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Sample records for boranes

  1. Numerical Sequence of Borane Series

    Directory of Open Access Journals (Sweden)

    Enos Masheija Kiremire

    2014-09-01

    Full Text Available A table of hydroborane families has been created. The table links boranes of different families(homologous series and members of the same family based on k number. The table is useful deducing straight away whether a borane( molecular formula is closo, nido or arachno or something else. The table also indicates that boranes are formed according to natural periodic function (arithmetical progression. The empirical formula utilized is extremely versatile, simple and based on the principle of Nobel gas configuration. It could be used in both simple and complex boranes and carboranes. The closo members which portray characteristic shapes also have characteristic k1 numbers.

  2. 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.

  3. 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.

  4. Method for releasing hydrogen from ammonia borane

    Science.gov (United States)

    Varma, Arvind; Diwan, Moiz; Shafirovich, Evgeny; Hwang, Hyun-Tae; Al-Kukhun, Ahmad

    2013-02-19

    A method of releasing hydrogen from ammonia borane is disclosed. The method comprises heating an aqueous ammonia borane solution to between about 80-135.degree. C. at between about 14.7 and 200 pounds per square inch absolute (psia) to release hydrogen by hydrothermolysis.

  5. Hydrazine borane-induced destabilization of ammonia borane, and vice versa

    Energy Technology Data Exchange (ETDEWEB)

    Petit, Jean-Fabien; Moussa, Georges [IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM2), Universite Montpellier 2, Place E. Bataillon, F-34095 Montpellier (France); Demirci, Umit B., E-mail: umit.demirci@um2.fr [IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM2), Universite Montpellier 2, Place E. Bataillon, F-34095 Montpellier (France); Toche, François; Chiriac, Rodica [Université Lyon 1, CNRS, UMR 5615, Laboratoire des Multimatériaux et Interfaces, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne (France); Miele, Philippe [IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM2), Universite Montpellier 2, Place E. Bataillon, F-34095 Montpellier (France)

    2014-08-15

    Graphical abstract: - Highlights: • Hydrazine borane and ammoniaborane (mole ratio 1:1) destabilize each other. • This is characterized by a melting point at ∼30 °C and decomposition into hydrazine. • Also, some hydrogen H{sub 2} is “explosively” liberated at around 90 °C. • The mixture can be however stabilized into a potential hydrogen storage material. • This hydrogen storage material dehydrogenates up to 300 °C to form boron nitride. - Abstract: In the field of solid-state chemical hydrogen storage, ammonia borane NH{sub 3}BH{sub 3} has been widely studied while hydrazine borane N{sub 2}H{sub 4}BH{sub 3} can be considered as a “novel” material. In the present work, we investigated the behaviour of these boranes when mixed together in a mole ratio of 1:1. Hydrazine borane and ammonia borane destabilize each other. Though stable at 20–25 °C, the mixture melts at ∼30 °C and then undergoes significant decomposition, with desorption of hydrogen H{sub 2} and hydrazine N{sub 2}H{sub 4} from 67 °C. This is explained by the fact that the presence of hydrazine borane disrupts the H{sup δ+}⋯H{sup δ−} network of ammonia borane, and vice versa; the mixture is then much less stable than the pristine boranes. The mixture can nevertheless be stabilized (by heat- or vacuum-treatment and thus extraction of evolving hydrogen and hydrazine), making the as-obtained solid a potential chemical hydrogen storage material. Over the range 25–300 °C, it is able to release ca. 11.4 wt% of almost pure H{sub 2}. Furthermore forms boron nitride as the solid residue, at temperatures as low as 300 °C.

  6. Catalytic dehydrogenation of amine borane complexes

    Science.gov (United States)

    Mohajeri, Nahid (Inventor); Tabatabaie-Raissi, Ali (Inventor); Bokerman, Gary (Inventor)

    2009-01-01

    A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

  7. Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hawthorne, M. Frederick; Jalisatgi, Satish S.; Safronov, Alexander V.; Lee, Han Beak; Wu, Jianguo

    2010-10-01

    Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100% which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum

  8. Ammonia-Borane and Amine-Borane Dehydrogenation Mediated by Complex Metal Hydrides.

    Science.gov (United States)

    Rossin, Andrea; Peruzzini, Maurizio

    2016-08-10

    This review is a comprehensive survey of the last 10 years of research on ammonia-borane and amine-borane dehydrogenation mediated by complex metal hydrides (CMHs), within the broader context of chemical hydrogen storage. The review also collects those cases where CMHs are the catalyst spent form or its resting state. Highlights on the reaction mechanism (strictly dependent on the CMH of choice) and the catalysts efficiency (in terms of equivalents of H2 produced and relative reaction rates) are provided throughout the discussion.

  9. Procedures for the synthesis of ethylenediamine bisborane and ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Ramachandran, Padi Veeraraghavan; Gagare, Pravin D.; Mistry, Hitesh; Biswas, Bidyut

    2017-01-03

    A method for synthesizing ammonia borane includes (a) preparing a reaction mixture in one or more solvents, the reaