured at 175 °C for 40 min, and the magnets prepared under this condition exhibit optimal properties. They exhibit usable magnetic properties of B{sub r} of 4.66 kGs, H{sub cj} of 4.84 kOe, and (BH){sub max} of 4.06 MGOe at 200 °C. Moreover, the magnets possess high compressive strength of 63 MPa.

A new luminescent montmorillonite/borane nanocomposite

Czech Academy of Sciences Publication Activity Database

Kolská, Z.; Matoušek, J.; Čapková, P.; Braborec, Jakub; Benkocká, M.; Černá, H.; Londesborough, Michael Geoffrey Stephen

2015-01-01

Roč. 118, DEC (2015), s. 295-300 ISSN 0169-1317 Institutional support: RVO:61388980 Keywords : Luminophore * Montmorillonite/borane nanocomposite * X-ray photoelectron spectroscopy * X-ray diffraction * UV–Vis spectra Subject RIV: CA - Inorganic Chemistry Impact factor: 2.586, year: 2015

Hydrogen production using ammonia borane

Science.gov (United States)

Hamilton, Charles W; Baker, R. Thomas; Semelsberger, Troy A; Shrestha, Roshan P

2013-12-24

Hydrogen ("H.sub.2") is produced when ammonia borane reacts with a catalyst complex of the formula L.sub.nM-X wherein M is a base metal such as iron, X is an anionic nitrogen- or phosphorus-based ligand or hydride, and L is a neutral ancillary ligand that is a neutral monodentate or polydentate ligand.

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

Science.gov (United States)

Davis, Benjamin L; Rekken, Brian D

2014-04-01

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

Molecular and crystal structure of nido-9-C5H5N-11-I-7,8-C2B9H10: supramolecular architecture via hydrogen bonding X-H...I (X = B, C)

International Nuclear Information System (INIS)

Polyanskaya, T.M.

2006-01-01

A monocrystal X-ray diffraction study of a new iodine-containing cluster compound 9-(pyridine)-11-iodo-decahydro-7,8-dicarba-nido-undecaborane [9-C 5 H 5 N-11-I-7,8-C 2 B 9 H 10 ] has been performed. Crystal data: C 7 H 15 B 9 NI, M = 337.39, monoclinic, space group P2 1 /c, unit cell parameters: a=9.348(1) A, b=11.159(1) A, c=13.442(2) A, β=98.13(1) deg, V=1388.1(5) A 3 , Z=4, d calc = 1.614 g/cm 3 , T = 295 K, F(000)=648, μ=2.276 mm -1 . The structure was solved by a direct method and refined in the full-matrix anisotropic approximation (isotropic for hydrogen atoms) to final agreement factors R 1 = 0.0254, wR 2 = 0.0454 for 2437 I hkl >2σ I from 3590 measured I hkl (an Enraf-Nonius CAD-4 diffractometer, λMoK α , graphite monochromator, θ/2θ-scanning). The molecules are joined into a supramolecular assembly by hydrogen bonds X-H...I (X = B, C) [ru

Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

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Tetsuo Umegaki

2015-07-01

Full Text Available Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based catalyst. The reaction performance depends on the morphology and/or structure of these materials. In this review, we survey the research on nanostructured materials, especially porous materials for hydrogen generation from hydrolysis of ammonia borane.

Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane.

Science.gov (United States)

Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

2015-07-21

Hydrogen storage is still one of the most significant issues hindering the development of a "hydrogen energy economy". Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based catalyst. The reaction performance depends on the morphology and/or structure of these materials. In this review, we survey the research on nanostructured materials, especially porous materials for hydrogen generation from hydrolysis of ammonia borane.

Reactivity of Amine/E(C6F53 (E = B, Al Lewis Pairs toward Linear and Cyclic Acrylic Monomers: Hydrogenation vs. Polymerization

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Jiawei Chen

2015-05-01

Full Text Available This work reveals the contrasting reactivity of amine/E(C6F53 (E = B, Al Lewis pairs toward linear and cyclic acrylic monomers, methyl methacrylate (MMA and biorenewable γ-methyl-α-methylene-γ-butyrolactone (γMMBL. While mixing of 2,2,6,6-tetramethylpiperidine (TMP and B(C6F53 leads to a frustrated Lewis pair (FLP, Et3N reacts with B(C6F53 to form disproportionation products, ammonium hydridoborate ionic pair and iminium zwitterion. On the other hand, the stoichiometric reaction of either TMP or Et3N with Al(C6F53 leads to clean formation of a classic Lewis adduct (CLA. Neither TMP nor Et3N, when paired with E(C6F53, polymerizes MMA, but the Et3N/2B(C6F53 pair promotes transfer hydrogenation of MMA to form methyl isobutyrate. In contrast, the amine/E(C6F53 pairs promote rapid polymerization of γMMBL carrying the more reactive exocyclic methylene moiety, achieving full conversion in less than 3 min even at a low catalyst loading of 0.0625 mol %. TMP is more effective than Et3N for the polymerization when paired with either the borane or the alane, while the alane exhibits higher polymerization activity than the borane when paired with Et3N. Overall, the TMP/Al(C6F53 system exhibits the highest polymerization activity, achieving a maximum turn-over frequency of 96,000 h−1 at 0.125 mol % of catalyst loading, producing high molecular weight PγMMBL with Mn = 1.29 × 105 g∙mol−1.

Kinetics of hydrogen release from dissolutions of ammonia borane in different ionic liquids

International Nuclear Information System (INIS)

Valero-Pedraza, María José; Martín-Cortés, Alexandra; Navarrete, Alexander; Bermejo, María Dolores; Martín, Ángel

2015-01-01

Ammonia borane is a promising hydrogen storage material that liberates hydrogen by thermolysis at moderate temperatures, but it also presents major limitations for practical applications including a long induction time before the initiation of hydrogen release and a difficult regeneration. Previous works have demonstrated that by dissolution of ammonia borane into several ionic liquids, and particularly in 1-butyl-3-methylimidazolium chloride bmimCl, the induction period at the beginning of the thermolysis is eliminated, but some problems persist, including foaming and the formation of a residue after thermolysis that is insoluble in the ionic liquid. In this work, the release of hydrogen from ammonia borane dissolved in different ionic liquids has been analyzed, measuring the kinetics of hydrogen release, visually following the evolution of the sample during the process using pressure glass tube reactors, and analyzing the residue by spectroscopic techniques. While dissolutions of ammonia borane in most ionic liquids analyzed show similar properties as dissolutions in bmimCl, using ionic liquids with bis(trifluoromethylsulfanyl)imide Tf_2N anion the foaming problem is reduced, and in some cases the residue remains dissolved in the ionic liquid, while with ionic liquids with choline anion higher hydrogen yields are achieved that indicate that the decomposition of ammonia borane proceeds through a different path. - Highlights: • Hydrogen release from ammonia borane dissolved in 13 ionic liquids has been studied. • Induction time is shortened and hydrogen release rate is accelerated in all cases. • The best results are obtained using ionic liquids with Tf_2N anion. • Ch cation ionic liquids enable higher H_2 yield, but cyclotriborazane is produced.

The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

DEFF Research Database (Denmark)

Clarke, Celia; Fox, David J; Pedersen, Daniel Sejer

2009-01-01

Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing...... that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just like their phosphine oxide counterparts. The obtained data show that phosphine oxides are easily lithiated and undergo phosphoryl transfer much more readily and faster than phosphine sulfides and phosphine...... boranes. The observations suggest that it would be possible to perform reactions involving phosphine oxides in the presence of phosphine boranes or phosphine sulfides, potentially allowing regioselective alkylation of phosphine oxides in the presence of phosphine boranes or phosphine sulfides....

Dihydrogen Phosphate Stabilized Ruthenium(0 Nanoparticles: Efficient Nanocatalyst for The Hydrolysis of Ammonia-Borane at Room Temperature

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Feyyaz Durap

2015-07-01

Full Text Available Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0 nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 ± 0.9 nm acting as a water-dispersible nanocatalyst in the hydrolysis of ammonia-borane. They provide an initial turnover frequency (TOF value of 80 min−1 in hydrogen generation from the hydrolysis of ammonia-borane at room temperature. Moreover, the high stability of these ruthenium(0 nanoparticles makes them long-lived and reusable nanocatalysts for the hydrolysis of ammonia-borane. They provide 56,800 total turnovers and retain ~80% of their initial activity even at the fifth catalytic run in the hydrolysis of ammonia-borane at room temperature.

Dihydrogen Phosphate Stabilized Ruthenium(0) Nanoparticles: Efficient Nanocatalyst for The Hydrolysis of Ammonia-Borane at Room Temperature

Science.gov (United States)

Durap, Feyyaz; Caliskan, Salim; Özkar, Saim; Karakas, Kadir; Zahmakiran, Mehmet

2015-01-01

Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0) nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 ± 0.9 nm acting as a water-dispersible nanocatalyst in the hydrolysis of ammonia-borane. They provide an initial turnover frequency (TOF) value of 80 min−1 in hydrogen generation from the hydrolysis of ammonia-borane at room temperature. Moreover, the high stability of these ruthenium(0) nanoparticles makes them long-lived and reusable nanocatalysts for the hydrolysis of ammonia-borane. They provide 56,800 total turnovers and retain ~80% of their initial activity even at the fifth catalytic run in the hydrolysis of ammonia-borane at room temperature. PMID:28793435

Bismuth-boron multiple bonding in BiB_2O"- and Bi_2B"-

International Nuclear Information System (INIS)

Jian, Tian; Cheung, Ling Fung; Chen, Teng-Teng; Wang, Lai-Sheng

2017-01-01

Despite its electron deficiency, boron is versatile in forming multiple bonds. Transition-metal-boron double bonding is known, but boron-metal triple bonds have been elusive. Two bismuth boron cluster anions, BiB_2O"- and Bi_2B"-, containing triple and double B-Bi bonds are presented. The BiB_2O"- and Bi_2B"- clusters are produced by laser vaporization of a mixed B/Bi target and characterized by photoelectron spectroscopy and ab initio calculations. Well-resolved photoelectron spectra are obtained and interpreted with the help of ab initio calculations, which show that both species are linear. Chemical bonding analyses reveal that Bi forms triple and double bonds with boron in BiB_2O"- ([Bi≡B-B≡O]"-) and Bi_2B"- ([Bi=B=Bi]"-), respectively. The Bi-B double and triple bond strengths are calculated to be 3.21 and 4.70 eV, respectively. This is the first experimental observation of Bi-B double and triple bonds, opening the door to design main-group metal-boron complexes with multiple bonding. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds.

Science.gov (United States)

Choi, Jongwook; Choliy, Yuriy; Zhang, Xiawei; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

2009-11-04

(PCP)Ir (PCP = kappa(3)-C(6)H(3)-2,6-[CH(2)P(t-Bu)(2)](2)) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH(3))(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [k(CH(3))(OAr)/k(CD(3))(OAr) = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and alpha-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by beta-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp(3))-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.

Polyhedral Boranes: A Versatile Building Block for Nanoporous Materials

Science.gov (United States)

Clingerman, Daniel Jon

The studies described in this dissertation examine several new concepts related to polyhedral boranes and their applications towards the synthesis of novel nanoporous materials. The unique thermal and chemical robustness, rigidity, quasi-spherical geometry, and high boron content of polyhedral boranes are explored to generate materials not possible with typical organic synthons. Aside from the fundamental synthetic work, this work was also aimed at solving larger global issues such as energy storage and new routes to therapeutics. Chapter 2 highlights the discovery of the first highly porous carborane-based metal-organic framework, where the spherical nature of the carborane increases volumetric surface area without reducing pore volume. Chapter 3 examines the first tritopic carborane-based ligand and the stabilizing effect the rigid, sterically bulky carboranyl groups have on highly porous topologies not stable with typical organic ligands. Chapters 4 and 5 describe the use of polyhedral borane-based ligands as a means to influence and generate unexpected topologies. Lastly, chapter 6 explores using a simple carborane-based ligand that harnesses the power of coordination-driven assembly to rapidly generate a high boron-containing supramolecular cuboctahedron.

Anion capture and sensing with cationic boranes: on the synergy of Coulombic effects and onium ion-centred Lewis acidity.

Science.gov (United States)

Zhao, Haiyan; Leamer, Lauren A; Gabbaï, François P

2013-06-21

Stimulated by the growing importance and recognized toxicity of anions such as fluoride, cyanide and azides, we have, in the past few years, developed a family of Lewis acidic triarylboranes that can be used for the complexation of these anions in organic and protic solvents, including water. A central aspect of our approach lies in the decoration of the boranes with peripheral ammonium, phosphonium, sulfonium stibonium or telluronium groups. The presence of these cationic groups provides a Coulombic drive for the capture of the anion, leading to boranes that can be used in aqueous solutions where anion hydration and/or protonation are usually competitive. The anion affinity of these boranes can be markedly enhanced by narrowing the separation between the anion binding site (i.e. the boron atom) and the onium ion. In such systems, the latent Lewis acidity of the onium ion also plays a role as manifested by the formation of B-X→E (E = P, S, Sb, or Te; X = F, CN or N3) chelate motifs that provide additional stability to the resulting complexes. These effects, which are maximum in stibonium and telluronium boranes, show that the Lewis acidity of heavy onium ions can be exploited for anion coordination and capture. The significance of these advances is illustrated by the development of applications in anion sensing, fluorination chemistry and (18)F radiolabeling for positron emission tomography.

Recent development in bonded NdFeB magnets

International Nuclear Information System (INIS)

Ma, B.M.; Herchenroeder, J.W.; Smith, B.; Suda, M.; Brown, D.N.; Chen, Z.

2002-01-01

The magnetic properties of isotropic NdFeB powders used for bonded magnets are compared. The characteristics of two newly developed powders, namely MQP-13-9 and MQP-S-9-8 were compared with respect to existing powders. The advantages of spherical powders for injection molding were highlighted. Development targets for the 180 deg. C application and NdFeB nanocomposites were also discussed

Efficient regeneration of partially spent ammonia borane fuel

International Nuclear Information System (INIS)

Davis, Benjamin Lee; Gordon, John C.; Stephens, Frances; Dixon, David A.; Matus, Myrna H.

2008-01-01

A necessary target in realizing a hydrogen (H 2 ) economy, especially for the transportation sector, is its storage for controlled delivery, presumably to an energy producing fuel cell. In this vein, the U.S. Department of Energy's (DOE) Centers of Excellence (CoE) in Hydrogen Storage have pursued different methodologies, including metal hydrides, chemical hydrides, and sorbents, for the expressed purpose of supplanting gasoline's current > 300 mile driving range. Chemical hydrogen storage has been dominated by one appealing material, ammonia borane (H 3 B-NH 3 , AB), due to its high gravimetric capacity of hydrogen (19.6 wt %) and low molecular weight (30.7 g mol -1 ). In addition, AB has both hydridic and protic moieties, yielding a material from which H2 can be readily released. As such, a number of publications have described H 2 release from amine boranes, yielding various rates depending on the method applied. Even though the viability of any chemical hydrogen storage system is critically dependent on efficient recyclability, reports on the latter subject are sparse, invoke the use of high energy reducing agents, and suffer from low yields. For example, the DOE recently decided to no longer pursue the use of NaBH 4 as a H 2 storage material, in part because of inefficient regeneration. We thus endeavored to find an energy efficient regeneration process for the spent fuel from H 2 depleted AB with a minimum number of steps.

Hair coat characteristics and thermophysiological stress response of Nguni and Boran cows raised under hot environmental conditions

Science.gov (United States)

Katiyatiya, C. L. F.; Muchenje, V.

2017-12-01

Breed, age, coat colour, month and temperature humidity index (THI) influence on body weight (W), body condition score (BCS), thermophysiological variables (rectal temperature (Tr), skin temperature (Tsk)) and hair length was studied in Nguni ( n = 19) and Boran ( n = 16). As a result of this study, breed influenced W, BCS and Tsk on the neck and belly ( P cows were higher than the Boran cows. Hair length of both breeds increased from February to August. The THI influenced thermophysiological variables ( P cows (3-8 years) had lower weight and high Tr and Tsk ( P cows had high neck and thurl temperatures in June while Boran cows had the highest in August ( P cows had increased BCS. Nguni cows with red, fawn and white cows had high BCS. Fawn-coloured Nguni cows and white-brown Boran cows had the more weight than cows with other colours compared in the study. White-red Nguni and Boran cows recorded the highest Tr. For Nguni cows, neck and belly temperatures were significantly ( P cows had significant ( P cows were more adapted to the prevailing bioclimatic changes. However, Boran cows have the potential of performing well under heat stress conditions over time.

Recent Advances in Ring-Opening Functionalization of Cycloalkanols by C-C σ-Bond Cleavage.

Science.gov (United States)

Wu, Xinxin; Zhu, Chen

2018-06-01

Cycloalkanols prove to be privileged precursors for the synthesis of distally substituted alkyl ketones and polycyclic aromatic hydrocarbons (PAHs) by virtue of cleavage of their cyclic C-C bonds. Direct functionalization of cyclobutanols to build up other chemical bonds (e. g., C-F, C-Cl, C-Br, C-N, C-S, C-Se, C-C, etc.) has been achieved by using the ring-opening strategy. Mechanistically, the C-C cleavage of cyclobutanols can be involved in two pathways: (a) transition-metal catalyzed β-carbon elimination; (b) radical-mediated 'radical clock'-type ring opening. The recent advances of our group for the ring-opening functionalization of tertiary cycloalkanols are described in this account. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and chemical bond characteristics of LaB6

International Nuclear Information System (INIS)

Bai Lina; Ma Ning; Liu Fengli

2009-01-01

The structure and chemical bond characteristics of LaB 6 have been achieved by means of the density functional theory using the state-of-the-art full-potential linearized augmented plane wave (FPLAPW) method, which are implemented within the EXCITING code. The results show our optimized lattice constant a (4.158 A), parameter z (0.1981) and bulk modulus B (170.4 GPa) are in good agreement with the corresponding experimental data. Electron localization function (ELF) shows the La-La bond mainly is ionic bond, La-B bond is between ionic and covalent bond while the covalent bond between the nearest neighbor B atoms (B2 and B3) is a little stronger than that between the nearer neighbor B atoms (B1 and B4).

Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon

KAUST Repository

Berke, Heinz; Barman, Smair; Remhof, Arndt; Koitz, Ralph; Iannuzzi, Marcella; Blacque, Olivier; Yan, Yigang; Fox, Thomas; Hutter, Jü rg; Zü ttel, Andreas

2017-01-01

We report a novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation utilizing gaseous diborane. The covalently confined amine borane derivative decorated on the framework backbone is stable when

Intermolecular and very strong intramolecular C-SeO/N chalcogen bonds in nitrophenyl selenocyanate crystals.

Science.gov (United States)

Wang, Hui; Liu, Ju; Wang, Weizhou

2018-02-14

Single-crystal X-ray diffraction reveals that polymorphic ortho-nitrophenyl selenocyanate (o-NSC, crystals 1a and 1b) and monomorphic para-nitrophenyl selenocyanate (p-NSC, crystal 2) crystals are all stabilized mainly by intermolecular and very strong intramolecular C-SeO/N chalcogen bonds, as well as by other different interactions. Thermogravimetric (TG) and differential scanning calorimetry thermogram (DSC) analyses show that the starting decomposition temperatures and melting points of the three crystals are different, following the order 1b > 1a > 2, which is consistent with the structural characteristics of the crystals. In addition, atoms in molecules (AIM) and natural bond orbital (NBO) analyses indicate that the total strengths of the C-SeO and C-SeN chalcogen bonds decrease in the order 1b > 1a > 2. This study could be significant for engineering functional crystals based on robust C-SeO and C-SeN chalcogen bonds, and for designing drugs containing selenium as well as understanding their interaction in biosystems.

Bipolaron formation in B/sub 12/ and (B/sub 11/C)/sup +/ icosahedra

International Nuclear Information System (INIS)

Howard, I.A.; Beckel, C.L.; Emin, D.

1987-01-01

Boron carbides, B/sub 1-x/C/sub x/ with 0.085 ≤ x ≤ 0.200, generally contain both B/sub 12/ and B/sub 11/C icosahedra. However, the electronic transport with 0.1 ≤ x ≤ 0.2 is believed to occur by means of bipolaron hopping between only B/sub 11/C icosahedra. The authors have calculated the changes in energy, atomic positions and charge distribution when a pair of electrons is added to the isoelectronic icosahedral clusters B/sub 12/ and (B/sub 11/C)/sup +/. They simulate an icosahedron in a neutral lattice by bonding the icosahedral atoms to hydrogenic atoms which the authors constrain to be neutral. The computations are performed with a self-consistent molecular-orbital method, PRDDO. They find a total energy reduction of -- 3.7 eV for two electrons added to a B/sub 12/ icosahedron. Of this, -- 2.7 eV arises from the electrons filling the icosahedron's bonding orbitals. The remaining -- 1.0 eV comes from the contraction of the icosahedron's radius by -- 0.09 A. For two electrons added to a (B/sub 11/C)/sup +/ icosahedron the authors find a total energy reduction of -- 18.2 eV. Of this, -- 16.5 eV arises from filling the icosahedron's bonding orbitals. The remainder arises from a -- 0.09 A contraction of the icosahedron's radius. Thus, the authors find (B/sub 11/C)/sup +/ icosahedra to be strongly energetically favored over B/sub 12/ icosahedra as bipolaron sites. The positive charge associated with a (B/sub 11/C)/sup +/ icosahedron is distributed over the eleven boron atoms. Concomitantly, they find the added two electrons of the bipolaron to be distributed over all twelve sites of the B/sub 11/C icosahedron. They find the energy difference between an electron pair added to B/sub 12/ and (B/sub 11/C)/sup +/ icosahedra to arise principally from the increased Coulombic attraction provided by the extra positive charge of the (B/sub 11/C)/sup +/ icosahedron

Forging C-C Bonds Through Decarbonylation of Aryl Ketones.

Science.gov (United States)

Somerville, Rosie J; Martin, Ruben

2017-06-06

The ability of nickel to cleave strong σ-bonds is again in the spotlight after a recent report that demonstrates the feasibility of using nickel complexes to promote decarbonylation of diaryl ketones. This transformation involves the cleavage of two strong C-C(O) bonds and avoids the use of noble metals, hence reinforcing the potential of decarbonylation as a technique for forging C-C bonds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

Science.gov (United States)

Pandey, Krishna K

2012-03-21

Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of

Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane.

Science.gov (United States)

Akbayrak, Serdar; Tonbul, Yalçın; Özkar, Saim

2016-07-05

Ruthenium(0) nanoparticles supported on ceria (Ru(0)/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru(0)/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru(0)/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru(0)/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru(0)/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, Ea = 60 ± 7 kJ mol(-1) for the nucleation and Ea = 47 ± 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of Ea = 51 ± 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane.

Enhanced catalytic activity of the nanostructured Co-W-B film catalysts for hydrogen evolution from the hydrolysis of ammonia borane.

Science.gov (United States)

Li, Chao; Wang, Dan; Wang, Yan; Li, Guode; Hu, Guijuan; Wu, Shiwei; Cao, Zhongqiu; Zhang, Ke

2018-08-15

In this work, nanostructured Co-W-B films are successfully synthesized on the foam sponge by electroless plating method and employed as the catalysts with enhanced catalytic activity towards hydrogen evolution from the hydrolysis of ammonia borane (NH 3 BH 3 , AB) at room temperature. The particle size of the as-prepared Co-W-B film catalysts is varied by adjusting the depositional pH value to identify the most suitable particle size for hydrogen evolution of AB hydrolysis. The Co-W-B film catalyst with the particle size of about 67.3 nm shows the highest catalytic activity and can reach a hydrogen generation rate of 3327.7 mL min -1 g cat -1 at 298 K. The activation energy of the hydrolysis reaction of AB is determined to be 32.2 kJ mol -1 . Remarkably, the as-obtained Co-W-B film is also a reusable catalyst preserving 78.4% of their initial catalytic activity even after 5 cycles in hydrolysis of AB at room temperature. Thus, the enhanced catalytic activity illustrates that the Co-W-B film is a promising catalyst for AB hydrolytic dehydrogenation in fuel cells and the related fields. Copyright © 2018 Elsevier Inc. All rights reserved.

Binder Jetting: A Novel NdFeB Bonded Magnet Fabrication Process

Science.gov (United States)

Paranthaman, M. Parans; Shafer, Christopher S.; Elliott, Amy M.; Siddel, Derek H.; McGuire, Michael A.; Springfield, Robert M.; Martin, Josh; Fredette, Robert; Ormerod, John

2016-07-01

The goal of this research is to fabricate near-net-shape isotropic (Nd)2Fe14B-based (NdFeB) bonded magnets using a three dimensional printing process to compete with conventional injection molding techniques used for bonded magnets. Additive manufacturing minimizes the waste of critical materials and allows for the creation of complex shapes and sizes. The binder jetting process works similarly to an inkjet printer. A print-head passes over a bed of NdFeB powder and deposits a polymer binding agent to bind the layer of particles together. The bound powder is then coated with another layer of powder, building the desired shape in successive layers of bonded powder. Upon completion, the green part and surrounding powders are placed in an oven at temperatures between 100°C and 150°C for 4-6 h to cure the binder. After curing, the excess powder can be brushed away to reveal the completed "green" part. Green magnet parts were then infiltrated with a clear urethane resin to achieve the measured density of the magnet of 3.47 g/cm3 close to 46% relative to the NdFeB single crystal density of 7.6 g/cm3. Magnetic measurements indicate that there is no degradation in the magnetic properties. This study provides a new pathway for preparing near-net-shape bonded magnets for various magnetic applications.

Fluoride ion recognition by chelating and cationic boranes.

Science.gov (United States)

Hudnall, Todd W; Chiu, Ching-Wen; Gabbaï, François P

2009-02-17

Because of the ubiquity of fluoride ions and their potential toxicity at high doses, researchers would like to design receptors that selectively detect this anion. Fluoride is found in drinking water, toothpaste, and osteoporosis drugs. In addition, fluoride ions also can be detected as an indicator of uranium enrichment (via hydrolysis of UF(6)) or of the chemical warfare agent sarin, which releases the ion upon hydrolysis. However, because of its high hydration enthalpy, the fluoride anion is one of the most challenging targets for anion recognition. Among the various recognition strategies that are available, researchers have focused a great deal of attention on Lewis acidic boron compounds. These molecules typically interact with fluoride anions to form the corresponding fluoroborate species. In the case of simple triarylboranes, the fluoroborates are formed in organic solvents but not in water. To overcome this limitation, this Account examines various methods we have pursued to increase the fluoride-binding properties of boron-based receptors. We first considered the use of bifunctional boranes, which chelate the fluoride anion, such as 1,8-diborylnaphthalenes or heteronuclear 1-boryl-8-mercurio-naphthalenes. In these molecules, the neighboring Lewis acidic atoms can cooperatively interact with the anionic guest. Although the fluoride binding constants of the bifunctional compounds exceed those of neutral monofunctional boranes by several orders of magnitude, the incompatibility of these systems with aqueous media limits their utility. More recently, we have examined simple triarylboranes whose ligands are decorated by cationic ammonium or phosphonium groups. These cationic groups increase the electrophilic character of these boranes, and unlike their neutral analogs, they are able to complex fluoride in aqueous media. We have also considered cationic boranes, which form chelate complexes with fluoride anions. Our work demonstrates that Coulombic and chelate

Facile insertion of a cyclic alkyl(amino) carbene carbon into the B-B bond of diboron(4) reagents.

Science.gov (United States)

Eichhorn, Antonius F; Kuehn, Laura; Marder, Todd B; Radius, Udo

2017-10-24

We report herein the room temperature insertion of the carbene carbon atom of the cyclic (alkyl)(amino) carbene cAAC Me into the B-B single bonds of the diboron(4) compounds B 2 pin 2 , B 2 cat 2 , B 2 neop 2 , and B 2 eg 2 (pin = pinacolato, cat = catecholato, neop = neopentylglycolato, eg = ethyleneglycolato).

Ovarian follicular dynamics in purebred and crossbred Boran cows ...

African Journals Online (AJOL)

Tuoyo Aghomotsegin

2016-08-17

Aug 17, 2016 ... purebred Boran cattle, adapted to Ethiopian conditions for centuries and ... fertility than crossbreds, would exhibit a different pattern of ovarian ..... Influence of dietary supplementation and partial suckling on body weight and ...

Revealing the synergetic effects in Ni nanoparticle-carbon nanotube hybrids by scanning transmission X-ray microscopy and their application in the hydrolysis of ammonia borane.

Science.gov (United States)

Zhao, Guanqi; Zhong, Jun; Wang, Jian; Sham, Tsun-Kong; Sun, Xuhui; Lee, Shuit-Tong

2015-06-07

The hybrids of carbon nanotubes (CNTs) and the supported Ni nanoparticles (NPs) have been studied by scanning transmission X-ray microscopy (STXM) and tested by the hydrolysis reaction of ammonia borane (AB, NH3BH3). Data clearly showed the existence of a strong interaction between Ni NPs and thin CNTs (C-O-Ni bonds), which favored the tunable (buffer) electronic structure of Ni NPs facilitating the catalytic process. The hydrolysis process of AB confirmed the hypothesis that the hybrids with a strong interfacial interaction would show superior catalytic performance, while the hybrids with a weak interfacial interaction show poor performance. Our results provide a wealth of detailed information regarding the electronic structure of the NP-CNT hybrids and provide guidance towards the rational design of high-performance catalysts for energy applications.

Alkane Activation at Ambient Temperatures: Unusual Selectivities, C-C, C-H Bond Scission versus C-C Bond Coupling

NARCIS (Netherlands)

Trionfetti, C.; Agiral, A.; Gardeniers, Johannes G.E.; Lefferts, Leonardus; Seshan, Kulathuiyer

2008-01-01

Activating bonds: A cold plasma generated by dielectric barrier discharge in a microreactor converts alkanes (C1–C3) at atmospheric pressure. Large amounts of products with higher molecular weight than the starting hydrocarbons are observed showing that C-H activation at lower T favourably leads to

Metal and alloy nanoparticles by amine-borane reduction of metal salts by solid-phase synthesis: atom economy and green process.

Science.gov (United States)

Sanyal, Udishnu; Jagirdar, Balaji R

2012-12-03

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNH(x) polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Unusual Closure of the Ten-Vertex Nido Cage via Alkylation: Regiospecific Synthesis of 3-Alkyl Derivatives of closo-1,2-C2B8H10

Czech Academy of Sciences Publication Activity Database

Bakardjiev, Mario; Štíbr, Bohumil; Tok, Oleg L.; Holub, Josef

2018-01-01

Roč. 57, č. 3 (2018), s. 1368-1372 ISSN 0020-1669 R&D Projects: GA ČR(CZ) GA16-01618S Institutional support: RVO:61388980 Keywords : electrophilic halogenation * nido-5,6-c2b8h12 * carboranes * decaborane * boranes * 5,6-dicarba-nido-decaborane(12) Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 4.857, year: 2016

Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

Science.gov (United States)

Heshmat, Mojgan; Privalov, Timofei

2017-07-06

By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 sp...... results are supported by ab initio calculations at the B3LYP-PCM/6-311++G(d,p) + LanL2DZ∗ level....

Wetting of B4C, TiC and graphite substrates by molten Mg

International Nuclear Information System (INIS)

Zhang Dan; Shen Ping; Shi Laixin; Jiang Qichuan

2011-01-01

Highlights: → The wettability of TiC, B4C and C by molten Mg was determined using an improved sessile drop method. → A new method to evaluate the wetting behavior coupled with evaporation and reaction was proposed. → The bonding characteristics in the Mg/B4C, Mg/TiC and Mg/graphite systems were evaluated. - Abstract: The isotherm wetting of B 4 C, TiC and graphite substrates by molten Mg was studied in a flowing Ar atmosphere at 973-1173 K using an improved sessile drop method. The initial contact angles are in the ranges of 95-87 deg., 74-60 deg. and 142-124 deg., respectively, moderately depending on the temperature. All the systems are non-reactive in nature; however, the presence of impurity of free boron at the B 4 C surface gave rise to the chemical reaction with molten Mg and thus promoted the wettability to a certain degree. A new method was proposed to evaluate the wetting behavior coupled with evaporation and chemical reaction. Furthermore, based on the comparison of the work of adhesion and cohesion, the bonding in the Mg/B 4 C and Mg/TiC systems is presumably mainly chemical while that in the Mg/graphite system is physical.

Molecular-Level Processing of Si-(B)-C Materials with Tailored Nano/Microstructures.

Science.gov (United States)

Schmidt, Marion; Durif, Charlotte; Acosta, Emanoelle Diz; Salameh, Chrystelle; Plaisantin, Hervé; Miele, Philippe; Backov, Rénal; Machado, Ricardo; Gervais, Christel; Alauzun, Johan G; Chollon, Georges; Bernard, Samuel

2017-12-01

The design of Si-(B)-C materials is investigated, with detailed insight into the precursor chemistry and processing, the precursor-to-ceramic transformation, and the ceramic microstructural evolution at high temperatures. In the early stage of the process, the reaction between allylhydridopolycarbosilane (AHPCS) and borane dimethyl sulfide is achieved. This is investigated in detail through solid-state NMR and FTIR spectroscopy and elemental analyses for Si/B ratios ranging from 200 to 30. Boron-based bridges linking AHPCS monomeric fragments act as crosslinking units, extending the processability range of AHPCS and suppressing the distillation of oligomeric fragments during the low-temperature pyrolysis regime. Polymers with low boron contents display appropriate requirements for facile processing in solution, leading to the design of monoliths with hierarchical porosity, significant pore volume, and high specific surface area after pyrolysis. Polymers with high boron contents are more appropriate for the preparation of dense ceramics through direct solid shaping and pyrolysis. We provide a comprehensive study of the thermal decomposition mechanisms, and a subsequent detailed study of the high-temperature behavior of the ceramics produced at 1000 °C. The nanostructure and microstructure of the final SiC-based ceramics are intimately linked to the boron content of the polymers. B 4 C/C/SiC nanocomposites can be obtained from the polymer with the highest boron content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon

KAUST Repository

Berke, Heinz

2017-05-11

We report a novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation utilizing gaseous diborane. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature leading to the development of an unusual borenium type species (-NH=BH2+) ion-paired with hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the -iminodiborane ((--NHB2H5) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.

Friction Stir Welding of Al-B4C Composite Fabricated by Accumulative Roll Bonding: Evaluation of Microstructure and Mechanical Behavior

Science.gov (United States)

Moradi Faradonbeh, Alireza; Shamanian, Morteza; Edris, Hossein; Paidar, Moslem; Bozkurt, Yahya

2018-02-01

In this investigation, friction stir welding (FSW) of Al-B4C composite fabricated by 10 cycles accumulative roll bonding was conducted. In order to investigate the influences of pin geometry on microstructure and mechanical properties, four different pin geometries (cylindrical, square, triangular and hexagonal) were selected. It was found that FSW parameters had a major effect on the fragmentation and distribution of reinforcement particles in stir zone. When the tool travel speed was increased, the distribution of B4C particles was become gradually uniform in the aluminum matrix. The effect of tool rotational speed on the peak temperature was determined to be greater than the tool travel speed. The attained data of tensile properties and microhardness tests showed that the tool travel speed had bilateral effect on the tensile strength. The maximum tensile joint efficiency was obtained as 238% for FSWed of Al-2%B4C composite to annealed base Al sheet.

X-ray spectral and quantum-chemical investigation of electronic structure of 6,9-bis-(ammonia)-nido-decarborane(12)

International Nuclear Information System (INIS)

Yumatov, V.D.; Il'inchik, E.A.; Murakhtanov, V.V.; Dunaev, S.T.; Volkov, V.V.

1993-01-01

Electron structure of 6.9-bis-(ammonia)-nide-decarborane(12), that is, B 10 H 12 (NH 3 ) 2 , is studied by means of ultrasoft X-ray spectroscopy using nitrogen and boron atoms. Calculations of MNDO and ab initio are conducted. Electron structure of ammonia and of /B 10 H 12 / cluster is studied and its variation at complex formation is investigated, as well. On the basis of calculations one shows, that some vacant orbitals belonging to borane cluster participate into chemical bond of donor-acceptor type among the fragments. Presence of π-component of bond between NH 3 and /B 10 H 12 / and occurrence of four-central bound in borane cluster are detected

Characterization of ammonia borane for chemical propulsion applications

Science.gov (United States)

Weismiller, Michael

Ammonia borane (NH3BH3; AB), which has a hydrogen content of 19.6% by weight, has been studied recently as a potential means of hydrogen storage for use in fuel cell applications. Its gaseous decomposition products have a very low molecular weight, which makes AB attractive in a propulsion application, since specific impulse is inversely related to the molecular weight of the products. AB also contains boron, which is a fuel of interest for solid propellants because of its high energy density per unit volume. Although boron particles are difficult to ignite due to their passivation layer, the boron molecularly bound in AB may react more readily. The concept of fuel depots in low-earth orbit has been proposed for use in deep space exploration. These would require propellants that are easily storable for long periods of time. AB is a solid at standard temperature and pressure and would not suffer from mass loss due to boil-off like cryogenic hydrogen. The goal of this work is to evaluate AB as a viable fuel in chemical propulsion. Many studies have examined AB decomposition at slow heating rates, but in a propellant, AB will experience rapid heating. Since heating rate has been shown to affect the thermolysis pathways in energetic materials, AB thermolysis was studied at high heating rates using molecular dynamics simulations with a ReaxFF reactive force field and experimental studies with a confined rapid thermolysis set-up using time-of-flight mass spectrometry and FTIR absorption spectroscopy diagnostics. Experimental results showed the formation of NH3, H2NBH2, H2, and at later times, c-(N3B3H6) in the gas phase, while polymer formation was observed in the condensed phase. Molecular dynamics simulations provided an atomistic description of the reactions which likely form these compounds. Another subject which required investigation was the reaction of AB in oxidizing environments, as there were no previous studies in the literature. Oxygen bond descriptions were

Reactive carbon-chain molecules: synthesis of 1-diazo-2,4-pentadiyne and spectroscopic characterization of triplet pentadiynylidene (H-C[triple bond]C-:C-C[triple bond]C-H).

Science.gov (United States)

Bowling, Nathan P; Halter, Robert J; Hodges, Jonathan A; Seburg, Randal A; Thomas, Phillip S; Simmons, Christopher S; Stanton, John F; McMahon, Robert J

2006-03-15

1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C[triple bond]C-:C-C[triple bond]C-H). Theory predicts an axially symmetric (D(infinity h)) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (absolute value(D/hc) = 0.6157 cm(-1), absolute value(E/hc) = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O2-doped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

From Two- to Three-Dimensional Structures of a Supertetrahedral Boran Using Density Functional Calculations.

Science.gov (United States)

Getmanskii, Iliya V; Minyaev, Ruslan M; Steglenko, Dmitrii V; Koval, Vitaliy V; Zaitsev, Stanislav A; Minkin, Vladimir I

2017-08-14

With help of the DFT calculations and imposing of periodic boundary conditions the geometrical and electronic structures were investigated of two- and three-dimensional boron systems designed on the basis of graphane and diamond lattices in which carbons were replaced with boron tetrahedrons. The consequent studies of two- and three-layer systems resulted in the construction of a three-dimensional supertetrahedral borane crystal structure. The two-dimensional supertetrahedral borane structures with less than seven layers are dynamically unstable. At the same time the three-dimensional superborane systems were found to be dynamically stable. Lack of the forbidden electronic zone for the studied boron systems testifies that these structures can behave as good conductors. The low density of the supertetrahedral borane crystal structures (0.9 g cm -3 ) is close to that of water, which offers the perspective for their application as aerospace and cosmic materials. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Bismuth-boron multiple bonding in BiB{sub 2}O{sup -} and Bi{sub 2}B{sup -}

Energy Technology Data Exchange (ETDEWEB)

Jian, Tian; Cheung, Ling Fung; Chen, Teng-Teng; Wang, Lai-Sheng [Department of Chemistry, Brown University, Providence, RI (United States)

2017-08-01

Despite its electron deficiency, boron is versatile in forming multiple bonds. Transition-metal-boron double bonding is known, but boron-metal triple bonds have been elusive. Two bismuth boron cluster anions, BiB{sub 2}O{sup -} and Bi{sub 2}B{sup -}, containing triple and double B-Bi bonds are presented. The BiB{sub 2}O{sup -} and Bi{sub 2}B{sup -} clusters are produced by laser vaporization of a mixed B/Bi target and characterized by photoelectron spectroscopy and ab initio calculations. Well-resolved photoelectron spectra are obtained and interpreted with the help of ab initio calculations, which show that both species are linear. Chemical bonding analyses reveal that Bi forms triple and double bonds with boron in BiB{sub 2}O{sup -} ([Bi≡B-B≡O]{sup -}) and Bi{sub 2}B{sup -} ([Bi=B=Bi]{sup -}), respectively. The Bi-B double and triple bond strengths are calculated to be 3.21 and 4.70 eV, respectively. This is the first experimental observation of Bi-B double and triple bonds, opening the door to design main-group metal-boron complexes with multiple bonding. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Borylnitrenes: electrophilic reactive intermediates with high reactivity towards C-H bonds.

Science.gov (United States)

Bettinger, Holger F; Filthaus, Matthias

2010-12-21

Borylnitrenes (catBN 3a and pinBN 3b; cat = catecholato, pin = pinacolato) are reactive intermediates that show high tendency towards insertion into the C-H bonds of unactivated hydrocarbons. The present article summarizes the matrix isolation investigations that were aimed at identifying, characterizing and investigating the chemical behaviour of 3a by spectroscopic means, and of the experiments in solution and in the gas phase that were performed with 3b. Comparison with the reactivity reported for difluorovinylidene 1a in solid argon indicates that 3a shows by and large similar reactivity, but only after photochemical excitation. The derivative 3b inserts into the C-H bonds of hydrocarbon solvents in high yields and thus allows the formation of primary amines, secondary amines, or amides from "unreactive" hydrocarbons. It can also be used for generation of methylamine or methylamide from methane in the gas phase at room temperature. Remaining challenges in the chemistry of borylnitrenes are briefly summarized.

The impact of processing parameters on the properties of Zn-bonded Nd–Fe–B magnets

Energy Technology Data Exchange (ETDEWEB)

Kelhar, Luka, E-mail: luka.kelhar@ijs.si [Department for Nanostructured Materials, Jožef Stefan Institute, Jamova cesta 39, Ljubljana 1000 (Slovenia); Zavašnik, Janez [Centre for Electron Microscopy and Microanalysis (CEMM), Jamova cesta 39, Ljubljana 1000 (Slovenia); McGuiness, Paul; Kobe, Spomenka [Department for Nanostructured Materials, Jožef Stefan Institute, Jamova cesta 39, Ljubljana 1000 (Slovenia); Jožef Stefan International Postgraduate School, Jamova cesta 39, Ljubljana 1000 (Slovenia)

2016-12-01

We report on the effect of loading factor and pressure on the density and the magnetic properties of Zn-bonded Nd–Fe–B magnets produced by pulsed-electric-current sintering (PECS). The idea behind this study is to fabricate bonded magnets with a metallic binder in order for the bonded magnet to operate at temperatures higher than 180 °C: the current upper-limit for polymer-bonded magnets. These composites are made of hard-magnetic powder in the form of melt-spun ribbons bonded with the low-melting-point metal Zn. The binder additions were varied from 10 to 30 wt%, and pressures of 50 and 500 MPa were applied. The high-pressure mode with 20 wt% Zn resulted in a 24% increase of J{sub r}, compared to the low-pressure mode. The magnetic measurements revealed a maximum remanence of 0.64 T for 10 wt% Zn, while the coercivity is largely unaffected by the processing conditions. The density of the composites was up to 7.0 g/cm{sup 3}, corresponding to 94% of the theoretical density. Compared to commercial polymer-bonded magnets, the Zn-bonded counterparts exhibit a slightly lower J{sub r}, but the coercivity is retained. We show that there is a minor diffusion of Zn into the Nd–Fe–B, forming a 1 μm thin transition layer, but it does not harm the magnetic properties. These metal-bonded Nd–Fe–B magnets are ideal for use in high-temperature automotive applications like under-the-hood sensors and other magnet-based devices that are close to the engine. - Highlights: • Fabrication of Zn-bonded Nd–Fe–B magnets by pulsed electric current sintering. • Interesting for automotive applications with temperature exceeding 180 °C. • Variations of pressure and loading factor result in higher density and remanence. • Minor diffusion of Zn binder into the MQP-B ribbons is revealed, but does not decrease the magnetic properties. • More stable magnetic properties at high-temperature due to metallic Zn-binder.

In Situ Formation of AgCo Stabilized on Graphitic Carbon Nitride and Concomitant Hydrolysis of Ammonia Borane to Hydrogen.

Science.gov (United States)

Wang, Qi; Xu, Caili; Ming, Mei; Yang, Yingchun; Xu, Bin; Wang, Yi; Zhang, Yun; Wu, Jie; Fan, Guangyin

2018-04-26

The development of highly-efficient heterogeneous supported catalysts for catalytic hydrolysis of ammonia borane to yield hydrogen is of significant importance considering the versatile usages of hydrogen. Herein, we reported the in situ synthesis of AgCo bimetallic nanoparticles supported on g-C₃N₄ and concomitant hydrolysis of ammonia borane for hydrogen evolution at room temperature. The as-synthesized Ag 0.1 Co 0.9 /g-C₃N₄ catalysts displayed the highest turnover frequency (TOF) value of 249.02 mol H₂·(mol Ag ·min) −1 for hydrogen evolution from the hydrolysis of ammonia borane, which was higher than many other reported values. Furthermore, the Ag 0.1 Co 0.9 /g-C₃N₄ catalyst could be recycled during five consecutive runs. The study proves that Ag 0.1 Co 0.9 /g-C₃N₄ is a potential catalytic material toward the hydrolysis of ammonia borane for hydrogen production.

Nickel-Catalyzed C sp2 –C sp3 Cross-Coupling via C–O Bond Activation

KAUST Repository

Guo, Lin

2016-06-13

A new and efficient nickel-catalyzed alkylation of CAr-O electrophiles with B-alkyl-9-BBNs is described. The transformation is characterized by its functional group tolerance and provides a practical and versatile access to various Csp2-Csp3 bonds through Csp2-O substitution, without the restriction of β-hydride elimination. Moreover, the advantage of the newly developed method was demonstrated in a selective and sequential C-O bond activation process. © 2016 American Chemical Society.

Valence electron structure and bonding features of RuB2 and OSB2: The empirical electron theory calculations

Institute of Scientific and Technical Information of China (English)

无

2010-01-01

The valence electron structure (VES) of RuB2 and OsB2 were calculated by the empirical electron theory (EET) of solids and molecules and compared with the results derived from the first-principles calculations. The distributions of covalent electrons in different bonds indicate that B-B and B-Me have remarkably covalent bonding characters. Lattice electrons cruising around Me-Me layers are found to have great influences on electronic conductivity and high temperature plasticity. The ultra-high values of elastic constant Cn in the two compounds originate from close-packed covalent bonding along the c axis. Uneven bond strengths and distributions of covalent bonds, especially for B-Afe bonds, yield significant anisotropy. Low ratios of lattice electrons to covalent electrons suggest the intrinsic embrittlement in crystals. The fact that the calculated cohesive energies well agree with experimental results demonstrates the good suitability of the EET calculations in estimating cohesive energy for transition-metal borides.

A study involving mordenite, titanate nanotubes, perfluoroalkoxy polymers, and ammonia borane

Science.gov (United States)

Nosheen, Shaneela

(anatase) and a temperature of only 100°C. When TiO2 (P-25) was used with the same concentration of alkaline solution (1 molar NaOH), the same processing time of 12 hours, and a higher temperature at 110°C, only titanate nano-tubes were observed. The linkages of 'Ti-O' play a very important role in the structural features of different phases. Two crystalline phases (tetragonal and monoclinic) were synthesized as products in the case of TiO 2 (anatase) and one crystalline phase (monoclinic) for products of TiO 2 (P-25). The third part of the thesis concerns surface modification of hydrophobic fluoropolymers that have low surface energies and are very difficult to metallize. Surface modification was done to enhance surface roughness and hence to boost surface energy for metallization processes. We used low impact, environmentally friendly non-thermal plasmas at atmospheric pressure to strip off F - ions and replace them with reactive unsaturated hydrocarbon functionalities such as CH=CH2 on the surface of a polymer. As these hydrocarbon functionalities are reactive with metals, they form composites that have good adhesion between layers of polymer. Due to surface modification, polymeric chains were broken by the loss of fluorine atoms (F/C = 0.33) and the gain of oxygen atoms (O/C = 0.17) using methane/argon plasmas. Methane/hydrogen/argon plasmas on the other hand produced extensive loss of fluorine atoms (F/C = 0.07-0.33) and gain of oxygen atoms (O/C = 0.08-0.16) that was far better than pristine PFA. The surface of PFA was modified by defluorination and oxidation. Further enhancement of COF and COO groups revealed that the surface was modified to a hydrophilic membrane that can further be easily hydrolyzed to COOH in the presence of atmospheric humidity. The last part of the thesis deals with ammonia borane which was studied as a potential source of hydrogen for fuel cells. We analyzed the viability of ammonia borane as a hydrogen carrier compound for fuel cell

A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.

Science.gov (United States)

Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M

2016-06-17

The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

Novel Carbon (C)-Boron (B)-Nitrogen (N)-Containing H2 Storage Materials

Energy Technology Data Exchange (ETDEWEB)

Liu, Shih-Yuan [Boston College, Chestnut Hill, MA (United States); Giustra, Zachary X. [Boston College, Chestnut Hill, MA (United States); Autrey, Tom [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Osenar, Paul [Protonex Technology Corporation, Southborough, MA (United States)

2017-09-20

exhibited in neat form a substantially higher onset temperature for spontaneous H2 release (70 °C). Solution-phase kinetic experiments using ReactIR established a second-order dependence for the initial loss of H2 from both B and J; Arrhenius analysis, however, revealed the activation barrier for this reaction was lower for B than for J, which presumably contributes to the diminished thermal stability of the former. On the basis of these and other experimental results, extensive computational efforts yielded a reasonable mechanistic model for the dehydrogenation of 1,2-BN-cycloalkane materials. While the prospect of neat B as a suitable hydrogen storage material was discarded, it was proposed that the combination of B with more thermally stable amine-borane-based materials might afford mixtures with improved properties. Indeed, when B was combined with ammonia borane (AB) in a 2:1 molar ratio, the two materials formed a liquid. More significantly, this mixture remained liquid even after complete dehydrogenation, thus establishing the potential for a single-phase fuel cycle. (In contrast, the dehydrogenation product of neat B is a low melting solid (mp = 28-30 °C).) Another advantage conferred by the blend formulation was a dramatic reduction in the amount of borazine produced by AB. Borazine is a well-known contaminant of H2 produced by the thermal decomposition of neat AB, and exerts deleterious effects on fuel cell performance. Residual gas analysis (RGA) of the gas stream generated from the B-AB blend, however, detected just 0.01% borazine content when a Pt-Ni nanoparticle dehydrogenation catalyst was used. In all ii then, the 2:1 B-AB blend marks a major achievement in the effort to develop a suitable liquid amine-borane hydrogen storage material, and merits further investigation into the optimization for practical adoption. Similar realization of the potential of J as a high % wt. H2 material required a method to dehydrogenate the carbonaceous components of the

Poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles-catalyzed hydrolysis of ammonia borane for hydrogen generation

Science.gov (United States)

Rakap, Murat

2015-02-01

The catalytic use of highly efficient poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles (4.2 ± 1.9 nm) in the hydrolysis of ammonia-borane is reported. The catalyst is prepared by co-reduction of two metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. They are recyclable and highly active for hydrogen generation from the hydrolysis of ammonia-borane even at very low concentrations and temperature, providing a record numbers of average turnover frequency value (125 mol H2/mol cat.min-1) and maximum hydrogen generation rate (3468 L H2 min-1 (mol cat)-1). They also provide activation energy of 51.7 ± 2 kJ/mol for the hydrolysis of ammonia borane.

Electron transport and nonlinear optical properties of substituted aryldimesityl boranes: a DFT study.

Directory of Open Access Journals (Sweden)

Altaf Hussain Pandith

Full Text Available A comprehensive theoretical study was carried out on a series of aryldimesityl borane (DMB derivatives using Density Functional theory. Optimized geometries and electronic parameters like electron affinity, reorganization energy, frontiers molecular contours, polarizability and hyperpolarizability have been calculated by employing B3PW91/6-311++G (d, p level of theory. Our results show that the Hammett function and geometrical parameters correlates well with the reorganization energies and hyperpolarizability for the series of DMB derivatives studied in this work. The orbital energy study reveals that the electron releasing substituents increase the LUMO energies and electron withdrawing substituents decrease the LUMO energies, reflecting the electron transport character of aryldimesityl borane derivatives. From frontier molecular orbitals diagram it is evident that mesityl rings act as the donor, while the phenylene and Boron atom appear as acceptors in these systems. The calculated hyperpolarizability of secondary amine derivative of DMB is 40 times higher than DMB (1. The electronic excitation contributions to the hyperpolarizability studied by using TDDFT calculation shows that hyperpolarizability correlates well with dipole moment in ground and excited state and excitation energy in terms of the two-level model. Thus the results of these calculations can be helpful in designing the DMB derivatives for efficient electron transport and nonlinear optical material by appropriate substitution with electron releasing or withdrawing substituents on phenyl ring of DMB system.

Characterization of B-H agostic compounds involved in the dehydrogenation of amine-boranes by group 4 metallocenes.

Science.gov (United States)

Zhu, Jingwen; Zins, Emilie-Laure; Alikhani, Mohammad Esmaïl

2016-12-01

For over a decade, amine-borane has been considered as a potential chemical hydrogen vector in the context of a search for cleaner energy sources. When catalyzed by organometallic complexes, the reaction mechanisms currently considered involve the formation of β-BH agostic intermediates. A thorough understanding of these intermediates may constitute a crucial step toward the identification of ideal catalysts. Topological approaches such as QTAIM and ELF revealed to be particularly suitable for the description of β-agostic interactions. When studying model catalysts, accurate theoretical calculations may be carried out. However, for a comparison with experimental data, calculations should also be carried out on large organo-metallic species, often including transition metals belonging to the second or the third row. In such a case, DFT methods are particularly attractive. Unfortunately, triple-ζ all electrons basis sets are not easily available for heavy transition metal elements. Thus, a subtle balance should be reached between the affordable level of calculations and the required accuracy of the electronic description of the systems. Herein we propose the use of B3LYP functional in combination with the LanL2DZ pseudopotential for the metal atom and 6-311++G(2d,2p) basis set for the other atoms, followed by a single point using the DKH2 relativistic Hamiltonian in combination with the B3LYP/DZP-DKH level, as a "minimum level of theory" leading to a consistent topological description of the interaction within the ELF and QTAIM framework, in the context of isolated (gas-phase) group 4 metallocene catalysts.

Effects of surface modification of Nd-Fe-B powders using parylene C by CVDP method on the properties of anisotropic bonded Nd–Fe–B magnets

Energy Technology Data Exchange (ETDEWEB)

Ma, Bin; Sun, Aizhi, E-mail: sunaizhi@126.com; Lu, Zhenwen; Cheng, Chuan; Xu, Chen

2016-10-15

This paper presents effects of surface modification of Nd–Fe–B powders using parylene C by means of chemical vapor deposition polymerization (CVDP) on the properties of anisotropic bonded Nd–Fe–B magnets. It can be well verified from SEM images and EDS analysis that the surface of Nd–Fe–B powder is coated with thin parylene C films. The maximum energy product ((BH)max), degree of alignment (DOA), actual density and corrosion resistance of parylene Nd–Fe–B magnets prepared at room temperature are much higher than that of non-parylene Nd–Fe–B magnets. (BH)max, DOA and actual density of parylene Nd–Fe–B magnets (70 kJ/m{sup 3}, 0.342, 5.82 g/cm{sup 3}) prepared at room temperature under 578 MPa are improved by 18.6%, 4.6%, 2.1% and 27.3%, 29.1%, 7.8% compared with non-parylene Nd‐Fe‐B magnets prepared at 140 °C (59 kJ/m{sup 3}, 0327, 5.70 g/cm{sup 3}) and room temperature (55 kJ/m{sup 3}, 0.265, 5.40 g/cm{sup 3}), respectively. Additional, the improvement of actual density and the room temperature process also solve problems such as powders’ sticking wall, non-uniform powder filling, non-uniform magnetic properties, seriously mould damage, short life cycle of mould and so on, which exists during warm compaction process. Parylene Nd–Fe–B magnets have better corrosion resistance and worse mechanical properties than that of non-parylene Nd–Fe–B magnets. The reason for the improvement of magnetic properties and actual density is the low friction cofficient of parylene C films, which results in lower frictional resistance and better lubricating property of parylene Nd–Fe–B powders. - Highlights: • Parylene Nd–Fe–B magnets prepared at room temperature show higher (BH)max and DOA. • Actual density of parylene Nd–Fe–B magnet is improved greatly. • Problems such as powders’ sticking wall, mould damage and so on are solved. • Parylene NdFeB magnets have better corrosion resistance. • Low friction cofficient of

Performance of vacuum plasma spray and HVOF bond coatings at 900° and 1100 °C

Energy Technology Data Exchange (ETDEWEB)

Lance, Michael J. [ORNL; Haynes, James A. [ORNL; Pint, Bruce A. [ORNL

2017-12-01

The effects of Ti and B additions to a vacuum plasma sprayed (VPS) NiCoCrAlYHfSi bond coating on thermal barrier coating (TBC) performance were studied at 1100 °C and 900 °C and compared to high-velocity oxy-fuel (HVOF) bond coatings. Using alloy 247 substrates and air plasma sprayed Y2O3-stabilized ZrO2 top coatings, additions of B or Ti + B did not improve the average TBC lifetime in 1-h cycles at 1100 °C in air with 10% H2O. The addition of Ti resulted in a decrease in lifetime. Photo-stimulated luminescence spectroscopy was used to map residual stresses in the thermally-grown Al2O3 scale. At 900 °C, closer to a typical land based turbine operating bond coating temperature, specimens were examined after ten 500-h cycles in laboratory air and air with 10%H2O to study the effect of H2O. The addition of water vapor had little effect on the measured parabolic rate constants at 900 °C and a comparison of the oxide microstructures in both environments is reported.

Changes in biochemical proxy indicators for nutritional stress resilience from Boran and Nguni cows reared in dry arid rangeland.

Science.gov (United States)

Mapfumo, Lizwell; Muchenje, Voster; Mupangwa, John F; Scholtz, Michiel M

2017-10-01

The objective of this study was to determine the changes in biochemical indicators for nutritional stress from a herd of Boran and Nguni cows. A total of 40 cows (20 from each herd) were randomly selected for the study. The animals were identified according to their parities as follows: parity 1 (n = 8), parity 2 (n = 16), parity 3 (n = 8) and parity 4 (n = 8). Serum chemistry levels of glucose, total cholesterol, urea, creatinine, albumin, globulin, aspartate aminotransferase (AST), alanine aminotransferase (ALT), alkaline phosphatase (ALP), gamma glutylaminotransferase (GGT), leukocytes, erythrocytes, haemoglobin, packed cell volume (PCV) and platelet counts were determined for 12 consecutive months spanning across the wet and dry seasons. The Boran cows had different creatinine concentration levels at different parities. The Boran cows in parity 1 had the highest (P cows in different parities within the herd. There were significant differences in enzymes such as AST, ALP and ALT among the herd and parities. Boran cows in parity 3 had the lowest (P cows in parity 4 had the highest concentration of ALP of 161.3 ± 8.10 U/L while Nguni cows in parity 1 had the highest concentration level of ALT 55.1 ± 1.56 U/L than all the cows within the same herd. The Nguni herd had significantly higher (P Cows from the Nguni herd maintained significantly higher amount of urea, creatinine, albumin and total protein in both the wet and dry seasons as compared with cows from the Boran herd. Cows from the Nguni herd maintained significantly higher amount of urea, creatinine, albumin and total protein in both the wet and dry seasons as compared with those from the Boran herd.

Sublimation and thermal decomposition of ammonia borane: Competitive processes controlled by pressure

Energy Technology Data Exchange (ETDEWEB)

Kondrat’ev, Yu.V.; Butlak, A.V.; Kazakov, I.V.; Timoshkin, A.Y., E-mail: a.y.timoshkin@spbu.edu

2015-12-20

Highlights: • We measured sublimation enthalpy of ammonia borane at 357 K by drop-calorimetry. • We determined activation energy for ammonia borane decomposition by tensimetry. • At 357 K decomposition and sublimation are competitive and depend on the pressure. • We propose new values for the Δ{sub f}H° of solid ammonia borane and polyamidoborane. - Abstract: Thermal behavior of ammonia borane BH{sub 3}NH{sub 3} (AB) has been studied by calorimetry, tensimetry and mass spectrometry methods. It is shown, that depending on vapor pressure in the system two competitive processes are taking place at 357 K. At atmospheric pressure thermal decomposition with hydrogen evolution is the dominant process: BH{sub 3}NH{sub 3(s)} = 1/n (BH{sub 2}NH{sub 2}){sub n(s)} + H{sub 2(g)} (1). At low pressures (circa 4 mTorr) the major process is endothermic sublimation of AB: BH{sub 3}NH{sub 3(s)} = BH{sub 3}NH{sub 3(g)} (2). At intermediate pressures both processes occur simultaneously. Enthalpies for the processes (1) and (2) have been determined by drop-calorimetry method: Δ{sub (1)}H{sub 357}° = −24.8 ± 2.3 kJ mol{sup −1} and Δ{sub sub}H{sub 357}°(BH{sub 3}NH{sub 3}) = 76.3 ± 3.0 kJ mol{sup −1}. Solid products after sublimation and decomposition have been characterized by IR and NMR spectroscopy; gaseous forms were studied by mass spectrometry. Activation energy of 94 ± 11 kJ mol{sup −1} for the process (1) in range 327–351 K was determined by static tensimetry method. Based on the analysis of available thermodynamic characteristics, new values for the standard formation enthalpy of solid AB −133.4 ± 5.2 kJ mol{sup −1} and polyamidoborane −156.7 ± 5.8 kJ mol{sup −1} are recommended.

Polymers containing borane or carborane cage compounds and related applications

Science.gov (United States)

Bowen, III, Daniel E.; Eastwood, Eric A [Raymore, MO

2012-06-05

Polymers comprising residues of borane and/or carborane cage compound monomers having at least one polyalkoxy silyl substituent. Such polymers can further comprise one or more reactive matrices and/or co-monomers covalently bound with the cage compound monomer residues. Methods of making and applications for using such polymers are also disclosed.

Catalytic hydrolysis of ammonia borane via cobalt palladium nanoparticles.

Science.gov (United States)

Sun, Daohua; Mazumder, Vismadeb; Metin, Önder; Sun, Shouheng

2011-08-23

Monodisperse 8 nm CoPd nanoparticles (NPs) with controlled compositions were synthesized by the reduction of cobalt acetylacetonate and palladium bromide in the presence of oleylamine and trioctylphosphine. These NPs were active catalysts for hydrogen generation from the hydrolysis of ammonia borane (AB), and their activities were composition dependent. Among the 8 nm CoPd catalysts tested for the hydrolysis of AB, the Co(35)Pd(65) NPs exhibited the highest catalytic activity and durability. Their hydrolysis completion time and activation energy were 5.5 min and 27.5 kJ mol(-1), respectively, which were comparable to the best Pt-based catalyst reported. The catalytic performance of the CoPd/C could be further enhanced by a preannealing treatment at 300 °C under air for 15 h with the hydrolysis completion time reduced to 3.5 min. This high catalytic performance of Co(35)Pd(65) NP catalyst makes it an exciting alternative in pursuit of practical implementation of AB as a hydrogen storage material for fuel cell applications. © 2011 American Chemical Society

Metal-organic cooperative catalysis in C-H and C-C bond activation and its concurrent recovery.

Science.gov (United States)

Park, Young Jun; Park, Jung-Woo; Jun, Chul-Ho

2008-02-01

The development of an efficient catalytic activation (cleavage) system for C-H and C-C bonds is an important challenge in organic synthesis, because these bonds comprise a variety of organic molecules such as natural products, petroleum oils, and polymers on the earth. Among many elegant approaches utilizing transition metals to activate C-H and C-C bonds facilely, chelation-assisted protocols based on the coordinating ability of an organic moiety have attracted great attention, though they have often suffered from the need for an intact coordinating group in a substrate. In this Account, we describe our entire efforts to activate C-H or C-C bonds adjacent to carbonyl groups by employing a new concept of metal-organic cooperative catalysis (MOCC), which enables the temporal installation of a 2-aminopyridyl group into common aldehydes or ketones in a catalytic way. Consequently, a series of new catalytic reactions such as alcohol hydroacylation, oxo-ester synthesis, C-C triple bond cleavage, hydrative dimerization of alkynes, and skeletal rearrangements of cyclic ketones was realized through MOCC. In particular, in the quest for an optimized MOCC system composed of a Wilkinson's catalyst (Ph 3P) 3RhCl and an organic catalyst (2-amino-3-picoline), surprising efficiency enhancements could be achieved when benzoic acid and aniline were introduced as promoters for the aldimine formation process. Furthermore, a notable accomplishment of C-C bond activation has been made using 2-amino-3-picoline as a temporary chelating auxiliary in the reactions of unstrained ketones with various terminal olefins and Wilkinson's catalyst. In the case of seven-membered cyclic ketones, an interesting ring contraction to five- or six-membered ones takes place through skeletal rearrangements initiated by the C-C bond activation of MOCC. On the other hand, the fundamental advances of these catalytic systems into recyclable processes could be achieved by immobilizing both metal and organic

C-C bond formation in the intramolecular Diels-Alder reaction of triene amides.

Science.gov (United States)

Benallou, Abdelilah; El Alaoui El Abdallaoui, Habib; Garmes, Hocine

2018-02-01

The mechanism nature of the intramolecular Diels-Alder reaction has been performed; and thus, the changes of C-C bond forming/breaking along IRC are characterized in this study. Conceptual DFT analyses of the most favorable adduct fused/exo shows that the flux electronic will take place from diene to dienophile moiety. Moreover, ELF topological analysis based on the electron density predicts that C-C bond is formed by the coupling of two pseudoradical centers generated at the most significant atoms of the molecules. However, C2 vs C3, also C1 and C4 interaction comes mainly from the global electron density transfer which takes place along the reaction. Two- stage one-step is the proposed mechanism of this reaction, the first stage aims for the formation of C2-C3 σ bond while the second stage aims for C1-C4 σ bond formation. Interestingly, the observed asynchronicity of this IMDA reaction due principally to the asymmetric reorganization of electron density at the most attractive centers.

A bonding study of c-C5H8 adsorption on Pt(111)

International Nuclear Information System (INIS)

Simonetti, S.; Jasen, P.; Gonzalez, E.; Juan, A.; Brizuela, G.

2006-01-01

The chemisorption of cyclopentane (c-C 5 H 8 ) on Pt(111) has been studied using a qualitative band-structure calculations in the framework of tight-binding implementation with the YAeHMOP package. We modeled the metal surface by a two-dimensional slab of finite thickness with an overlayer of c-C 5 H 8 , in a (3x3) di-σ geometry. The c-C 5 H 8 molecule is attached to the surface with its C?C atoms bonded mainly with two Pt atoms while the opposite CH 2 bends towards the surface. The Pt?Pt bonds in the underlying surface and the C?C bonds of c-C 5 H 8 are weakened upon the chemisorption. A noticeable Pt-H and Pt-C interactions has been observed. We found that of Pt 5d z 2 band plays an important role in the bonding between c-C 5 H 8 and the surface, as do the Pt 6s and 6p z bands. The HOMO-LUMO bands of c-C 5 H 8 are very dispersed, indicative of a strong interaction with the metal surface

A rationally designed amino-borane complex in a metal organic framework: A novel reusable hydrogen storage and size-selective reduction material

KAUST Repository

Wang, Xinbo

2015-01-01

A novel amino-borane complex inside a stable metal organic framework was synthesized for the first time. It releases hydrogen at a temperature of 78 °C with no volatile contaminants and can be well reused. Its application as a size-selective reduction material in organic synthesis was also demonstrated. © The Royal Society of Chemistry 2015.

Graphene-supported Ag-based core-shell nanoparticles for hydrogen generation in hydrolysis of ammonia borane and methylamine borane.

Science.gov (United States)

Yang, Lan; Luo, Wei; Cheng, Gongzhen

2013-08-28

Well-dispersed magnetically recyclable core-shell Ag@M (M = Co, Ni, Fe) nanoparticles (NPs) supported on graphene have been synthesized via a facile in situ one-step procedure, using methylamine borane (MeAB) as a reducing agent under ambient condition. Their catalytic activity toward hydrolysis of ammonia borane (AB) were studied. Although the Ag@Fe/graphene NPs are almost inactive, the as-prepared Ag@Co/graphene NPs are the most reactive catalysts, followed by Ag@Ni/graphene NPs. Compared with AB and NaBH4, the as-synthesized Ag@Co/graphene catalysts which reduced by MeAB exert the highest catalytic activity. Additionally, the Ag@Co NPs supported on graphene exhibit higher catalytic activity than the catalysts with other conventional supports, such as the SiO2, carbon black, and γ-Al2O3. The as-synthesized Ag@Co/graphene NPs exert satisfied catalytic activity, with the turnover frequency (TOF) value of 102.4 (mol H2 min(-1) (mol Ag)(-1)), and the activation energy Ea value of 20.03 kJ/mol. Furthermore, the as-synthesized Ag@Co/graphene NPs show good recyclability and magnetically reusability for the hydrolytic dehydrogenation of AB and MeAB, which make the practical reusing application of the catalysts more convenient. Moreover, this simple synthetic method indicates that MeAB could be used as not only a potential hydrogen storage material but also an efficient reducing agent. It can be easily extended to facile preparation of other graphene supported metal NPs.

The morphology of ceramic phases in B x C-SiC-Si infiltrated composites

International Nuclear Information System (INIS)

Hayun, S.; Frage, N.; Dariel, M.P.

2006-01-01

The present communication is concerned with the effect of the carbon source on the morphology of reaction bonded boron carbide (B 4 C). Molten silicon reacts strongly and rapidly with free carbon to form large, faceted, regular polygon-shaped SiC particles, usually embedded in residual silicon pools. In the absence of free carbon, the formation of SiC relies on carbon that originates from within the boron carbide particles. Examination of the reaction bonded boron carbide revealed a core-rim microstructure consisting of boron carbide particles surrounded by secondary boron carbide containing some dissolved silicon. This microstructure is generated as the outcome of a dissolution-precipitation process. In the course of the infiltration process molten Si dissolves some boron carbide until its saturation with B and C. Subsequently, precipitation of secondary boron carbide enriched with boron and silicon takes place. In parallel, elongated, strongly twinned, faceted SiC particles are generated by rapid growth along preferred crystallographic directions. This sequence of events is supported by X-ray diffraction and microcompositional analysis and well accounted for by the thermodynamic analysis of the ternary B-C-Si system. - Graphical abstract: Bright field TEM image of the rim area between two boron carbide grains

Studies on the selectivity of the reaction of (CO){sub 5}W=C(aryl)H with enynes: transfer of the carbene ligand to the C=C Bond versus insertion of the C triple bond C into the W=C Bond

Energy Technology Data Exchange (ETDEWEB)

Fischer, H.; Volkland, H.P.; Stumpf, R.

1996-10-01

The strongly electrophilic monophenylcarbene complex [(CO){sub 5}W=C(Ph)H] (2a) reacts with the enynes H-C triple bond C-R(R=-C(Me)=CH{sub 2})(3), -C{sub 6}H{sub 4}-CH=CH{sub 2}-p (5) and subsequently with PMe{sub 3} to form the C{sub a}lpha-PMe{sub 3} adducts of the vinylidene complexes [(CO){sub 5}W-{l_brace}C(PMe{sub 3})=CH-C{sub 3}H{sub 3}(Me)Ph{r_brace}] (4) and [(CO){sub 5}W {l_brace}C(PMe{sub 3})=CH-C{sub 6}H{sub 4}-C{sub 3}H{sub 4}Ph{r_brace}] (6). The reaction very likely proceeds by transfer of the carbene ligand to the C=C bond of the enyne to form a cyclopropyl-substituted alkyne complex which is in equilibrium with its vinylidene isomer.

Room temperature hydrogen generation from hydrolysis of ammonia-borane over an efficient NiAgPd/C catalyst

KAUST Repository

Hu, Lei

2014-12-01

NiAgPd nanoparticles are successfully synthesized by in-situ reduction of Ni, Ag and Pd salts on the surface of carbon. Their catalytic activity was examined in ammonia borane (NH3BH3) hydrolysis to generate hydrogen gas. This nanomaterial exhibits a higher catalytic activity than those of monometallic and bimetallic counterparts and a stoichiometric amount of hydrogen was produced at a high generation rate. Hydrogen production rates were investigated in different concentrations of NH3BH3 solutions, including in the borates saturated solution, showing little influence of the concentrations on the reaction rates. The hydrogen production rate can reach 3.6-3.8 mol H2 molcat -1 min-1 at room temperature (21 °C). The activation energy and TOF value are 38.36 kJ/mol and 93.8 mol H2 molcat -1 min-1, respectively, comparable to those of Pt based catalysts. This nanomaterial catalyst also exhibits excellent chemical stability, and no significant morphology change was observed from TEM after the reaction. Using this catalyst for continuously hydrogen generation, the hydrogen production rate can be kept after generating 6.2 L hydrogen with over 10,000 turnovers and a TOF value of 90.3 mol H2 molcat -1 min-1.

Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

OpenAIRE

Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

2015-01-01

Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based ...

Ligand-Controlled Chemoselective C(acyl)–O Bond vs C(aryl)–C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)–C(sp3) Cross-Couplings

KAUST Repository

Chatupheeraphat, Adisak

2018-02-20

A ligand-controlled and site-selective nickel catalyzed Suzuki-Miyaura cross-coupling reaction with aromatic esters and alkyl organoboron reagents as coupling partners was developed. This methodology provides a facile route for C(sp2)-C(sp3) bond formation in a straightforward fashion by successful suppression of the undesired β-hydride elimination process. By simply switching the phosphorus ligand, the ester substrates are converted into the alkylated arenes and ketone products, respectively. The utility of this newly developed protocol was demonstrated by its wide substrate scope, broad functional group tolerance and application in the synthesis of key intermediates for the synthesis of bioactive compounds. DFT studies on the oxidative addition step helped rationalizing this intriguing reaction chemoselectivity: whereas nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step leading to the alkylated product via a decarbonylative process, nickel complexes with monodentate phosphorus ligands favor activation of the C(acyl)-O bond, which later generates the ketone product.

The impact of processing parameters on the properties of Zn-bonded Nd-Fe-B magnets

Science.gov (United States)

Kelhar, Luka; Zavašnik, Janez; McGuiness, Paul; Kobe, Spomenka

2016-12-01

We report on the effect of loading factor and pressure on the density and the magnetic properties of Zn-bonded Nd-Fe-B magnets produced by pulsed-electric-current sintering (PECS). The idea behind this study is to fabricate bonded magnets with a metallic binder in order for the bonded magnet to operate at temperatures higher than 180 °C: the current upper-limit for polymer-bonded magnets. These composites are made of hard-magnetic powder in the form of melt-spun ribbons bonded with the low-melting-point metal Zn. The binder additions were varied from 10 to 30 wt%, and pressures of 50 and 500 MPa were applied. The high-pressure mode with 20 wt% Zn resulted in a 24% increase of Jr, compared to the low-pressure mode. The magnetic measurements revealed a maximum remanence of 0.64 T for 10 wt% Zn, while the coercivity is largely unaffected by the processing conditions. The density of the composites was up to 7.0 g/cm3, corresponding to 94% of the theoretical density. Compared to commercial polymer-bonded magnets, the Zn-bonded counterparts exhibit a slightly lower Jr, but the coercivity is retained. We show that there is a minor diffusion of Zn into the Nd-Fe-B, forming a 1 μm thin transition layer, but it does not harm the magnetic properties. These metal-bonded Nd-Fe-B magnets are ideal for use in high-temperature automotive applications like under-the-hood sensors and other magnet-based devices that are close to the engine.

Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

Science.gov (United States)

Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin

2014-09-14

An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage.

Science.gov (United States)

Wang, Teng; Jiao, Ning

2014-04-15

Because of the importance of nitrogen-containing compounds in chemistry and biology, organic chemists have long focused on the development of novel methodologies for their synthesis. For example, nitrogen-containing compounds show up within functional materials, as top-selling drugs, and as bioactive molecules. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C-H or C-C bond cleavage. Although researchers have made significant progress in the direct functionalization of simple hydrocarbons, direct C-N bond formation via C-H or C-C bond cleavage remains challenging, in part because of the unstable character of some N-nucleophiles under oxidative conditions. The nitriles are versatile building blocks and precursors in organic synthesis. Recently, chemists have achieved the direct C-H cyanation with toxic cyanide salts in the presence of stoichiometric metal oxidants. In this Account, we describe recent progress made by our group in nitrile synthesis. C-H or C-C bond cleavage is a key process in our strategy, and azides or DMF serve as the nitrogen source. In these reactions, we successfully realized direct nitrile synthesis using a variety of hydrocarbon groups as nitrile precursors, including methyl, alkenyl, and alkynyl groups. We could carry out C(sp(3))-H functionalization on benzylic, allylic, and propargylic C-H bonds to produce diverse valuable synthetic nitriles. Mild oxidation of C═C double-bonds and C≡C triple-bonds also produced nitriles. The incorporation of nitrogen within the carbon skeleton typically involved the participation of azide reagents. Although some mechanistic details remain unclear, studies of these nitrogenation reactions implicate the involvement of a cation or radical intermediate, and an oxidative rearrangement of azide intermediate produced the nitrile. We also explored environmentally friendly oxidants, such as molecular oxygen, to make our

Tribological properties of B{sub 4}C-TiB{sub 2}-TiC-Ni cermet coating produced by HVOF

Energy Technology Data Exchange (ETDEWEB)

Rafiei, Mahdi [Islamic Azad Univ., Najafabad (Iran, Islamic Republic of). Dept. of Materials Engineering; Isfahan Univ. of Technology, Isfahan (Iran, Islamic Republic of). Depr. of Materials Engineering; Shamanian, Morteza; Salehi, Mehdi [Isfahan Univ. of Technology, Isfahan (Iran, Islamic Republic of). Depr. of Materials Engineering; Mostaan, Hossein [Arak Univ., Arak (Iran, Islamic Republic of). Dept. of Materials and Metallurgical Engineering

2017-08-15

In this study, B{sub 4}C-TiB{sub 2}-TiC-Ni coating was sprayed on the surface of 4130 steel by high velocity oxy-fuel torch. The tribological behavior of samples was studied by ball on disk wear testing. Structural evolution of the coating was analyzed by X-ray diffractometry. The microstructure of the coating, wear track and Al{sub 2}O{sub 3} ball was investigated by scanning electron microscopy, field emission scanning electron microscopy and optical microscopy. Elemental analysis of the wear track was done by energy dispersive X-ray spectroscopy. It was found that a cermet coating containing B{sub 4}C, TiB{sub 2}, TiC and Ni phases with good bonding to the 4130 steel substrate with no sign of any cracking or pores was formed. The wear mechanism of the composite coating was delamination. The friction coefficient of samples was decreased with increasing load because of higher frictional heat and creation of more oxide islands.

Synthesis of boron nitride nanotubes with SiC nanowire as template

International Nuclear Information System (INIS)

Zhong, B.; Song, L.; Huang, X.X.; Wen, G.W.; Xia, L.

2011-01-01

Highlights: → Boron nitride nanotubes (BNNTs) have been fabricated using SiC nanowires as template. → SiC nanowires could be effectively etched out by the vapors decomposed from ammonia borane, leading to the formation of BNNTs. → A template self-sacrificing mechanism is responsible for the formation of BNNTs. -- Abstract: A novel template method for the preparation of boron nitride nanotubes (BNNTs) using SiC nanowire as template and ammonia borane as precursor is reported. We find out that the SiC nanowires could be effectively etched out by the vapors decomposed from ammonia borane, leading to the formation of BNNTs. The as-prepared products are well characterized by means of complementary analytical techniques. A possible formation mechanism is disclosed. The method developed here paves the way for large scale production of BNNTs.

Thermal shock resistances of a bonding material of C/C composite and copper

International Nuclear Information System (INIS)

Kurumada, Akira; Oku, Tatsuo; Kawamata, Kiyohiro; Motojima, Osamu; Noda, Nobuaki; McEnaney, B.

1997-01-01

The purpose of this study is to contribute to the development and the safety design of plasma facing components for fusion reactor devices. We evaluated the thermal shock resistance and the thermal shock fracture toughness of a bonding material which was jointed a carbon-fiber-reinforced carbon composite (C/C composite) to oxygen-free copper. We also examined the microstructures of the bonding layers using a scanning electron microscope before and after thermal shock tests. The bonding material did not fracture during thermal shock tests. However, thermal cracks and delamination cracks were observed in the bonding layers. (author)

Regeneration of ammonia borane spent fuel

International Nuclear Information System (INIS)

Sutton, Andrew David; Davis, Benjamin L.; Gordon, John C.

2009-01-01

A necessary target in realizing a hydrogen (H 2 ) economy, especially for the transportation sector, is its storage for controlled delivery, presumably to an energy producing fuel cell. In this vein, the U.S. Department of Energy's Centers of Excellence (CoE) in Hydrogen Storage have pursued different methodologies, including metal hydrides, chemical hydrides, and sorbents, for the expressed purpose of supplanting gasoline's current > 300 mile driving range. Chemical H 2 storage has been dominated by one appealing material, ammonia borane (H 3 N-BH 3 , AB), due to its high gravimetric capacity of H 2 (19.6 wt %) and low molecular weight (30.7 g mol -1 ). In addition, AB has both hydridic and protic moieties, yielding a material from which H 2 can be readily released in contrast to the loss of H 2 from C 2 H 6 which is substantially endothermic. As such, a number of publications have described H 2 release from amine boranes, yielding various rates depending on the method applied. The viability of any chemical H 2 storage system is critically dependent on efficient recyclability, but reports on the latter subject are sparse, invoke the use of high energy reducing agents, and suffer from low yields. Our group is currently engaged in trying to find and fully demonstrate an energy efficient regeneration process for the spent fuel from H 2 depleted AB with a minimum number of steps. Although spent fuel composition depends on the dehydrogenation method, we have focused our efforts on the spent fuel resulting from metal-based catalysis, which has thus far shown the most promise. Metal-based catalysts have produced the fastest rates for a single equivalent of H 2 released from AB and up to 2.5 equiv. of H 2 can be produced within 2 hours. While ongoing work is being carried out to tailor the composition of spent AB fuel, a method has been developed for regenerating the predominant product, polyborazylene (PB) which can be obtained readily from the decomposition of borazine

26 CFR 1.147(b)-1 - Bond maturity limitation-treatment of working capital.

Science.gov (United States)

2010-04-01

... and Local Bonds § 1.147(b)-1 Bond maturity limitation-treatment of working capital. Section 147(b) does not apply to proceeds of a private activity bond issue used to finance working capital... 26 Internal Revenue 2 2010-04-01 2010-04-01 false Bond maturity limitation-treatment of working...

Tyrosine B10 triggers a heme propionate hydrogen bonding network loop with glutamine E7 moiety

International Nuclear Information System (INIS)

Ramos-Santana, Brenda J.; López-Garriga, Juan

2012-01-01

Highlights: ► H-bonding network loop by PheB10Tyr mutation is proposed. ► The propionate group H-bonding network restricted the flexibility of the heme. ► The hydrogen bonding interaction modulates the electron density of the iron. ► Propionate H-bonding network loop explains the heme-ligand stabilization. -- Abstract: Propionates, as peripheral groups of the heme active center in hemeproteins have been described to contribute in the modulation of heme reactivity and ligand selection. These electronic characteristics prompted the question of whether the presence of hydrogen bonding networks between propionates and distal amino acids present in the heme ligand moiety can modulate physiological relevant events, like ligand binding association and dissociation activities. Here, the role of these networks was evaluated by NMR spectroscopy using the hemoglobin I PheB10Tyr mutant from Lucina pectinata as model for TyrB10 and GlnE7 hemeproteins. 1 H-NMR results for the rHbICN PheB10Tyr derivative showed chemical shifts of TyrB10 OHη at 31.00 ppm, GlnE7 N ε1 H/N ε2 H at 10.66 ppm/−3.27 ppm, and PheE11 C δ H at 11.75 ppm, indicating the presence of a crowded, collapsed, and constrained distal pocket. Strong dipolar contacts and inter-residues crosspeaks between GlnE7/6-propionate group, GlnE7/TyrB10 and TyrB10/CN suggest that this hydrogen bonding network loop between GlnE7, TyrB10, 6-propionate group, and the heme ligand contribute significantly to the modulation of the heme iron electron density as well as the ligand stabilization mechanism. Therefore, the network loop presented here support the fact that the electron withdrawing character of the hydrogen bonding is controlled by the interaction of the propionates and the nearby electronic environments contributing to the modulation of the heme electron density state. Thus, we hypothesize that in hemeproteins with similar electrostatic environment the flexibility of the heme-6-propionate promotes a hydrogen

Hydrolysis of solid ammonia borane

Energy Technology Data Exchange (ETDEWEB)

Demirci, Umit B.; Miele, Philippe [Universite Lyon 1, CNRS, UMR 5615, Laboratoire des Multimateriaux et Interfaces, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne (France)

2010-07-01

Ammonia borane NH{sub 3}BH{sub 3} is a promising hydrogen storage material by virtue of a theoretical gravimetric hydrogen storage capacity (GHSC) of 19.5 wt%. However, stored hydrogen has to be effectively released, one way of recovering this hydrogen being the metal-catalyzed hydrolysis. The present study focuses on CoCl{sub 2}-catalyzed hydrolysis of NH{sub 3}BH{sub 3} with the concern of improving the effective GHSC of the system NH{sub 3}BH{sub 3}-H{sub 2}O. For that, NH{sub 3}BH{sub 3} is stored as a solid and H{sub 2}O is provided in stoichiometric amount. By this way, an effective GHSC of 7.8 wt% has been reached at 25 C. To our knowledge, it is the highest value ever reported. Besides, one of the highest hydrogen generation rates (HGRs, 21 ml(H{sub 2}) min{sup -1}) has been found. In parallel, the increases of the water amount and temperature have been studied and the reaction kinetics has been determined. Finally, it has been observed that some NH{sub 3} release, what is detrimental for a fuel cell. To summarize, high performances in terms of GHSCs and HGRs can be reached with NH{sub 3}BH{sub 3} and since research devoted to this boron hydride is at the beginning we may be confident in making it viable in a near future. (author)

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer† †Electronic supplementary information (ESI) available: Syntheses, structure characterization data, and UV/vis absorption and emission spectra. See DOI: 10.1039/c4sc03865g

Science.gov (United States)

Guo, Song; Xu, Liang; Xu, Kejing; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-01-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C60 was used as the complementary hydrogen bonding module (C-1), in which the C60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C60 module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C60 module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion. PMID:29218142

Bond deformation paths and electronic instabilities of ultraincompressible transition metal diborides: Case study of OsB2 and IrB2

Science.gov (United States)

Zhang, R. F.; Legut, D.; Wen, X. D.; Veprek, S.; Rajan, K.; Lookman, T.; Mao, H. K.; Zhao, Y. S.

2014-09-01

The energetically most stable orthorhombic structure of OsB2 and IrB2 is dynamically stable for OsB2 but unstable for IrB2. Both diborides have substantially lower shear strength in their easy slip systems than their metal counterparts. This is attributed to an easy sliding facilitated by out-of-plane weakening of metallic Os-Os bonds in OsB2 and by an in-plane bond splitting instability in IrB2. A much higher shear resistance of Os-B and B-B bonds than Os-Os ones is found, suggesting that the strengthened Os-B and B-B bonds are responsible for hardness enhancement in OsB2. In contrast, an in-plane electronic instability in IrB2 limits its strength. The electronic structure of deformed diborides suggests that the electronic instabilities of 5d orbitals are their origin of different bond deformation paths. Neither IrB2 nor OsB2 can be intrinsically superhard.

Molecularly Tuning the Radicaloid N-H···O═C Hydrogen Bond.

Science.gov (United States)

Lu, Norman; Chung, Wei-Cheng; Ley, Rebecca M; Lin, Kwan-Yu; Francisco, Joseph S; Negishi, Ei-Ichi

2016-03-03

Substituent effects on the open shell N-H···O═C hydrogen-bond has never been reported. This study examines how 12 functional groups composed of electron donating groups (EDG), halogen atoms and electron withdrawing groups (EWG) affect the N-H···O═C hydrogen-bond properties in a six-membered cyclic model system of O═C(Y)-CH═C(X)N-H. It is found that group effects on this open shell H-bonding system are significant and have predictive trends when X = H and Y is varied. When Y is an EDG, the N-H···O═C hydrogen-bond is strengthened; and when Y is an EWG, the bond is weakened; whereas the variation in electronic properties of X group do not exhibit a significant impact upon the hydrogen bond strength. The structural impact of the stronger N-H···O═C hydrogen-bond are (1) shorter H and O distance, r(H···O) and (2) a longer N-H bond length, r(NH). The stronger N-H···O═C hydrogen-bond also acts to pull the H and O in toward one another which has an effect on the bond angles. Our findings show that there is a linear relationship between hydrogen-bond angle and N-H···O═C hydrogen-bond energy in this unusual H-bonding system. In addition, there is a linear correlation of the r(H···O) and the hydrogen bond energy. A short r(H···O) distance corresponds to a large hydrogen bond energy when Y is varied. The observed trends and findings have been validated using three different methods (UB3LYP, M06-2X, and UMP2) with two different basis sets.

Multiple C-H Bond Activations and Ring-Opening C-S Bond Cleavage of Thiophene by Dirhenium Carbonyl Complexes.

Science.gov (United States)

Adams, Richard D; Dhull, Poonam; Tedder, Jonathan D

2018-06-14

The reaction of Re 2 (CO) 8 (μ-C 6 H 5 )(μ-H) (1) with thiophene in CH 2 Cl 2 at 40 °C yielded the new compound Re 2 (CO) 8 (μ-η 2 -SC 4 H 3 )(μ-H) (2), which contains a bridging σ-π-coordinated thienyl ligand formed by the activation of the C-H bond at the 2 position of the thiophene. Compound 2 exhibits dynamical activity on the NMR time scale involving rearrangements of the bridging thienyl ligand. The reaction of compound 2 with a second 1 equiv of 1 at 45 °C yielded the doubly metalated product [Re 2 (CO) 8 (μ-H)] 2 (μ-η 2 -2,3-μ-η 2 -4,5-C 4 H 2 S) (3), formed by the activation of the C-H bond at the 5 position of the thienyl ligand in 2. Heating 3 in a hexane solvent to reflux transformed it into the ring-opened compound Re(CO) 4 [μ-η 5 -η 2 -SCC(H)C(H)C(H)][Re(CO) 3 ][Re 2 (CO) 8 (μ-H)] (4) by the loss of one CO ligand. Compound 4 contains a doubly metalated 1-thiapentadienyl ligand formed by the cleavage of one of the C-S bonds. When heated to reflux (125 °C) in an octane solvent in the presence of H 2 O, the new compound Re(CO) 4 [η 5 -μ-η 2 -SC(H)C(H)C(H)C(H)]Re(CO) 3 (5) was obtained by cleavage of the Re 2 (CO) 8 (μ-H) group from 4 with formation of the known coproduct [Re(CO) 3 (μ 3 -OH)] 4 . All new products were characterized by single-crystal X-ray diffraction analyses.

Preparation and characterization of B-C-N hybrid thin films

International Nuclear Information System (INIS)

Uddin, Md. Nizam; Shimoyama, Iwao; Sekiguchi, Tetsuhiro; Baba, Yuji; Nath, Krishna G.; Nagano, Masamitsu

2006-06-01

Two dimensional thin films composed of boron, carbon and nitrogen (B-C-N hybrid) were synthesized by ion beam deposition, and their electronic and geometrical structures were characterized by core-level spectroscopy using synchrotron radiation. B-C-N hybrid thin films were grown from ion beam plasma of borazine on highly oriented pyrolitic graphite (HOPG) at various temperatures. The films were characterized in-situ by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS). XPS study suggested that B, N and C atoms in the deposited films were in a wide variety of chemical bonds e.g., B-C, B-N, N-C, and B-C-N. It was found that B-C-N hybrid formation was enhanced at high temperature, and that the B-C-N component was dominantly synthesized at low boron content. In the NEXAFS spectra, the resonance peaks from B 1s to unoccupied π * -like orbitals were clearly observed. The polarization dependence of the B 1s → π * resonance peaks confirmed that the highly oriented graphite-like B-C-N hybrids surely exist at low boron content. (author)

The complex compounds of manganese (II) with poly dental ligands and polyhedron borane anions

International Nuclear Information System (INIS)

Buranova, S.A.

1996-01-01

The purpose of the present work is synthesis of complex compounds of manganese with organic ligands. Their studying by spectroscopic methods purposely to determinate the influence of borane anions on composition and structure of coordinating sphere of manganese

Selective C(sp2)-C(sp) bond cleavage: the nitrogenation of alkynes to amides.

Science.gov (United States)

Qin, Chong; Feng, Peng; Ou, Yang; Shen, Tao; Wang, Teng; Jiao, Ning

2013-07-22

Breakthrough: A novel catalyzed direct highly selective C(sp2)-C(sp) bond functionalization of alkynes to amides has been developed. Nitrogenation is achieved by the highly selective C(sp2)-C(sp) bond cleavage of aryl-substituted alkynes. The oxidant-free and mild conditions and wide substrate scope make this method very practical. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

Science.gov (United States)

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructural evolution during transient liquid phase bonding of Inconel 617 using Ni-Si-B filler metal

International Nuclear Information System (INIS)

Jalilian, F.; Jahazi, M.; Drew, R.A.L.

2006-01-01

The influence of process parameters on microstructural characteristics of transient liquid phase (TLP) bonded Inconel 617 alloy was investigated. Experiments were carried out at 1065 deg. C using nickel based filler metal (Ni-4.5% Si-3% B) with B as the melting point depressant (MPD) element. Two different thickness of interlayer and various holding times were employed. The influence of these processing parameters on the characteristics of the joint area particularly size, morphology and composition of precipitates was investigated. The presence of MoB, Mo 2 B, M 23 C 6 , TiC, M 23 (B, C) 6 and Ni 3 B precipitates in the diffusion layer and Ni 3 B, Ni 3 Si and Ni 5 Si 2 precipitates in the interlayer at the interface between the base metal and interlayer were demonstrated using electron back scattered diffraction (EBSD), energy dispersive spectrometry (EDS) and TEM

Process for synthesis of ammonia borane for bulk hydrogen storage

Science.gov (United States)

Autrey, S Thomas [West Richland, WA; Heldebrant, David J [Richland, WA; Linehan, John C [Richland, WA; Karkamkar, Abhijeet J [Richland, WA; Zheng, Feng [Richland, WA

2011-03-01

The present invention discloses new methods for synthesizing ammonia borane (NH.sub.3BH.sub.3, or AB). Ammonium borohydride (NH.sub.4BH.sub.4) is formed from the reaction of borohydride salts and ammonium salts in liquid ammonia. Ammonium borohydride is decomposed in an ether-based solvent that yields AB at a near quantitative yield. The AB product shows promise as a chemical hydrogen storage material for fuel cell powered applications.

Microstructure Evolution and Mechanical Properties of Al-TiB2/TiC In Situ Aluminum-Based Composites during Accumulative Roll Bonding (ARB Process

Directory of Open Access Journals (Sweden)

Jinfeng Nie

2017-01-01

Full Text Available In this study, a kind of Al-TiB2/TiC in situ composite was successfully prepared using the melt reaction method and the accumulative roll-bonding (ARB technique. The microstructure evolution of the composites with different deformation treatments was characterized using field emission scanning electron microscopy (FESEM and a transmission electron microscope (TEM. The mechanical properties of the Al-TiB2/TiC in situ composite were also studied with tensile and microhardness tests. It was found that the distribution of reinforcement particles becomes more homogenous with an increasing ARB cycle. Meanwhile, the mechanical properties showed great improvement during the ARB process. The ultimate tensile strength (UTS and microhardness of the composites were increased to 173.1 MPa and 63.3 Hv after two ARB cycles, respectively. Furthermore, the strengthening mechanism of the composite was analyzed based on its fracture morphologies.

On the Michael addition of water to C = C bonds

NARCIS (Netherlands)

Chen, B.

2015-01-01

?-Hydroxy carbonyl compounds are an important class of compounds often found as a common structural motif in natural products. Although the molecules themselves look rather simple, their synthesis can be challenging. Water addition to conjugated C = C bonds opens up a straightforward route for the

Copper-catalyzed transformation of ketones to amides via C(CO)-C(alkyl) bond cleavage directed by picolinamide.

Science.gov (United States)

Ma, Haojie; Zhou, Xiaoqiang; Zhan, Zhenzhen; Wei, Daidong; Shi, Chong; Liu, Xingxing; Huang, Guosheng

2017-09-13

Copper catalyzed chemoselective cleavage of the C(CO)-C(alkyl) bond leading to C-N bond formation with chelation assistance of N-containing directing groups is described. Inexpensive Cu(ii)-acetate serves as a convenient catalyst for this transformation. This method highlights the emerging strategy to transform unactivated alkyl ketones into amides in organic synthesis and provides a new strategy for C-C bond cleavage.

A chiral synthesis of dapoxetine hydrochloride, a serotonin re-uptake inhibitor, and its 14C isotopomer

International Nuclear Information System (INIS)

Wheeler, W.J.; O'Bannon, D.D.

1992-01-01

The 14 C-isotopmer of dapoxetine-[ 14 C] HCl (S (+) -N,N-dimethyl-α[2-(1-naphthalenyloxy)ethyl-2- 14 C]benzenemeth a-n amine hydrochloride, 1a), a potent serotonin re-uptake inhibitor has been prepared by a chiral synthesis, starting with tert. -butyloxyphenylglycine (3). Borane reduction, followed by activation of the resulting alcohol 4 as its mesylate 5b, provided the chiral starting material. The radiolabel was introduced by reaction of 5b with sodium cyanide-[ 14 C]. The desired product (1) was then elaborated from nitrile 6a,b via a five step synthesis in an overall 19.5% radiochemical yield. (Author)

Microstructural evolution during transient liquid phase bonding of Inconel 617 using Ni-Si-B filler metal

Energy Technology Data Exchange (ETDEWEB)

Jalilian, F. [McGill University, Department of Mining, Metals and Materials Engineering, 3610 University St., M.H. Wong Building, Montreal Que., H3A 2B2 (Canada); Jahazi, M. [Aerospace Manufacturing Technology Center, National Research Council of Canada (Canada); Drew, R.A.L. [McGill University, Department of Mining, Metals and Materials Engineering, 3610 University St., M.H. Wong Building, Montreal Que., H3A 2B2 (Canada)]. E-mail: robin.drew@mcgill.ca

2006-05-15

The influence of process parameters on microstructural characteristics of transient liquid phase (TLP) bonded Inconel 617 alloy was investigated. Experiments were carried out at 1065 deg. C using nickel based filler metal (Ni-4.5% Si-3% B) with B as the melting point depressant (MPD) element. Two different thickness of interlayer and various holding times were employed. The influence of these processing parameters on the characteristics of the joint area particularly size, morphology and composition of precipitates was investigated. The presence of MoB, Mo{sub 2}B, M{sub 23}C{sub 6}, TiC, M{sub 23}(B, C){sub 6} and Ni{sub 3}B precipitates in the diffusion layer and Ni{sub 3}B, Ni{sub 3}Si and Ni{sub 5}Si{sub 2} precipitates in the interlayer at the interface between the base metal and interlayer were demonstrated using electron back scattered diffraction (EBSD), energy dispersive spectrometry (EDS) and TEM.

C=C bond cleavage on neutral VO3(V2O5)n clusters.

Science.gov (United States)

Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

2009-01-28

The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

Ligand-Controlled Chemoselective C(acyl)–O Bond vs C(aryl)–C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)–C(sp3) Cross-Couplings

KAUST Repository

Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Srimontree, Watchara; Guo, Lin; Minenkov, Yury; Poater, Albert; Cavallo, Luigi; Rueping, Magnus

2018-01-01

step helped rationalizing this intriguing reaction chemoselectivity: whereas nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step leading to the alkylated product via a decarbonylative process, nickel

Catalytic hydrolysis of ammonia borane for hydrogen generation using cobalt nanocluster catalyst supported on polydopamine functionalized multiwalled carbon nanotube

International Nuclear Information System (INIS)

Arthur, Ernest Evans; Li, Fang; Momade, Francis W.Y.; Kim, Hern

2014-01-01

Hydrogen was generated from ammonia borane complex by hydrolysis using cobalt nanocluster catalyst supported on polydopamine functionalized MWCNTs (multi-walled carbon nanotubes). The impregnation-chemical reduction method was used for the preparation of the supported catalyst. The nanocluster catalyst support was formed by in-situ oxidative polymerization of dopamine on the MWCNTs in alkaline solution at room temperature. The structural and physical–chemical properties of the nanocluster catalyst were characterized by FT-IR (Fourier transform infrared spectroscopy), EDX (energy-dispersive X-ray spectroscopy), SEM (scanning electron microscope), XRD (X-ray diffraction) and TEM (transmission electron microscopy). The nanocluster catalyst showed good catalytic activity for the hydrogen generation from aqueous ammonia borane complex. A reusability test to determine the practical usage of the catalyst was also investigated. The result revealed that the catalyst maintained an appreciable catalytic performance and stability in terms of its reusability after three cycle of reuse for the hydrolysis reaction. Also, the activation energy for the hydrolysis of ammonia borane complex was estimated to be 50.41 kJmol −1 , which is lower than the values of some of the reported catalyst. The catalyst can be considered as a promising candidate in developing highly efficient portable hydrogen generation systems such as PEMFC (proton exchange membrane fuel cells). - Highlights: • Co/Pdop-o-MWCNT (Pdop functionalized MWCNT supported cobalt nanocluster) catalyst was synthesized for hydrogen generation. • It is an active catalyst for hydrogen generation via hydrolysis of ammonia borane. • It showed good stability in terms of reusability for the hydrogen generation

Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

Science.gov (United States)

Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

2018-06-29

The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physical and magnetic properties, microstructure of bonded magnet NdFeB prepared by using synthesis rubber

International Nuclear Information System (INIS)

Suprapedi; Sardjono, P.; Muljadi

2016-01-01

The magnet permanent has been made by using NdFeB (NQP-B) powder with purity 99.90% and polymer rubber with purity 90%. This research was done to determine the effect of the polymer (rubber) composition as binder in the manufacture of bonded magnet NdFeB on physical properties, microstructure and magnetic properties. Bonded magnets are magnet material made from a mixture of magnetic powder as a filler and the polymer as a matrix material or as binder to bind the magnetic particles. The NdFeB (NQP-B) powder fractions of bonded magnets NdFeB investigated were as follows: a) 97 wt.% of NdFeB (NQP-B) and 3 wt.% of rubber,b) 95wt.% of NdFeB (NQP-B) and 5 wt.% of rubber, c) 93 wt.% of NdFeB (NQP-B) and 7 wt.% of rubber, d) 91 wt.% of NdFeB (NQP-B) and 9 wt.% of rubber. Both raw materials were mixed by using mixer until homogen with total weight about 16 g for each sample, then added 0.3 ml of catalyst and mixed again and put in dies mould and compacted at pressure 30 MPa, then dried for 2 hours at room temperature. The dried samples was characterized such as: bulk density measurement and magnetic properties by using BH-curve permeagraph. The bulk density values of the sample bonded NdFeB magnets using the binder 3% wt. and 5% wt. rubber are respectively 4,70 g/cm 3 and 4.88 g/cm 3 . The result from BH- curve shows that the highest value of remanence (Br = 5.12 kGauss) is at sample with 3% wt. of rubber, but sample with 5% wt. of rubber has lowest value of remanance (Br = 4.40 kGauss). Based on the observation of the SEM photograph shown that the rubber material has been successfully covered the whole surface of the grain and fill some of the voids that are in the grain boundary. (paper)

Physical and magnetic properties, microstructure of bonded magnet NdFeB prepared by using synthesis rubber

Science.gov (United States)

Suprapedi; Sardjono, P.; Muljadi

2016-11-01

The magnet permanent has been made by using NdFeB (NQP-B) powder with purity 99.90% and polymer rubber with purity 90%. This research was done to determine the effect of the polymer (rubber) composition as binder in the manufacture of bonded magnet NdFeB on physical properties, microstructure and magnetic properties. Bonded magnets are magnet material made from a mixture of magnetic powder as a filler and the polymer as a matrix material or as binder to bind the magnetic particles. The NdFeB (NQP-B) powder fractions of bonded magnets NdFeB investigated were as follows: a) 97 wt.% of NdFeB (NQP-B) and 3 wt.% of rubber,b) 95wt.% of NdFeB (NQP-B) and 5 wt.% of rubber, c) 93 wt.% of NdFeB (NQP-B) and 7 wt.% of rubber, d) 91 wt.% of NdFeB (NQP-B) and 9 wt.% of rubber. Both raw materials were mixed by using mixer until homogen with total weight about 16 g for each sample, then added 0.3 ml of catalyst and mixed again and put in dies mould and compacted at pressure 30 MPa, then dried for 2 hours at room temperature. The dried samples was characterized such as: bulk density measurement and magnetic properties by using BH-curve permeagraph. The bulk density values of the sample bonded NdFeB magnets using the binder 3% wt. and 5% wt. rubber are respectively 4,70 g/cm3 and 4.88 g/cm3. The result from BH- curve shows that the highest value of remanence (Br = 5.12 kGauss) is at sample with 3% wt. of rubber, but sample with 5% wt. of rubber has lowest value of remanance (Br = 4.40 kGauss). Based on the observation of the SEM photograph shown that the rubber material has been successfully covered the whole surface of the grain and fill some of the voids that are in the grain boundary.

Metal interactions with boron clusters

International Nuclear Information System (INIS)

Grimes, R.N.

1982-01-01

This book presents information on the following topics: the structural and bonding features of metallaboranes and metallacarboranes; transition-metal derivatives of nido-boranes and some related species; interactions of metal groups with the octahydrotriborate (1-) anion, B 3 H 8 ; metallaboron cage compounds of the main group metals; closo-carborane-metal complexes containing metal-carbon and metal-boron omega-bonds; electrochemistry of metallaboron cage compounds; and boron clusters with transition metal-hydrogen bonds

Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

Science.gov (United States)

Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

2014-12-08

A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy and Rate Determinations to Activate the C-C σ-BOND of Acetone by Gaseous NI^+

Science.gov (United States)

Castleberry, Vanessa A.; Dee, S. Jason; Villarroel, Otsmar J.; Laboren, Ivanna E.; Frey, Sarah E.; Bellert, Darrin J.

2009-06-01

A unique application of a custom fabricated photodissociation spectrometer permits the determination of thermodynamic properties (activation energies), reaction rates, and mechanistic details of bare metal cation mediated C-C σ-bond activation in the gas phase. Specifically, the products and rates resulting from the unimolecular decomposition of the Ni^+Acetone (Ni^+Ac) adduct are monitored after absorption of a known amount of energy. The three dissociative products which are observed in high yield are Ni^+, Ni^+CO, and CH3CO^+. The latter two fragment ions result from the activation of a C-C σ-bond. It was found that minimally 14 000 cm^{-1} of energy must be deposited into the adduct ion to induce C-C bond breakage. Preliminary results for the Ni^+ activation of the C-C σ-bond of acetone indicate that there are (at least) two low energy reaction coordinates leading to C-C bond breakage. The lower energy pathway emerges from the doublet ground state with an upper limit to the activation energy of 14 000 cm^{-1} and reaction rate ≈0.14 molecules/μs. The higher energy path is assumed to be along the quartet reaction coordinate with a minimum activation energy of 18 800 cm^{-1} (relative to the ground state) and a slightly slower reaction rate.

Composite bonding to stainless steel crowns using a new universal bonding and single-bottle systems.

Science.gov (United States)

Hattan, Mohammad Ali; Pani, Sharat Chandra; Alomari, Mohammad

2013-01-01

Aim. The aim of this study is to evaluate the shear bond strength of nanocomposite to stainless steel crowns using a new universal bonding system. Material and Methods. Eighty (80) stainless steel crowns (SSCs) were divided into four groups (20 each). Packable nanocomposite was bonded to the lingual surface of the crowns in the following methods: Group A without adhesive (control group), Group B using a new universal adhesive system (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany), and Group C and Group D using two different brands of single-bottle adhesive systems. Shear bond strengths were calculated and the types of failure also were recorded. Results. The shear strength of Group B was significantly greater than that of other groups. No significant differences were found between the shear bond strengths of Groups C and D. The control group had significantly lower shear bond strength (P universal bonding agent (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany) show significantly greater shear bond strengths and fewer adhesive failures when compared to traditional single-bottle systems.

The demagnetising factors for bonded neodymium iron boron (NdFeB) magnets

International Nuclear Information System (INIS)

Wang, Z.

2000-10-01

Both analytical and computational methods have been, for the first time, employed to study the demagnetising factors for bonded magnets. The demagnetising factors for bonded NdFeB magnets are dependent on the external shape of the bonded magnet, the shapes of magnetic particles, the magnetic loading percentage and the distributions of magnetic particles. Particularly, it has been shown that the demagnetising factor along the length of an infinitely long bonded magnet is not equal to zero but that it also depends on the shapes of the magnetic particles, magnetic loading percentage and the distribution of magnetic particles. However, the sum of the demagnetising factors along the x, y and z directions is, as expected, unity for all bonded magnets. The demagnetising factor for a fully dense magnet, which is dependent only on the external shape of the magnet, can be considered as a special case of bonded magnets in which the magnetic loading is 100%. Simplified formulae for calculating the demagnetising factors for simple shaped magnets such as cuboid, cylindroid and ellipsoid shapes were obtained and the values are in reasonable agreement with precise analytical solutions. A Lorentz ''sphere'' concept has, for the first time, been employed to calculate the demagnetising factors for hollow magnets and bonded NdFeB magnets. The simplified formulae for hollow magnets and bonded magnets were derived. Computer programmes based on the basic energy method were developed and employed to calculate the demagnetising factors for bonded magnet models, such as a one-dimensional NdFeB ribbon array, two-dimensional bonded magnets and three-dimensional bonded magnets. A finite difference method and a finite element method have been, for the first time, employed to calculate the demagnetising factors for two-dimensional bonded magnet models and the results are comparable with those obtained using the basic energy method. Procedures for calculating demagnetising curves (J vs H) for

Composite Bonding to Stainless Steel Crowns Using a New Universal Bonding and Single-Bottle Systems

Directory of Open Access Journals (Sweden)

Mohammad Ali Hattan

2013-01-01

Full Text Available Aim. The aim of this study is to evaluate the shear bond strength of nanocomposite to stainless steel crowns using a new universal bonding system. Material and Methods. Eighty (80 stainless steel crowns (SSCs were divided into four groups (20 each. Packable nanocomposite was bonded to the lingual surface of the crowns in the following methods: Group A without adhesive (control group, Group B using a new universal adhesive system (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany, and Group C and Group D using two different brands of single-bottle adhesive systems. Shear bond strengths were calculated and the types of failure also were recorded. Results. The shear strength of Group B was significantly greater than that of other groups. No significant differences were found between the shear bond strengths of Groups C and D. The control group had significantly lower shear bond strength ( to composite than the groups that utilized bonding agents. Conclusion. Composites bonding to stainless steel crowns using the new universal bonding agent (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany show significantly greater shear bond strengths and fewer adhesive failures when compared to traditional single-bottle systems.

Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(mu-C triple bondCC triple bond C)].

Science.gov (United States)

Bruce, Michael I; Costuas, Karine; Davin, Thomas; Halet, Jean-François; Kramarczuk, Kathy A; Low, Paul J; Nicholson, Brian K; Perkins, Gary J; Roberts, Rachel L; Skelton, Brian W; Smith, Mark E; White, Allan H

2007-12-14

The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os([=C=CH2)(dppe)Cp*]PF6 ([11]PF6), [Os(C triple bond CH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{mu-(=C=CH-CH=C=)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}(2)(mu-C triple bond CC triple bond C)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(mu-C triple bond CC triple bond C)] (M = Fe, Ru, Os). The molecular structures of []PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(C triple bond CPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe approximately Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(mu-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.

46 CFR 308.529 - Surety Bond B, Form MA-309.

Science.gov (United States)

2010-10-01

... Shipping MARITIME ADMINISTRATION, DEPARTMENT OF TRANSPORTATION EMERGENCY OPERATIONS WAR RISK INSURANCE War Risk Cargo Insurance Ii-Open Policy War Risk Cargo Insurance § 308.529 Surety Bond B, Form MA-309. An Assured who elects to substitute a surety bond for a collateral deposit fund shall submit Form MA-309...

Al-Si/B{sub 4}C composite coatings on Al-Si substrate by plasma spray technique

Energy Technology Data Exchange (ETDEWEB)

Sarikaya, Ozkan [Sakarya University, Faculty of Engineering, Department of Mechanical Engineering, Esentepe Campus, Sakarya 54187 (Turkey); Anik, Selahaddin [Sakarya University, Faculty of Engineering, Department of Mechanical Engineering, Esentepe Campus, Sakarya 54187 (Turkey); Aslanlar, Salim [Sakarya University, Faculty of Technical Education, Department of Mechanical Engineering, Esentepe Campus, Sakarya 54187 (Turkey); Cem Okumus, S. [Sakarya University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, Esentepe Campus, Sakarya 54187 (Turkey); Celik, Erdal [Dokuz Eylul University, Engineering Faculty, Department of Metallurgical and Materials Engineering, Buca, Izmir 35160 (Turkey)]. E-mail: erdal.celik@deu.edu.tr

2007-07-01

Plasma-sprayed coatings of Al-Si/B{sub 4}C have been prepared on Al-Si piston alloys for diesel engine motors. The Al-Si/B{sub 4}C composite powders including 5-25 wt% B{sub 4}C were prepared by mixing and ball-milling processes. These powders were deposited on Al-Si substrate using an atmospheric plasma spray technique. The coatings have been characterised with respect to phase composition, microstructure, microhardness, bond strength and thermal expansion. It was found that Al, Si, B{sub 4}C and Al{sub 2}O{sub 3} phases were determined in the coatings with approximately 600 {mu}m thick by using X-ray diffraction analysis. Scanning electron microscope observation revealed that boron carbide particles were uniformly distributed in composite coatings and B{sub 4}C particles were fully wetted by Al-Si alloy. Also, no reaction products were observed in Al-Si/B{sub 4}C composite coatings. It was found that surface roughness, porosity, bond strength and thermal expansion coefficient of composite coatings decreased with increasing fraction of the boron carbide particle. It was demonstrated that the higher the B{sub 4}C content, the higher the hardness of coatings because the hardness of B{sub 4}C is higher than that of Al-Si.

Inhibition of enamel demineralization and bond-strength properties of bioactive glass containing 4-META/MMA-TBB-based resin adhesive.

Science.gov (United States)

Kohda, Naohisa; Iijima, Masahiro; Kawaguchi, Kyotaro; Toshima, Hirokazu; Muguruma, Takeshi; Endo, Kazuhiko; Mizoguchi, Itaru

2015-06-01

We investigated the enamel demineralization-prevention ability and shear bond strength (SBS) properties of 4-methacryloxyethyl trimellitic anhydride/methyl methacrylate-tri-n-butyl borane (4-META/MMA-TBB)-based resin containing various amounts (0-50%) of bioactive glass (BG). Disk-shaped specimens were immersed in distilled water and ions released were analysed by inductively coupled plasma atomic-emission spectroscopy. Samples were also immersed in lactic acid solution (pH 4.6) to estimate acid-neutralizing ability. Brackets were bonded to human premolars with BG-containing resins and the bonded teeth were alternately immersed in demineralizing (pH 4.55) and remineralizing (pH 6.8) solutions for 14 d. The enamel hardness was determined by nanoindentation testing at twenty equidistant distances from the external surface. The SBS for each sample was examined. The amounts of ions released [calcium (Ca), sodium (Na), silicon (Si), and boron (B)] and the acid-neutralizing ability increased with increasing BG content. After alternating immersion, the specimens bonded with the BG-containing resin with high BG content were harder than those in the other groups in some locations 1-18.5 μm from the enamel surface. Bioactive glass-containing (10-40%) resin had bond strength equivalent to the control specimen. Thus, the SBS obtained for BG-containing resin (6.5-9.2 MPa) was clinically acceptable, suggesting that this material has the ability to prevent enamel demineralization. © 2015 Eur J Oral Sci.

Catalytic hydrolysis of ammonia borane: Intrinsic parameter estimation and validation

Energy Technology Data Exchange (ETDEWEB)

Basu, S.; Gore, J.P. [School of Mechanical Engineering, Purdue University, West Lafayette, IN 47907-2088 (United States); School of Chemical Engineering, Purdue University, West Lafayette, IN 47907-2100 (United States); Energy Center in Discovery Park, Purdue University, West Lafayette, IN 47907-2022 (United States); Zheng, Y. [School of Mechanical Engineering, Purdue University, West Lafayette, IN 47907-2088 (United States); Energy Center in Discovery Park, Purdue University, West Lafayette, IN 47907-2022 (United States); Varma, A.; Delgass, W.N. [School of Chemical Engineering, Purdue University, West Lafayette, IN 47907-2100 (United States); Energy Center in Discovery Park, Purdue University, West Lafayette, IN 47907-2022 (United States)

2010-04-02

Ammonia borane (AB) hydrolysis is a potential process for on-board hydrogen generation. This paper presents isothermal hydrogen release rate measurements of dilute AB (1 wt%) hydrolysis in the presence of carbon supported ruthenium catalyst (Ru/C). The ranges of investigated catalyst particle sizes and temperature were 20-181 {mu}m and 26-56 C, respectively. The obtained rate data included both kinetic and diffusion-controlled regimes, where the latter was evaluated using the catalyst effectiveness approach. A Langmuir-Hinshelwood kinetic model was adopted to interpret the data, with intrinsic kinetic and diffusion parameters determined by a nonlinear fitting algorithm. The AB hydrolysis was found to have an activation energy 60.4 kJ mol{sup -1}, pre-exponential factor 1.36 x 10{sup 10} mol (kg-cat){sup -1} s{sup -1}, adsorption energy -32.5 kJ mol{sup -1}, and effective mass diffusion coefficient 2 x 10{sup -10} m{sup 2} s{sup -1}. These parameters, obtained under dilute AB conditions, were validated by comparing measurements with simulations of AB consumption rates during the hydrolysis of concentrated AB solutions (5-20 wt%), and also with the axial temperature distribution in a 0.5 kW continuous-flow packed-bed reactor. (author)

PVP-stabilized Ru–Rh nanoparticles as highly efficient catalysts for hydrogen generation from hydrolysis of ammonia borane

International Nuclear Information System (INIS)

Rakap, Murat

2015-01-01

Herein, the utilization of poly(N-vinyl-2-pyrrolidone)-protected ruthenium–rhodium nanoparticles (3.4 ± 1.4 nm) as highly efficient catalysts in the hydrolysis of ammonia borane for hydrogen generation is reported. They are prepared by co-reduction of ruthenium and rhodium metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy-energy dispersive X-ray spectroscopy, ultraviolet–visible spectroscopy, and X-ray photoelectron spectroscopy. They are durable and highly efficient catalysts for hydrogen generation from the hydrolysis of ammonia borane even at very low concentrations and temperature, providing average turnover frequency of 386 mol H 2 (mol cat) −1 min −1 and maximum hydrogen generation rate of 10,680 L H 2 min −1 (mol cat) −1 . Poly(N-vinyl-2-pyrrolidone)-protected ruthenium–rhodium nanoparticles also provide activation energy of 47.4 ± 2.1 kJ/mol for the hydrolysis of ammonia borane. - Highlights: • Ru-Rh@PVP NPs provide a TOF of 386 mol H 2 (mol cat) −1 min −1 for hydrolysis of AB. • Maximum HG rate is 9680 L H 2 min −1 (mol cat) −1 for the hydrolysis of AB. • Activation energy is 47.4 ± 2.1 kJ mol −1 for the hydrolysis of AB

Catalyst-Dependent Chemoselective Formal Insertion of Diazo Compounds into C-C or C-H Bonds of 1,3-Dicarbonyl Compounds.

Science.gov (United States)

Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A; Bi, Xihe

2018-05-08

A catalyst-dependent chemoselective one-carbon insertion of diazo compounds into the C-C or C-H bonds of 1,3-dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)-C bond of the 1,3-dicarbonyl substrate leads to a 1,4-dicarbonyl product containing an all-carbon α-quaternary center. This reaction constitutes the first example of an insertion of diazo-derived carbenoids into acyclic C-C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C-H insertion, affording 2-alkylated 1,3-dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst-dependent chemoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interfacial push-out measurements of fully-bonded SiC/SiC composites

International Nuclear Information System (INIS)

Snead, L.L.; Steiner, D.; Zinkle, S.J.

1990-01-01

The direct measurement of interfacial bond strength and frictional resistance to sliding in a fully-bonded SiC/SiC composite is measured. It is shown that a fiber push-out technique can be utilized for small diameter fibers and very thin composite sections. Results are presented for a 22 micron thick section for which 37 out of 44 Nicalon fibers tested were pushed-out within the maximum nanoindentor load of 120 mN. Fiber interfacial yielding, push-out and sliding resistance were measured for each fiber. The distribution of interfacial strengths is treated as being Weibull in form. 14 refs., 5 figs

Hydrogen bond disruption in DNA base pairs from (14)C transmutation.

Science.gov (United States)

Sassi, Michel; Carter, Damien J; Uberuaga, Blas P; Stanek, Christopher R; Mancera, Ricardo L; Marks, Nigel A

2014-09-04

Recent ab initio molecular dynamics simulations have shown that radioactive carbon does not normally fragment DNA bases when it decays. Motivated by this finding, density functional theory and Bader analysis have been used to quantify the effect of C → N transmutation on hydrogen bonding in DNA base pairs. We find that (14)C decay has the potential to significantly alter hydrogen bonds in a variety of ways including direct proton shuttling (thymine and cytosine), thermally activated proton shuttling (guanine), and hydrogen bond breaking (cytosine). Transmutation substantially modifies both the absolute and relative strengths of the hydrogen bonding pattern, and in two instances (adenine and cytosine), the density at the critical point indicates development of mild covalent character. Since hydrogen bonding is an important component of Watson-Crick pairing, these (14)C-induced modifications, while infrequent, may trigger errors in DNA transcription and replication.

dC-dG alternating oligonucleotides: Thermodynamic and kinetic aspects of the B-Z transformation

International Nuclear Information System (INIS)

Manzini, G.; Xodo, L.E.; Quadrifoglio, F.; van Boom, J.H.; van der Marel, G.A.

1987-01-01

The alternating cytosine-guanine oligodeoxyribonucleotides (dCdG)n, (dGdC)n, (dCdG)ndC (n = 3,4), (dGdC)7 and dG(dCdG)3 have been studied by UV and CD spectroscopy at different temperatures and NaCl concentrations. The analysis of the melting data, assuming an all-or-none model, reveals that in the B-conformation the 5'G/C3' stacking interactions are enthalpically favoured with respect to the 5'C/G3' one. The CD investigation of the B-Z equilibrium shows that the Z-conformation is enthalpically stabilized, while the B-conformation is entropically favoured, in the range of NaCl concentration considered (1 to 5 M). The kinetic data for the B-Z transformation, obtained with a salt-jump technique for the hexamer (dCdG)3, support a mechanism by which the Watson-Crick hydrogen bonds are broken before the bases flip over separately and eventually stack, reforming the H-bonds, in the new helix

Use of paired, bonded NdFeB magnets in redox magnetohydrodynamics.

Science.gov (United States)

Arumugam, Prabhu U; Clark, Emily A; Fritsch, Ingrid

2005-02-15

Bonded neodymium-iron-boron (NdFeB) permanent magnets in a paired configuration were successfully used to control mass transport in redox-based, magnetohydrodynamics (MHD). Control of fluid flow based on magnetic fields has potential for use in portable lab-on-a-chip (LOAC) and analytical devices. Bonded magnets, composed of magnetic powder and organic binder materials, are less expensive and easier to fabricate and pattern than electromagnets and sintered permanent magnets, which have been previously used in MHD studies on electrochemical systems. The ability to pattern bonded magnets near and around the electrodes is expected to allow for better control over the magnetic field distribution and solution flow. Current was generated at an 800-microm-radius platinum disk electrode in a solution of 0.06 M nitrobenzene and 0.5 M tetra-n-butylammonium hexafluorophosphate in acetonitrile. Increases in limiting current in the presence of the magnetic field, which indicate enhancement in mass transport, for sintered (210+/-14%, N = 4, where B(r) = 1.23 T and magnetic field strength is 0.55 T) and bonded (94+/-8%, N = 4, where B(r) = 0.41 T and magnetic field strength is 0.20 T) magnets, were similar to those obtained using an electromagnet with the same magnetic flux densities. The magnetic field strength and not the magnet type is important in controlling fluid flow, which is encouraging for integration of bonded permanent magnets into LOAC devices.

The molecular, electronic, bonding, and photophysical features of the [(c-Pt3)Tl(c-Pt3)]+ inorganic metallocenes.

Science.gov (United States)

Tsipis, Athanassios C; Gkekas, George N

2013-06-21

The molecular, electronic, bonding and photophysical properties of a series of inorganic metallocenes with the general formula {[Pt3(μ2-L)3(L')3]2(μ6-Tl)}(+) (L = CO, CH3CN, PH2, C6F5, or SO2 and L' = CO, PH3, CH3CN, C6F5) have been studied by means of DFT electronic structure calculations. The estimated Tl-cd distances between Tl(+) cations and the centroids (cd) of the trimetallic Pt3(μ2-L)3(L')3 {3 : 3 : 3} decks were found in the range 2.932-3.397 Å. The predicted bond dissociation energy, D0, of the (c-Pt3)···Tl(+) bonds was found to lie within the range -31.5 up to -77.5 kcal mol(-1) at the B3LYP/LANL2TZ(f)(Pt) ∪ 6-31G(d,p)(E) ∪ SRLC(Tl) level of theory. Most of the [(c-Pt3)Tl(c-Pt3)](+) inorganic metallocenes adopt a bend titanocene-like structure. The Localized Orbital Locator (LOL) contour maps along with the 3D contour plots of the Reduced Gradient Density (RDG) mirror the composite nature of the interaction of Tl(+) with the triangular Pt3 metallic ring cores consisting of electrostatic, covalent and dispersion interaction components. The Pt3···Tl(+)···Pt3 bonding mode was further validated by Energy Decomposition Analysis (EDA) calculations which demonstrated that the electrostatic and covalent components of the interaction contribute almost equally to the bonding interactions. Furthermore, Charge Decomposition Analysis (CDA) and Natural Bond Orbital Analysis (NBO) calculations indicated that charge transfer from the Tl(+) cation to the Pt3(0) {3 : 3 : 3} decks also occurs. The {[Pt3(μ2-L)3(L')3]2(μ6-Tl)}(+) sandwiches absorb in the UV-Vis region (300-500 nm) and emit in the visible-near IR region (600-1000 nm). The absorption bands are mainly of MLCT/MC character while phosphorescence is predicted to occur via the first triplet excited state, T1, since the spin density of this excited state could be described as a SOMO - 1/SOMO combination. Generally, no significant distortions occur upon excitation of these systems

Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

Science.gov (United States)

Zhou, Tian

Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

The Dominant Role of Chalcogen Bonding in the Crystal Packing of 2D/3D Aromatics

Czech Academy of Sciences Publication Activity Database

Fanfrlík, Jindřich; Přáda, A.; Padělková, Z.; Pecina, Adam; Macháček, Jan; Lepšík, Martin; Holub, Josef; Růžička, A.; Hnyk, Drahomír; Hobza, Pavel

2014-01-01

Roč. 53, č. 38 (2014), s. 10139-10142 ISSN 1433-7851 R&D Projects: GA ČR GBP208/12/G016; GA ČR GAP208/10/2269 Grant - others:GA MŠk(CZ) ED2.1.00/03.0058; GA MŠk(CZ) ED1.1.00/02.0070; GA MŠk(CZ) LM2011033 Program:ED; ED Institutional support: RVO:61388963 ; RVO:61388980 Keywords : boranes * chalcogen bonds * crystal structures * sulfur * X-ray diffraction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 11.261, year: 2014

PVP-stabilized Ru–Rh nanoparticles as highly efficient catalysts for hydrogen generation from hydrolysis of ammonia borane

Energy Technology Data Exchange (ETDEWEB)

Rakap, Murat, E-mail: mrtrakap@gmail.com

2015-11-15

Herein, the utilization of poly(N-vinyl-2-pyrrolidone)-protected ruthenium–rhodium nanoparticles (3.4 ± 1.4 nm) as highly efficient catalysts in the hydrolysis of ammonia borane for hydrogen generation is reported. They are prepared by co-reduction of ruthenium and rhodium metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy-energy dispersive X-ray spectroscopy, ultraviolet–visible spectroscopy, and X-ray photoelectron spectroscopy. They are durable and highly efficient catalysts for hydrogen generation from the hydrolysis of ammonia borane even at very low concentrations and temperature, providing average turnover frequency of 386 mol H{sub 2} (mol cat){sup −1} min{sup −1} and maximum hydrogen generation rate of 10,680 L H{sub 2} min{sup −1} (mol cat){sup −1}. Poly(N-vinyl-2-pyrrolidone)-protected ruthenium–rhodium nanoparticles also provide activation energy of 47.4 ± 2.1 kJ/mol for the hydrolysis of ammonia borane. - Highlights: • Ru-Rh@PVP NPs provide a TOF of 386 mol H{sub 2} (mol cat){sup −1} min{sup −1} for hydrolysis of AB. • Maximum HG rate is 9680 L H{sub 2} min{sup −1} (mol cat){sup −1} for the hydrolysis of AB. • Activation energy is 47.4 ± 2.1 kJ mol{sup −1} for the hydrolysis of AB.

The production and characterization of Ptfe bonded Nd-Fe-B magnets

International Nuclear Information System (INIS)

Mokal, B.; Williams, A.J.; Hay, J.N.; Harris, I.R.

1996-01-01

A study of the processing and characteristics of PTFE bonded Nd Fe B magnets has been carried out. PTFE was used because of its low coefficient of friction, thus enabling its flow between the particles of Nd Fe B powder. PTFE also increases the resistance to corrosion of the magnet. In these investigations, the production of bonded magnets by cold compaction and by hot processing (HP) of MQ powders using PTFE as the binder was investigated . Magnetic, microstructural, and mechanical properties were investigated and are presented together with a correlation with the different processing techniques used. The corrosion behaviour of the hot pressed magnets was also investigated. These studies could lead to the development of simpler and more effective processing routes for the production of bonded magnets. (author)

Electronic Structures and Bonding Properties of Ti2AlC and Ti3AlC2

Institute of Scientific and Technical Information of China (English)

MIN Xinmin; REN Yi

2007-01-01

The relation among electronic structure, chemical bond and property of Ti2AlC, Ti3AlC2 and doping Si into Ti2AlC was studied by density function and the discrete variation (DFT-DVM) method. After adding Si into Ti2AlC, the interaction between Si and Ti is weaker than that between Al and Ti, and the strengths of ionic and covalent bonds decrease both. The ionic and covalent bonds in Ti3AlC2, especially in Ti-Al, are stronger than those in Ti2AlC. Therefore, in synthesis of Ti2AlC, the addition of Si enhances the Ti3AlC2 content instead of Ti2AlC. The density of state (DOS) shows that there is mixed conductor characteristic in Ti2AlC and Ti3AlC2. The DOS of Ti3AlC2 is much like that of Ti2AlC. Ti2SixAl1-x C has more obvious tendency to form a semiconductor than Ti2AlC, which is seen from the obvious difference of partial DOS between Si and Al3p.

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

NARCIS (Netherlands)

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

2009-01-01

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

Growth and characterization of stoichiometric BCN films on highly oriented pyrolytic graphite by radiofrequency plasma enhanced chemical vapor deposition

Energy Technology Data Exchange (ETDEWEB)

Mannan, Md. Abdul, E-mail: amannan75@yahoo.co [Department of Chemistry and Applied Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo, Saga 840-8502 (Japan); Synchrotron Radiation Research Unit, Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan); Noguchi, Hideyuki; Kida, Tetsuya; Nagano, Masamitsu [Department of Chemistry and Applied Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo, Saga 840-8502 (Japan); Hirao, Norie; Baba, Yuji [Synchrotron Radiation Research Unit, Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan)

2010-05-31

Hexagonal boron carbonitride (h-BCN) hybrid films have been synthesized on highly oriented pyrolytic graphite by radiofrequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane as a single-source molecular precursor. The films were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopic measurements. XPS measurement showed that the B atoms were bonded to C and N atoms to form the sp{sup 2}-B-C-N atomic hybrid chemical environment. The atomic composition estimated from the XPS of the typical sample was found to be almost B{sub 1}C{sub 1}N{sub 1}. NEXAFS spectra of the B K-edge and the N K-edge had the peaks due to the {pi}* and {sigma}* resonances of sp{sup 2} hybrid orbitals implying the existence of the sp{sup 2} hybrid configurations of h-BCN around the B atoms. The G band at 1592 and D band at 1352 cm{sup -1} in the Raman spectra also suggested the presence of the graphite-like sp{sup 2}-B-C-N atomic hybrid bonds. The films consisted of micrometer scale crystalline structure of around 10 {mu}m thick has been confirmed by the field emission scanning electron microscopy.

Rhenium-Promoted C-C Bond-Cleavage Reactions of Internal Propargyl Alcohols.

Science.gov (United States)

Lee, Kui Fun; Bai, Wei; Sung, Herman H Y; Williams, Ian D; Lin, Zhenyang; Jia, Guochen

2018-06-07

The first examples of C-C bond cleavage reactions of internal propargyl alcohols to give vinylidene complexes are described. Treatment of [Re(dppm) 3 ]I with RC≡CC(OH)R'R'' (R=aryl, alkyl; C(OH)R'R''=C(OH)Ph 2, C(OH)Me 2 , C(OH)HPh, C(OH)H 2 ) produced the vinylidene complexes ReI(=C=CHR)(dppm) 2 with the elimination of C(O)R'R''. Computational studies support that the reactions proceed through a β-alkynyl elimination of alkoxide intermediates Re{OC(R')(R'')C≡CR}(dppm) 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

13C Kinetic isotopic effect of polymerization on monomers with multiple bond

International Nuclear Information System (INIS)

Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

1988-01-01

13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

C-H Bond Functionalization via Hydride Transfer: Direct Coupling of Unactivated Alkynes and sp3 C-H Bonds Catalyzed by Platinum Tetraiodide

Science.gov (United States)

Vadola, Paul A.; Sames, Dalibor

2010-01-01

We report a catalytic intramolecular coupling between terminal unactivated alkynes and sp3 C-H bonds via the through-space hydride transfer (HT-cyclization of alkynes). This method enables one-step preparation of complex heterocyclic compounds by α-alkenylation of readily available cyclic ethers and amines. We show that PtI4 is an effective Lewis acid catalyst for the activation of terminal alkynes for the hydride attack and subsequent C-C bond formation. In addition, we have shown that the activity of neutral platinum salts (PtXn) can be modulated by the halide ligands. This modulation in turn allows for fine-tuning of the platinum center reactivity to match the reactivity and stability of selected substrates and products. PMID:19852462

Evaluation of ammonia-borane as a laser-fusion-target material. Final progress report, March 1, 1978-May 31, 1978

International Nuclear Information System (INIS)

Geanangel, R.A.

1978-01-01

Significant results from the previous three quarterly reports are reviewed. Ammonia-borane should be zone sublimed prior to use in fabrication experiments because it is found to undergo an unspecified decomposition which lowers the melting point but does not release significant amounts of hydrogen. Ammonia-borane microballoons, formed by the liquid droplet method, were mounted on glass stalks using epoxy cement and inspected by optical and electron microscopy. Microballoons which had been gold-coated showed expansion and severe surface cracking not visible in optical micrographs or in electron micrographs of uncoated shells. Heating from gold deposition is believed to be responsible for the degradation. Several good quality microballoons were observed. Uncoated, these showed no expansion or surface cracking in the vacuum of the SEM

Synthesis of silylated pyrimidines nucleosides. Catalytic condensations with organo-zinc, organo-zirconium, and organo-borane compounds

International Nuclear Information System (INIS)

Vincent, Patrice

1982-01-01

This research thesis addressed the synthesis of new desoxy-2' uridines substituted in C-5. The starting compound was the iodo-5 0-3',5' bis(trimethylsilyl) dUrd. It has been coupled with acetylenic organo-zinc in presence of organo-palladium and nickel compounds to obtain alkynyl-5 dUrd, with ethylenic organo-zirconium compounds in presence of organo-palladium complexes to obtain (E)-alkenyl-5 dUrd, with ethylenic organo-boranes in presence of organo-palladium complexes to obtain (E) and (Z) alkenyl-5 uRd, and with cyclic or heterocyclic organo-zinc compounds in presence of organo-palladium complexes. Thirty new pyrimidine nucleosides have thus been obtained, and some of them have been used for biological tests [fr

In vitro antibacterial and cytotoxicity assessments of an orthodontic bonding agent containing benzalkonium chloride.

Science.gov (United States)

Saito, Kayo; Hayakawa, Tohru; Kawabata, Rihito; Meguro, Daijiro; Kasai, Kazutaka

2009-03-01

To assess the antibacterial activity and cytotoxicity of an orthodontic bonding material containing an antibacterial agent. Superbond C&B (4-methacryloxyethyl trimellitate anhydride/methyl methacrylate-tri-n-butyl borane [4-META/MMA-TBB]) resin was mixed with benzalkonium chloride (BAC) to obtain final BAC concentrations of 0.25%, 0.75%, 1.25%, 1.75%, 2.5%, and 5.0% (wt/ wt). Antibacterial activity against Streptococcus mutans and Streptococcus sobrinus was evaluated by soaking the BAC-resin in distilled water at 37 degrees C for periods of 30, 90, and 180 days. Antibacterial activity of the BAC-resin was measured by the disk diffusion method, and the inhibition zone around each sample was measured and recorded. For evaluation of cytotoxicity, BAC-resin samples were put into cell culture inserts placed above human gingival cells and were incubated at 37 degrees C for 1, 3, and 6 days. Cytotoxicity was assessed with a tetrazolium bromide reduction assay. The antibacterial activity of BAC-incorporated resin samples decreased significantly after immersion in water for 180 days, regardless of BAC concentration. The antibacterial activity of nonimmersed resin containing 0.25% or 1.75% BAC was comparable with that of 5.0% BAC-resin immersed for 180 days. In cytotoxicity tests, most cells died when exposed to resins containing 1.75%, 2.5%, and 5% BAC. No difference was observed between resins containing 0.25% and 0.75% BAC at 1, 3, and 6 days of culture. The addition of BAC to 4-META/MMA-TBB resin confers an antibacterial effect even after immersion in water, and 4-META/MMA-TBB resin containing 0.25% to 0.75% BAC has no significant cytotoxic effect.

5 CFR 2640.302 - Waivers issued pursuant to 18 U.S.C. 208(b)(3).

Science.gov (United States)

2010-01-01

... actual or potential profit or loss or cost of the matter to the company issuing the stock, the change in...) Requirements for issuing an individual waiver under 18 U.S.C. 208(b)(3). Pursuant to 18 U.S.C. 208(b)(3), an...) The type of interest that is creating the disqualification (e.g. stock, bonds, real estate, other...

Pairing Heterocyclic Cations with closo-Icosahedral Borane and Carborane Anions, II: Benchtop Alternative Synthetic Methodologies for Binary Triazolium and Tetrazolium Salts with Significant Water Solubility (POSTPRINT)

Science.gov (United States)

2012-01-01

in the stirbar=recovery flask apparatus, a proton NMR ( dimethylsulfoxide , DMSO -d6, solvent ) performed on the residue indicated essentially complete...of KX by-product that a given dry volume of silica gel might have retained using a reasonable volume of eluting solvent . For KCl, 0.4473 g (6.0mmol...collected after solvent removal. Scheme 2. Formation of the mixed mono-K=triazolium borane salt. WATER-SOLUBLE HETEROCYCLIUM BORANE-BASED SALTS 157 In this

Acidity enhancement of unsaturated bases of group 15 by association with borane and beryllium dihydride. Unexpected boron and beryllium Brønsted acids.

Science.gov (United States)

Martín-Sómer, Ana; Mó, Otilia; Yáñez, Manuel; Guillemin, Jean-Claude

2015-01-21

The intrinsic acidity of CH2[double bond, length as m-dash]CHXH2, HC[triple bond, length as m-dash]CXH2 (X = N, P, As, Sb) derivatives and of their complexes with BeH2 and BH3 has been investigated by means of high-level density functional theory and molecular orbital ab initio calculations, using as a reference the ethyl saturated analogues. The acidity of the free systems steadily increases down the group for the three series of derivatives, ethyl, vinyl and ethynyl. The association with both beryllium dihydride and borane leads to a very significant acidity enhancement, being larger for BeH2 than for BH3 complexes. This acidity enhancement, for the unsaturated compounds, is accompanied by a change in the acidity trends down the group, which do not steadily decrease but present a minimum value for both the vinyl- and the ethynyl-phosphine. When the molecule acting as the Lewis acid is beryllium dihydride, the π-type complexes in which the BeH2 molecules interact with the double or triple bond are found, in some cases, to be more stable, in terms of free energies, than the conventional complexes in which the attachment takes place at the heteroatom, X. The most important finding, however, is that P, As, and Sb ethynyl complexes with BeH2 do not behave as P, As, or Sb Brønsted acids, but unexpectedly as Be acids.

Modelling magnetism of C at O and B monovacancies in graphene

KAUST Repository

Kaloni, Thaneshwor P.

2013-11-01

The presence of defects can introduce important changes in the electronic structure of graphene, leading to phenomena such as C magnetism. In addition, vacancies are reactive and permit the incorporation of dopants. This paper discusses the electronic properties of defective graphene for O and B decoration. Phonon calculations allow us to address directly the stability of the systems under study. We show that it is possible to obtain magnetic solutions with and without dangling bonds, demonstrating that C magnetism can be achieved in the presence of B and O. © 2013 Elsevier Ltd. All rights reserved.

Modelling magnetism of C at O and B monovacancies in graphene

KAUST Repository

Kaloni, Thaneshwor P.; Kahaly, M. Upadhyay; Faccio, Ricardo; Schwingenschlö gl, Udo

2013-01-01

The presence of defects can introduce important changes in the electronic structure of graphene, leading to phenomena such as C magnetism. In addition, vacancies are reactive and permit the incorporation of dopants. This paper discusses the electronic properties of defective graphene for O and B decoration. Phonon calculations allow us to address directly the stability of the systems under study. We show that it is possible to obtain magnetic solutions with and without dangling bonds, demonstrating that C magnetism can be achieved in the presence of B and O. © 2013 Elsevier Ltd. All rights reserved.

Synthesis and crystal structure of Mg2B24C, a new boron-rich boride related to 'tetragonal boron I'

International Nuclear Information System (INIS)

Adasch, Volker; Hess, Kai-Uwe; Ludwig, Thilo; Vojteer, Natascha; Hillebrecht, Harald

2006-01-01

Single crystals of Mg 2 B 24 C, a new boron-rich boridecarbide of magnesium, were synthesized as black needles and columns by reaction of the elements in Ta ampoules and BN crucibles at 1300 deg. C. The crystal structure was determined by X-ray diffraction (P-4n2, a=8.9391(13)A, c=5.0745(10)A, Z=2, 713 reflections, 64 variables, R 1 (F)=0.0235, wR 2 (I)=0.0591). It is closely related to 'tetragonal boron I' and can be described as a tetragonal rod packing of corner-linked B 12 icosahedra with C and Mg atoms in the voids. Each B 12 icosahedron has 2 B-C bonds and 10 exohedral bonds to other icosahedra, 2 within the rod and 4x2 to neighbouring rods. The isolated C atoms are 4-fold coordinated forming distorted tetrahedra. Mg is placed on two crystallographically independent positions within the three-dimensional B 12 C network. Mg 2 B 24 C is the first example for a compound related to 'tetragonal boron I' with a stoichiometric composition

Regeneration of polyborazylene

Science.gov (United States)

Davis, Benjamin L.; Gordon, John C.

2010-12-07

Method of producing ammonia borane, comprising providing polyborazylene; digesting the polyborazylene with a dithiol-containing agent to produce a boro-sulfide compound and a byproduct; converting the byproduct to the boro-sulfide product of step (b) by reaction with a first alkyl-tin hydride; and, converting the boro-sulfide compound produced in steps (b) and (c) to ammonia borane by reaction with a second alkyl-tin hydride.

Hydrogen bonded C-H···Y (Y = O, S, Hal) molecular complexes: A natural bond orbital analysis

Science.gov (United States)

Isaev, A. N.

2016-03-01

Hydrogen bonded C-H···Y complexes formed by H2O, H2S molecules, hydrogen halides, and halogen-ions with methane, halogen substituted methane as well as with the C2H2 and NCH molecules were studied at the MP2/aug-cc-pVDZ level. The structure of NBOs corresponding to lone pair of acceptor Y, n Y, and vacant anti-σ-bond C-H of proton donor was analyzed and estimates of second order perturbation energy E(2) characterizing donor-acceptor n Y → σ C-H * charge-transfer interaction were obtained. Computational results for complexes of methane and its halogen substituted derivatives show that for each set of analogous structures, the EnY→σ*C-H (2) energy tends to grow with an increase in the s-component percentage in the lone pair NBO of acceptor Y. Calculations for different C···Y distances show that the equilibrium geometries of complexes lie in the region where the E(2) energy is highest and it changes symbatically with the length of the covalent E-H bond when the R(C···Y) distance is varied. The performed analysis allows us to divide the hydrogen bonded complexes into two groups, depending on the pattern of overlapping for NBOs of the hydrogen bridge.

C—C bond formation in the intramolecular Diels-Alder reaction of triene amides

Directory of Open Access Journals (Sweden)

Abdelilah Benallou

2018-02-01

Full Text Available The mechanism nature of the intramolecular Diels–Alder reaction has been performed; and thus, the changes of C—C bond forming/breaking along IRC are characterized in this study. Conceptual DFT analyses of the most favorable adduct fused/exo shows that the flux electronic will take place from diene to dienophile moiety. Moreover, ELF topological analysis based on the electron density predicts that C—C bond is formed by the coupling of two pseudoradical centers generated at the most significant atoms of the molecules. However, C2 vs C3, also C1 and C4 interaction comes mainly from the global electron density transfer which takes place along the reaction. Two- stage one-step is the proposed mechanism of this reaction, the first stage aims for the formation of C2—C3 σ bond while the second stage aims for C1—C4 σ bond formation. Interestingly, the observed asynchronicity of this IMDA reaction due principally to the asymmetric reorganization of electron density at the most attractive centers.

New Insights from Domain-averaged Fermi holes and Bond Order Analysis into the Bonding Conundrum in C2.

Czech Academy of Sciences Publication Activity Database

Cooper, D.L.; Ponec, Robert; Kohout, M.

2016-01-01

Roč. 114, 7-8 (2016), s. 1270-1284 ISSN 0026-8976 Institutional support: RVO:67985858 Keywords : peculiarity of C2 bonding * domain-averaged Fermi holes (DAFH) * cioslowski bond orders Subject RIV: CC - Organic Chemistry Impact factor: 1.870, year: 2016

Microstructure of reactive synthesis TiC/Cr18Ni8 stainless steel bonded carbides

Institute of Scientific and Technical Information of China (English)

Jiang Junsheng; Liu Junbo; Wang Limei

2008-01-01

TiC/Cr18Ni8 steel bonded carbides were synthesized by vacuum sintering with mixed powders of iron, ferrotitanium, ferrochromium, colloidal graphite and nickel as raw materials. The microstructure and microhardness of the steel bonded carbides were analyzed by scanning electron microscope (SEM),X-ray diffraction (XRD) and Rockwell hardometer. Results show that the phases of steel bonded carbides mainly consist of TiC and Fe-Cr-Ni solid solution. The synthesized TiC particles are fine. Most of them are not more than 1 μm With the increase of sintering temperature, the porosity of TiC/Cr18Ni8 steel bonded carbides decreases and the density and hardness increase, but the size of TiC panicles slightly increases. Under the same sintering conditions, the density and hardness of steel bonded carbides with C/Ti atomic ratio 0.9 are higher than those with C/Ti atomic ratio 1.0.The TiC particles with C/Ti atomic ratio 0.9 are much finer and more homogeneous.

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

KAUST Repository

Yang, Wenguo; Tan, Davin; Lee, Richmond; Li, Lixin; Pan, Yuanhang; Huang, Kuo-Wei; Tan, Choonhong; Jiang, Zhiyong

2012-01-01

Through the cleavage of the C-C bond, the first catalytic tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts has been presented. Various S N2′-like C-, S-, and P-allylic compounds could be obtained with exclusive E

Detection and function of an intramolecular disulfide bond in the pH-responsive CadC of Escherichia coli

Directory of Open Access Journals (Sweden)

Dönhöfer Alexandra

2011-04-01

Full Text Available Abstract Background In an acidic and lysine-rich environment Escherichia coli induces expression of the cadBA operon which encodes CadA, the lysine decarboxylase, and CadB, the lysine/cadaverine antiporter. cadBA expression is dependent on CadC, a membrane-integrated transcriptional activator which belongs to the ToxR-like protein family. Activation of CadC requires two stimuli, lysine and low pH. Whereas lysine is detected by an interplay between CadC and the lysine-specific transporter LysP, pH alterations are sensed by CadC directly. Crystal structural analyses revealed a close proximity between two periplasmic cysteines, Cys208 and Cys272. Results Substitution of Cys208 and/or Cys272 by alanine resulted in CadC derivatives that were active in response to only one stimulus, either lysine or pH 5.8. Differential in vivo thiol trapping revealed a disulfide bond between these two residues at pH 7.6, but not at pH 5.8. When Cys208 and Cys272 were replaced by aspartate and lysine, respectively, virtually wild-type behavior was restored indicating that the disulfide bond could be mimicked by a salt bridge. Conclusion A disulfide bond was found in the periplasmic domain of CadC that supports an inactive state of CadC at pH 7.6. At pH 5.8 disulfide bond formation is prevented which transforms CadC into a semi-active state. These results provide new insights into the function of a pH sensor.

Interactions and encapsulation of vitamins C, B3, and B6 with dendrimers in water.

Science.gov (United States)

Boisselier, Elodie; Liang, Liyuan; Dalko-Csiba, Maria; Ruiz, Jaime; Astruc, Didier

2010-05-25

Titrations of commercial diaminobutane (DAB) and polyamidoamine (PAMAM) dendrimers by vitamins C (ascorbic acid, AA), B(3) (nicotinic acid), and B(6) (pyridoxine) were monitored by (1)H NMR spectroscopy using the chemical shifts of both dendrimer and vitamin protons and analyzed by comparison with the titration of propylamine. Quaternarizations of the terminal primary amino groups and intradendritic tertiary amino groups, which are nearly quantitative with vitamin C, were characterized by more or less sharp variations (Deltadelta) of the (1)H chemical shift (delta) at the equivalence points. The peripheral primary amino groups of the DAB dendrimers were quaternarized first, but not selectively, whereas a sharp chemical-shift variation was recorded for the inner methylene protons near the tertiary amines, thereby indicating encapsulation, when all the dendritic amines were quaternarized. With DAB-G5-64-NH(2), some excess acid is required to protonate the inner amino groups, presumably because of basicity decrease due to excess charge repulsion. On the other hand, this selectivity was not observed with PAMAM dendrimers. The special case of the titration of the dendrimers by vitamin B(6) indicates only dominant supramolecular hydrogen-bonding interactions and no quaternarization, with core amino groups being privileged, which indicates the strong tendency to encapsulate vitamins. With vitamin B(3), a carboxylic acid, titration of DAB-G3-16-NH(2) shows that only six peripheral amino groups are protonated on average, even with excess vitamin B(3), because protonation is all the more difficult due to increased charge repulsion, as positive charges accumulate around the dendrimer. Inner amino groups interact with this vitamin, however, thus indicating encapsulation presumably with supramolecular hydrogen bonding without much charge transfer.

Ab initio calculations of the electronic structure and bonding characteristics of LaB6

International Nuclear Information System (INIS)

Hossain, Faruque M.; Riley, Daniel P.; Murch, Graeme E.

2005-01-01

Lanthanum hexaboride (LaB 6 , NIST SRM-660a) is widely used as a standard reference material for calibrating the line position and line shape parameters of powder diffraction instruments. The accuracy of this calibration technique is highly dependent on how completely the reference material is characterized. Critical to x-ray diffraction, this understanding must include the valence of the La atomic position, which in turn will influence the x-ray form factor (f) and hence the diffracted intensities. The electronic structure and bonding properties of LaB 6 have been investigated using ab initio plane-wave pseudopotential total energy calculations. The electronic properties and atomic bonding characteristics were analyzed by estimating the energy band structure and the density of states around the Fermi energy level. The calculated energy band structure is consistent with previously reported experimental findings; de Haas-van Alphen and two-dimensional angular correlation of electron-positron annihilation radiation. In addition, the bond strengths and types of atomic bonds in the LaB 6 compound were estimated by analyzing the Mulliken charge density population. The calculated result revealed the coexistence of covalent, ionic, and metallic bonding in the LaB 6 system and partially explains its high efficiency as a thermionic emitter

Photo-assisted cyanation of transition metal nitrates coupled with room temperature C-C bond cleavage of acetonitrile.

Science.gov (United States)

Zou, Shihui; Li, Renhong; Kobayashi, Hisayoshi; Liu, Juanjuan; Fan, Jie

2013-03-07

It is a challenge to use acetonitrile as a cyanating agent because of the difficulty in cleaving its C-CN bond. Herein, we report a mild photo-assisted route to conduct the cyanation of transition metal nitrates using acetonitrile as the cyanating agent coupled with room-temperature C-C bond cleavage. DFT calculations and experimental observations suggest a radical-involved reaction mechanism, which excludes toxicity from free cyanide ions.

Beyond benzyl grignards: facile generation of benzyl carbanions from styrenes.

Science.gov (United States)

Grigg, R David; Rigoli, Jared W; Van Hoveln, Ryan; Neale, Samuel; Schomaker, Jennifer M

2012-07-23

Benzylic functionalization is a convenient approach towards the conversion of readily available aromatic hydrocarbon feedstocks into more useful molecules. However, the formation of carbanionic benzyl species from benzyl halides or similar precursors is far from trivial. An alternative approach is the direct reaction of a styrene with a suitable coupling partner, but these reactions often involve the use of precious-metal transition-metal catalysts. Herein, we report the facile and convenient generation of reactive benzyl anionic species from styrenes. A Cu(I)-catalyzed Markovnikov hydroboration of the styrenic double bond by using a bulky pinacol borane source is followed by treatment with KOtBu to facilitate a sterically induced cleavage of the C-B bond to produce a benzylic carbanion. Quenching this intermediate with a variety of electrophiles, including CO(2), CS(2), isocyanates, and isothiocyanates, promotes C-C bond formation at the benzylic carbon atom. The utility of this methodology was demonstrated in a three-step, two-pot synthesis of the nonsteroidal anti-inflammatory drug (±)-flurbiprofen. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Probing the electronic structure of M-graphene oxide (M = Ni, Co, NiCo) catalysts for hydrolytic dehydrogenation of ammonia borane

Energy Technology Data Exchange (ETDEWEB)

Zhao, Binhua; Liu, Jinyin; Zhou, Litao [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China); Long, Dan, E-mail: legend_long@aliyun.com [Department of Radiology, Zhejiang Cancer Hospital, Hangzhou 310022 (China); Feng, Kun; Sun, Xuhui [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China); Zhong, Jun, E-mail: jzhong@suda.edu.cn [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China)

2016-01-30

Graphical abstract: An interaction between metal and graphene oxide was probed to enhance the hydrolysis efficiency of ammonia borane. - Highlights: • Various metal elements (M = Ni, Co, NiCo) were dispersed on graphene oxide (GO) for the hydrolysis of ammonia borane (AB). • The electronic structure of the hybrids has been probed by scanning transmission X-ray microscopy (STXM). • An interfacial interaction between metal and GO was observed which could be related to the hydrolysis performance. • The results provide new insight into the enhanced performance of the M-GO hybrids. - Abstract: Various metal elements (M = Ni, Co, NiCo) were dispersed on graphene oxide (GO) to form the M-GO hybrids by a facile way. The hybrids showed good catalytic activities in the hydrolytic dehydrogenation of ammonia borane (AB, NH{sub 3}BH{sub 3}), which were significantly enhanced when compared to the metal nanoparticles or GO alone. The electronic structure of the hybrids has been probed by scanning transmission X-ray microscopy (STXM). The distribution of metal elements was clearly imaged with identical electronic structure. Moreover, an interfacial interaction between metal and GO was observed with the peak intensity proportional to the catalytic performance in the hydrolysis of AB. The results provide new insight into the enhanced performance of the M-GO hybrids and may help for the design of advanced catalysts.

ZIF-8 immobilized nickel nanoparticles: highly effective catalysts for hydrogen generation from hydrolysis of ammonia borane.

Science.gov (United States)

Li, Pei-Zhou; Aranishi, Kengo; Xu, Qiang

2012-03-28

Highly dispersed Ni nanoparticles have been successfully immobilized by the zeolitic metal-organic framework ZIF-8 via sequential deposition-reduction methods, which show high catalytic activity and long durability for hydrogen generation from hydrolysis of aqueous ammonia borane (NH(3)BH(3)) at room temperature. This journal is © The Royal Society of Chemistry 2012

Activation of the Hg-C Bond of Methylmercury by [S2]-Donor Ligands.

Science.gov (United States)

Karri, Ramesh; Banerjee, Mainak; Chalana, Ashish; Jha, Kunal Kumar; Roy, Gouriprasanna

2017-10-16

Here we report that [S 2 ]-donor ligands Bmm OH , Bmm Me , and Bme Me bind rapidly and reversibly to the mercury centers of organomercurials, RHgX, and facilitate the cleavage of Hg-C bonds of RHgX to produce stable tetracoordinated Hg(II) complexes and R 2 Hg. Significantly, the rate of cleavage of Hg-C bonds depends critically on the X group of RHgX (X = BF 4 - , Cl - , I - ) and the [S 2 ]-donor ligands used to induce the Hg-C bonds. For instance, the initial rate of cleavage of the Hg-C bond of MeHgI induced by Bme Me is almost 2-fold higher than the initial rate obtained by Bmm OH or Bmm Me , indicating that the spacer between the two imidazole rings of [S 2 ]-donor ligands plays a significant role here in the cleavage of Hg-C bonds. Surprisingly, we noticed that the initial rate of cleavage of the Hg-C bond of MeHgI induced by Bme Me (or Bmm Me ) is almost 10-fold and 100-fold faster than the cleavage of Hg-C bonds of MeHgCl and [MeHg]BF 4 respectively, under identical reaction conditions, suggesting that the Hg-C bond of [MeHg]BF 4 is highly inert at room temperature (21 °C). We also show here that the nature of the final stable cleaved products, i.e. Hg(II) complexes, depends on the X group of RHgX and the [S 2 ]-donor ligands. For instance, the reaction of Bmm Me with MeHgCl (1:1 molar ratio) afforded the formation of the 16-membered metallacyclic dinuclear mercury compound (Bmm Me ) 2 Hg 2 Cl 4 , in which the two Cl atoms are located inside the ring, whereas due to the large size of the I atom, a similar reaction with MeHgI yielded polymeric [(Bmm Me ) 2 HgI 2 ] m ·(MeHgI) n . However, the treatment of Bmm Me with ionic [RHg]BF 4 led to the formation of the tetrathione-coordinated mononuclear mercury compound [(Bmm Me ) 2 Hg](BF 4 ) 2 , where BF 4 - serves as a counteranion.

Variation in diffusion-induced solidification rate of liquated Ni-Cr-B insert during TLP bonding of Waspaloy superalloy

International Nuclear Information System (INIS)

Tokoro, K.; Wikstrom, N.P.; Ojo, O.A.; Chaturvedi, M.C.

2008-01-01

A microstructural study was performed on transient liquid phase (TLP) bonded Waspaloy superalloy with a Ni-Cr-B filler. The applicability of a diffusion model based on Fick's second law of diffusion to determine the time required for complete isothermal solidification (t f ) was investigated. Over the temperature range of 1065-1110 deg. C, experimental observations of t f were in reasonable agreement with t f values predicted by the diffusion model. However, a notable deviation was observed in joints prepared between 1175 and 1225 deg. C in that the rate of isothermal solidification was reduced at these temperatures resulting in the formation of a centerline eutectic-type microconstituent, which in contrast, was prevented from forming after holding the brazing assembly for an equivalent bonding time at a lower temperature of 1145 deg. C. Boride particles were observed as part of the eutectic product, which suggested that diffusion of boron out of the liquated insert was also reduced at these higher temperatures. A decrease in solubility of the melting point depressing solute, boron, with increase in temperature is suggested to be an important factor contributing to the reduction in isothermal solidification rate observed at the higher bonding temperatures

Early-transition-metal ketenimine complexes. Synthesis, reactivity, and structural characterization of complexes with. eta. sup 2 (C,N)-ketenimine groups bound to the halogenobis((trimethylsilyl)cyclopentadienyl)niobium unit. X-ray structure of Nb(. eta. sup 5 -C sub 5 H sub 4 SiMe sub 3 ) sub 2 Cl(. eta. sup 2 (C,N)-PhN double bond C double bond CPh sub 2 )

Energy Technology Data Exchange (ETDEWEB)

Antinolo, A.; Fajardo, M.; Lopez Mardomingo, C.; Otero, A. (Univ. de Alcala de Henares (Spain)); Mourad, Y.; Mugnier, Y. (Centre National de la Recherche Scientifique, Dijon (France)); Sanz-Aparicio, J.; Fonseca, I.; Florencio, F. (CSIC, Madrid (Spain))

1990-11-01

The reaction of Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X (X = Cl, Br) with 1 equiv of various ketenimines, R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}, leads to the niobium derivatives Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X({eta}{sup 2}(C,N)-R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}) (1, X = Cl, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 2, X = Cl, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 3, X = Br, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 4, X = Br, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 5, X = Cl, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}; 6, X = Br, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}) with the expected ketenimine C{double bond}N bonding mode. Reduction of 1 with 1 equiv of Na/Hg gives the complex Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}({eta}{sup 2}(C,N)-PhN{double bond}C{double bond}CPh{sub 2}) (9) as a paramagnetic compound. The reduction of 9 with 1 equiv of Na/Hg and the subsequent addition of a proton source (ethanol) leads to the iminoacyl compound Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}(CRNR{sup 1}) (10, R = CH(Ph{sub 2}), R{sup 1} = Ph). The one- and two-electron reductions of 1 have been studied by cyclic voltammetry experiments. The structure of 1 was determined by single-crystal X-ray diffractometry: a = 24.4904 (14) {angstrom}, b = 11.0435 (04) {angstrom}, c = 26.6130 (15) {angstrom}, {beta} = 109.890 (5){degree}, monoclinic, space group C2/c, Z = 8, V = 6,768.4 (5) {angstrom}{sup 3}, {rho}{sub calcd} = 1.3194 g/mL, R = 0.048, R{sub w} = 0.060 based on 4,806 observed reflections. The structure contains a niobium atom bonded to two cyclopentadienyl rings in a {eta}{sup 5} fashion; the coordination of the metal is completed by a Cl atom and a {eta}{sup 2}(C,N)-bonded ketenimine ligand.

Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

Science.gov (United States)

Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

2016-08-19

Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.

Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: making ir capable of splitting C-C bond.

Science.gov (United States)

Li, Meng; Cullen, David A; Sasaki, Kotaro; Marinkovic, Nebojsa S; More, Karren; Adzic, Radoslav R

2013-01-09

Splitting the C-C bond is the main obstacle to electrooxidation of ethanol (EOR) to CO(2). We recently demonstrated that the ternary PtRhSnO(2) electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article, we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We characterized and compared the properties of several carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO(2) NP core decorated with multimetallic nanoislands (MM' = PtIr, PtRh, IrRh, PtIrRh) prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM'/SnO(2) NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity toward CO(2) formation of several of these MM'/SnO(2)/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO(2)/C catalysts. We demonstrate that the PtIr/SnO(2)/C catalyst with high Ir content shows outstanding catalytic properties with the most negative EOR onset potential and reasonably good selectivity toward ethanol complete oxidation to CO(2).

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

Science.gov (United States)

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

2013-04-28

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

Liquid coated melt-spun Nd-Fe-B powders for bonded magnets

Science.gov (United States)

Li, D.; Gaiffi, S.; Kirk, D.; Young, K.; Herchenroeder, J.; Berwald, T.

1999-04-01

The liquid coating (LC) has been employed to apply epoxy and lubricant over the surface of rapidly solidified Nd-Fe-B powder particles. The LC led to an improvement of physical and magnetic properties for the powders and magnets compared to the dry blending and the encapsulation methods. The LC powders have excellent flowability and can be used for bonded magnets requiring very close tolerances; further bonded magnets made using this powder posses higher strength.

Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

Science.gov (United States)

Zhang, Chun; Feng, Peng; Jiao, Ning

2013-10-09

The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

Blue-shifted and red-shifted hydrogen bonds: Theoretical study of the CH3CHO· · ·HNO complexes

Science.gov (United States)

Yang, Yong; Zhang, Weijun; Gao, Xiaoming

The blue-shifted and red-shifted H-bonds have been studied in complexes CH3CHO?HNO. At the MP2/6-31G(d), MP2/6-31+G(d,p) MP2/6-311++G(d,p), B3LYP/6-31G(d), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels, the geometric structures and vibrational frequencies of complexes CH3CHO?HNO are calculated by both standard and CP-corrected methods, respectively. Complex A exhibits simultaneously red-shifted C bond H?O and blue-shifted N bond H?O H-bonds. Complex B possesses simultaneously two blue-shifted H-bonds: C bond H?O and N bond H?O. From NBO analysis, it becomes evident that the red-shifted C bond H?O H-bond can be explained on the basis of the two opposite effects: hyperconjugation and rehybridization. The blue-shifted C bond H?O H-bond is a result of conjunct C bond H bond strengthening effects of the hyperconjugation and the rehybridization due to existence of the significant electron density redistribution effect. For the blue-shifted N bond H?O H-bonds, the hyperconjugation is inhibited due to existence of the electron density redistribution effect. The large blue shift of the N bond H stretching frequency is observed because the rehybridization dominates the hyperconjugation.

Reductive Elimination Leading to C-C Bond Formation in Gold(III) Complexes: A Mechanistic and Computational Study.

Science.gov (United States)

Rocchigiani, Luca; Fernandez-Cestau, Julio; Budzelaar, Peter H M; Bochmann, Manfred

2018-06-21

The factors affecting the rates of reductive C-C cross-coupling reactions in gold(III) aryls were studied by using complexes that allow easy access to a series of electronically modified aryl ligands, as well as to gold methyl and vinyl complexes, by using the pincer compounds [(C^N^C)AuR] (R=C 6 F 5 , CH=CMe 2 , Me and p-C 6 H 4 X, where X=OMe, F, H, tBu, Cl, CF 3 , or NO 2 ) as starting materials (C^N^C=2,6-(4'-tBuC 6 H 3 ) 2 pyridine dianion). Protodeauration followed by addition of one equivalent SMe 2 leads to the quantitative generation of the thioether complexes [(C^N-CH)AuR(SMe 2 )] + . Upon addition of a second SMe 2 pyridine is displaced, which triggers the reductive aryl-R elimination. The rates for these cross-couplings increase in the sequence k(vinyl)>k(aryl)≫k(C 6 F 5 )>k(Me). Vinyl-aryl coupling is particularly fast, 1.15×10 -3  L mol -1  s -1 at 221 K, whereas both C 6 F 5 and Me couplings encountered higher barriers for the C-C bond forming step. The use of P(p-tol) 3 in place of SMe 2 greatly accelerates the C-C couplings. Computational modelling shows that in the C^N-bonded compounds displacement of N by a donor L is required before the aryl ligands can adopt a conformation suitable for C-C bond formation, so that elimination takes place from a four-coordinate intermediate. The C-C bond formation is the rate-limiting step. In the non-chelating case, reductive C(sp 2 )-C(sp 2 ) elimination from three-coordinate ions [(Ar 1 )(Ar 2 )AuL] + is almost barrier-free, particularly if L=phosphine. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of composition polymeric PVB binder on physical, magnetic properties and microstructure of bonded magnet NdFeB

Science.gov (United States)

Sardjono, P.; Muljadi; Suprapedi; Sinuaji, P.; Ramlan; Gulo, F.

2017-04-01

The bonded magnet NdFeB has been made by using the hot press method and using Poly Vinyl Butiral (PVB) as a binder. The composition of polymeric binder was varied: 0, 2, 4, 6 and 7 % of weight. Both raw materials are weighed and mixed according to the composition of PVB, then formed by hot press with a pressure 30 MPa, a temperature of 160 ° C and holding time for 30 minutes. The bulk density was measured by using Archimedes method. SEM observation was done to determine the microstructure of bonded magnet NdFeB. The flux magnetic value was measured by using a Gauss meter and the measurement of hysteresis curves was done to know value of remanence Br, coercivity Hc and energy product BHmax by using VSM. According to the characterization results show that the best composition of PVB is 2 of weight. The properties of bonded magnet NdFeB of those compositions are the bulk density around 5.66 g/cm3. Flux Magnetic value: 1862 Gauss, Br value: 5000 kGauss, Hc value: 8.49 kOe and BHmax value : 5.10 MGOe. According of SEM observation results show that the polymer matrix of PVB appears to have covered on all surface grain and filled grain boundary.

Effects of extrinsic point defects in phosphorene: B, C, N, O and F Adatoms

OpenAIRE

Wang, Gaoxue; Pandey, Ravindra; Karna, Shashi P.

2015-01-01

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 sp3 bonds of pho...

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

Science.gov (United States)

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

2016-11-10

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

c-C5H5 on a Ni(1 1 1) surface: Theoretical study of the adsorption, electronic structure and bonding

International Nuclear Information System (INIS)

German, E.; Simonetti, S.; Pronsato, E.; Juan, A.; Brizuela, G.

2008-01-01

In the present work the ASED-MO method is applied to study the adsorption of cyclopentadienyl anion on a Ni(1 1 1) surface. The adsorption with the centre of the aromatic ring placed above the hollow position has been identified to be energetically the most favourable. The aromatic ring remains almost flat, the H atoms are tilted 17 deg. away from the metal surface. We modelled the metal surface by a two-dimensional slab of finite thickness, with an overlayer of c-C 5 H 5 - , one c-C 5 H 5 - per nine surface Ni atoms. The c-C 5 H 5 - molecule is attached to the surface with its five C atoms bonding mainly with three Ni atoms. The Ni-Ni bond in the underlying surface and the C-C bonds of c-C 5 H 5 - are weakened upon adsorption. We found that the band of Ni 5d z 2 orbitals plays an important role in the bonding between c-C 5 H 5 - and the surface, as do the Ni 6s and 6p z bands

Nature of Bonding in Bowl-Like B36 Cluster Revisited: Concentric (6π+18π) Double Aromaticity and Reason for the Preference of a Hexagonal Hole in a Central Location.

Science.gov (United States)

Li, Rui; You, Xue-Rui; Wang, Kang; Zhai, Hua-Jin

2018-05-04

The bowl-shaped C 6v B 36 cluster with a central hexagon hole is considered an ideal molecular model for low-dimensional boron-based nanosystems. Owing to the electron deficiency of boron, chemical bonding in the B 36 cluster is intriguing, complicated, and has remained elusive despite a couple of papers in the literature. Herein, a bonding analysis is given through canonical molecular orbitals (CMOs) and adaptive natural density partitioning (AdNDP), further aided by natural bond orbital (NBO) analysis and orbital composition calculations. The concerted computational data establish the idea of concentric double π aromaticity for the B 36 cluster, with inner 6π and outer 18π electron counting, which both conform to the (4n+2) Hückel rule. The updated bonding picture differs from existing knowledge of the system. A refined bonding model is also proposed for coronene, of which the B 36 cluster is an inorganic analogue. It is further shown that concentric double π aromaticity in the B 36 cluster is retained and spatially fixed, irrespective of the migration of the hexagonal hole; the latter process changes the system energetically. The hexagonal hole is a destabilizing factor for σ/π CMOs. The central hexagon hole affects substantially fewer CMOs, thus making the bowl-shaped C 6v B 36 cluster the global minimum. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of Purine and Pyrimidine Nucleosides by Direct C-H Bond Activation

Directory of Open Access Journals (Sweden)

Yong Liang

2015-03-01

Full Text Available Transition metal-catalyzed modifications of the activated heterocyclic bases of nucleosides as well as DNA or RNA fragments employing traditional cross-coupling methods have been well-established in nucleic acid chemistry. This review covers advances in the area of cross-coupling reactions in which nucleosides are functionalized via direct activation of the C8-H bond in purine and the C5-H or C6-H bond in uracil bases. The review focuses on Pd/Cu-catalyzed couplings between unactivated nucleoside bases with aryl halides. It also discusses cross-dehydrogenative arylations and alkenylations as well as other reactions used for modification of nucleoside bases that avoid the use of organometallic precursors and involve direct C-H bond activation in at least one substrate. The scope and efficiency of these coupling reactions along with some mechanistic considerations are discussed.

Structure and bonding of transition metal-boryl compounds. Theoretical study of [(PH3)2(CO)ClOs-BR2] and [(PH3)2(CO)2ClOs-BR2] (BR2 = BH2, BF2, B(OH)2, B(OCH=CHO), Bcat).

Science.gov (United States)

Giju, K T; Bickelhaupt, F M; Frenking, G

2000-10-16

Quantum chemical DFT calculations using the B3LYP functionals have been carried out for the electronically unsaturated 16 VE five-coordinate osmium boryl-complexes [(PH3)2(CO)ClOs-BR2] and the 18 VE six-coordinate complexes [(PH3)2(CO)2ClOs-BR2] with BR2 = BH2, BF2, B(OH)2, B(OHC=CHO), and Bcat (cat = catecholate O2C6H4). The bonding situation of the Os-BR2 bond was analyzed with the help of the NBO partitioning scheme. The Os-B bond dissociation energies of the 16 VE complexes are very high, and they do not change very much for the different boryl ligands. The 18 VE complexes have only slightly lower bond energies than the 16 VE species. The Os-B bond in both classes of compounds is provided by a covalent sigma-bond which is polarized toward osmium and by strong charge attraction. Os-->B pi-donation is not important for the Os-B binding interactions, except for the Os-BH2 complexes. The stability of the boryl complexes [Os]-BR2 comes mainly from BB pi-donation. The intraligand charge distribution of the BR2 group changes little when the Os-B bond is formed, except for BH2. The CO ligand in [(PH3)2(CO)2ClOs-BR2] which is trans to BR2 has a relatively weak bond to the osmium atom.

Gas-phase reactivity of lanthanide cations with fluorocarbons: C-F versus C-H and C-C bond activation

International Nuclear Information System (INIS)

Cornehl, H.H.; Hornung, G.; Schwarz, H.

1996-01-01

The gas-phase reactivity of the fluorinated hydrocarbons CF 4 , CHF 3 , CH 3 F, C 2 F 6 , 1,1-C 2 H 4 F 2 , and C 6 F 6 with the lanthanide cations Ce + , Pr + , Sm + , Ho + , Tm + , and Yb + and the reactivity of C 6 H 5 F with all lanthanide cations Ln + (Ln = La-Lu, with the exception of Pm + ) have been examined by Fourier-transform ion cyclotron resonance mass spectrometry. The perfluorinated compounds tetrafluoromethane and hexafluoroethane as well as trifluoromethane do not react with any lanthanide cation. Selective activation of the strong C-F bonds in fluoromethane, 1,1-difluoroethane, hexafluorobenzene, and fluorobenzene appears as a general reaction scheme along the 4f row. Experimental evidence is given for a 'harpoon'-like mechanism for the F atom abstraction process which operates via an initial electron transfer from the lanthanide cation to the fluorinated substrate in the encounter complex Ln + RF. The most reactive lanthanides La + , Ce + , Gd + , and Tb + and also the formal closed-shell species Lu + exhibit additional C-H and C-C bond activation pathways in the reaction with fluorobenzene, namely dehydrohalogenation as well as loss of a neutral acetylene molecule. In the case of Tm + and Yb + the formation of neutral LnF 3 is observed in a multistep process via C-C coupling and charge transfer. 17 refs., 2 figs., 2 tabs

26 CFR 1.1394-1 - Enterprise zone facility bonds.

Science.gov (United States)

2010-04-01

... business definition. City J issues enterprise zone facility bonds, the proceeds of which are loaned to... TAX (CONTINUED) INCOME TAXES Definitions; Special Rules § 1.1394-1 Enterprise zone facility bonds. (a... (zones). See sections 1394, 1397B, and 1397C for other rules and definitions. (b) Period of compliance—(1...

A cascade of acid-promoted C-O bond cleavage and redox reactions: from oxa-bridged benzazepines to benzazepinones.

Science.gov (United States)

Zhang, Yuewei; Yang, Fengzhi; Zheng, Lianyou; Dang, Qun; Bai, Xu

2014-12-05

A sequence of C-O bond cleavage and redox reactions in oxa-bridged azepines was realized under acid promoted conditions. This protocol provides an atom-economical and straightforward approach to access benzo[b]azepin-5(2H)-ones in high yields. The formal synthesis of tolvaptan was achieved by exploiting this new transformation.

Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

Science.gov (United States)

Souillart, Laetitia; Cramer, Nicolai

2014-09-01

The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes

KAUST Repository

Chen, Shuli; Chiew, Jun Xuan; Pullarkat, Sumod A.; Li, Yongxin; Leung, Pak Hing

2013-01-01

, whereas the P→Pd bond is labile. Upon heating of these phosphane complexes at 70 °C, one of the C≡C bonds in the coordinated PhP(C≡CPh)2 was activated towards an intermolecular Pd-C bond insertion reaction with an external ortho-palladated naphthylamine

Ni-polymer nanogel hybrid particles: A new strategy for hydrogen production from the hydrolysis of dimethylamine-borane and sodium borohydride

International Nuclear Information System (INIS)

Cai, Haokun; Liu, Liping; Chen, Qiang; Lu, Ping; Dong, Jian

2016-01-01

Efficient non-precious metal catalysts are crucial for hydrogen production from borohydride compounds in aqueous media via hydrogen atoms in water. A method for preparing magnetic polymer nanoparticles is developed in this study based on the chemical deposition of nickel onto hydrophilic polymer nanogels. High-resolution transmission electron microscopic and XPS analyses show that Ni exists mainly in the form of NiO in nanogels. Excellent catalytic activities of the nanoparticles are demonstrated for hydrogen generation from the hydrolysis of dimethylamine-borane and sodium borohydride in which the initial TOF (turn-over frequencies) are 376 and 1919 h"−"1, respectively. Kinetic studies also reveal an Arrhenius activation energy of 50.96 kJ mol"−"1 for the hydrolysis of dimethylamine-borane and 47.82 kJ mol"−"1 for the hydrolysis of sodium borohydride, which are lower than those catalyzed by Ru metal. Excellent reusability and the use of water for hydrogen production from dimethylamine-borane provide the additional benefit of using a hybrid catalyst. The principle illustrated in the present study offers a new strategy to explore polymer-transition metal hybrid particles for hydrogen energy technology. - Highlights: • Electroless Ni plating on polymer nanogels generated recyclable catalysts. • The Ni particles proved efficient for H_2 production from borohydride compounds. • The catalysts have lower activation energies than Ru for the hydrolysis. • Borohydride hydrolysis is more beneficial than dehydrogenation in organic solvent.

C1 Polymerization: a unique tool towards polyethylene-based complex macromolecular architectures

KAUST Repository

Wang, De

2017-05-09

The recent developments in organoborane initiated C1 polymerization (chain grows by one atom at a time) of ylides opens unique horizons towards well-defined/perfectly linear polymethylenes (equivalent to polyethylenes, PE) and PE-based complex macromolecular architectures. The general mechanism of C1 polymerization (polyhomologation) involves the formation of a Lewis complex between a methylide (monomer) and a borane (initiator), followed by migration/insertion of a methylene into the initiator and after oxidation/hydrolysis to afford OH-terminated polyethylenes. This review summarizes efforts towards conventional and newly discovered borane-initiators and ylides (monomers), as well as a combination of polyhomologation with other polymerization methods. Initial efforts dealing with C3 polymerization and the synthesis of the first C1/C3 copolymers are also given. Finally, some thoughts for the future of these polymerizations are presented.

C1 Polymerization: a unique tool towards polyethylene-based complex macromolecular architectures

KAUST Repository

Wang, De; Zhang, Zhen; Hadjichristidis, Nikolaos

2017-01-01

The recent developments in organoborane initiated C1 polymerization (chain grows by one atom at a time) of ylides opens unique horizons towards well-defined/perfectly linear polymethylenes (equivalent to polyethylenes, PE) and PE-based complex macromolecular architectures. The general mechanism of C1 polymerization (polyhomologation) involves the formation of a Lewis complex between a methylide (monomer) and a borane (initiator), followed by migration/insertion of a methylene into the initiator and after oxidation/hydrolysis to afford OH-terminated polyethylenes. This review summarizes efforts towards conventional and newly discovered borane-initiators and ylides (monomers), as well as a combination of polyhomologation with other polymerization methods. Initial efforts dealing with C3 polymerization and the synthesis of the first C1/C3 copolymers are also given. Finally, some thoughts for the future of these polymerizations are presented.

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

Science.gov (United States)

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

2012-01-21

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

Interface interaction in the B4C/(Fe-B-C) system

International Nuclear Information System (INIS)

Aizenshtein, M.; Mizrahi, I.; Froumin, N.; Hayun, S.; Dariel, M.P.; Frage, N.

2008-01-01

The wetting behavior in the B 4 C/(Fe-C-B) system was investigated in order to clarify the role of Fe additions on the sinterability of B 4 C. Iron and its alloys with C and B react with the boron carbide substrate and form a reaction zone consisting of a fine mixture of FeB and graphite. The apparent contact angles are relatively low for the alloys with a moderate concentration of the boron and carbon and allow liquid phase sintering to occur in the B 4 C-Fe mixtures. A dilatometric study of the sintering kinetics confirms that liquid phase sintering actually takes place and leads to improved mass transfer. A thermodynamic analysis of the ternary Fe-B-C system allows accounting for the experimental observations

Unwilling U-U bonding in U-2@C-80: cage-driven metal-metal bonds in di-uranium fullerenes

Czech Academy of Sciences Publication Activity Database

Foroutan-Nejad, C.; Vícha, J.; Marek, R.; Patzschke, M.; Straka, Michal

2015-01-01

Roč. 17, č. 37 (2015), s. 24182-24192 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GA14-03564S Institutional support: RVO:61388963 Keywords : actinide-actinide bond * endohedral actinide fullerene * cage-driven bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.449, year: 2015 http://pubs.rsc.org/en/content/articlepdf/2015/cp/c5cp04280a

Selective Complexation of Cyanide and Fluoride Ions with Ammonium Boranes: A Theoretical Study on Sensing Mechanism Involving Intramolecular Charge Transfer and Configurational Changes.

Science.gov (United States)

Bhat, Haamid R; Jha, Prakash C

2017-05-18

The anion binding selectivity and the recognition mechanism of two isomeric boranes, namely, 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 1, where "Mes" represents mesitylene and "Me" represents methyl) and 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 2) has been investigated using density functional theory (DFT) and time dependent-density functional theory (TD-DFT) methods. Natural population analysis indicates that the central boron atoms in 1 and 2 are the most active centers for nucleophilic addition of anions. The negative magnitude of free energy changes (ΔG) reveals that out of CN - , F - , Cl - , Br - , NO 3 - , and HSO 4 - only the binding of CN - and F - with 1 and 2 is thermodynamically feasible and spontaneous. In addition, the calculated binding energies reveal that the CN - is showing lesser binding affinity than F - both with 1 and 2, while other ions, viz. NO 3 - , HSO 4 - , Br - , and Cl - , either do not bind at all or show very insignificant binding energy. The first excited states (S 1 ) of 1 and 2 are shown to be the local excited states with π → σ* transition by frontier molecular orbital analysis, whereas fourth excited states (S 4 ) of 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline cyanide ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] CN, 1CN, the cyano form of 1) and 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 1F, the fluoro form of 1) and fifth excited state (S 5 ) of 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 2F, the fluoro form of 2) are charge separation states that are found to be responsible for the intramolecular charge transfer (ICT) process. The synergistic effect of ICT and partial configuration changes induce fluorescence quenching in 1CN, 1F, and 2F after a significant internal conversion (IC) from S 4 and

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-06-07

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

The effect of ion irradiation and elevated temperature on the microstructure and the properties of C/W/C/B multilayer coating

Energy Technology Data Exchange (ETDEWEB)

Vlcak, Petr, E-mail: petr.vlcak@fs.cvut.cz

2016-03-01

Graphical abstract: - Highlights: • C/W/C/B multilayer PVD coating was treated by 45 keV nitrogen ion irradiation. • The effect of ion irradiation and elevated temperature on microstructure was analyzed. • Formation of new compounds and degradation of carbon fraction were observed. • The causes of the observed changes in surface properties were discussed. - Abstract: C/W/C/B multi-layer PVD coating with a layer period of 10 nm and 500 nm in thickness was irradiated with 45 keV N ions at fluence of 1 × 10{sup 17} cm{sup −2}. Ion irradiation was performed at room temperature or at an elevated temperature of 500 °C. The microstructure was investigated by X-ray diffraction, by X-ray photoelectron spectroscopy, and by Raman spectroscopy. The results showed that implanted N ions bond both with W atoms and with C atoms. N ion irradiation induced the formation of WC and WC{sub 1−x} phases. The energetic ions transformed the C bonds in defect sp{sup 2} and defect sp{sup 3} hybridizations, resulting in graphitization of the carbon fraction in the multilayer coating. Ion irradiation reduced the cohesive strength of the monolayers, reduced hardness of the C/W/C/B coating, increased its surface roughness and increased its friction coefficient. An elevated temperature during ion irradiation caused a better arrangement of the WC phase and further graphitization of the carbon fraction, in comparison with a coating treated by ion irradiation at room temperature. There is discussion of the causes of the observed changes in surface properties.

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.

Ab initio computational study of –N-C and –O-C bonding formation : functional group modification reaction based chitosan

Science.gov (United States)

Siahaan, P.; Salimah, S. N. M.; Sipangkar, M. J.; Hudiyanti, D.; Djunaidi, M. C.; Laksitorini, M. D.

2018-04-01

Chitosan application in pharmaceutics and cosmeceutics industries is limited by its solubility issue. Modification of -NH2 and -OH fuctional groups of chitosan by adding carboxyl group has been shown to improve its solubility and application. Attempt to synthesize carboxymethyl chitosan (CMC) from monocloroacetic acid (MCAA) has been done prior this report. However no information is available wether –OH (-O-C bonding formation) or -NH2 (-N-C bonding formation) is the preference for - CH2COOH to attach. In the current study, the reaction mechanism between chitosan and MCAA reactants into carboxymethyl chitosan (CMC) was examined by computational approach. Dimer from of chitosan used as a molecular model in calculation All the molecular structure involved in the reaction mechanism was optimized by ab initio computational on the theory and basis set HF/6-31G(d,p). The results showed that the - N-C bonding formation via SN2 than the -O-C bonding formation via SN2 which have activation energy 469.437 kJ/mol and 533.219 kJ/mol respectively. However, the -O-C bonding formation more spontaneous than the -N-C bonding formation because ΔG the formation of O-CMC-2 reaction is more negative than ΔG of formation N-CMC-2 reaction is -4.353 kJ/mol and -1.095 kJ/mol respectively. The synthesis of N,O-CMC first forms -O-CH2COOH, then continues to form -NH-CH2COOH. This information is valuable to further optimize the reaction codition for CMC synthesis.

Characterization and photoconductivity study of well-defined C60 terminated poly(tert-butyl acrylate-b-styrene)

International Nuclear Information System (INIS)

Yang Dong; Li Lang; Wang Changchun

2004-01-01

Atom transfer radical polymerization (ATRP) catalyzed by N,N',N',N'',N''-pentamethyldiethylenetriamine (PMDETA)/CuBr was performed to synthesize poly (tert-butyl acrylate) (PtBA-Br) with predesigned molecular weight and narrow polydispersity. Using the PtBA-Br as macroinitiator, the PtBA-block-PS copolymer was prepared through ATRP. After terminated bromine atom was converted to end-functional azide group (P(tBA-b-St)-N 3 ), C 60 end-capped PtBA-PS block copolymers (P(tBA-b-St)-C 60 ) were synthesized by reacting C 60 with P(tBA-b-St)-N 3 . GPC characterizations showed that C 60 was chemically bonded to the end of P(tBA-b-St) chain and the products were mono-substituted. FT-IR, UV-Vis measurements confirmed that hydrolysis of P(tBA-b-St)-C 60 resulted in amphiphilic C 60 end-capped PAA-PS block copolymers. In additional, the photoconductivity of P(tBA-b-St)-C 60 was measured

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.

The superfamily of C3b/C4b-binding proteins

DEFF Research Database (Denmark)

Kristensen, Torsten; D'Eustachio, P; Ogata, R T

1987-01-01

The determination of primary structures by amino acid and nucleotide sequencing for the C3b-and/or C4b-binding proteins H, C4BP, CR1, B, and C2 has revealed the presence of a common structural element. This element is approximately 60 amino acids long and is repeated in a tandem fashion, commencing...... at the amino-terminal end of each molecule. Two other complement components, C1r and C1s, have two of these repeating units in the carboxy-terminal region of their noncatalytic A chains. Three noncomplement proteins, beta 2-glycoprotein I (beta 2I), the interleukin 2 receptor (IL 2 receptor), and the b chain...... of factor XIII, have 4, 2 and 10 of these repeating units, respectively. These proteins obviously belong to the above family, although there is no evidence that they interact with C3b and/or C4b. Human haptoglobin and rat leukocyte common antigen also contain two and three repeating units, respectively...

Oxidative addition of C--H bonds in organic molecules to transition metal centers

International Nuclear Information System (INIS)

Bergman, R.G.

1989-04-01

Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs

Synthesis of [2-13C, 2-14C] 2-aminoethanol, [1-13C, 1-14C] 2-chloroethylamine, N,N'-bis([1-13C, 1-14C] 2-chloroethyl)-N-nitrosourea(BCNU) and N-([1-13C, 1-14C] 2-chloroethyl)-N-nitrosourea(CNU)

International Nuclear Information System (INIS)

Narayan, R.; Chang, C-j.

1982-01-01

[2- 13 C, 2- 14 C]2-Aminoethanol hydrochloride was prepared in good yield from Na*CN in a two step sequence by first converting the Na*CN to OHCH 2 *CN and then reducing the nitrile directly with a solution of borane-tetrahydrofuran complex. The reaction procedure was simple and the pure product could be obtained readily. Using this specifically labelled precursor, the synthesis of [1- 13 C, 1- 14 C]2-chloroethylamine hydrochloride, N-([1- 13 C, 1- 14 C]2-chloroethyl)-N-nitrosourea(CNU) and N,N'-bis([1- 13 C, 1- 14 C]2-chloroethyl)-N-nitrosourea(BCNU) in good yield without isotope scrambling was also reported. (author)

Structural and Biochemical Characterization of Organotin and Organolead Compounds Binding to the Organomercurial Lyase MerB Provide New Insights into Its Mechanism of Carbon–Metal Bond Cleavage

Energy Technology Data Exchange (ETDEWEB)

Wahba, Haytham M. [Département; Faculty; Stevenson, Michael J. [Department; Mansour, Ahmed [Département; Sygusch, Jurgen [Département; Wilcox, Dean E. [Department; Omichinski, James G. [Département

2017-01-03

The organomercurial lyase MerB has the unique ability to cleave carbon–Hg bonds, and structural studies indicate that three residues in the active site (C96, D99, and C159 in E. coli MerB) play important roles in the carbon–Hg bond cleavage. However, the role of each residue in carbon–metal bond cleavage has not been well-defined. To do so, we have structurally and biophysically characterized the interaction of MerB with a series of organotin and organolead compounds. Studies with two known inhibitors of MerB, dimethyltin (DMT) and triethyltin (TET), reveal that they inhibit by different mechanisms. In both cases the initial binding is to D99, but DMT subsequently binds to C96, which induces a conformation change in the active site. In contrast, diethyltin (DET) is a substrate for MerB and the SnIV product remains bound in the active site in a coordination similar to that of HgII following cleavage of organomercurial compounds. The results with analogous organolead compounds are similar in that trimethyllead (TML) is not cleaved and binds only to D99, whereas diethyllead (DEL) is a substrate and the PbIV product remains bound in the active site. Binding and cleavage is an exothermic reaction, while binding to D99 has negligible net heat flow. These results show that initial binding of organometallic compounds to MerB occurs at D99 followed, in some cases, by cleavage and loss of the organic moieties and binding of the metal ion product to C96, D99, and C159. The N-terminus of MerA is able to extract the bound PbVI but not the bound SnIV. These results suggest that MerB could be utilized for bioremediation applications, but certain organolead and organotin compounds may present an obstacle by inhibiting the enzyme.

77 FR 213 - United States Savings Bonds, Series EE and I

Science.gov (United States)

2012-01-04

... savings bonds and $10,000 for Series I savings bonds. (b) Bonds purchased or transferred as gifts will be... are delivered to the recipient. (c) Bonds purchased as gifts or in a fiduciary capacity are not... Series I savings bonds a person may acquire each year. Prior to this change, an investor could purchase...

Deuterium isotope effects on 13C and 15N chemical shifts of intramolecularly hydrogen-bonded enaminocarbonyl derivatives of Meldrum’s and Tetronic acid

Science.gov (United States)

Ullah, Saif; Zhang, Wei; Hansen, Poul Erik

2010-07-01

Secondary deuterium isotope effects on 13C and 15N nuclear shieldings in a series of cyclic enamino-diesters and enamino-esters and acyclic enaminones and enamino-esters have been examined and analysed using NMR and DFT (B3LYP/6-31G(d,p)) methods. One-dimensional and two-dimensional NMR spectra of enaminocarbonyl and their deuterated analogues were recorded in CDCl 3 and CD 2Cl 2 at variable temperatures and assigned. 1JNH coupling constants for the derivatives of Meldrum's and tetronic acids reveal that they exist at the NH-form. It was demonstrated that deuterium isotope effects, for the hydrogen bonded compounds, due to the deuterium substitution at the nitrogen nucleus lead to large one-bond isotope effects at nitrogen, 1Δ 15N(D), and two-bond isotope effects on carbon nuclei, 2ΔC(ND), respectively. A linear correlations exist between 2ΔC(ND) and 1Δ 15N(D) whereas the correlation with δNH is divided into two. A good agreement between the experimentally observed 2ΔC(ND) and calculated dσ 13C/dR NH was obtained. A very good correlation between calculated NH bond lengths and observed NH chemical shifts is found. The observed isotope effects are shown to depend strongly on Resonance Assisted Hydrogen bonding.

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.

Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

Science.gov (United States)

Corbin, Joshua R; Schomaker, Jennifer M

2017-04-13

Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

Science.gov (United States)

Sharma, Ankit; Hartwig, John F

2013-11-27

We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

Low-pressure c-BN deposition - is a CVD process possible?

International Nuclear Information System (INIS)

Haubner, R.; Tang, X.

2001-01-01

Since the low-pressure diamond deposition was discovered in 1982 there is a high interest to find a similar process for the c-BN synthesis. A review about the c-BN deposition process as well as its characterization is given. Experiments with a simple chemical vapor deposition(CVD) reactor using tris(dimethylamino)borane as precursor were carried out. In a cold-wall reactor substrates were heated up by high-frequency. Argon was used as protecting and carrying the precursor, it was saturated with tris(dimethylamino)borane (precursor) according to its vapor pressure and transports the pressure to the hot substrate, where deposition occurs. WC-Co hardmetal plates containing 6 wt. % Co, Mo and Si were used as substrates. Various BN layers were deposited and characterized. X-ray diffraction, IR-spectroscopy and SIMS indicate that BN-coatings containing c-BN were deposited. However a final verification of c-BN crystallites by TEM investigations was not possible till now. (nevyjel)

Effects of Surface Treatment Processes of SiC Ceramic on Interfacial Bonding Property of SiC-AFRP

Directory of Open Access Journals (Sweden)

WEI Ru-bin

2016-12-01

Full Text Available To improve the interfacial bonding properties of SiC-aramid fiber reinforced polymer matrix composites (SiC-AFRP, the influences of etching process of SiC ceramic, coupling treatment process, and the adhesives types on the interfacial peel strength of SiC-AFRP were studied. The results show that the surface etching process and coupling treatment process of silicon carbide ceramic can effectively enhance interfacial bonding property of the SiC-AFRP. After soaked the ceramic in K3Fe(CN6 and KOH mixed etching solution for 2 hours, and coupled with vinyl triethoxy silane coupling agent, the interfacial peel strength of the SiC-AFRP significantly increases from 0.45kN/m to 2.20kN/m. EVA hot melt film with mass fraction of 15%VA is ideal for interface adhesive.

Effect of newer antioxidants on the bond strength of composite on bleached enamel

Directory of Open Access Journals (Sweden)

M Manoharan

2016-01-01

Full Text Available Aim: The study aims to evaluate the effect of the application of two antioxidants on the bond strength of composite resin to bleached enamel. Materials and Methods: Eighty enamel surfaces were obtained from forty human extracted premolars. Specimens were randomly divided into four groups (n = 20. Group 1: No bleaching (control; Group 2a: Bleaching with 15% carbamide peroxide gel; Group 2b: Bleaching, followed by application of 10% sodium ascorbate gel; Group 2c: Bleaching, followed by application of 5% proanthocyanidin agent. Surfaces were etched followed by application of total etch bonding system, and composite resin cylinders were bonded. Specimens were tested for shear bond strength. Statistical Analysis Used: One-way analysis of variance was used for multiple group comparison and post hoc Tukey′s test for individual group-wise comparison. Results: Significantly higher shear bond strength values were observed in Group 2c and 2b as compared with Group 1 and 2a (P < 0.05. Among the antioxidants, Group 2c showed significantly higher shear bond strength values than Group 2b (P < 0.05. Conclusion: It can be concluded that the use of antioxidant before bonding procedures on bleached enamel completely neutralizes the deleterious effects of bleaching and increases the bond strength significantly.

Preparation and characterization of LTA-type zeolite framework dispersed ruthenium nanoparticles and their catalytic application in the hydrolytic dehydrogenation of ammonia–borane for efficient hydrogen generation

International Nuclear Information System (INIS)

Zahmakiran, Mehmet

2012-01-01

Highlights: ► Ru(0)NPs-ZK-4 were prepared and characterized by advanced analytical techniques. ► They achieve the hydrolysis of ammonia-borane with TOF = 5410 h −1 and TTO = 36700. ► They maintain 85% of their activity even at the fifth catalytic run. - Abstract: The safe and efficient hydrogen storage and production are major obstacles to use hydrogen as an energy carrier. Therefore, significant efforts have been focused on the development of new materials for the chemical hydrogen storage and production. Of particular importance, ammonia–borane (NH 3 BH 3 ) is emerging as one of the most promising solid hydrogen carrier due to its high gravimetric hydrogen storage capacity (19.6 wt.%) and low molecular weight (30.8 g/mol). ammonia–borane can release hydrogen gas upon catalytic hydrolysis under mild conditions. Herein, the discovery of a new catalytic material, ruthenium nanoparticles stabilized by ZK-4 zeolite framework, for this important reaction has been reported. This new catalyst system was prepared by borohydride reduction of ruthenium(III)-exchanged ZK-4 zeolite in water at room temperature. The characterization of the resulting material by advanced analytical tools shows the formation of ZK-4 zeolite dispersed ruthenium nanoparticles (2.9 ± 0.9 nm). The catalytic performance of the resulting supported ruthenium nanoparticles depending on activity, lifetime and reusability was demonstrated in the hydrolytic dehydrogenation of ammonia–borane. They were found to be highly active (initial TOF = 5410 h −1 ), long-lived (TTO = 36,700) and reusable catalyst (retaining of >85% of initial activity in the 5th reuse) in this important catalytic reaction at room temperature under air.

Interface interaction in the B{sub 4}C/(Fe-B-C) system

Energy Technology Data Exchange (ETDEWEB)

Aizenshtein, M. [Department of Material Engineering, Ben-Gurion University, P.O. Box 653, Beer-Sheva 84105 (Israel); NRC-Negev, P.O. Box 9001, Beer-Sheva 84190 (Israel); Mizrahi, I.; Froumin, N.; Hayun, S.; Dariel, M.P. [Department of Material Engineering, Ben-Gurion University, P.O. Box 653, Beer-Sheva 84105 (Israel); Frage, N. [Department of Material Engineering, Ben-Gurion University, P.O. Box 653, Beer-Sheva 84105 (Israel)], E-mail: nfrage@bgu.ac.il

2008-11-15

The wetting behavior in the B{sub 4}C/(Fe-C-B) system was investigated in order to clarify the role of Fe additions on the sinterability of B{sub 4}C. Iron and its alloys with C and B react with the boron carbide substrate and form a reaction zone consisting of a fine mixture of FeB and graphite. The apparent contact angles are relatively low for the alloys with a moderate concentration of the boron and carbon and allow liquid phase sintering to occur in the B{sub 4}C-Fe mixtures. A dilatometric study of the sintering kinetics confirms that liquid phase sintering actually takes place and leads to improved mass transfer. A thermodynamic analysis of the ternary Fe-B-C system allows accounting for the experimental observations.

A method of coupling the Paternò-Büchi reaction with direct infusion ESI-MS/MS for locating the C[double bond, length as m-dash]C bond in glycerophospholipids.

Science.gov (United States)

Stinson, Craig A; Xia, Yu

2016-06-21

Tandem mass spectrometry (MS/MS) coupled with soft ionization is established as an essential platform for lipid analysis; however, determining high order structural information, such as the carbon-carbon double bond (C[double bond, length as m-dash]C) location, remains challenging. Recently, our group demonstrated a method for sensitive and confident lipid C[double bond, length as m-dash]C location determination by coupling online the Paternò-Büchi (PB) reaction with nanoelectrospray ionization (nanoESI) and MS/MS. Herein, we aimed to expand the scope of the PB reaction for lipid analysis by enabling the reaction with infusion ESI-MS/MS at much higher flow rates than demonstrated in the nanoESI setup (∼20 nL min(-1)). In the new design, the PB reaction was effected in a fused silica capillary solution transfer line, which also served as a microflow UV reactor, prior to ESI. This setup allowed PB reaction optimization and kinetics studies. Under optimized conditions, a maximum of 50% PB reaction yield could be achieved for a standard glycerophosphocholine (PC) within 6 s of UV exposure over a wide flow rate range (0.1-10 μL min(-1)). A solvent composition of 7 : 3 acetone : H2O (with 1% acid or base modifier) allowed the highest PB yields and good lipid ionization, while lower yields were obtained with an addition of a variety of organic solvents. Radical induced lipid peroxidation was identified to induce undesirable side reactions, which could be effectively suppressed by eliminating trace oxygen in the solution via N2 purge. Finally, the utility of coupling the PB reaction with infusion ESI-MS/MS was demonstrated by analyzing a yeast polar lipid extract where C[double bond, length as m-dash]C bond locations were revealed for 35 glycerophospholipids (GPs).

BPN, a marine-derived PTP1B inhibitor, activates insulin signaling and improves insulin resistance in C2C12 myotubes.

Science.gov (United States)

Xu, Qi; Luo, Jiao; Wu, Ning; Zhang, Renshuai; Shi, Dayong

2018-01-01

Insulin resistance is a key feature of type 2 diabetes mellitus (T2DM) and is characterized by defects in insulin signaling. Protein tyrosine phosphatase 1B (PTP1B) is a major negative regulator of insulin signaling cascade and has attracted intensive investigation in recent T2DM therapy study. BPN, a marine-derived bromophenol compound, was isolated from the red alga Rhodomela confervoides. This study investigated the effects of BPN on the insulin signaling pathway in insulin-resistant C2C12 myotubes by inhibiting PTP1B. Molecular docking study and analysis of small- molecule interaction with PTP1B all showed BPN inhibited PTP1B activity via binding to the catalytic site through hydrogen bonds. We then found that BPN permeated into C2C12 myotubes, on the one hand, activated insulin signaling in an insulin-independent manner in C2C12 cells; on the other hand, ameliorated palmitate-induced insulin resistance through augmenting insulin sensitivity. Moreover, our studies also showed that PTP1B inhibition by BPN increased glucose uptake in normal and insulin-resistant C2C12 myotubes through glucose transporter 4 (GLUT4) translocation. Taken together, BPN activates insulin signaling and alleviates insulin resistance and represents a potential candidate for further development as an antidiabetic agent. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of nanotechnology in self-etch bonding systems on the shear bond strength of stainless steel orthodontic brackets

OpenAIRE

Hammad, Shaza M.; El-Wassefy, Noha; Maher, Ahmed; Fawakerji, Shafik M.

2017-01-01

ABSTRACT Objective: To evaluate the effect of silica dioxide (SiO2) nanofillers in different bonding systems on shear bond strength (SBS) and mode of failure of orthodontic brackets at two experimental times. Methods: Ninety-six intact premolars were divided into four groups: A) Conventional acid-etch and primer Transbond XT; B) Transbond Plus self-etch primer; and two self-etch bonding systems reinforced with silica dioxide nanofiller at different concentrations: C) Futurabond DC at 1%; D...

Bonding techniques for flexural strengthening of R.C. beams using CFRP laminates

Directory of Open Access Journals (Sweden)

Alaa Morsy

2013-09-01

Full Text Available This paper presents an experimental study of an alternative method of attaching FRP laminates to reinforced concrete beams by the way of fasting steel rivets through the FRP laminate and concrete substrate. Five full scale R.C. beams were casted and strengthened in flexural using FRP laminate bonded with conventional epoxy and compared with other beams strengthened with FRP laminate and bonded with fastener “steel rivets” of 50 mm length and 10 mm diameter. Based on experimental evidence the beam strengthened with conventional bonding methods failed due to de-bonding with about 13% increase over the un-strengthened beam. On the other hand, the beams strengthened with FRP laminate and bonded by four steel fastener rivets only failed by de-bonding also but at higher flexural capacity with increase 19% over the un-strengthened beam.

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.

Finding high-temperature superconductors by metallizing the σ-bonding electrons

International Nuclear Information System (INIS)

Gao Miao; Lu Zhongyi; Xiang Tao

2015-01-01

Raising superconducting transition temperature (T_c) is an important task of fundamental research on superconductivity. It is also a prerequisite for the large scale application of superconductors. Since the microscopic mechanism of high-T_c superconductivity is unknown, the conventional approach for increasing T_c is either to apply high pressure to a material which has the potential to become superconducting, or to push it close to an antiferromagnetic or some other quantum instability point by chemical doping. In this article, the authors point out that another general approach for raising T_c is to lift the σ-bonding bands to the Fermi level, or to metallize the σ-bonding elections. This approach can increase the probability of finding a novel high-T_c superconductor because the coupling of σ-bonding electrons with phonons is generally strong and the superconducting transition induced by this interaction can occur at relatively high temperatures. After elucidating the underlying mechanism, the authors discuss a number of schemes to metallize σ-bonding electrons, and present their recent prediction for the crystalline and electronic structures of two potential high-T_c superconductors, Li_2B_3C and Li_3B_4C_2, with T_c higher than 50 K. (authors)

Hydrogenation of the Exocyclic Olefinic Bond at C-16/C-17 Position of ent-Kaurane Diterpene Glycosides of Stevia rebaudiana Using Various Catalysts

Science.gov (United States)

Chaturvedula, Venkata Sai Prakash; Prakash, Indra

2013-01-01

Catalytic hydrogenation of the exocyclic double bond present between C16 and C17 carbons of the four ent-kaurane diterpene glycosides namely rebaudioside A, rebaudioside B, rebaudioside C, and rebaudioside D isolated from Stevia rebaudiana has been carried out using Pt/C, Pd(OH)2, Rh/C, Raney Ni, PtO2, and 5% Pd/BaCO3 to their corresponding dihydro derivatives with 17α and 17β methyl group isomers. Reactions were performed using the above-mentioned catalysts with the solvents methanol, water, and ethanol/water (8:2) under various conditions. Synthesis of reduced steviol glycosides was performed using straightforward chemistry and their structures were characterized on the basis of 1D and 2D NMR spectral data, including a comparison with reported spectral data. PMID:23896597

Hydrogenation of the Exocyclic Olefinic Bond at C-16/C-17 Position of ent-Kaurane Diterpene Glycosides of Stevia rebaudiana Using Various Catalysts

Directory of Open Access Journals (Sweden)

Indra Prakash

2013-07-01

Full Text Available Catalytic hydrogenation of the exocyclic double bond present between C16 and C17 carbons of the four ent-kaurane diterpene glycosides namely rebaudioside A, rebaudioside B, rebaudioside C, and rebaudioside D isolated from Stevia rebaudiana has been carried out using Pt/C, Pd(OH2, Rh/C, Raney Ni, PtO2, and 5% Pd/BaCO3 to their corresponding dihydro derivatives with 17α and 17β methyl group isomers. Reactions were performed using the above-mentioned catalysts with the solvents methanol, water, and ethanol/water (8:2 under various conditions. Synthesis of reduced steviol glycosides was performed using straightforward chemistry and their structures were characterized on the basis of 1D and 2D NMR spectral data, including a comparison with reported spectral data.

Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes

KAUST Repository

Chen, Shuli

2013-09-17

Phenylbis(phenylethynyl)phosphane PhP(C≡CPh)2 coordinates regiospecifically to the α-methyl-chiral ortho-platinated and -palladated naphthylamine units at the positions trans to the nitrogen donors. The P→Pt coordination bond is kinetically inert, whereas the P→Pd bond is labile. Upon heating of these phosphane complexes at 70 °C, one of the C≡C bonds in the coordinated PhP(C≡CPh)2 was activated towards an intermolecular Pd-C bond insertion reaction with an external ortho-palladated naphthylamine ring. No intramolecular insertion reaction occurred. In contrast to its palladium analogue, the ortho-platinated ring is not reactive towards coordinated PhP(C≡CPh)2, although it can promote the Pd-C bond insertion reaction. However, despite the high kinetic stability of the P→Pt coordination, the organoplatinum unit is a noticeably weaker activator than its organopalladium counterpart. The chirality of the reacting ortho-metallated naphthylamine ligand exhibited high stereochemical influence on the formation of the new stereogenic phosphorus center during the course of these C-C bond-formation reactions. The coordination chemistry and the absolute stereochemistry of the dimetallic products were determined by single-crystal X-ray crystallographic analysis. The asymmetric monoinsertion of PhP(C≡CPh)2 coordinated to a cyclometallated N,N-dimethyl naphthyl/benzylamine template into the Pd-C bonds of N,N-dimethylnaphthylamine palladacycles has been demonstrated for the synthesis of a variety of new P-stereogenic homo- or heterodimetallic complexes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

Science.gov (United States)

Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B

2015-01-28

(1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

A theoretical study of the hydrogen bonding between the vic-, cis- and trans-C 2H 2F 2 isomers and hydrogen fluoride

Science.gov (United States)

Rusu, Victor H.; da Silva, João Bosco P.; Ramos, Mozart N.

2009-04-01

MP2/6-31++G(d,p) and B3LYP/6-31++G(d,p) theoretical calculations have been employed to investigate the hydrogen bonding formation involving the vic-, cis- and trans-C 2H 2F 2 isomers and hydrogen fluoride. Our calculations have revealed for each isomer the preferential existence of two possible hydrogen-bonded complexes: a non-cyclic complex and a cyclic complex. For all the three isomers the binding energies for the non-cyclic and cyclic hydrogen complexes are essentially equal using both the MP2 and B3LYP calculations, being that the cyclic structure is slightly more stable. For instance, the binding energies including BSSE and ZPE corrections for the non-cyclic and cyclic structures of cis-C 2H 2F···HF are 8.7 and 9.0 kJ mol -1, respectively, using B3LYP calculations. The cyclic complex formation reduces the polarity, in contrast to what occurs with the non-cyclic complex. This result is more accentuated in vic-C 2H 2F 2···HF. In this latter, Δ μ(cyclic) is -3.07 D, whereas Δ μ(non-cyclic) is +1.92 D using B3LYP calculations. Their corresponding MP2 values are +0.44 D and -1.89 D, respectively. As expected, the complexation produces an H sbnd F stretching frequency downward shift, whereas its IR intensity is enhanced. On the other hand, the vibrational modes of the vic-, cis- and trans-C 2H 2F 2 isomers are little affected by complexation. The new vibrational modes due to hydrogen bonding formation show several interesting features, in particular the HF bending modes which are pure rotations in the free molecule.

Growth curves of crossbred cows sired by Hereford, Angus, Belgian Blue, Brahman, Boran, and Tuli bulls, and the fraction of mature body weight and height at puberty.

Science.gov (United States)

Freetly, H C; Kuehn, L A; Cundiff, L V

2011-08-01

The objective of this study was to evaluate the growth curves of females to determine if mature size and relative rates of maturation among breeds differed. Body weight and hip height data were fitted to the nonlinear function BW = f(age) = A - Be(k×age), where A is an estimate of mature BW and k determines the rate that BW or height moves from B to A. Cows represented progeny from 28 Hereford, 38 Angus, 25 Belgian Blue, 34 Brahman, 8 Boran, and 9 Tuli sires. Bulls from these breeds were mated by AI to Angus, Hereford, and MARC III composite (1/4 Angus, 1/4 Hereford, 1/4 Red Poll, and 1/4 Pinzgauer) cows to produce calves in 1992, 1993, and 1994. These matings resulted in 516 mature cows whose growth curves were subsequently evaluated. Hereford-sired cows tended to have heavier mature BW, as estimated by parameter A, than Angus- (P=0.09) and Brahman-sired cows (P=0.06), and were heavier than the other breeds (P Angus-sired cows were heavier than Boran- (P Angus-sired cows did not differ from Brahman-sired cows (P=0.94). Brahman-sired cows had a heavier mature BW than Boran- (P Angus-sired cows matured faster (k) than cows sired by Hereford (P=0.03), Brahman (P Angus-sired cows (P=0.09), and had reached a greater proportion of their mature BW at puberty than had Hereford- (P < 0.001), Tuli- (P < 0.001), and Belgian Blue-sired cows (P < 0.001). Within species of cattle, the relative range in proportion of mature BW at puberty (Bos taurus 0.56 through 0.58, and Bos indicus 0.60) was highly conserved, suggesting that proportion of mature BW is a more robust predictor of age at puberty across breeds than is absolute weight or age. © 2011 American Society of Animal Science. All rights reserved.

[Evaluation of shear bond strengths of self-etching and total-etching dental adhesives to enamel and dentin].

Science.gov (United States)

Yu, Ling; Liu, Jing-Ming; Wang, Xiao-Yan; Gao, Xue-Jun

2009-03-01

To evaluate the shear bond strengths of four dental adhesives in vitro. The facial surfaces of 20 human maxillary incisors were prepared to expose fresh enamel and randomly divided into four groups, in each group 5 teeth were bonded with one adhesives: group A (Clearfil Protect Bond, self-etching two steps), group B (Adper( Prompt, self-etching one step), group C (SwissTEC SL Bond, total-etching two steps), group D (Single Bond, total-etching two steps). Shear bond strengths were determined using an universal testing machine after being stored in distilled water for 24 h at 37 degrees C. The bond strengths to enamel and dentin were (25.33 +/- 2.84) and (26.07 +/- 5.56) MPa in group A, (17.08 +/- 5.13) and (17.93 +/- 4.70) MPa in group B, (33.14 +/- 6.05) and (41.92 +/- 6.25) MPa in group C, (22.51 +/- 6.25) and (21.45 +/- 7.34) MPa in group D. Group C showed the highest and group B the lowest shear bond strength to enamel and dentin among the four groups. The two-step self-etching adhesive showed comparable shear bond strength to some of the total-etching adhesives and higher shear bond strength than one-step self-etching adhesive.

The Hydrogen Bonded Structures of Two 5-Bromobarbituric Acids and Analysis of Unequal C5–X and C5–X′ Bond Lengths (X = X′ = F, Cl, Br or Me in 5,5-Disubstituted Barbituric Acids

Directory of Open Access Journals (Sweden)

Thomas Gelbrich

2016-04-01

Full Text Available The crystal structure of the methanol hemisolvate of 5,5-dibromobarbituric acid (1MH displays an H-bonded layer structure which is based on N–H∙∙∙O=C, N–H∙∙∙O(MeOH and (MeOHO–H∙∙∙O interactions. The barbiturate molecules form an H-bonded substructure which has the fes topology. 5,5′-Methanediylbis(5-bromobarbituric acid 2, obtained from a solution of 5,5-dibromobarbituric acid in nitromethane, displays a N–H···O=C bonded framework of the sxd type. The conformation of the pyridmidine ring and the lengths of the ring substituent bonds C5–X and C5–X′ in crystal forms of 5,5-dibromobarbituric acid and three closely related analogues (X = X′ = Br, Cl, F, Me have been investigated. In each case, a conformation close to a C5-endo envelope is correlated with a significant lengthening of the axial C5–X′ in comparison to the equatorial C5–X bond. Isolated molecule geometry optimizations at different levels of theory confirm that the C5-endo envelope is the global conformational energy minimum of 5,5-dihalogenbarbituric acids. The relative lengthening of the axial bond is therefore interpreted as an inherent feature of the preferred envelope conformation of the pyrimidine ring, which minimizes repulsive interactions between the axial substituent and pyrimidine ring atoms.

Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.

Science.gov (United States)

Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen

2016-02-04

A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.

Sequential Camouflage of the arachno-6,9-C2B8H14 Cage by Substituents

Czech Academy of Sciences Publication Activity Database

Bakardjiev, Mario; Štíbr, Bohumil; Holub, Josef; Tok, Oleg L.; Švec, Petr; Růžičková, Z.; Růžička, A.

2016-01-01

Roč. 55, č. 14 (2016), s. 7068-7074 ISSN 0020-1669 R&D Projects: GA ČR(CZ) GA16-01618S Institutional support: RVO:61388980 Keywords : boranes * derivatives * magnetic - resonance -spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 4.857, year: 2016

Mechanical properties and chemical bonding of the Os–B system: A first-principles study

International Nuclear Information System (INIS)

Ji Zongwei; Hu Chaohao; Wang Dianhui; Zhong Yan; Yang Jiong; Zhang Wenqing; Zhou Huaiying

2012-01-01

The mechanical properties of Os–B compounds containing different boron contents have been investigated systemically by first-principles calculations. Two previously unreported crystal structures of Os 2 B 5 and OsB 3 , crystallizing in space groups R3m and P-6m2 respectively, are determined using the ab initio evolutionary structure prediction. The calculated elastic constants, bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio, and hardness for Os–B compounds are in good agreement with the available experimental values. Our results show that the hardness of osmium borides increases with increasing boron content. Os 2 B 5 and OsB 3 , with hardnesses of 34.4 and 36.9 GPa respectively, can almost be considered as potential superhard materials. Further analyses on density of states, crystal orbital Hamilton population, and electron localization function demonstrate that the electronic structure of Os–B compounds is directly responsible for their particular mechanical properties. High hardness in Os 2 B 5 and OsB 3 is mainly attributed to the occurrence of strong B–B covalent bonds and the disappearance of some ductile Os–Os metallic bonds.

Cytochrome c6B of Synechococcus sp. WH 8102 – Crystal structure and basic properties of novel c6-like family representative

International Nuclear Information System (INIS)

Zatwarnicki, Pawel; Barciszewski, Jakub; Krzywda, Szymon; Jaskolski, Mariusz; Kolesinski, Piotr; Szczepaniak, Andrzej

2014-01-01

Highlights: • Crystal structure of cytochrome c 6B from Synechococcus sp. WH 8102 was solved. • Basic biophysical properties of cytochrome c 6B were determined. • Cytochrome c 6B exhibits similar architecture to cytochrome c 6 . • Organization of heme binding pocket of cytochrome c 6B differs from that of c 6 . • Midpoint potential of cytochrome c 6B is significantly lower than of cytochrome c 6 . - Abstract: Cytochromes c are soluble electron carriers of relatively low molecular weight, containing single heme moiety. In cyanobacteria cytochrome c 6 participates in electron transfer from cytochrome b 6 f complex to photosystem I. Recent phylogenetic analysis revealed the existence of a few families of proteins homologous to the previously mentioned. Cytochrome c 6A from Arabidopsis thaliana was identified as a protein responsible for disulfide bond formation in response to intracellular redox state changes and c 550 is well known element of photosystem II. However, function of cytochromes marked as c 6B , c 6C and c M as well as the physiological process in which they take a part still remain unidentified. Here we present the first structural and biophysical analysis of cytochrome from the c 6B family from mesophilic cyanobacteria Synechococcus sp. WH 8102. Purified protein was crystallized and its structure was refined at 1.4 Å resolution. Overall architecture of this polypeptide resembles typical I-class cytochromes c. The main features, that distinguish described protein from cytochrome c 6 , are slightly red-shifted α band of UV–Vis spectrum as well as relatively low midpoint potential (113.2 ± 2.2 mV). Although, physiological function of cytochrome c 6B has yet to be determined its properties probably exclude the participation of this protein in electron trafficking between b 6 f complex and photosystem I

The extended variant of the bond valence-bond length correlation curve for boron(III)-oxygen bonds

International Nuclear Information System (INIS)

Sidey, Vasyl

2015-01-01

The extended variant of the bond valence (s)-bond length (r) correlation curve for boron(III)-oxygen bonds has been closely approximated using the three-parameter function s = [k/(r - l)] - m, where s is measured in valence units (vu), r is measured in Aa, k = 0.53 Aa.vu, l = 0.975(1) Aa and m = 0.32 vu. The function s = exp[(r 0 - r)/b] traditionally used in the modern bond valence model requires the separate set of the bond valence parameters (r 0 = 1.362 Aa; b = 0.23 Aa) in order to approximate the above s-r curve for the bonds shorter than ∝1.3 Aa.

Aplikasi Magnet Berpengikat (Bonded NdFeB untuk S-band Circulator pada Rentang Frekuensi 2,00-4,00 GHz

Directory of Open Access Journals (Sweden)

Tony Kristiantoro

2016-06-01

Full Text Available Circulator merupakan perangkat elektronik yang memiliki fungsi penting pada suatu sistem pemancar dan penerima gelombang frekuensi radio (RF, di mana magnet permanen dapat berfungsi sebagai pengarah gelombang (waveguide. Penelitian ini bertujuan untuk menggantikan magnet permanen barium ferit (BaFe12O19 yang umumnya digunakan pada circulator dengan magnet permanen berpengikat (bonded neodymium besi boron (NdFeB. Bahan baku yang digunakan adalah serbuk NdFeB crashed ribbon dengan menggunakan metode pengepresan green-compact yang divariasikan pada tekanan 25, 50, 75, dan 100 kg.cm-2 dan dilanjutkan proses pemanasan pada temperatur 200 C selama 60 menit. Karakterisasi sifat magnet dilakukan dengan Permagraph, diperoleh nilai intrinsik optimum dari sampel 100 kg.cm-2 , induksi remanen (Br = 5,37 kG, koersifitas (HcJ = 4,74 kOe, produk energi maksimum (BHmax = 2,39 MGOe, dan densitas (ρ = 4,89 gr.cm-3 . Hasil pengukuran kuat medan permukaan (B dengan Gauss-meter menunjukkan nilai 800 G. Magnet dengan karakteristik optimum diterapkan pada circulator kemudian dikarakterisasi dengan Vector Network Analyzer dan menghasilkan voltage standing wave ratio (VSWR = 1,354, isolasi = -17,165 dB dan kerugian penyisipan = -0,200 dB pada titik kerja 3,00 GHz, sehingga magnet berpengikat (bonded NdFeB ini dapat diterapkan pada S-band circulator yang bekerja pada rentang frekuensi 2,00-4,00 GHz.

Elimination of C3 as the Bond-Neff depression opacity source in Hr 774

International Nuclear Information System (INIS)

Baird, S.R.

1982-01-01

The pseudocontinuum of C 3 has been proposed by Fix as the source of the Bond-Neff depression in HR 774. In such a case the strongest rotational lines of the 4050 A vibrational band of C 3 should be clearly evident at high dispersion. A 2.2 A mm -1 plate of HR 774 is examined in the 4050--4060 A region where the strongest lines should form. The absence of C 3 rotational lines indicates that C 3 cannot be the major contributor to the Bond-Neff depression in HR 774

Electronic Structure and Chemical Bond of Ti3SiC2 and Adding Al Element

Institute of Scientific and Technical Information of China (English)

MIN Xinmin; LU Ning; MEI Bingchu

2006-01-01

The relation among electronic structure, chemical bond and property of Ti3SiC2 and Al-doped was studied by density function and discrete variation (DFT-DVM) method. When Al element is added into Ti3SiC2, there is a less difference of ionic bond, which does not play a leading role to influent the properties. After adding Al, the covalent bond of Al and the near Ti becomes somewhat weaker, but the covalent bond of Al and the Si in the same layer is obviously stronger than that of Si and Si before adding. Therefore, in preparation of Ti3SiC2, adding a proper quantity of Al can promote the formation of Ti3SiC2. The density of state shows that there is a mixed conductor character in both of Ti3SiC2 and adding Al element. Ti3SiC2 is with more tendencies to form a semiconductor. The total density of state near Fermi lever after adding Al is larger than that before adding, so the electric conductivity may increase after adding Al.

Simple Synthesis, Halogenation, and Rearrangement of closo-1,6-C2B8H10

Czech Academy of Sciences Publication Activity Database

Bakardjiev, Mario; Štíbr, Bohumil; Holub, Josef; Padělková, Z.; Růžička, A.

2015-01-01

Roč. 34, č. 2 (2015), s. 450-454 ISSN 0276-7333 R&D Projects: GA ČR(CZ) GAP207/11/0705 Institutional support: RVO:61388980 Keywords : MAGNETIC-RESONANCE-SPECTROSCOPY * ORGANOELEMENTAL DERIVATIVES * CLOSO-BORANES * CARBORANES * 5,6-DICARBA-NIDO-DECABORANE(12) Subject RIV: CA - Inorganic Chemistry Impact factor: 4.186, year: 2015

Electrodeposited Ni-B coatings: Formation and evaluation of hardness and wear resistance

International Nuclear Information System (INIS)

Krishnaveni, K.; Sankara Narayanan, T.S.N.; Seshadri, S.K.

2006-01-01

The formation of electrodeposited Ni-B alloy coatings using a dimethylamine borane (DMAB) modified Watt's nickel bath and evaluation of their structural characteristics, hardness and wear resistance are discussed. The boron content in the electrodeposited Ni-B alloy coating is determined by the ratio of rate of reduction of nickel and rate of decomposition of DMAB. The boron content of the electrodeposited Ni-B coating decreases as the current density increased from 0.4 to 4 A dm -2 . XRD diffraction pattern of electrodeposited Ni-B coatings in their as-plated condition exhibits the presence of Ni (1 1 1) (2 0 0) and (2 2 0) reflections with (1 1 1) texture. Heat treatment at 400 deg. C for 1 h has resulted in the formation of nickel boride phases, which results in an increase in hardness and wear resistance. The mechanism of wear in electrodeposited Ni-B coatings is intensive plastic deformation of the coating due to the ploughing action of the hard counter disk

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

DEFF Research Database (Denmark)

Nielsen, Lone; Skrydstrup, Troels

2008-01-01

and the first new carbon-silicon bond. The next step is the reduction of this hydridosilane with lithium metal providing a silyl lithium reagent, which undergoes a highly diastereoselective addition to an optically active tert-butanesulfinimine, thus generating the second C-Si bond. This method allows...

CRADA/NFE-15-05761 Report: Additive Manufacturing of Isotropic NdFeB Bonded Permanent Magnets

Energy Technology Data Exchange (ETDEWEB)

Paranthaman, M Parans [ORNL

2016-07-18

The technical objective of this technical collaboration phase I proposal is to fabricate net shape isotropic NdFeB bonded magnets utilizing additive manufacturing technologies at the ORNL MDF. The goal is to form complex shapes of thermoplastic and/or thermoset bonded magnets without expensive tooling and with minimal wasted material. Two additive manufacturing methods; the binder jet process; and big area additive manufacturing (BAAM) were used. Binder jetting produced magnets with the measured density of the magnet of 3.47 g/cm³, close to 46% relative to the NdFeB single crystal density of 7.6 g/cm³ were demonstrated. Magnetic measurements indicate that there is no degradation in the magnetic properties. In addition, BAAM was used to fabricate isotropic near-net-shape NdFeB bonded magnets with magnetic and mechanical properties comparable or better than those of traditional injection molded magnets. The starting polymer magnet composite pellets consist of 65 vol% isotropic NdFeB powder and 35 vol% polyamide (Nylon-12). The density of the final BAAM magnet product reached 4.8 g/cm³, and the room temperature magnetic properties are: Intrinsic coercivity Hci = 8.65 kOe, Remanence Br = 5.07 kG, and energy product (BH)_max = 5.47 MGOe (43.50 kJ/m³). This study provides a new pathway for preparing near-net shape bonded magnets for various magnetic applications.

compounds with N=N, C≡C or conjugated double-bonded systems

Indian Academy of Sciences (India)

Unusual products in the reactions of phosphorus(III) compounds with. N=N, C≡C or conjugated double-bonded systems. K C KUMARA SWAMY,* E BALARAMAN, M PHANI PAVAN, N N BHUVAN KUMAR,. K PRAVEEN KUMAR and N SATISH KUMAR. School of Chemistry, University of Hyderabad, Hyderabad 500 046.

Mass spectroscopic evidence for icosaborane(26)

International Nuclear Information System (INIS)

Greenwood, N.N.; Kennedy, J.D.; Taylorson, D.

1978-01-01

Icosaborane is the heaviest neutral borane to be identified by features of the mass spectrum of crude decaborane. Although its composition, B 20 H 26 , formally corresponds to that of arachno-borane, B/sub n/H/sub n+6/, its stability over an indefinite period of time as a persistent impurity in technical-grade decaborane, together with its alternative method of preparation by deuteron irradiation of decaborane, suggests that it is an a conjuncto-nido-borane (B 10 H 13 ) 2 . The only other conjuncto-nido-borane is (B 5 H 8 ) 2 , which exists in three isomeric forms

Activation of C-H bond in methane by Pd atom from the bonding evolution theory perspective.

Science.gov (United States)

Nizovtsev, Anton S

2013-08-15

We report detailed study focused on the electron density redistribution during the simple oxidative addition reaction being the crucial stage of various catalytic processes. The bonding evolution theory based on the electron localization function and Thom's catastrophe theory shows that activation of methane's C-H bond by Pd atom consist of six elementary steps. The important feature revealed is the pronounced reorganization of Pd's outer core maxima corresponding to N-shell electrons of metal. Electronic rearrangements identified in this model reaction are likely to be the case in the more complex reactions of the same type involving transition metal compounds and, in principle, can be observed by modern ultrafast spectroscopy and diffraction techniques. Copyright © 2013 Wiley Periodicals, Inc.

13C-NMR spectra and bonding situation in ketenimines

International Nuclear Information System (INIS)

Firl, J.; Runge, W.; Hartmann, W.; Utikal, H.P.

1975-01-01

13 C-NMR spectra of a series of substituted ketenimines are reported. The terminal carbon resonances are found at unusual high fields between delta 37 and 78, while the central carbon signals appear around delta 189 - 196. On the basis of these results, the bonding situation in ketenimines has been discussed. (auth.)

Recent Developments in Organophosphorus Flame Retardants Containing P-C Bond and Their Applications

Directory of Open Access Journals (Sweden)

Sophie Wendels

2017-07-01

Full Text Available Organophosphorus compounds containing P-C bonds are increasingly developed as flame retardant additives due to their excellent thermal and hydrolytic stability and ease of synthesis. The latest development (since 2010 in organophosphorus flame retardants containing P-C bonds summarized in this review. In this review, we have broadly classified such phosphorus compounds based on the carbon unit linked to the phosphorus atom i.e., could be a part of either an aliphatic or an aromatic unit. We have only considered those published literature where a P-C bond was created as a part of synthetic strategy to make either an intermediate or a final organophosphorus compound with an aim to use it as a flame retardant. General synthetic strategies to create P-C bonds are briefly discussed. Most popular synthetic strategies used for developing P-C containing phosphorus based flame retardants include Michael addition, Michaelis–Arbuzov, Friedels–Crafts and Grignard reactions. In general, most flame retardant derivatives discussed in this review have been prepared via a one- to two-step synthetic strategy with relatively high yields greater than 80%. Specific examples of P-C containing flame retardants synthesized via suitable synthetic strategy and their applications on various polymer systems are described in detail. Aliphatic phosphorus compounds being liquids or low melting solids are generally applied in polymers via coatings (cellulose or are incorporated in the bulk of the polymers (epoxy, polyurethanes during their polymerization as reactive or non-reactive additives. Substituents on the P atoms and the chemistry of the polymer matrix greatly influence the flame retardant behavior of these compounds (condensed phase vs. the gas phase. Recently, aromatic DOPO based phosphinate flame retardants have been developed with relatively higher thermal stabilities (>250 °C. Such compounds have potential as flame retardants for high temperature processable

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

KAUST Repository

Yang, Wenguo

2012-02-08

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

The coloring problem in the solid-state metal boride carbide ScB{sub 2}C{sub 2}. A theoretical analysis

Energy Technology Data Exchange (ETDEWEB)

Lassoued, Souheila [Universite de Rennes, Ecole Nationale Superieure de Chimie, UMR 6226 CNRS (France). Inst. des Sciences Chimiques; Universite Kasdi Merbah-Ouargla (Algeria). Faculte des Mathematiques et des Sciences de la Matiere; Boucher, Benoit [Universite de Rennes, Ecole Nationale Superieure de Chimie, UMR 6226 CNRS (France). Inst. des Sciences Chimiques; Max-Planck-Institut fuer Chemische Physik Fester Stoffe, Dresden (Germany); Boutarfaia, Ahmed [Universite Kasdi Merbah-Ouargla (Algeria). Faculte des Mathematiques et des Sciences de la Matiere; Gautier, Regis; Halet, Jean-Francois [Universite de Rennes, Ecole Nationale Superieure de Chimie, UMR 6226 CNRS (France). Inst. des Sciences Chimiques

2016-08-01

The electronic properties of the layered ternary metal boride carbide ScB{sub 2}C{sub 2}, the structure of which consists of B/C layers made of fused five- and seven-membered rings alternating with scandium sheets, are analyzed. In particular, the respective positions of the B and C atoms (the so-called coloring problem) are tackled using density functional theory, quantum theory of atoms in molecules, and electron localizability indicator calculations. Results reveal that (i) the most stable coloring minimizes the number of B-B and C-C contacts and maximizes the number of boron atoms in the heptagons, (ii) the compound is metallic in character, and (iii) rather important covalent bonding occurs between the metallic sheets and the boron-carbon network.

Why is the Bond Multiplicity in C2 so Elusive?

Czech Academy of Sciences Publication Activity Database

Cooper, D.L.; Penotti, F.E.; Ponec, Robert

2015-01-01

Roč. 1053, SI (2015), s. 189-194 ISSN 2210-271X Institutional support: RVO:67985858 Keywords : bond multiplicity in C2 * spin correlation matrices * full GVB and spin-coupled Subject RIV: CC - Organic Chemistry Impact factor: 1.403, year: 2015

Comparative analysis of electron-density and electron-localization function for dinuclear manganese complexes with bridging boron- and carbon-centered ligands.

Science.gov (United States)

Götz, Kathrin; Kaupp, Martin; Braunschweig, Holger; Stalke, Dietmar

2009-01-01

Bonding in borylene-, carbene-, and vinylidene-bridged dinuclear manganese complexes [MnCp(CO)(2)](2)X (X = B-tBu, B = NMe(2), CH(2), C=CH(2)) has been compared by analyses based on quantum theory of atoms in molecules (QTAIM), on the electron-localization function (ELF), and by natural-population analyses. All of the density functional theory based analyses agree on the absence of a significant direct Mn-Mn bond in these complexes and confirm a dominance of delocalized bonding via the bridging ligand. Interestingly, however, the topology of both charge density and ELF related to the Mn-bridge-Mn bonding depend qualitatively on the chosen density functional (except for the methylene-bridged complex, which exhibits only one three-center-bonding attractor both in -nabla(2)rho and in ELF). While gradient-corrected functionals provide a picture with localized two-center X-Mn bonding, increasing exact-exchange admixture in hybrid functionals concentrates charge below the bridging atom and suggests a three-center bonding situation. For example, the bridging boron ligands may be described either as substituted boranes (e.g., at BLYP or BP86 levels) or as true bridging borylenes (e.g., at BHLYP level). This dependence on the theoretical level appears to derive from a bifurcation between two different bonding situations and is discussed in terms of charge transfer between X and Mn, and in the context of self-interaction errors exhibited by popular functionals.

Direct 13C-detected NMR experiments for mapping and characterization of hydrogen bonds in RNA

International Nuclear Information System (INIS)

Fürtig, Boris; Schnieders, Robbin; Richter, Christian; Zetzsche, Heidi; Keyhani, Sara; Helmling, Christina; Kovacs, Helena; Schwalbe, Harald

2016-01-01

In RNA secondary structure determination, it is essential to determine whether a nucleotide is base-paired and not. Base-pairing of nucleotides is mediated by hydrogen bonds. The NMR characterization of hydrogen bonds relies on experiments correlating the NMR resonances of exchangeable protons and can be best performed for structured parts of the RNA, where labile hydrogen atoms are protected from solvent exchange. Functionally important regions in RNA, however, frequently reveal increased dynamic disorder which often leads to NMR signals of exchangeable protons that are broadened beyond 1 H detection. Here, we develop 13 C direct detected experiments to observe all nucleotides in RNA irrespective of whether they are involved in hydrogen bonds or not. Exploiting the self-decoupling of scalar couplings due to the exchange process, the hydrogen bonding behavior of the hydrogen bond donor of each individual nucleotide can be determined. Furthermore, the adaption of HNN-COSY experiments for 13 C direct detection allows correlations of donor–acceptor pairs and the localization of hydrogen-bond acceptor nucleotides. The proposed 13 C direct detected experiments therefore provide information about molecular sites not amenable by conventional proton-detected methods. Such information makes the RNA secondary structure determination by NMR more accurate and helps to validate secondary structure predictions based on bioinformatics.

Phase composition and tribomechanical properties of Ti-B-C nanocomposite coatings prepared by magnetron sputtering

International Nuclear Information System (INIS)

Sánchez-López, J C; Abad, M D; Justo, A; Gago, R; Endrino, J L; García-Luis, A; Brizuela, M

2012-01-01

Protective nanocomposite coatings based on hard ceramic phases (TiC, TiB 2 ) combined with amorphous carbon (a-C) are of interest because of their adequate balance between mechanical and tribological performances. In this work, Ti-B-C nanocomposite coatings were prepared by co-sputtering of graphite and TiB 2 targets. Varying the discharge power ratio applied to the graphite and TiB 2 targets from 0 to 2, the a-C content in the coatings could be tuned from 0 to 60%, as observed by means of Raman and x-ray photoelectron spectroscopy (XPS). The microstructural characterization demonstrated a progressive decrease in crystallinity from an initial nanocrystalline (nc) TiB 2 -like structure to a distorted TiB x C y ternary compound with increasing C concentration. X-ray absorption near-edge structure measurements on the B K-edge helped to determine a hexagonal arrangement around the B atoms in the ternary TiB x C y phase. A fitting analysis of the C 1s XPS peak allowed us to evaluate the relative amount of a-C and TiB x C y components. A drastic change in hardness (from 52 to 13 GPa) and friction coefficient values (from 0.8 to 0.2) is noticed when moving from nc-TiB 2 to TiBC/a-C nanocomposites. The fraction of a-C necessary to decrease the friction below 0.2 was found to be 45%. Raman observation of the wear tracks determined the presence of disordered sp 2 -bonded carbon phase associated with the diminution of the friction level.

Structural, bonding, anisotropic mechanical and thermal properties of Al4SiC4 and Al4Si2C5 by first-principles investigations

Directory of Open Access Journals (Sweden)

Liang Sun

2016-09-01

Full Text Available The structural, bonding, electronic, mechanical and thermal properties of ternary aluminum silicon carbides Al4SiC4 and Al4Si2C5 are investigated by first-principles calculations combined with the Debye quasi-harmonic approximation. All the calculated mechanical constants like bulk, shear and Young's modulus are in good agreement with experimental values. Both compounds show distinct anisotropic elastic properties along different crystalline directions, and the intrinsic brittleness of both compounds is also confirmed. The elastic anisotropy of both aluminum silicon carbides originates from their bonding structures. The calculated band gap is obtained as 1.12 and 1.04 eV for Al4SiC4 and Al4Si2C5 respectively. From the total electron density distribution map, the obvious covalent bonds exist between Al and C atoms. A distinct electron density deficiency sits between AlC bond along c axis among Al4SiC4, which leads to its limited tensile strength. Meanwhile, the anisotropy of acoustic velocities for both compounds is also calculated and discussed.

Hydrogenation of graphene nanoflakes and C-H bond dissociation of hydrogenated graphene nanoflakes: a density functional theory study

Institute of Scientific and Technical Information of China (English)

Sheng Tao; Hui-Ting Liu; Liu-Ming Yan; Bao-Hua Yue; Ai-Jun Li

2017-01-01

The Gibbs free energy change for the hydrogenation of graphene nanoflakes Cn (n =24,28,30 and 32) and the C-H bond dissociation energy of hydrogenated graphene nanoflakes CnHm (n =24,28,30 and 32;and m =1,2 and 3) are evaluated using density functional theory calculations.It is concluded that the graphene nanoflakes and hydrogenated graphene nanoflakes accept the ortharyne structure with peripheral carbon atoms bonded via the most triple bonds and leaving the least unpaired dangling electrons.Five-membered rings are formed at the deep bay sites attributing to the stabilization effect from the pairing of dangling electrons.The hydrogenation reactions which eliminate one unpaired dangling electron and thus decrease the overall multiplicity of the graphene nanoflakes or hydrogenated graphene nanoflakes are spontaneous with negative or near zero Gibbs free energy change.And the resulting C-H bonds are stable with bond dissociation energy in the same range as those of aromatic compounds.The other C-H bonds are not as stable attributing to the excessive unpaired dangling electrons being filled into the C-H anti-bond orbital.

Impulse Pressuring Diffusion Bonding of TiC Cermet to Stainless Steel Using Ti/Nb Interlayer

Directory of Open Access Journals (Sweden)

LI Jia

2017-03-01

Full Text Available Impulse pressuring diffusion bonding(IPDB and constant pressuring diffusion bonding(CPDB of TiC cermet to 304 stainless steel(304SS using Ti/Nb interlayer was carried out at 890℃ under a impulse pressuring of 2-10MPa and a constant pressuring of 10MPa within a duration of only 4-12min, and a robust metallurgical bonding was achieved. Microstructure characterization and shear performance of the IPDB and CPDB joints were analyzed by SEM, EDS, XRD and shearing test. The results show that the interface phases in those two kinds of joints are similar, which are mainly σ phase,(β-Ti, Nb and α+β-Ti solid solution. When the joint is bonded for 10min, shear strength of TiC/304SS CPDB joints is 55.6MPa, while the shear strength of IPDB joints reaches 110MPa. The fracture of CPDB joints is TiC cermet fracture, while that of IPDB joints is mixed fracture by alternated between TiC cermet and reaction layer.

Process and magnetic properties of cold pressed Ne Fe B bonded magnets

International Nuclear Information System (INIS)

Rodrigues, DAniel; Concilio, Gilberto Vicente; Landgraf, Fernando Jose Gomes; Zanchetta, Antonio Carlos

1996-01-01

Bonded magnets are polymer composites based on a mixture of a hard magnetic powder and a polymer. This mixture is processed as a traditional powder metallurgy material, cold pressed, or like a thermoplastic material, by injection molding. The polymeric phase to a large extent determines the mechanical properties of the composite, while magnetic powder determines its magnetic properties. They are less expensive and easier to produce, specially in the case of high complexity parts. This paper presents the relationship between process variables and magnetic properties of cold pressed Nd Fe B bonded magnets produced from melt spun flakes mixed with thermosetting resins. The experiments were done using Statistical Design of Experiments. The variables investigates were: uniaxial compaction pressure, binder type; binder content; size of Nd Fe B particles; addition of lubricant; and addition of small quantities of magnetic additives, particles of ferrites, iron, or alnico. (author)

Inefficient binding of IgM immune complexes to erythrocyte C3b-C4b receptors (CR1) and weak incorporation of C3b-iC3b into the complexes

DEFF Research Database (Denmark)

Kávai, M; Rasmussen, J M; Baatrup, G

1988-01-01

, but the binding was low (2-3%) when compared to the binding of the corresponding IgG-IC (50-60%). Solid phase IC were prepared by coating microwells with heat-aggregated bovine serum albumin (BSA) followed by incubation with rabbit IgM anti-BSA antibody. The IC were reacted with human serum at 37 degrees C....... The binding of C3b-iC3b was determined by use of biotinylated F(ab')2 antibodies to C3b-C3c and avidin-coupled alkaline phosphatase. The incorporation of C3b-iC3b into solid-phase IgM-IC increased when increasing amounts of IgM antibody were reacted with the antigen. The binding reaction was slow, reaching...

B97-3c: A revised low-cost variant of the B97-D density functional method

Science.gov (United States)

Brandenburg, Jan Gerit; Bannwarth, Christoph; Hansen, Andreas; Grimme, Stefan

2018-02-01

A revised version of the well-established B97-D density functional approximation with general applicability for chemical properties of large systems is proposed. Like B97-D, it is based on Becke's power-series ansatz from 1997 and is explicitly parametrized by including the standard D3 semi-classical dispersion correction. The orbitals are expanded in a modified valence triple-zeta Gaussian basis set, which is available for all elements up to Rn. Remaining basis set errors are mostly absorbed in the modified B97 parametrization, while an established atom-pairwise short-range potential is applied to correct for the systematically too long bonds of main group elements which are typical for most semi-local density functionals. The new composite scheme (termed B97-3c) completes the hierarchy of "low-cost" electronic structure methods, which are all mainly free of basis set superposition error and account for most interactions in a physically sound and asymptotically correct manner. B97-3c yields excellent molecular and condensed phase geometries, similar to most hybrid functionals evaluated in a larger basis set expansion. Results on the comprehensive GMTKN55 energy database demonstrate its good performance for main group thermochemistry, kinetics, and non-covalent interactions, when compared to functionals of the same class. This also transfers to metal-organic reactions, which is a major area of applicability for semi-local functionals. B97-3c can be routinely applied to hundreds of atoms on a single processor and we suggest it as a robust computational tool, in particular, for more strongly correlated systems where our previously published "3c" schemes might be problematic.

Oxidative C-C bond cleavage of 1,2-diols by silver(II)

International Nuclear Information System (INIS)

Kumar, A.

1981-01-01

Oxidation of ethylene glycol and related compounds by Ag(II) has been investigated. Complexation of these substrates by Ag(II) precedes their oxidation. Oxidation occurs through electron transfer from an OH group to the Ag(II) within the complex resulting in the formation of alkoxyl-type radicals. The radicals thus formed undergo β-scission to give cleavage products. For ethylene glycol a complexation rate 1.3 x 10 6 M -1 s -1 and oxidation rate approx. 3 x 10 3 s -1 were observed. A general trend for the type of the substrates which would undergo C-C bond scission by Ag(II) is discussed

Structural Characterization of N-Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N-C Cleavage.

Science.gov (United States)

Hu, Feng; Lalancette, Roger; Szostak, Michal

2016-04-11

Herein, we describe the first structural characterization of N-alkylated twisted amides prepared directly by N-alkylation of the corresponding non-planar lactams. This study provides the first experimental evidence that N-alkylation results in a dramatic increase of non-planarity around the amide N-C(O) bond. Moreover, we report a rare example of a molecular wire supported by the same amide C=O-Ag bonds. Reactivity studies demonstrate rapid nucleophilic addition to the N-C(O) moiety of N-alkylated amides, indicating the lack of n(N) to π*(C=O) conjugation. Most crucially, we demonstrate that N-alkylation activates the otherwise unreactive amide bond towards σ N-C cleavage by switchable coordination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical interaction of B4C, B, and C with Mo/Si layered structures

International Nuclear Information System (INIS)

Rooij-Lohmann, V. I. T. A. de; Veldhuizen, L. W.; Zoethout, E.; Yakshin, A. E.; Kruijs, R. W. E. van de; Thijsse, B. J.; Gorgoi, M.; Schaefers, F.; Bijkerk, F.

2010-01-01

To enhance the thermal stability, B 4 C diffusion barrier layers are often added to Mo/Si multilayer structures for extreme ultraviolet optics. Knowledge about the chemical interaction between B 4 C and Mo or Si, however is largely lacking. Therefore, the chemical processes during annealing up to 600 deg. C of a Mo/B 4 C/Si layered structure have been investigated in situ with hard x-ray photoelectron spectroscopy and ex situ with depth profiling x-ray photoelectron spectroscopy. Mo/B/Si and Mo/C/Si structures have also been analyzed as reference systems. The chemical processes in these systems have been identified, with two stages being distinguished. In the first stage, B and C diffuse and react predominantly with Mo. MoSi x forms in the second stage. If the diffusion barrier consists of C or B 4 C, a compound forms that is stable up to the maximum probed temperature and annealing time. We suggest that the diffusion barrier function of B 4 C interlayers as reported in literature can be caused by the stability of the formed compound, rather than by the stability of B 4 C itself.

Electrochemistry of different boranes, carbaboranes and their exo-skeletal hydroxy derivatives at the graphite carbon electrode in aqueous phosphate buffers

Czech Academy of Sciences Publication Activity Database

Fojt, Lukáš; Fojta, Miroslav; Holub, Josef; Grüner, Bohumír; Vespalec, Radim

2016-01-01

Roč. 205, JUL 2016 (2016), s. 8-14 ISSN 0013-4686 R&D Projects: GA ČR(CZ) GBP206/12/G151; GA ČR(CZ) GA15-05677S Institutional support: RVO:68081707 ; RVO:61388980 Keywords : boranes * carbaboranes * glassy carbon electrode Subject RIV: BO - Biophysics; CA - Inorganic Chemistry (UACH-T) Impact factor: 4.798, year: 2016

Theoretical study of actinide monocarbides (ThC, UC, PuC, and AmC)

Science.gov (United States)

Pogány, Peter; Kovács, Attila; Visscher, Lucas; Konings, Rudy J. M.

2016-12-01

A study of four representative actinide monocarbides, ThC, UC, PuC, and AmC, has been performed with relativistic quantum chemical calculations. The two applied methods were multireference complete active space second-order perturbation theory (CASPT2) including the Douglas-Kroll-Hess Hamiltonian with all-electron basis sets and density functional theory with the B3LYP exchange-correlation functional in conjunction with relativistic pseudopotentials. Beside the ground electronic states, the excited states up to 17 000 cm-1 have been determined. The molecular properties explored included the ground-state geometries, bonding properties, and the electronic absorption spectra. According to the occupation of the bonding orbitals, the calculated electronic states were classified into three groups, each leading to a characteristic bond distance range for the equilibrium geometry. The ground states of ThC, UC, and PuC have two doubly occupied π orbitals resulting in short bond distances between 1.8 and 2.0 Å, whereas the ground state of AmC has significant occupation of the antibonding orbitals, causing a bond distance of 2.15 Å.

Reactivity differences of Pt0 phosphine complexes in C-C bond activation of asymmetric acetylenes

NARCIS (Netherlands)

Gunay, A.; Müller, C.; Lachicotte, R.J.; Brennessel, W.W.; Jones, W.D.

2009-01-01

Carbon-carbon bond activation reactions of asymmetric acetylene derivatives of the type L2Pt(PhC=CR) were studied with 1,2-bis(diisopropylphosphino)ethane (dippe), 1,2-bis(di-tert-butylphosphino)ethane (dtbpe), and 1-diisopropylphosphino-2-dimethylaminoethane (dippdmae) chelates.

Evidence for an Intermediate in the Methylation of CB11H12- with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Arenes

Czech Academy of Sciences Publication Activity Database

Kaleta, Jiří; Akdag, Akin; Crespo, R.; Piqueras, M. C.; Michl, Josef

2013-01-01

Roč. 78, č. 9 (2013), s. 1174-1183 ISSN 2192-6506 Institutional support: RVO:61388963 Keywords : alkylation * boranes * carboranes * electrophilic substitution * hydrogen scrambling Subject RIV: CC - Organic Chemistry Impact factor: 3.242, year: 2013

Insertion reactions into Pd[bond]O and Pd[bond]N bonds: preparation of alkoxycarbonyl, carbonato, carbamato, thiocarbamate, and thioureide complexes of palladium(II).

Science.gov (United States)

Ruiz, José; Martínez, M Teresa; Florenciano, Félix; Rodríguez, Venancio; López, Gregorio; Pérez, José; Chaloner, Penny A; Hitchcock, Peter B

2003-06-02

Mononuclear palladium hydroxo complexes of the type [Pd(N[bond]N)(C(6)F(5))(OH)] [(N[bond]N = 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (Me(2)bipy), 1,10-phenanthroline (phen), or N,N,N',N'-tetramethylethylenediamine (tmeda)] have been prepared by reaction of [Pd(N[bond]N)(C(6)F(5))(acetone)]ClO(4) with KOH in methanol. These hydroxo complexes react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)Me)]. Similar alkoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)R)] (N[bond]N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me, Et, or (i)Pr) are obtained when [Pd(N[bond]N)(C(6)F(5))Cl] is treated with KOH in the corresponding alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N[bond]N)(C(6)F(5))(OH)] (N[bond]N = bipy or Me(2)bipy) with CO(2), in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N[bond]N)(C(6)F(5))Pd(mu-eta(2)-CO(3))Pd(C(6)F(5))(N[bond]N)]. Complexes [Pd(N[bond]N)(C(6)F(5))(OH)] react in alcohol with PhNCS to yield the corresponding N-phenyl-O-alkylthiocarbamate complexes [Pd(N[bond]N)(C(6)F(5))[SC(OR)NPh

Role of dispersion corrected hybrid GGA class in accurately calculating the bond dissociation energy of carbon halogen bond: A benchmark study

Science.gov (United States)

Kosar, Naveen; Mahmood, Tariq; Ayub, Khurshid

2017-12-01

Benchmark study has been carried out to find a cost effective and accurate method for bond dissociation energy (BDE) of carbon halogen (Csbnd X) bond. BDE of C-X bond plays a vital role in chemical reactions, particularly for kinetic barrier and thermochemistry etc. The compounds (1-16, Fig. 1) with Csbnd X bond used for current benchmark study are important reactants in organic, inorganic and bioorganic chemistry. Experimental data of Csbnd X bond dissociation energy is compared with theoretical results. The statistical analysis tools such as root mean square deviation (RMSD), standard deviation (SD), Pearson's correlation (R) and mean absolute error (MAE) are used for comparison. Overall, thirty-one density functionals from eight different classes of density functional theory (DFT) along with Pople and Dunning basis sets are evaluated. Among different classes of DFT, the dispersion corrected range separated hybrid GGA class along with 6-31G(d), 6-311G(d), aug-cc-pVDZ and aug-cc-pVTZ basis sets performed best for bond dissociation energy calculation of C-X bond. ωB97XD show the best performance with less deviations (RMSD, SD), mean absolute error (MAE) and a significant Pearson's correlation (R) when compared to experimental data. ωB97XD along with Pople basis set 6-311g(d) has RMSD, SD, R and MAE of 3.14 kcal mol-1, 3.05 kcal mol-1, 0.97 and -1.07 kcal mol-1, respectively.

Effect of process on the magnetic properties of bonded NdFeB magnet

International Nuclear Information System (INIS)

Li, J.; Liu, Y.; Gao, S.J.; Li, M.; Wang, Y.Q.; Tu, M.J.

2006-01-01

The effects of magnetic separation, coupling treatment, lubricating treatment, preform and biaxial molding on the density and magnetic properties of bonded NdFeB magnet were investigated. The results demonstrate that magnetic separation separates the powders with low coercive force; coupling treatment improves the interfaces between the powders and the binders; decrease in volume fraction of the binder increases magnetic properties of the magnet; granular arrangement improves both the magnetic and mechanical properties when powders are arranged in certain size; lubricating treatment improves the formability of the magnet and preform and biaxial molding improves both density and magnetic properties greatly. Combining these methods, the density of the bonded NdFeB magnet can reach 6.52 g/cm 3 and the maximum energy product can reach 114 kJ/m 3

Effect of process on the magnetic properties of bonded NdFeB magnet

Energy Technology Data Exchange (ETDEWEB)

Li, J. [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China); Liu, Y. [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China)]. E-mail: liuying5536@163.com; Gao, S.J. [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China); Li, M. [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China); Wang, Y.Q. [South-West Magnetic Science and Technology Developing Company, Mianyang, 621600 (China); Tu, M.J. [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China)

2006-04-15

The effects of magnetic separation, coupling treatment, lubricating treatment, preform and biaxial molding on the density and magnetic properties of bonded NdFeB magnet were investigated. The results demonstrate that magnetic separation separates the powders with low coercive force; coupling treatment improves the interfaces between the powders and the binders; decrease in volume fraction of the binder increases magnetic properties of the magnet; granular arrangement improves both the magnetic and mechanical properties when powders are arranged in certain size; lubricating treatment improves the formability of the magnet and preform and biaxial molding improves both density and magnetic properties greatly. Combining these methods, the density of the bonded NdFeB magnet can reach 6.52 g/cm{sup 3} and the maximum energy product can reach 114 kJ/m{sup 3}.

Regulator-dependent mechanisms of C3b processing by factor i allow differentiation of immune responses

NARCIS (Netherlands)

Xue, Xiaoguang|info:eu-repo/dai/nl/413576841; Wu, Jin|info:eu-repo/dai/nl/304829552; Ricklin, Daniel; Forneris, Federico|info:eu-repo/dai/nl/341358622; Di Crescenzio, Patrizia; Schmidt, Christoph Q.; Granneman, Joke|info:eu-repo/dai/nl/304839396; Sharp, Thomas H; Lambris, John D; Gros, Piet|info:eu-repo/dai/nl/075243016

2017-01-01

The complement system labels microbes and host debris for clearance. Degradation of surface-bound C3b is pivotal to direct immune responses and protect host cells. How the serine protease factor I (FI), assisted by regulators, cleaves either two or three distant peptide bonds in the CUB domain of

Theoretical estimation of pnicogen bonds and hydrogen bonds in small heterocyclic complexes: Red-shifts and blue-shifts ruled by polarization effects

International Nuclear Information System (INIS)

Oliveira, Boaz G.

2014-01-01

Graphical abstract: - Highlights: • This paper definitively discusses the interaction strength. • Analyses of the red-shifts and blue-shift. • Stretch frequencies of the hydrogen bonds and pnicogen bonds in heterocyclic compounds. • Theoretical calculations derived from topological parameters of the Quantum Theory of Atoms in Molecules (QTAIM). • The analysis of the Natural Bond Orbital (NBO) in line with the Bent’s rule of the chemical bonding. - Abstract: The occurrence of pnicogen bonds (N⋯P) and hydrogen bonds (F⋯H or Cl⋯H) in heterocyclic complexes formed by C 2 H 5 N⋯PH 3 , C 2 H 5 N⋯PH 2 F and C 2 H 5 N⋯PH 2 Cl was investigated at the B3LYP/6-311++G(d,p) level of theory. Analysis of the infrared spectra revealed the appearance of both red and blue shifts for the P–H bonds. However, in the case of the P–F and P–Cl bonds only red shifts were observed. The phenomenology of these vibration modes was interpreted on the basis of the QTAIM atomic radii as well as the contributions of the s and p orbitals determined via NBO calculations. The results of this latter investigation are consistent with the rehybridization theory and the Bent rule for chemical bonding. The charge transfer between N and P was determined in order to verify whether these atoms present an acid or base profile upon the formation of the pnicogen bonds

Study of the adsorption, electronic structure and bonding of C2H4 on the FeNi(1 1 1) surface

International Nuclear Information System (INIS)

Simonetti, S.; Brizuela, G.; Juan, A.

2010-01-01

The adsorption of C 2 H 4 on the FeNi(1 1 1) alloy surface has been studied by ASED-MO tight binding calculations. The C 2 H 4 molecule presents its most stable geometry with the C=C bond axis parallel to the surface along the [1, -1, 0] direction, bonded on top Fe atom and bonded along a Fe-Fe bridge site. As a consequence, the strength of the local Fe-Fe bond decreases between 37 and 62% of its original bulk value. This bond weakening is mainly due to the new C-Fe interactions however no Fe 3 C carbide formation is evidenced on surface. The Fe-Ni and Ni-Ni superficial bonds are only slightly modified.

Origin of the Ability of α-Fe2 O3 Mesopores to Activate C-H Bonds in Methane.

Science.gov (United States)

Dong, Bing; Han, Zhen; Zhang, Yongbo; Yu, Youyi; Kong, Aiguo; Shan, Yongkui

2016-02-01

Methane is a most abundant and inexpensive hydrocarbon feedstock for the production of chemicals and fuels. However, it is extremely difficult to directly convert methane to higher hydrocarbons because the C-H bonds in methane are the most stable C-H bonds of all hydrocarbons. The activation of the C-H bonds in methane by using an efficient and mild route remains a daunting challenge. Here, we show that the inner surface structures of the pore walls in mesoporous α-Fe 2 O 3 possess excellent catalytic performance for methane activation and convert C-H bonds into the C-O bonds in an O 2 atmosphere at 140 °C. We found that such unusual structures are mainly comprised of turbostratic ribbons and K crystal faces and have higher catalytic activity than the (110) plane. These results are without precedent in the history of catalysis chemistry and will provide a new pathway for designing and preparing highly efficient catalytic materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Mo-Mo Quintuple Bond is Highly Reactive in H-H, C-H, and O-H σ-Bond Cleavages Because of the Polarized Electronic Structure in Transition State.

Science.gov (United States)

Chen, Yue; Sakaki, Shigeyoshi

2017-04-03

The recently reported high reactivity of the Mo-Mo quintuple bond of Mo 2 (N ∧ N) 2 (1) {N ∧ N = μ-κ 2 -CH[N(2,6-iPr 2 C 6 H 3 )] 2 } in the H-H σ-bond cleavage was investigated. DFT calculations disclosed that the H-H σ-bond cleavage by 1 occurs with nearly no barrier to afford the cis-dihydride species followed by cis-trans isomerization to form the trans-dihydride product, which is consistent with the experimental result. The O-H and C-H bond cleavages by 1 were computationally predicted to occur with moderate (ΔG° ⧧ = 9.0 kcal/mol) and acceptable activation energies (ΔG° ⧧ = 22.5 kcal/mol), respectively, suggesting that the Mo-Mo quintuple bond can be applied to various σ-bond cleavages. In these σ-bond cleavage reactions, the charge-transfer (CT Mo→XH ) from the Mo-Mo quintuple bond to the X-H (X = H, C, or O) bond and that (CT XH→Mo ) from the X-H bond to the Mo-Mo bond play crucial roles. Though the HOMO (dδ-MO) of 1 is at lower energy and the LUMO + 2 (dδ*-MO) of 1 is at higher energy than those of RhCl(PMe 3 ) 2 (LUMO and LUMO + 1 of 1 are not frontier MO), the H-H σ-bond cleavage by 1 more easily occurs than that by the Rh complex. Hence, the frontier MO energies are not the reason for the high reactivity of 1. The high reactivity of 1 arises from the polarization of dδ-type MOs of the Mo-Mo quintuple bond in the transition state. Such a polarized electronic structure enhances the bonding overlap between the dδ-MO of the Mo-Mo bond and the σ*-antibonding MO of the X-H bond to facilitate the CT Mo→XH and reduce the exchange repulsion between the Mo-Mo bond and the X-H bond. This polarized electronic structure of the transition state is similar to that of a frustrated Lewis pair. The easy polarization of the dδ-type MOs is one of the advantages of the metal-metal multiple bond, because such polarization is impossible in the mononuclear metal complex.

Effect of the nitrogen unshared electron pair on the direct /sup 13/C-/sup 13/C spin-spin coupling constant of a neighboring bond in oximes

Energy Technology Data Exchange (ETDEWEB)

Shcherbakov, V.V.; Krivdin, L.B.; Kalabin, G.A.; Trofimov, B.A.

1986-11-20

The authors have previously established that the direct /sup 13/C-/sup 13/C coupling constants are stereospecific relative to the orientation of unshared electron pairs (UEP) of nitrogen and oxygen atoms. Here they show that the nitrogen UEP produces a positive contribution to the direct /sup 13/C-/sup 13/C coupling constant of an adjacent syn-periplanar carbon-carbon bond and not to a negative contribution of the corresponding constant of the anti-periplanar bond. Thus, the observed effect is not a consequence of the interaction of the heteroatom UEP with the anti-bonding orbital of the adjacent anti-periplanar bond (n/sub o-o/* interaction) as in the case of anomeric and related effects.

The pseudohydrogen bond structures between 2-F-epoxy-butane and three kinds of bimolecular

International Nuclear Information System (INIS)

Liu Yanzhi; Yuan Kun; Lu Lingling; Zhu Yuancheng; Dong Xiaoning

2012-01-01

The weak intermolecular interactions between 2-F-epoxy-butane and Iminazole, Thiazole and Oxazole were theoretically discussed by using density functional B3LYP (Becke, three-parameter, Lee- Yang-Parr)/6-311++G ** and HF (Hartree Fock)/6-311++G ** methods. The results showed that both the N…H conventional hydrogen bond and C-F…H-C pseudohydrogen bond (PHB) structures are coexisting in the three complexes. The weak intermolecular interactions energies indicate the relative stabilities of the three complexes are proportionable. The calculated results showed that the stretch vibrational frequency of C-H bond (electronic acceptor) presents blue shift, but that of C-F bond, which is intensely related to F group (electronic donor), presents red shift. Electron density topological properties demonstrates that the covalent and ionic characteristics of the C-F…H-C pseudohydrogen bond are proportional to that of convention hydrogen bond. (authors)

Sequential plasma activation methods for hydrophilic direct bonding at sub-200 °C

Science.gov (United States)

He, Ran; Yamauchi, Akira; Suga, Tadatomo

2018-02-01

We present our newly developed sequential plasma activation methods for hydrophilic direct bonding of silica glasses and thermally grown SiO2 films. N2 plasma was employed to introduce a metastable oxynitride layer on wafer surfaces for the improvement of bond energy. By using either O2-plasma/N2-plasma/N-radical or N2-plasma/N-radical sequential activation, the quartz-quartz bond energy was increased from 2.7 J/m2 to close to the quartz bulk fracture energy that was estimated to be around 9.0 J/m2 after post-bonding annealing at 200 °C. The silicon bulklike bond energy between thermal SiO2 films was also obtained. We suggest that the improvement is attributable to surface modification such as N-related defect formation and asperity softening by the N2 plasma surface treatment.

Nickel-Catalyzed C sp2 –C sp3 Cross-Coupling via C–O Bond Activation

KAUST Repository

Guo, Lin; Hsiao, Chien-Chi; Yue, Huifeng; Liu, Xiangqian; Rueping, Magnus

2016-01-01

through Csp2-O substitution, without the restriction of β-hydride elimination. Moreover, the advantage of the newly developed method was demonstrated in a selective and sequential C-O bond activation process. © 2016 American Chemical Society.

Phase composition and tribomechanical properties of Ti-B-C nanocomposite coatings prepared by magnetron sputtering

Science.gov (United States)

Sánchez-López, J. C.; Abad, M. D.; Justo, A.; Gago, R.; Endrino, J. L.; García-Luis, A.; Brizuela, M.

2012-09-01

Protective nanocomposite coatings based on hard ceramic phases (TiC, TiB2) combined with amorphous carbon (a-C) are of interest because of their adequate balance between mechanical and tribological performances. In this work, Ti-B-C nanocomposite coatings were prepared by co-sputtering of graphite and TiB2 targets. Varying the discharge power ratio applied to the graphite and TiB2 targets from 0 to 2, the a-C content in the coatings could be tuned from 0 to 60%, as observed by means of Raman and x-ray photoelectron spectroscopy (XPS). The microstructural characterization demonstrated a progressive decrease in crystallinity from an initial nanocrystalline (nc) TiB2-like structure to a distorted TiBxCy ternary compound with increasing C concentration. X-ray absorption near-edge structure measurements on the B K-edge helped to determine a hexagonal arrangement around the B atoms in the ternary TiBxCy phase. A fitting analysis of the C 1s XPS peak allowed us to evaluate the relative amount of a-C and TiBxCy components. A drastic change in hardness (from 52 to 13 GPa) and friction coefficient values (from 0.8 to 0.2) is noticed when moving from nc-TiB2 to TiBC/a-C nanocomposites. The fraction of a-C necessary to decrease the friction below 0.2 was found to be 45%. Raman observation of the wear tracks determined the presence of disordered sp2-bonded carbon phase associated with the diminution of the friction level.

Powder alignment system for anisotropic bonded NdFeB Halbach cylinders \\ud

OpenAIRE

Zhu, Z.Q.; Xia, Z.P.; Atallah, K.; Jewell, G.W.; Howe, D.

2000-01-01

A Halbach cylinder, fabricated from pre-magnetized sintered NdFeB magnet segments, is proposed for the powder aligning system during the compression or injection moulding of anisotropic bonded Halbach oriented NdFeB ring magnets. The influence of leading design parameters of the powder aligning system, viz. the number of magnet segments per pole, their axial length and radial thickness, and their clearance from the mould, is investigated by finite element analysis, and validated experimentally

Catalytic Hydrolysis of Ammonia Borane by Cobalt Nickel Nanoparticles Supported on Reduced Graphene Oxide for Hydrogen Generation

Directory of Open Access Journals (Sweden)

Yuwen Yang

2014-01-01

Full Text Available Well dispersed magnetically recyclable bimetallic CoNi nanoparticles (NPs supported on the reduced graphene oxide (RGO were synthesized by one-step in situ coreduction of aqueous solution of cobalt(II chloride, nickel (II chloride, and graphite oxide (GO with ammonia borane (AB as the reducing agent under ambient condition. The CoNi/RGO NPs exhibits excellent catalytic activity with a total turnover frequency (TOF value of 19.54 mol H2 mol catalyst−1 min−1 and a low activation energy value of 39.89 kJ mol−1 at room temperature. Additionally, the RGO supported CoNi NPs exhibit much higher catalytic activity than the monometallic and RGO-free CoNi counterparts. Moreover, the as-prepared catalysts exert satisfying durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB, which make the practical reusing application of the catalysts more convenient. The usage of the low-cost, easy-getting catalyst to realize the production of hydrogen under mild condition gives more confidence for the application of ammonia borane as a hydrogen storage material. Hence, this general method indicates that AB can be used as both a potential hydrogen storage material and an efficient reducing agent, and can be easily extended to facile preparation of other RGO-based metallic systems.

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.

Alignment of paired molecules of C60 within a hexagonal platform networked through hydrogen-bonds.

Science.gov (United States)

Hisaki, Ichiro; Nakagawa, Shoichi; Sato, Hiroyasu; Tohnai, Norimitsu

2016-07-28

We demonstrate, for the first time, that a hydrogen-bonded low-density organic framework can be applied as a platform to achieve periodic alignment of paired molecules of C60, which is the smallest example of a finite-numbered cluster of C60. The framework is a layered assembly of a hydrogen-bonded 2D hexagonal network (LA-H-HexNet) composed of dodecadehydrotribenzo[18]annulene derivatives.

Direct {sup 13}C-detected NMR experiments for mapping and characterization of hydrogen bonds in RNA

Energy Technology Data Exchange (ETDEWEB)

Fürtig, Boris, E-mail: fuertig@nmr.uni-frankfurt.de; Schnieders, Robbin; Richter, Christian; Zetzsche, Heidi; Keyhani, Sara; Helmling, Christina [Johann Wolfgang Goethe Universität Frankfurt, Center for Biomolecular Magnetic Resonance (BMRZ), Institute of Organic Chemistry and Chemical Biology (Germany); Kovacs, Helena [Bruker BioSpin (Switzerland); Schwalbe, Harald, E-mail: schwalbe@nmr.uni-frankfurt.de [Johann Wolfgang Goethe Universität Frankfurt, Center for Biomolecular Magnetic Resonance (BMRZ), Institute of Organic Chemistry and Chemical Biology (Germany)

2016-03-15

In RNA secondary structure determination, it is essential to determine whether a nucleotide is base-paired and not. Base-pairing of nucleotides is mediated by hydrogen bonds. The NMR characterization of hydrogen bonds relies on experiments correlating the NMR resonances of exchangeable protons and can be best performed for structured parts of the RNA, where labile hydrogen atoms are protected from solvent exchange. Functionally important regions in RNA, however, frequently reveal increased dynamic disorder which often leads to NMR signals of exchangeable protons that are broadened beyond {sup 1}H detection. Here, we develop {sup 13}C direct detected experiments to observe all nucleotides in RNA irrespective of whether they are involved in hydrogen bonds or not. Exploiting the self-decoupling of scalar couplings due to the exchange process, the hydrogen bonding behavior of the hydrogen bond donor of each individual nucleotide can be determined. Furthermore, the adaption of HNN-COSY experiments for {sup 13}C direct detection allows correlations of donor–acceptor pairs and the localization of hydrogen-bond acceptor nucleotides. The proposed {sup 13}C direct detected experiments therefore provide information about molecular sites not amenable by conventional proton-detected methods. Such information makes the RNA secondary structure determination by NMR more accurate and helps to validate secondary structure predictions based on bioinformatics.

Directional crystallization of B4C-NbB2 and B4C-MoB2 eutectic compositions

International Nuclear Information System (INIS)

Paderno, Varvara; Paderno, Y.B.; Filippov, Vladimir; Liashchenko, Alfred

2004-01-01

We studied the directional crystallization of different compositions in B 4 C-NbB 2 and B 4 C-MoB 2 systems. The eutectic compositions for both systems are evaluated. It is shown that in the first system the rod-like eutectic structure is formed, in second, the 'Chinese hieroglyphics'. In both cases high hardness and high microplasticity are observed, which are much more than for individual component phases. These compositions may be considered as a new kind of self-strengthening composite materials

Effect of bonding and bakeout thermal cycles on the properties of copper alloys irradiated at 350 degrees C

DEFF Research Database (Denmark)

Singh, B.N.; Edwards, D.J.; Eldrup, Morten Mostgaard

2001-01-01

Screening experiments were carried out to determine the effect of bonding and bakeout thermal cycles on microstructure, mechanical properties and electrical resistivity of the oxide dispersion strengthened (GlidCop, CuAl-25) and the precipitation hardened (CuCrZr, CuNiBe) copper alloys. Tensile...... results are described and their salient features discussed. The most significant effect of neutron irradiation is a severe loss of ductility in the case of CuNiBe alloys. (C) 2001 Elsevier Science B.V. All rights reserved....

Bond formation in hafnium atom implantation into SiC induced by high-energy electron irradiation

International Nuclear Information System (INIS)

Yasuda, H.; Mori, H.; Sakata, T.; Naka, M.; Fujita, H.

1992-01-01

Bilayer films of Hf (target atoms)/α-SiC (substrate) were irradiated with 2 MeV electrons in an ultra-high voltage electron microscope (UHVEM), with the electron beam incident on the hafnium layer. As a result of the irradiation, hafnium atoms were implanted into the SiC substrate. Changes in the microstructure and valence electronic states associated with the implantation were studied by a combination of UHVEM and Auger valence electron spectroscopy. The implantation process is summarized as follows. (1) Irradiation with 2 MeV electrons first induces a crystalline-to-amorphous transition in α-SiC. (2) Hafnium atoms which have been knocked-off from the hafnium layer by collision with the 2 MeV electrons are implanted into the resultant amorphous SiC. (3) The implanted hafnium atoms make preferential bonding to carbon atoms. (4) With continued irradiation, the hafnium atoms repeat the displacement along the beam direction and the subsequent bonding with the dangling hybrids of carbon and silicon. The repetition of the displacement and subsequent bonding lead to the deep implantation of hafnium atoms into the SiC substrate. It is concluded that implantation successfully occurs when the bond strength between a constituent atom of a substrate and an injected atom is stronger than that between constituent atoms of a substrate. (Author)

New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

KAUST Repository

Samantaray, Manoja

2015-08-18

In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

Measurements of B(c)+ production and mass with the B(c)+ → J/ψπ+ decay.

Science.gov (United States)

Aaij, R; Abellan Beteta, C; Adametz, A; Adeva, B; Adinolfi, M; Adrover, C; Affolder, A; Ajaltouni, Z; Albrecht, J; Alessio, F; Alexander, M; Ali, S; Alkhazov, G; Alvarez Cartelle, P; Alves, A A; Amato, S; Amhis, Y; Anderlini, L; Anderson, J; Appleby, R B; Aquines Gutierrez, O; Archilli, F; Artamonov, A; Artuso, M; Aslanides, E; Auriemma, G; Bachmann, S; Back, J J; Baesso, C; Baldini, W; Barlow, R J; Barschel, C; Barsuk, S; Barter, W; Bates, A; Bauer, Th; Bay, A; Beddow, J; Bediaga, I; Belogurov, S; Belous, K; Belyaev, I; Ben-Haim, E; Benayoun, M; Bencivenni, G; Benson, S; Benton, J; Berezhnoy, A; Bernet, R; Bettler, M-O; van Beuzekom, M; Bien, A; Bifani, S; Bird, T; Bizzeti, A; Bjørnstad, P M; Blake, T; Blanc, F; Blanks, C; Blouw, J; Blusk, S; Bobrov, A; Bocci, V; Bondar, A; Bondar, N; Bonivento, W; Borghi, S; Borgia, A; Bowcock, T J V; Bozzi, C; Brambach, T; van den Brand, J; Bressieux, J; Brett, D; Britsch, M; Britton, T; Brook, N H; Brown, H; Büchler-Germann, A; Burducea, I; Bursche, A; Buytaert, J; Cadeddu, S; Callot, O; Calvi, M; Calvo Gomez, M; Camboni, A; Campana, P; Carbone, A; Carboni, G; Cardinale, R; Cardini, A; Carson, L; Carvalho Akiba, K; Casse, G; Cattaneo, M; Cauet, Ch; Charles, M; Charpentier, Ph; Chen, P; Chiapolini, N; Chrzaszcz, M; Ciba, K; Cid Vidal, X; Ciezarek, G; Clarke, P E L; Clemencic, M; Cliff, H V; Closier, J; Coca, C; Coco, V; Cogan, J; Cogneras, E; Collins, P; Comerma-Montells, A; Contu, A; Cook, A; Coombes, M; Corti, G; Couturier, B; Cowan, G A; Craik, D; Cunliffe, S; Currie, R; D'Ambrosio, C; David, P; David, P N Y; De Bonis, I; De Bruyn, K; De Capua, S; De Cian, M; De Miranda, J M; De Paula, L; De Simone, P; Decamp, D; Deckenhoff, M; Degaudenzi, H; Del Buono, L; Deplano, C; Derkach, D; Deschamps, O; Dettori, F; Di Canto, A; Dickens, J; Dijkstra, H; Diniz Batista, P; Domingo Bonal, F; Donleavy, S; Dordei, F; Dosil Suárez, A; Dossett, D; Dovbnya, A; Dupertuis, F; Dzhelyadin, R; Dziurda, A; Dzyuba, A; Easo, S; Egede, U; Egorychev, V; Eidelman, S; van Eijk, D; Eisenhardt, S; Ekelhof, R; Eklund, L; El Rifai, I; Elsasser, Ch; Elsby, D; Esperante Pereira, D; Falabella, A; Färber, C; Fardell, G; Farinelli, C; Farry, S; Fave, V; Fernandez Albor, V; Ferreira Rodrigues, F; Ferro-Luzzi, M; Filippov, S; Fitzpatrick, C; Fontana, M; Fontanelli, F; Forty, R; Francisco, O; Frank, M; Frei, C; Frosini, M; Furcas, S; Gallas Torreira, A; Galli, D; Gandelman, M; Gandini, P; Gao, Y; Garnier, J-C; Garofoli, J; Garosi, P; Garra Tico, J; Garrido, L; Gaspar, C; Gauld, R; Gersabeck, E; Gersabeck, M; Gershon, T; Ghez, Ph; Gibson, V; Gligorov, V V; Göbel, C; Golubkov, D; Golutvin, A; Gomes, A; Gordon, H; Grabalosa Gándara, M; Graciani Diaz, R; Granado Cardoso, L A; Graugés, E; Graziani, G; Grecu, A; Greening, E; Gregson, S; Grünberg, O; Gui, B; Gushchin, E; Guz, Yu; Gys, T; Hadjivasiliou, C; Haefeli, G; Haen, C; Haines, S C; Hall, S; Hampson, T; Hansmann-Menzemer, S; Harnew, N; Harnew, S T; Harrison, J; Harrison, P F; Hartmann, T; He, J; Heijne, V; Hennessy, K; Henrard, P; Hernando Morata, J A; van Herwijnen, E; Hicks, E; Hill, D; Hoballah, M; Hopchev, P; Hulsbergen, W; Hunt, P; Huse, T; Hussain, N; Hutchcroft, D; Hynds, D; Iakovenko, V; Ilten, P; Imong, J; Jacobsson, R; Jaeger, A; Jahjah Hussein, M; Jans, E; Jansen, F; Jaton, P; Jean-Marie, B; Jing, F; John, M; Johnson, D; Jones, C R; Jost, B; Kaballo, M; Kandybei, S; Karacson, M; Karbach, T M; Keaveney, J; Kenyon, I R; Kerzel, U; Ketel, T; Keune, A; Khanji, B; Kim, Y M; Kochebina, O; Komarov, V; Koopman, R F; Koppenburg, P; Korolev, M; Kozlinskiy, A; Kravchuk, L; Kreplin, K; Kreps, M; Krocker, G; Krokovny, P; Kruse, F; Kucharczyk, M; Kudryavtsev, V; Kvaratskheliya, T; La Thi, V N; Lacarrere, D; Lafferty, G; Lai, A; Lambert, D; Lambert, R W; Lanciotti, E; Lanfranchi, G; Langenbruch, C; Latham, T; Lazzeroni, C; Le Gac, R; van Leerdam, J; Lees, J-P; Lefèvre, R; Leflat, A; Lefrançois, J; Leroy, O; Lesiak, T; Li, Y; Li Gioi, L; Liles, M; Lindner, R; Linn, C; Liu, B; Liu, G; von Loeben, J; Lopes, J H; Lopez Asamar, E; Lopez-March, N; Lu, H; Luisier, J; Mac Raighne, A; Machefert, F; Machikhiliyan, I V; Maciuc, F; Maev, O; Magnin, J; Maino, M; Malde, S; Manca, G; Mancinelli, G; Mangiafave, N; Marconi, U; Märki, R; Marks, J; Martellotti, G; Martens, A; Martin, L; Martín Sánchez, A; Martinelli, M; Martinez Santos, D; Massafferri, A; Mathe, Z; Matteuzzi, C; Matveev, M; Maurice, E; Mazurov, A; McCarthy, J; McGregor, G; McNulty, R; Meissner, M; Merk, M; Merkel, J; Milanes, D A; Minard, M-N; Molina Rodriguez, J; Monteil, S; Moran, D; Morawski, P; Mountain, R; Mous, I; Muheim, F; Müller, K; Muresan, R; Muryn, B; Muster, B; Mylroie-Smith, J; Naik, P; Nakada, T; Nandakumar, R; Nasteva, I; Needham, M; Neufeld, N; Nguyen, A D; Nguyen-Mau, C; Nicol, M; Niess, V; Nikitin, N; Nikodem, T; Nomerotski, A; Novoselov, A; Oblakowska-Mucha, A; Obraztsov, V; Oggero, S; Ogilvy, S; Okhrimenko, O; Oldeman, R; Orlandea, M; Otalora Goicochea, J M; Owen, P; Pal, B K; Palano, A; Palutan, M; Panman, J; Papanestis, A; Pappagallo, M; Parkes, C; Parkinson, C J; Passaleva, G; Patel, G D; Patel, M; Patrick, G N; Patrignani, C; Pavel-Nicorescu, C; Pazos Alvarez, A; Pellegrino, A; Penso, G; Pepe Altarelli, M; Perazzini, S; Perego, D L; Perez Trigo, E; Pérez-Calero Yzquierdo, A; Perret, P; Perrin-Terrin, M; Pessina, G; Petridis, K; Petrolini, A; Phan, A; Picatoste Olloqui, E; Pie Valls, B; Pietrzyk, B; Pilař, T; Pinci, D; Playfer, S; Plo Casasus, M; Polci, F; Polok, G; Poluektov, A; Polycarpo, E; Popov, D; Popovici, B; Potterat, C; Powell, A; Prisciandaro, J; Pugatch, V; Puig Navarro, A; Qian, W; Rademacker, J H; Rakotomiaramanana, B; Rangel, M S; Raniuk, I; Rauschmayr, N; Raven, G; Redford, S; Reid, M M; dos Reis, A C; Ricciardi, S; Richards, A; Rinnert, K; Rives Molina, V; Roa Romero, D A; Robbe, P; Rodrigues, E; Rodriguez Perez, P; Rogers, G J; Roiser, S; Romanovsky, V; Romero Vidal, A; Rouvinet, J; Ruf, T; Ruiz, H; Sabatino, G; Saborido Silva, J J; Sagidova, N; Sail, P; Saitta, B; Salzmann, C; Sanmartin Sedes, B; Sannino, M; Santacesaria, R; Santamarina Rios, C; Santinelli, R; Santovetti, E; Sapunov, M; Sarti, A; Satriano, C; Satta, A; Savrie, M; Schaack, P; Schiller, M; Schindler, H; Schleich, S; Schlupp, M; Schmelling, M; Schmidt, B; Schneider, O; Schopper, A; Schune, M-H; Schwemmer, R; Sciascia, B; Sciubba, A; Seco, M; Semennikov, A; Senderowska, K; Sepp, I; Serra, N; Serrano, J; Seyfert, P; Shapkin, M; Shapoval, I; Shatalov, P; Shcheglov, Y; Shears, T; Shekhtman, L; Shevchenko, O; Shevchenko, V; Shires, A; Silva Coutinho, R; Skwarnicki, T; Smith, N A; Smith, E; Smith, M; Sobczak, K; Soler, F J P; Soomro, F; Souza, D; Souza De Paula, B; Spaan, B; Sparkes, A; Spradlin, P; Stagni, F; Stahl, S; Steinkamp, O; Stoica, S; Stone, S; Storaci, B; Straticiuc, M; Straumann, U; Subbiah, V K; Swientek, S; Szczekowski, M; Szczypka, P; Szumlak, T; T'Jampens, S; Teklishyn, M; Teodorescu, E; Teubert, F; Thomas, C; Thomas, E; van Tilburg, J; Tisserand, V; Tobin, M; Tolk, S; Tonelli, D; Topp-Joergensen, S; Torr, N; Tournefier, E; Tourneur, S; Tran, M T; Tsaregorodtsev, A; Tsopelas, P; Tuning, N; Ubeda Garcia, M; Ukleja, A; Urner, D; Uwer, U; Vagnoni, V; Valenti, G; Vazquez Gomez, R; Vazquez Regueiro, P; Vecchi, S; Velthuis, J J; Veltri, M; Veneziano, G; Vesterinen, M; Viaud, B; Videau, I; Vieira, D; Vilasis-Cardona, X; Visniakov, J; Vollhardt, A; Volyanskyy, D; Voong, D; Vorobyev, A; Vorobyev, V; Voss, H; Voss, C; Waldi, R; Wallace, R; Wandernoth, S; Wang, J; Ward, D R; Watson, N K; Webber, A D; Websdale, D; Whitehead, M; Wicht, J; Wiedner, D; Wiggers, L; Wilkinson, G; Williams, M P; Williams, M; Wilson, F F; Wishahi, J; Witek, M; Witzeling, W; Wotton, S A; Wright, S; Wu, S; Wyllie, K; Xie, Y; Xing, F; Xing, Z; Yang, Z; Young, R; Yuan, X; Yushchenko, O; Zangoli, M; Zavertyaev, M; Zhang, F; Zhang, L; Zhang, W C; Zhang, Y; Zhelezov, A; Zhong, L; Zvyagin, A

2012-12-07

Measurements of B(c)(+) production and mass are performed with the decay mode B(c)(+)→J/ψπ(+) using 0.37 fb(-1) of data collected in pp collisions at √[s]=7 TeV by the LHCb experiment. The ratio of the production cross section times branching fraction between the B(c)(+)→J/ψπ(+) and the B(+)→J/ψK(+) decays is measured to be (0.68±0.10(stat)±0.03(syst)±0.05(lifetime))% for B(c)(+) and B(+) mesons with transverse momenta p(T)>4 GeV/c and pseudorapidities 2.5M(B(c)(+))-M(B(+))=994.6±1.3(stat)±0.6(syst) MeV/c(2).

Measurements of $B_c^+$ production and mass with the $B_c^+ \\to J/\\psi \\pi^+$ decay

CERN Document Server

Aaij, R; Adametz, A; Adeva, B; Adinolfi, M; Adrover, C; Affolder, A; Ajaltouni, Z; Albrecht, J; Alessio, F; Alexander, M; Ali, S; Alkhazov, G; Alvarez Cartelle, P; Alves Jr, A A; Amato, S; Amhis, Y; Anderlini, L; Anderson, J; Appleby, R B; Aquines Gutierrez, O; Archilli, F; Artamonov, A; Artuso, M; Aslanides, E; Auriemma, G; Bachmann, S; Back, J J; Baesso, C; Baldini, W; Barlow, R J; Barschel, C; Barsuk, S; Barter, W; Bates, A; Bauer, Th; Bay, A; Beddow, J; Bediaga, I; Belogurov, S; Belous, K; Belyaev, I; Ben-Haim, E; Benayoun, M; Bencivenni, G; Benson, S; Benton, J; Berezhnoy, A; Bernet, R; Bettler, M -O; van Beuzekom, M; Bien, A; Bifani, S; Bird, T; Bizzeti, A; Bjørnstad, P M; Blake, T; Blanc, F; Blanks, C; Blouw, J; Blusk, S; Bobrov, A; Bocci, V; Bondar, A; Bondar, N; Bonivento, W; Borghi, S; Borgia, A; Bowcock, T J V; Bozzi, C; Brambach, T; van den Brand, J; Bressieux, J; Brett, D; Britsch, M; Britton, T; Brook, N H; Brown, H; Büchler-Germann, A; Burducea, I; Bursche, A; Buytaert, J; Cadeddu, S; Callot, O; Calvi, M; Calvo Gomez, M; Camboni, A; Campana, P; Carbone, A; Carboni, G; Cardinale, R; Cardini, A; Carson, L; Carvalho Akiba, K; Casse, G; Cattaneo, M; Cauet, Ch; Charles, M; Charpentier, Ph; Chen, P; Chiapolini, N; Chrzaszcz, M; Ciba, K; Cid Vidal, X; Ciezarek, G; Clarke, P E L; Clemencic, M; Cliff, H V; Closier, J; Coca, C; Coco, V; Cogan, J; Cogneras, E; Collins, P; Comerma-Montells, A; Contu, A; Cook, A; Coombes, M; Corti, G; Couturier, B; Cowan, G A; Craik, D; Cunliffe, S; Currie, R; D'Ambrosio, C; David, P; David, P N Y; De Bonis, I; De Bruyn, K; De Capua, S; De Cian, M; De Miranda, J M; De Paula, L; De Simone, P; Decamp, D; Deckenhoff, M; Degaudenzi, H; Del Buono, L; Deplano, C; Derkach, D; Deschamps, O; Dettori, F; Di Canto, A; Dickens, J; Dijkstra, H; Diniz Batista, P; Domingo Bonal, F; Donleavy, S; Dordei, F; Dosil Suárez, A; Dossett, D; Dovbnya, A; Dupertuis, F; Dzhelyadin, R; Dziurda, A; Dzyuba, A; Easo, S; Egede, U; Egorychev, V; Eidelman, S; van Eijk, D; Eisenhardt, S; Ekelhof, R; Eklund, L; El Rifai, I; Elsasser, Ch; Elsby, D; Esperante Pereira, D; Falabella, A; Färber, C; Fardell, G; Farinelli, C; Farry, S; Fave, V; Fernandez Albor, V; Ferreira Rodrigues, F; Ferro-Luzzi, M; Filippov, S; Fitzpatrick, C; Fontana, M; Fontanelli, F; Forty, R; Francisco, O; Frank, M; Frei, C; Frosini, M; Furcas, S; Gallas Torreira, A; Galli, D; Gandelman, M; Gandini, P; Gao, Y; Garnier, J-C; Garofoli, J; Garosi, P; Garra Tico, J; Garrido, L; Gaspar, C; Gauld, R; Gersabeck, E; Gersabeck, M; Gershon, T; Ghez, Ph; Gibson, V; Gligorov, V V; Göbel, C; Golubkov, D; Golutvin, A; Gomes, A; Gordon, H; Grabalosa Gándara, M; Graciani Diaz, R; Granado Cardoso, L A; Graugés, E; Graziani, G; Grecu, A; Greening, E; Gregson, S; Grünberg, O; Gui, B; Gushchin, E; Guz, Yu; Gys, T; Hadjivasiliou, C; Haefeli, G; Haen, C; Haines, S C; Hall, S; Hampson, T; Hansmann-Menzemer, S; Harnew, N; Harnew, S T; Harrison, J; Harrison, P F; Hartmann, T; He, J; Heijne, V; Hennessy, K; Henrard, P; Hernando Morata, J A; van Herwijnen, E; Hicks, E; Hill, D; Hoballah, M; Hopchev, P; Hulsbergen, W; Hunt, P; Huse, T; Hussain, N; Hutchcroft, D; Hynds, D; Iakovenko, V; Ilten, P; Imong, J; Jacobsson, R; Jaeger, A; Jahjah Hussein, M; Jans, E; Jansen, F; Jaton, P; Jean-Marie, B; Jing, F; John, M; Johnson, D; Jones, C R; Jost, B; Kaballo, M; Kandybei, S; Karacson, M; Karbach, T M; Keaveney, J; Kenyon, I R; Kerzel, U; Ketel, T; Keune, A; Khanji, B; Kim, Y M; Kochebina, O; Komarov, V; Koopman, R F; Koppenburg, P; Korolev, M; Kozlinskiy, A; Kravchuk, L; Kreplin, K; Kreps, M; Krocker, G; Krokovny, P; Kruse, F; Kucharczyk, M; Kudryavtsev, V; Kvaratskheliya, T; La Thi, V N; Lacarrere, D; Lafferty, G; Lai, A; Lambert, D; Lambert, R W; Lanciotti, E; Lanfranchi, G; Langenbruch, C; Latham, T; Lazzeroni, C; Le Gac, R; van Leerdam, J; Lees, J -P; Lefèvre, R; Leflat, A; Lefrançois, J; Leroy, O; Lesiak, T; Li, Y; Li Gioi, L; Liles, M; Lindner, R; Linn, C; Liu, B; Liu, G; von Loeben, J; Lopes, J H; Lopez Asamar, E; Lopez-March, N; Lu, H; Luisier, J; Mac Raighne, A; Machefert, F; Machikhiliyan, I V; Maciuc, F; Maev, O; Magnin, J; Maino, M; Malde, S; Manca, G; Mancinelli, G; Mangiafave, N; Marconi, U; Märki, R; Marks, J; Martellotti, G; Martens, A; Martin, L; Martín Sánchez, A; Martinelli, M; Martinez Santos, D; Massafferri, A; Mathe, Z; Matteuzzi, C; Matveev, M; Maurice, E; Mazurov, A; McCarthy, J; McGregor, G; McNulty, R; Meissner, M; Merk, M; Merkel, J; Milanes, D A; Minard, M -N; Molina Rodriguez, J; Monteil, S; Moran, D; Morawski, P; Mountain, R; Mous, I; Muheim, F; Müller, K; Muresan, R; Muryn, B; Muster, B; Mylroie-Smith, J; Naik, P; Nakada, T; Nandakumar, R; Nasteva, I; Needham, M; Neufeld, N; Nguyen, A D; Nguyen-Mau, C; Nicol, M; Niess, V; Nikitin, N; Nikodem, T; Nomerotski, A; Novoselov, A; Oblakowska-Mucha, A; Obraztsov, V; Oggero, S; Ogilvy, S; Okhrimenko, O; Oldeman, R; Orlandea, M; Otalora Goicochea, J M; Owen, P; Pal, B K; Palano, A; Palutan, M; Panman, J; Papanestis, A; Pappagallo, M; Parkes, C; Parkinson, C J; Passaleva, G; Patel, G D; Patel, M; Patrick, G N; Patrignani, C; Pavel-Nicorescu, C; Pazos Alvarez, A; Pellegrino, A; Penso, G; Pepe Altarelli, M; Perazzini, S; Perego, D L; Perez Trigo, E; Pérez-Calero Yzquierdo, A; Perret, P; Perrin-Terrin, M; Pessina, G; Petridis, K; Petrolini, A; Phan, A; Picatoste Olloqui, E; Pie Valls, B; Pietrzyk, B; Pilař, T; Pinci, D; Playfer, S; Plo Casasus, M; Polci, F; Polok, G; Poluektov, A; Polycarpo, E; Popov, D; Popovici, B; Potterat, C; Powell, A; Prisciandaro, J; Pugatch, V; Puig Navarro, A; Qian, W; Rademacker, J H; Rakotomiaramanana, B; Rangel, M S; Raniuk, I; Rauschmayr, N; Raven, G; Redford, S; Reid, M M; dos Reis, A C; Ricciardi, S; Richards, A; Rinnert, K; Rives Molina, V; Roa Romero, D A; Robbe, P; Rodrigues, E; Rodriguez Perez, P; Rogers, G J; Roiser, S; Romanovsky, V; Romero Vidal, A; Rouvinet, J; Ruf, T; Ruiz, H; Sabatino, G; Saborido Silva, J J; Sagidova, N; Sail, P; Saitta, B; Salzmann, C; Sanmartin Sedes, B; Sannino, M; Santacesaria, R; Santamarina Rios, C; Santinelli, R; Santovetti, E; Sapunov, M; Sarti, A; Satriano, C; Satta, A; Savrie, M; Schaack, P; Schiller, M; Schindler, H; Schleich, S; Schlupp, M; Schmelling, M; Schmidt, B; Schneider, O; Schopper, A; Schune, M -H; Schwemmer, R; Sciascia, B; Sciubba, A; Seco, M; Semennikov, A; Senderowska, K; Sepp, I; Serra, N; Serrano, J; Seyfert, P; Shapkin, M; Shapoval, I; Shatalov, P; Shcheglov, Y; Shears, T; Shekhtman, L; Shevchenko, O; Shevchenko, V; Shires, A; Silva Coutinho, R; Skwarnicki, T; Smith, N A; Smith, E; Smith, M; Sobczak, K; Soler, F J P; Soomro, F; Souza, D; Souza De Paula, B; Spaan, B; Sparkes, A; Spradlin, P; Stagni, F; Stahl, S; Steinkamp, O; Stoica, S; Stone, S; Storaci, B; Straticiuc, M; Straumann, U; Subbiah, V K; Swientek, S; Szczekowski, M; Szczypka, P; Szumlak, T; T'Jampens, S; Teklishyn, M; Teodorescu, E; Teubert, F; Thomas, C; Thomas, E; van Tilburg, J; Tisserand, V; Tobin, M; Tolk, S; Tonelli, D; Topp-Joergensen, S; Torr, N; Tournefier, E; Tourneur, S; Tran, M T; Tsaregorodtsev, A; Tsopelas, P; Tuning, N; Ubeda Garcia, M; Ukleja, A; Urner, D; Uwer, U; Vagnoni, V; Valenti, G; Vazquez Gomez, R; Vazquez Regueiro, P; Vecchi, S; Velthuis, J J; Veltri, M; Veneziano, G; Vesterinen, M; Viaud, B; Videau, I; Vieira, D; Vilasis-Cardona, X; Visniakov, J; Vollhardt, A; Volyanskyy, D; Voong, D; Vorobyev, A; Vorobyev, V; Voss, H; Voß, C; Waldi, R; Wallace, R; Wandernoth, S; Wang, J; Ward, D R; Watson, N K; Webber, A D; Websdale, D; Whitehead, M; Wicht, J; Wiedner, D; Wiggers, L; Wilkinson, G; Williams, M P; Williams, M; Wilson, F F; Wishahi, J; Witek, M; Witzeling, W; Wotton, S A; Wright, S; Wu, S; Wyllie, K; Xie, Y; Xing, F; Xing, Z; Yang, Z; Young, R; Yuan, X; Yushchenko, O; Zangoli, M; Zavertyaev, M; Zhang, F; Zhang, L; Zhang, W C; Zhang, Y; Zhelezov, A; Zhong, L; Zvyagin, A

2012-01-01

Measurements of $B_c^+$ production and mass are performed with the decay mode $B_c^+ \\to J/\\psi \\pi^+$ using 0.37 fb$^{-1}$ of data collected in $pp$ collisions at $\\sqrt{s}=7$~TeV by the LHCb experiment. The ratio of the production cross-section times branching fraction between the $B_c^+ \\to J/\\psi \\pi^+$ and the $B^+ \\to J/\\psi K^+$ decays is measured to be $(0.68 \\pm 0.10\\,({\\rm stat.}) \\pm 0.03\\,({\\rm syst.}) \\pm 0.05\\,({\\rm lifetime}) )\\%$ for $B_c^+$ and $B^+$ mesons with transverse momenta $p_{\\rm T}>4~$GeV/$c$ and pseudorapidities $2.5<\\eta<4.5$. The $B_c^+$ mass is directly measured to be $6273.7 \\pm 1.3\\,({\\rm stat.}) \\pm 1.6 \\,({\\rm syst.})$~MeV/$c^2$, and the measured mass difference with respect to the $B^+$ meson is $M(B_c^+)-M(B^+) = 994.6 \\pm 1.3\\,({\\rm stat.}) \\pm 0.6\\,({\\rm syst.})$~MeV/$c^2$.

Hepatitis B & C and HIV

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... Find Services HIV SERVICES LOCATOR Locator Search Search Hepatitis B & C Topics Hepatitis B Hepatitis C Hepatitis ... Infections Sexually Transmitted Diseases Smoking Women's Health Issues Hepatitis B Virus and Hepatitis C Virus Infection People ...

Defining B-c, B* and B-phi for YBCO Thin Films

DEFF Research Database (Denmark)

Paturi, Petriina; Irjala, Matti; Abrahamsen, Asger Bech

2009-01-01

of superconducting films. Similarly, the characteristic field, B c, can be obtained from magneto-optical (MO) images from when the flux fronts meet in the middle of the film. The matching field, B phi, at which there is one vortex line per pinning site, is sometimes thought to be the same as B*, but in BaZrO3-doped...... YBa2Cu3O7 films the calculated B phi is much higher than the observed B*. B phi can be determined from angular dependent transport measurements. All of the field values correspond to some special case in the flux pinning in the film and relate to J c. In this work we have determined B c, B* and B phi...

A comparative computational study of Csbnd N and Csbnd C bonding visible to NIR absorbing croconines

Science.gov (United States)

Chetti, Prabhakar; Tripathi, Anuj

2018-03-01

The lowest electronic excitations and charge transfer properties in two series of croconine dyes; 1) molecules with Csbnd N bonding, having an absorption in the visible region (400-600 nm) and 2) molecules with Csbnd C bonding, showing absorption in visible to near infrared (NIR) region (600-1100 nm) are analyzed by quantum-chemical calculations. The absorption maxima in Csbnd C bonding croconines (CCR) are always having 200-300 nm red shifted than its corresponding Csbnd N bonding croconines (NCR). The reason for this drastic red shift in CCR series than its corresponding NCR has been systematically studied by DFT, TDDFT and SAC-CI methods. It is found that, CCR series are with less charge transfer in nature and are having larger diradical character, whereas NCR series molecules showing larger charge transfer with lower diradical character. The change in bonding mode of central five membered croconate ring, from Csbnd N to Csbnd C, destabilization and/stabilization of HOMO LUMO levels were observed. This study may helpful in the design and synthesis of new visible to NIR absorbing croconine dyes which are useful in materials applications.

Oxidative addition of the ethane C-C bond to Pd. An ab initio benchmark and DFT validation study

NARCIS (Netherlands)

De Jong, G.T.; Geerke, D.P.; Diefenbach, A.; Sola, M.; Bickelhaupt, F.M.

2005-01-01

We have computed a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the ethane C-C bond to the palladium atom and have used this to evaluate the performance of 24 popular density functionals, covering LDA, GGA, meta-GGA, and hybrid density

CuCo2O4 nanoplate film as a low-cost, highly active and durable catalyst towards the hydrolytic dehydrogenation of ammonia borane for hydrogen production

Science.gov (United States)

Liu, Quanbing; Zhang, Shengjie; Liao, Jinyun; Feng, Kejun; Zheng, Yuying; Pollet, Bruno G.; Li, Hao

2017-07-01

Catalytic dehydrogenation of ammonia borane is one of the most promising routes for the production of clean hydrogen as it is seen as a highly efficient and safe method. However, its large-scale industrial application is either limited by the high cost of the catalyst (usually a noble metal based catalyst) or by the low activity and poor reusability (usually a non-noble metal catalyst). In this study, we have successfully prepared three low-cost CuCo2O4 nanocatalysts, namely: (i) Ti supported CuCo2O4 film made of CuCo2O4 nanoplates, (ii) Ti supported CuCo2O4 film made of CuCo2O4 nanosheets, and (iii) unsupported CuCo2O4 nanoparticles. Among the three catalysts used for the hydrolytic dehydrogeneration of ammonia borane, the CuCo2O4 nanoplate film exhibits the highest catalytic activity with a turnover frequency (TOF) of ∼44.0 molhydrogen min-1 molcat-1. This is one of the largest TOF value for noble-metal-free catalysts ever reported in the literature. Moreover, the CuCo2O4 nanoplate film almost keeps its original catalytic activity after eight cycles, indicative of its high stability and good reusability. Owing to its advantages, the CuCo2O4 nanoplate film can be a promising catalyst for the hydrolytic dehydrogenation of ammonia borane, which may find important applications in the field of hydrogen energy.

Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation.

Science.gov (United States)

Liu, Chengwei; Szostak, Michal

2017-05-29

The concept of using amide bond distortion to modulate amidic resonance has been known for more than 75 years. Two classic twisted amides (bridged lactams) ingeniously designed and synthesized by Kirby and Stoltz to feature fully perpendicular amide bonds, and as a consequence emanate amino-ketone-like reactivity, are now routinely recognized in all organic chemistry textbooks. However, only recently the use of amide bond twist (distortion) has advanced to the general organic chemistry mainstream enabling a host of highly attractive N-C amide bond cross-coupling reactions of broad synthetic relevance. In this Minireview, we discuss recent progress in this area and present a detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of thermocycling on tensile bond strength of two soft liners.

Science.gov (United States)

Geramipanah, Farideh; Ghandari, Masoumeh; Zeighami, Somayeh

2013-09-01

Failure of soft liners depends mostly on separation from the denture base resin; therefore measurement of the bond strength is very important. The purpose of this study was to compare the tensile bond strength of two soft liners (Acropars, Molloplast-B) to denture base resin before and after thermocycling. Twenty specimens fromeach of the two different soft liners were processed according to the manufacturer's instructions between two polymethyl methacrylate (PMMA) sheets. Ten specimens in each group were maintained in 37°C water for 24 hours and 10 were thermocycled (5000 cycles) among baths of 5° and 55°C. The tensile bond strength was measured using a universal testing machine at a crosshead speed of 5 mm/min. Mode of failure was determined with SEM (magnification ×30). Two-way ANOVA was used to analyze the data. The mean and standard deviation of tensile bond strength of Acropars and Molloplast-B before thermocycling were 6.59±1.85 and1.51±0.22 MPa, respectively and 5.89±1.52 and1.37±0.18 MPa, respectively after thermocycling. There was no significant difference before and after thermocycling. Mode of failure in Acropars and Molloplast-B were adhesive and cohesive, respectivley. The bond strength of Acropars was significantly higher than Molloplast-B (P<0.05).

Recent advances in C(sp3–H bond functionalization via metal–carbene insertions

Directory of Open Access Journals (Sweden)

Bo Wang

2016-04-01

Full Text Available The recent development of intermolecular C–H insertion in the application of C(sp3–H bond functionalizations, especially for light alkanes, is reviewed. The challenging problem of regioselectivity in C–H bond insertions has been tackled by the use of sterically bulky metal catalysts, such as metal porphyrins and silver(I complexes. In some cases, high regioselectivity and enantioselectivity have been achieved in the C–H bond insertion of small alkanes. This review highlights the most recent accomplishments in this field.

26 CFR 1.381(c)(9)-1 - Amortization of bond discount or premium.

Science.gov (United States)

2010-04-01

... 26 Internal Revenue 4 2010-04-01 2010-04-01 false Amortization of bond discount or premium. 1.381(c)(9)-1 Section 1.381(c)(9)-1 Internal Revenue INTERNAL REVENUE SERVICE, DEPARTMENT OF THE TREASURY (CONTINUED) INCOME TAX (CONTINUED) INCOME TAXES Insolvency Reorganizations § 1.381(c)(9)-1 Amortization of...

A novel stibacarbaborane cluster with adjacent antimony atoms exhibiting unique pnictogen bond formation that dominates its crystal packing.

Science.gov (United States)

Holub, Josef; Melichar, Petr; Růžičková, Zdeňka; Vrána, Jan; Wann, Derek A; Fanfrlík, Jindřich; Hnyk, Drahomír; Růžička, Aleš

2017-10-17

We have prepared nido-7,8,9,11-Sb 2 C 2 B 7 H 9 , the first cluster with simultaneous Sb-B, Sb-C and Sb-Sb atom pairs with interatomic separations with magnitudes that approach the respective sums of covalent radii. However, the length of the Sb-Sb separation in this cluster is slightly less than the sum of the covalent radii. Quantum chemical analysis has revealed that the crystal packing of nido-7,8,9,11-Sb 2 C 2 B 7 H 9 is predominantly dictated by pnictogen (Pn) bonding, an unconventional σ-hole interaction. Indeed, the interaction energy of a very strong Sb 2 H-B Pn-bond in the nido-7,8,9,11-Sb 2 C 2 B 7 H 9 dimer exceeds -6.0 kcal mol -1 . This is a very large value and is comparable to the strengths of known Pn-bonds in Cl 3 Pnπ complexes (Pn = As, Sb).

Solidification and solid state phenomena during TLP bonding of IN718 superalloy using Ni–Si–B ternary filler alloy

Energy Technology Data Exchange (ETDEWEB)

Pouranvari, M., E-mail: mpouranvari@yahoo.com [Department of Materials Science and Engineering, Sharif University of Technology, Tehran 11365-11155 (Iran, Islamic Republic of); Ekrami, A.; Kokabi, A.H. [Department of Materials Science and Engineering, Sharif University of Technology, Tehran 11365-11155 (Iran, Islamic Republic of)

2013-06-25

Highlights: ► Microstructure evolution during TLP bonding of IN718 using Ni–Si–B filler. ► Athermal solidification path is influenced by severe segregation of B and Si in residual liquid. ► High hardness of ASZ microconstituents necessitates designing a PBHT to avert brittleness. ► Diffusion induced Cr–Mo–Nb based boride precipitation was observed in DAZ. ► Boride precipitates in DAZ influence the corrosion resistance and aging behavior. -- Abstract: This paper addresses solidification and solid state precipitation phenomena during transient liquid phase (TLP) bonding of wrought IN718 nickel base superalloy using Ni–4.5Si–3.2B (wt.%) ternary filler alloy. The solidification sequence of the residual liquid in the joint centerline was found to be (1) formation of proeutectic γ, followed by (2) γ/Ni{sub 3}B eutectic reaction, followed by (3) ternary eutectic of γ/Ni{sub 3}B/Ni{sub 6}Si{sub 2}B. Extensive fine Ni{sub 3}Si formed within the eutectic-γ via solid state precipitation during cooling. Extensive Cr–Mo–Nb rich boride precipitates were formed in the substrate region due to boron diffusion into the base metal during bonding process. The implications of the phase transformations on the mechanical properties, corrosion resistance and aging behavior of the joint, which are pertinent to the development of an optimum post bond heat treatment, are highlighted.

Solidification and solid state phenomena during TLP bonding of IN718 superalloy using Ni–Si–B ternary filler alloy

International Nuclear Information System (INIS)

Pouranvari, M.; Ekrami, A.; Kokabi, A.H.

2013-01-01

Highlights: ► Microstructure evolution during TLP bonding of IN718 using Ni–Si–B filler. ► Athermal solidification path is influenced by severe segregation of B and Si in residual liquid. ► High hardness of ASZ microconstituents necessitates designing a PBHT to avert brittleness. ► Diffusion induced Cr–Mo–Nb based boride precipitation was observed in DAZ. ► Boride precipitates in DAZ influence the corrosion resistance and aging behavior. -- Abstract: This paper addresses solidification and solid state precipitation phenomena during transient liquid phase (TLP) bonding of wrought IN718 nickel base superalloy using Ni–4.5Si–3.2B (wt.%) ternary filler alloy. The solidification sequence of the residual liquid in the joint centerline was found to be (1) formation of proeutectic γ, followed by (2) γ/Ni 3 B eutectic reaction, followed by (3) ternary eutectic of γ/Ni 3 B/Ni 6 Si 2 B. Extensive fine Ni 3 Si formed within the eutectic-γ via solid state precipitation during cooling. Extensive Cr–Mo–Nb rich boride precipitates were formed in the substrate region due to boron diffusion into the base metal during bonding process. The implications of the phase transformations on the mechanical properties, corrosion resistance and aging behavior of the joint, which are pertinent to the development of an optimum post bond heat treatment, are highlighted

Metallacarborane chemistry of the hypho-[6,7-C2B6H13](-)1-anion: the formation of uniquely structured metallacarboranes [5-Cp*-arachno-5,4,6-RhC2B6H12] and [2,5-Cp-2(*)-10-Me-nido-2,5,1-Rh2CB6H9] (Cp-* = eta(5)-C5Me5-): complete rhodium analogues of arachno-4,6-C2B7H13 and nido-1-CB8H12

Czech Academy of Sciences Publication Activity Database

Londesborough, Michael Geoffrey Stephen; Janoušek, Zbyněk; Štíbr, Bohumil; Císařová, I.

2004-01-01

Roč. 689, č. 16 (2004), s. 2702-2706 ISSN 0022-328X R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * metallacarboranes * rhodium complex Subject RIV: CA - Inorganic Chemistry Impact factor: 1.905, year: 2004

Photoelectron Diffraction Imaging for C2H2 and C2H4 Chemisorbed on Si(100) Reveals a New Bonding Configuration

International Nuclear Information System (INIS)

Xu, S. H.; Keeffe, M.; Yang, Y.; Chen, C.; Yu, M.; Lapeyre, G. J.; Rotenberg, E.; Denlinger, J.; Yates, J. T. Jr.

2000-01-01

A new adsorption site for adsorbed acetylene on Si(100) is observed by photoelectron imaging based on the holographic principle. The diffraction effects in the carbon 1s angle-resolved photoemission are inverted (including the small-cone method) to obtain an image of the atom's neighboring carbon. The chemisorbed acetylene molecule is bonded to four silicon surface atoms. In contrast to the C 2 H 2 case, the image for adsorbed C 2 H 4 shows it bonded to two Si surface atoms. (c) 2000 The American Physical Society

Relationships for the impact sensitivities of energetic C-nitro compounds based on bond dissociation energy.

Science.gov (United States)

Li, Jinshan

2010-02-18

The ZPE-corrected C-NO(2) bond dissociation energies (BDEs(ZPE)) of a series of model C-nitro compounds and 26 energetic C-nitro compounds have been calculated using density functional theory methods. Computed results show that for C-nitro compounds the UB3LYP calculated BDE(ZPE) is less than the UB3P86 using the 6-31G** basis set, and the UB3P86 BDE(ZPE) changes slightly with the basis set varying from 6-31G** to 6-31++G**. For the series of model C-nitro compounds with different chemical skeletons, it is drawn from NBO analysis that the order of BDE(ZPE) is not only in line with that of the NAO bond order but also with that of the energy gap between C-NO(2) bonding and antibonding orbitals. It is found that for the energetic C-nitro compounds whose drop energies (Es(dr)) are below 24.5 J a good linear correlation exists between E(dr) and BDE(ZPE), implying that these compounds ignite through the C-NO(2) dissociation mechanism. After excluding the so-called trinitrotoluene mechanism compounds, a polynomial correlation of ln(E(dr)) with the BDE(ZPE) calculated at density functional theory levels has been established successfully for the 18 C-NO(2) dissociation energetic C-nitro compounds.

Evaluation of the anti-cariogenic potential and bond strength to enamel of different fluoridated materials used for bracket bonding

Directory of Open Access Journals (Sweden)

Sérgio Ricardo da SILVA

2017-05-01

Full Text Available Abstract Objective To evaluate the in vitro and in situ anti-cariogenic potential and bond strength to enamel of materials containing fluoride (F, used for bracket bonding: Transbond XT (GT, negative control, Transbond Plus Color Change (GTF, Transbond-Self-Etching Primer (GSAF and Vitremer (GV, positive control. Material and method In the in vitro study, the specimens were premolars with bonded brackets (n=12/group. After pH cycling, the F release, bond strength, fracture mode and presence of white spot lesions were assessed. In the in situ study, the specimens were enamel fragments with bonded brackets (n=12/group. Twelve volunteers wore palatal appliances in 4 phases, with cariogenic challenge. Bond strength, fracture mode and change in surface hardness (%SH were determined. Result Relative to the in vitro study, F release (ppm was: GT=0.257±0.068c; GTF=0.634±0.100b; GSAF=0.630±0.067b; GV=2.796±1.414a. Only GV showed no white spot lesions. Bond strength values (MPa were GT=7.62±7.18a; GTF=5.15±6.91ab; GSAF=3.42±2.97bc; GV=2.87±2.09c. Adhesive fracture was the most frequent type, except for GTF. In the in situ study, %SH was: GT=-56.0±18.3a; GTF=-57.6±11.9a; GSAF=-57.1±11.3a; GV=-52.4±25.8a. Bond strength values were GT=9.5±4.4a; GTF=11.1±5.9a; GSAF=13.2± 6.6a; GV=6.6±4.0a. Cohesive fracture in material was the most frequent type, except for GTF. Conclusion Vitremer (GV showed the highest anti-cariogenic potential in the in vitro study. However, it was not confirmed by the in situ study. Regarding bond strength values from the in situ study, all materials were shown to be adequate for clinical practice.

Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions.

Science.gov (United States)

Cui, Li-Qian; Liu, Kai; Zhang, Chi

2011-04-07

Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu(4)NHSO(4) could be applied to the effective oxidation of alkanes as well.

A novel approach for a C-11C bond formation: synthesis of 17α-([11C]prop-1-ynyl)-3-methoxy-3,17β-estradiol

International Nuclear Information System (INIS)

Wuest, F.; Zessin, J.

2002-01-01

A novel method for a 11 C-C bond formation was developed, employing a cross-coupling reaction between a terminal acetylene and [ 11 C]methyl iodide. The method was used for the synthesis of 17α-([ 11 C]prop-1-ynyl)-3-methoxy-3,17β-estadiol. (orig.)

Enantioselective carbenoid insertion into C(sp3–H bonds

Directory of Open Access Journals (Sweden)

J. V. Santiago

2016-05-01

Full Text Available The enantioselective carbenoid insertion into C(sp3–H bonds is an important tool for the synthesis of complex molecules due to the high control of enantioselectivity in the formation of stereogenic centers. This paper presents a brief review of the early issues, related mechanistic studies and recent applications on this chemistry area.

Synthesis and chemistry of the open-cage cobaltaheteroborane cluster [{(η(5)-C5Me5)Co}2B2H2Se2]: a combined experimental and theoretical study.

Science.gov (United States)

Barik, Subrat Kumar; Dorcet, Vincent; Roisnel, Thierry; Halet, Jean-François; Ghosh, Sundargopal

2015-08-28

Reaction of [(η(5)-C5Me5)CoCl]2 with a two-fold excess of [LiBH4·thf] followed by heating with an excess of Se powder produces the dicobaltaselenaborane species [{(η(5)-C5Me5)Co}2B2H2Se2], , in good yield. The geometry of resembles a nido pentagonal [Co2B2Se2] bipyramid with a missing equatorial vertex. It can alternatively be seen as an open cage triple-decker cluster. Isolation of permits its reaction with [Fe2(CO)9] to give heterometallic diselenametallaborane [{(η(5)-C5Me5)Co}Fe(CO)3B2H2Se2], . The geometry of is similar to that of with one of the [(η(5)-C5Me5)Co] groups replaced by the isolobal, two-electron fragment [Fe(CO)3]. Both new compounds have been characterized by mass spectrometry, and by (1)H, (11)B and (13)C NMR spectroscopy. The structural architectures have been unequivocally established by crystallographic analysis. In addition, density functional theory calculations were performed to investigate the bonding and electronic properties. The large HOMO-LUMO gaps computed for both clusters are consistent with their thermodynamic stability. Natural bond order calculations predict the absence of metal-metal bonding interaction.

75 FR 16513 - B&C Corporation, JR Engineering Division, Including B&C Distribution Center, Including On-Site...

Science.gov (United States)

2010-04-01

... Engineering Division, Including B&C Distribution Center, Including On-Site Leased Workers From B&C Services... occurred during the relevant time period at the B&C Distribution Center, Inc. of the B&C Corporation, JR Engineering Division, Barberton, Ohio. The B&C Distribution Center provides distribution and logistical...

Electron densities and chemical bonding in TiC, TiN and TiO derived from energy band calculations

International Nuclear Information System (INIS)

Blaha, P.

1983-10-01

It was the aim of this paper to describe the chemical bonding of TiC, TiN and TiO by means of energy bands and electron densities. Using the respective potentials we have calculated the bandstructure of a finer k-grid with the linearized APW method to obtain accurate densities of states (DOS). These DOS wer partitioned into local partial contributions and the metal d DOS were further decomposed into tsub(2g) and esub(g) symmetry components in order to additionally characterize bonding. The electron densities corresponding to the occupied valence states are obtained from the LAPW calculations. They provide further insight into characteristic trends in the series from TiC to TiO: around the nonmetal site the density shows increasing localisation; around the metal site the deviation from spherical symmetry changes from esub(g) to tsub(2g). Electron density plots of characteristic band states allow to describe different types of bonding occurring in these systems. For TiC and TiN recent measurements of the electron densities exist for samples of TiCsub(0.94) and TiNsub(0.99), where defects cause static displacements of the Ti atoms. If this effect can be compensated by an atomic model one hopefully can extrapolate to stoichiometric composition. This procedure allows a comparison with structure factors derived from theoretical electron densities. The agreement for TiN is very good. For TiC the extrapolated data agree in terms of the deviations from spherical symmetry near the Ti site with the LAPW data, but the densities around both atoms are more localized than in theory. An explanation could be: a) the defects affect the electronic structure in TiCsub(0.94) with respect to TiCsub(1.0): b) the applied atomic model does not properly extrapolate to stoichiometry, because parameters of this model correlate or become unphysical. (Author)

Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water.

Science.gov (United States)

Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

2014-11-24

Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000 h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density functional theory study of the structural and bonding mechanism of molecular oxygen (O2) with C3Si

Science.gov (United States)

Parida, Saroj K.; Behera, C.; Sahu, Sridhar

2018-07-01

The investigations of pure and heteroatom doped carbon clusters have created great interest because of their enormous prospective applications in various research zones, for example, optoelectronics, semiconductors, material science, energy storage devices, astro-science and so on. In this article, the interaction of molecular oxygen (O2) with C3Si has explored within a density functional theory (DFT). Different possible types of structure for C3SiO2 have collected. Among five different kinds of structure, the structure-1a, 1A1 is more energetically stable. The nature of the bonding of O2 and C3Si, in C3SiO2 has been studied by using Bader's topological analysis of the electron charge density distribution ρ(r) , Laplacian ∇2 ρ(r) and total energy density H(r) at the bond critical points (BCPs) of the structures within the framework of the atoms in molecules theory (AIM). The bonding mechanism of O2 and C3Si in C3SiO2 prompts to the fundamental understanding of the interaction of C3Si with oxygen molecule. It is interesting to note that, two types of bonding mechanism are established in same C3SiO2 system such as (i) shared-kind interactions (ii) closed-shell interactions. From various kinds of structure, Csbnd C bonds in all structures are shown as shared-kind interactions whereas Csbnd Si, Osbnd O bonds are classified as closed-shell type interactions with a certain degree of covalent character.

Characterisation of the aqueous corrosion process in NdFeB melt spun ribbon and MQI bonded magnets

Science.gov (United States)

McCain, Stephen

A major factor limiting the use and longevity of rare earth based magnetic materials is their susceptibility to aqueous corrosion and associated detrimental effects upon the magnetic properties of the material. This process was investigated through a combination of exposure to simulated environmental conditions and hydrogen absorption/desorption studies (HADS) in conjunction with magnetic characterisation. This study utilises NdFeB MQP-B melt-spun ribbon manufactured by Magnequench, in the form of MQI bonded magnets and also in its unbonded state as MQ powder. Specifically, it was concerned with how effective a variety of bonding media (epoxy resin,PTFE, zinc) and surface coatings (PTFE, Qsil, zinc LPPS, Dex-Cool) were at limiting the impact of aqueous corrosion in MQI bonded magnets. To characterise the effect of hydrogen absorption upon the magnetic properties of the MQP-B, hydrogen uptake was induced followed by a series of outgassing heat treatments with subsequent magnetic characterisation accompanied by HADS techniques performed after each outgas. This allowed comparisons to be made between the effects of aqueous corrosion process and hydrogen absorption upon the magnetic properties of the alloy.. This study has clearly demonstrated the link between the abundance of environmental moisture and rate of Hci losses in MQI bonded magnets. In addition to this the key mechanism responsible for the degradation of magnetic properties has been identified. These losses have been attributed to the absorption of hydrogen generated by the dissociation of water in the presence of NdFeB during the aqueous corrosion process. It has been shown that the use of a bonding media that is impermeable to water can limit the effects of aqueous corrosion by limiting water access to the Magnequench particles (MQP) and also the positive effects of the use of suitable surface coatings has been shown to be effective for the same reason..

Direct, CMOS In-Line Process Flow Compatible, Sub 100 °C Cu-Cu Thermocompression Bonding Using Stress Engineering

Science.gov (United States)

Panigrahi, Asisa Kumar; Ghosh, Tamal; Kumar, C. Hemanth; Singh, Shiv Govind; Vanjari, Siva Rama Krishna

2018-03-01

Diffusion of atoms across the boundary between two bonding layers is the key for achieving excellent thermocompression Wafer on Wafer bonding. In this paper, we demonstrate a novel mechanism to increase the diffusion across the bonding interface and also shows the CMOS in-line process flow compatible Sub 100 °C Cu-Cu bonding which is devoid of Cu surface treatment prior to bonding. The stress in sputtered Cu thin films was engineered by adjusting the Argon in-let pressure in such a way that one film had a compressive stress while the other film had tensile stress. Due to this stress gradient, a nominal pressure (2 kN) and temperature (75 °C) was enough to achieve a good quality thermocompression bonding having a bond strength of 149 MPa and very low specific contact resistance of 1.5 × 10-8 Ω-cm2. These excellent mechanical and electrical properties are resultant of a high quality Cu-Cu bonding having grain growth between the Cu films across the boundary and extended throughout the bonded region as revealed by Cross-sectional Transmission Electron Microscopy. In addition, reliability assessment of Cu-Cu bonding with stress engineering was demonstrated using multiple current stressing and temperature cycling test, suggests excellent reliable bonding without electrical performance degradation.

Direct, CMOS In-Line Process Flow Compatible, Sub 100 °C Cu-Cu Thermocompression Bonding Using Stress Engineering

Science.gov (United States)

Panigrahi, Asisa Kumar; Ghosh, Tamal; Kumar, C. Hemanth; Singh, Shiv Govind; Vanjari, Siva Rama Krishna

2018-05-01

Diffusion of atoms across the boundary between two bonding layers is the key for achieving excellent thermocompression Wafer on Wafer bonding. In this paper, we demonstrate a novel mechanism to increase the diffusion across the bonding interface and also shows the CMOS in-line process flow compatible Sub 100 °C Cu-Cu bonding which is devoid of Cu surface treatment prior to bonding. The stress in sputtered Cu thin films was engineered by adjusting the Argon in-let pressure in such a way that one film had a compressive stress while the other film had tensile stress. Due to this stress gradient, a nominal pressure (2 kN) and temperature (75 °C) was enough to achieve a good quality thermocompression bonding having a bond strength of 149 MPa and very low specific contact resistance of 1.5 × 10-8 Ω-cm2. These excellent mechanical and electrical properties are resultant of a high quality Cu-Cu bonding having grain growth between the Cu films across the boundary and extended throughout the bonded region as revealed by Cross-sectional Transmission Electron Microscopy. In addition, reliability assessment of Cu-Cu bonding with stress engineering was demonstrated using multiple current stressing and temperature cycling test, suggests excellent reliable bonding without electrical performance degradation.

Low-temperature neutron structure determinations of a series of scorpionate complexes of molybdenum containing B sbnd H sbnd Mo agostic bonds

Science.gov (United States)

Piccoli, Paula M. B.; Cowan, John A.; Schultz, Arthur J.; Koetzle, Thomas F.; Yap, Glenn P. A.; Trofimenko, Swiatoslaw

2008-11-01

The structures of four dihydrobis(pyrazol-1-yl)borate (Bp) complexes of molybdenum have been determined at low temperature by single crystal neutron diffraction in order to accurately characterize the three-center B sbnd H sbnd Mo agostic bonding. The B sbnd H1A (agostic) distance is found to be elongated by about 0.05-0.08 Å compared to the B sbnd H1B distance (not agostically bound to the metal center). This systematic study of a series of molecules with different substituents on the Bp ligand permits us to examine the effects of electronic and steric factors on the overall structure and bonding, and particularly on the agostic bond. It is observed that a closer approach of H1A to Mo leads to a longer trans-Mo sbnd CO bond distance, analogous to the trans hydride structural effect in hydride complexes. In addition Fenske-Hall calculations were performed on these complexes, and the results are reported herein.

Reconstitution of nucleotide excision nuclease with UvrA and UvrB proteins from Escherichia coli and UvrC protein from Bacillus subtilis

International Nuclear Information System (INIS)

Lin, J.J.; Sancar, A.

1990-01-01

Recently, an open reading frame which has a deduced amino acid sequence that shows 38% homology to Escherichia coli UvrC protein was found upstream of the aspartokinase II gene (ask) in Bacillus subtilis. We found that plasmids containing this open reading frame complement the uvrC mutations in E. coli. We joined the open reading frame to a tac promoter to amplify the gene product in E. coli and purified the protein to near homogeneity. The apparent molecular weight of the gene product is 69,000, which is consistent with the calculated molecular weight of 69,378 fro the deduced gene product of the open reading frame. The purified gene product causes the nicking of DNA at the 8th phosphodiester bond 5' and the 5th phosphodiester bond 3' to a thymine dimer when mixed with E. coli UvrA and UvrB proteins and a DNA substrate containing a uniquely located thymine dimer. We conclude that the gene product of the open reading frame is the B. subtilis UvrC protein. Our results suggest that the B. subtilis nucleotide excision repair system is quite similar to that of E. coli. Furthermore, complementation of the UvrA and UvrB proteins from a Gram-negative bacterium with the UvrC protein of Gram-positive B. subtilis indicates a significant evolutionary conservation of the nucleotide excision repair system

Millimeter-wave spectroscopy of CrC (X(3)Σ(-)) and CrCCH (X̃ (6)Σ(+)): Examining the chromium-carbon bond.

Science.gov (United States)

Min, J; Ziurys, L M

2016-05-14

Pure rotational spectroscopy of the CrC (X(3)Σ(-)) and CrCCH (X̃ (6)Σ(+)) radicals has been conducted using millimeter/sub-millimeter direct absorption methods in the frequency range 225-585 GHz. These species were created in an AC discharge of Cr(CO)6 and either methane or acetylene, diluted in argon. Spectra of the CrCCD were also recorded for the first time using deuterated acetylene as the carbon precursor. Seven rotational transitions of CrC were measured, each consisting of three widely spaced, fine structure components, arising from spin-spin and spin-rotation interactions. Eleven rotational transitions were recorded for CrCCH and five for CrCCD; each transition in these cases was composed of a distinct fine structure sextet. These measurements confirm the respective (3)Σ(-) and (6)Σ(+) ground electronic states of these radicals, as indicated from optical studies. The data were analyzed using a Hund's case (b) Hamiltonian, and rotational, spin-spin, and spin-rotation constants have been accurately determined for all three species. The spectroscopic parameters for CrC were significantly revised from previous optical work, while those for CrCCH are in excellent agreement; completely new constants were established for CrCCD. The chromium-carbon bond length for CrC was calculated to be 1.631 Å, while that in CrCCH was found to be rCr-C = 1.993 Å - significantly longer. This result suggests that a single Cr-C bond is present in CrCCH, preserving the acetylenic structure of the ligand, while a triple bond exists in CrC. Analysis of the spin constants suggests that CrC has a nearby excited (1)Σ(+) state lying ∼16 900 cm(-1) higher in energy, and CrCCH has a (6)Π excited state with E ∼ 4800 cm(-1).

Core-level photoabsorption study of defects and metastable bonding configurations in boron nitride

Energy Technology Data Exchange (ETDEWEB)

Jimenez, I.; Jankowski, A.F.; Terminello, L.J. [Lawrence Berkeley National Lab., CA (United States)] [and others

1997-04-01

Boron nitride is an interesting material for technological applications and for fundamental solid state physics investigations. It is a compound isoelectronic with carbon and, like carbon can possess sp{sup 2} and sp{sup 3} bonded phases resembling graphite and diamond. BN crystallizes in the sp{sup 2}-bonded hexagonal (h-BN), rhombohedral (r-BN) and turbostratic phases, and in the sp{sup 3}-bonded cubic (c-BN) and wurtzite (w-BN) phases. A new family of materials is obtained when replacing C-C pairs in graphite with isoelectronic B-N pairs, resulting in C{sub 2}BN compounds. Regarding other boron compounds, BN is exceptional in the sense that it has standard two-center bonds with conventional coordination numbers, while other boron compounds (e.g. B{sub 4}C) are based on the boron icosahedron unit with three-center bonds and high coordination numbers. The existence of several allotropic forms and fullerene-like structures for BN suggests a rich variety of local bonding and poses the questions of how this affects the local electronic structure and how the material accommodates the stress induced in the transition regions between different phases. One would expect point defects to play a crucial role in stress accommodation, but these must also have a strong influence in the electronic structure, since the B-N bond is polar and a point defect will thus be a charged structure. The study of point defects in relationship to the electronic structure is of fundamental interest in these materials. Recently, the authors have shown that Near-Edge X-ray Absorption Fine Structure (NEXAFS) is sensitive to point defects in h-BN, and to the formation of metastable phases even in amorphous materials. This is significant since other phase identification techniques like vibrational spectroscopies or x-ray diffraction yield ambiguous results for nanocrystalline and amorphous samples. Serendipitously, NEXAFS also combines chemical selectivity with point defect sensitivity.

In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

Science.gov (United States)

Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

2012-03-20

The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

rac-[2-(Dicyclohexylphosphanylphenyl](phenylphosphinic diisopropylamide–borane hemihydrate

Directory of Open Access Journals (Sweden)

Stephen J. Evans

2013-02-01

Full Text Available In the title compound, C30H48BNOP2·0.5H2O, the water molecule is disordered about an inversion centre. Both phosphorus atoms shows distortions in their tetrahedral environments with the cyclohexyl substituents disordered over two orientations in a 0.851 (3:0.149 (3 occupancy ratio. The crystal structure is assembled via O—H...O interactions between pairs of phosphininc amide molecules and water molecules, creating hydrogen-bonded dimers with graph-set R24(8 along [001]. Weak C—H...O interactions are also observed.

Influence of Pressure on Physical Property of Ammonia Borane and its Re-hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Chen, Jiuhua [Florida Intl Univ., Miami, FL (United States)

2015-08-14

The project systematically studied the high pressure behavior of ammonia borane and its derivative lithium amidoborane. Phase transitions in these materials are investigated in the pressure range up to 20 GPa and temperature range from 80 K to 400K. A number of new phase transitions are discovered in this pressure and temperature range including a second order transformation at 5 GPa and a first order transformation at 12 GPa at room temperature, and four new transitions at high pressure and low temperatures. The Clapeyron slopes for both pressure-induce tetragonal (I4mm) phase to orthorhombic (Cmc21) phase and temperature-induce tetragonal (I4mm) phase to orthorhombic (Pmn21) phase are determined to be positive, indicating these phase transitions are exothermic. This result demonstrates that the high pressure orthorhombic phase of ammonia borane has lower enthalpy than that of tetragonal phase at ambient conditions. If we assume decomposition from the orthorhombic phase yields the same products as that from the tetragonal phase, the decomposition of the orthorhombic phase will be less exothermic. Therefore rehydrogenation from the decomposed product into the orthorhombic phase at high pressure may become easier. The project also studied the influences of nanoconfinement on the phase transitions. Comparative study using Raman spectroscopy indicates that the temperature induced I4mm to Pmn21 transition is suppressed from 217 K to 195 K when the sample is confined in SBA15 (7-9 nm pore size). When the pore size is reduced from 7-9 nm to 3-4 nm, this transition is totally suppressed in the temperature down to 80 K. A similar influence of the nanoconfiement on pressure induced phase transitions is also observed using Raman spectroscopy. The phase boundary between the I4mm phase and high pressure Cmc21 phase at ambient temperature shifts from 0.9 GPa to 0.5 GPa; and that between the Cmc21 phase and higher pressure P21 phase shifts from 10.2 GPa to 9.7 GPa.

Development and Performance Evaluations of HfO2-Si and Rare Earth-Si Based Environmental Barrier Bond Coat Systems for SiC/SiC Ceramic Matrix Composites

Science.gov (United States)

Zhu, Dongming

2014-01-01

Ceramic environmental barrier coatings (EBC) and SiCSiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft propulsion systems because of their ability to significantly increase engine operating temperatures, improve component durability, reduce engine weight and cooling requirements. Advanced EBC systems for SiCSiC CMC turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant material development challenges for the high temperature CMC components is to develop prime-reliant, high strength and high temperature capable environmental barrier coating bond coat systems, since the current silicon bond coat cannot meet the advanced EBC-CMC temperature and stability requirements. In this paper, advanced NASA HfO2-Si based EBC bond coat systems for SiCSiC CMC combustor and turbine airfoil applications are investigated. The coating design approach and stability requirements are specifically emphasized, with the development and implementation focusing on Plasma Sprayed (PS) and Electron Beam-Physic Vapor Deposited (EB-PVD) coating systems and the composition optimizations. High temperature properties of the HfO2-Si based bond coat systems, including the strength, fracture toughness, creep resistance, and oxidation resistance were evaluated in the temperature range of 1200 to 1500 C. Thermal gradient heat flux low cycle fatigue and furnace cyclic oxidation durability tests were also performed at temperatures up to 1500 C. The coating strength improvements, degradation and failure modes of the environmental barrier coating bond coat systems on SiCSiC CMCs tested in simulated stress-environment interactions are briefly discussed and supported by modeling. The performance enhancements of the HfO2-Si bond coat systems with rare earth element dopants and rare earth-silicon based bond coats are also highlighted. The advanced bond coat systems, when

Phase Behavior of Binary Blends of AB+AC Block Copolymers with compatible B and C blocks

Science.gov (United States)

Pryamitsyn, Victor; Ganesan, Venkat

2012-02-01

Recently the experimental studies of phase behavior of binary blends of PS-b-P2VP and PS-b-PHS demonstrated an interesting effect: blends of symmetric PS-b-P2VP and shorter symmetric (PS-b-PHS) formed cylindrical HEX and spherical BCC phases, while each pure component formed lamellas. The miscibility of P2VP and PHS is caused by the hydrogen bonding between P2VP and PHS,which can be described as a negative Flory ?-parameter between P2VP and PHS. We developed a theory of the microphase segregation of AB+AC blends of diblock copolymers based on strong stretching theory. The main result of our theory is that in the copolymer brush-like layer formed by longer B chain and shorter C chains, the attraction between B and shorter C chains causes relative stretching of short C chains and compression of longer B chains. The latter manifests in an excessive bending force towards the grafting surface (BC|AA interface). Such bending force causes a transition from a symmetric lamella phase to a HEX cylinder or BCC spherical phases with the BC phase being a ``matrix'' component. In a blend of asymmetric BCC sphere forming copolymers (where B and C segments are the minor components), such bending force may unfold BCC spherical phase to a HEX cylinder phase, or even highly uneven lamella phases.

Analyzing velocity map images to distinguish the primary methyl photofragments from those produced upon C-Cl bond photofission in chloroacetone at 193 nm

Science.gov (United States)

Alligood, Bridget W.; Straus, Daniel B.; Butler, Laurie J.

2011-07-01

We use a combination of crossed laser-molecular beam scattering experiments and velocity map imaging experiments to investigate the three primary photodissociation channels of chloroacetone at 193 nm: C-Cl bond photofission yielding CH3C(O)CH2 radicals, C-C bond photofission yielding CH3CO and CH2Cl products, and C-CH3 bond photofission resulting in CH3 and C(O)CH2Cl products. Improved analysis of data previously reported by our group quantitatively identifies the contribution of this latter photodissociation channel. We introduce a forward convolution procedure to identify the portion of the signal, derived from the methyl image, which results from a two-step process in which C-Cl bond photofission is followed by the dissociation of the vibrationally excited CH3C(O)CH2 radicals to CH3 + COCH2. Subtracting this from the total methyl signal identifies the methyl photofragments that result from the CH3 + C(O)CH2Cl photofission channel. We find that about 89% of the chloroacetone molecules undergo C-Cl bond photofission to yield CH3C(O)CH2 and Cl products; approximately 8% result in C-C bond photofission to yield CH3CO and CH2Cl products, and the remaining 2.6% undergo C-CH3 bond photofission to yield CH3 and C(O)CH2Cl products.

Ruthenium(II)-catalyzed synthesis of pyrrole- and indole-fused isocoumarins by C-H bond activation in DMF and water

Digital Repository Service at National Institute of Oceanography (India)

Singh, K.S.; Sawant, S.G.; Dixneuf, P.H.

stream_size 26907 stream_content_type text/plain stream_name ChemCatChem_8_1046a.pdf.txt stream_source_info ChemCatChem_8_1046a.pdf.txt Content-Encoding UTF-8 Content-Type text/plain; charset=UTF-8 Author version...: ChemCatChem, vol.8(6); 2016; 1046-1050 Ruthenium(II) catalysed synthesis of pyrrole and indole fused isocoumarins via C-H bond activation in DMF and water† Keisham S. Singh*,a Sneha G. Sawanta, Pierre H. Dixneuf*,b Abstract: Pyrrole and indole...

26 CFR 48.4061(a)-2 - Bonding of importers.

Science.gov (United States)

2010-04-01

... or stocks, or by bonds issued by a State or political subdivision thereof, of recognized stability... given. (b) The model number of each such article. (c) The name and address of the importer of such...

P-wave excited {B}_{c}^{* * } meson photoproduction at the LHeC

Science.gov (United States)

Kai, He; Huan-Yu, Bi; Ren-You, Zhang; Xiao-Zhou, Li; Wen-Gan, Ma

2018-05-01

As an important sequential work of the S-wave {B}c(* ) ({}1{S}0({}3{S}1) ) meson production at the large hadron electron collider (LHeC), we investigate the production of the P-wave excited {B}c* * states (1 P 1 and 3 P J with J = 0, 1, 2) via photoproduction mechanism within the framework of nonrelativistic QCD at the LHeC. Generally, the {e}-+P\\to γ +g\\to {B}c* * +b+\\bar{c} process is considered as the main production mechanism at an electron–proton collider due to the large luminosity of the gluon. However, according to our experience on the S-wave {B}c(* ) meson production at the LHeC, the extrinsic production mechanism, i.e., {e}-+P\\to γ +c\\to {B}c* * +b and {e}-+P\\to γ +\\bar{b} \\to {B}c* * +\\bar{c}, could also provide dominating contributions at low p T region. A careful treatment between these channels is performed and the results on total and differential cross sections, together with main uncertainties are discussed. Taking the quark masses m b = 4.90 ± 0.40 GeV and m c = 1.50 ± 0.20 GeV into account and summing up all the production channels, we expect to accumulate ({2.48}-1.75+3.55)× {10}4 {B}c* * ({}1{P}1), ({1.14}-0.82+1.49)× {10}4 {B}c* * ({}3{P}0),({2.38}-1.74+3.39)× {10}4 {B}c* * ({}3{P}1) and ({5.59}-3.93+7.84)× {10}4 {B}c* * ({}3{P}2) events at the \\sqrt{S}=1.30 {{T}}{{e}}{{V}} LHeC in one operation year with luminosity { \\mathcal L }={10}33 cm‑2 s‑1. With such sizable events, it is worth studying the properties of excited P-wave {B}c* * states at the LHeC.

Hot pressing of B4C/SiC composites

International Nuclear Information System (INIS)

Sahin, F.C.; Turhan, E.; Yesilcubuk, S.A.; Addemir, O.

2005-01-01

B 4 C/SiC ceramic composites containing 10-20-30 vol % SiC were prepared by hot pressing method. The effect of SiC addition and hot pressing temperature on sintering behaviour and mechanical properties of hot pressed composites were investigated. Microstructures of hot pressed samples were examined by SEM technique. Three different temperatures (2100 deg. C, 2200 deg. C and 2250 deg. C) were used to optimize hot pressing temperature applying 100 MPa pressure under argon atmosphere during the sintering procedure. The highest relative density of 98.44 % was obtained by hot pressing at 2250 deg. C. However, bending strengths of B 4 C/SiC composite samples were lower than monolithic B 4 C in all experimental conditions. (authors)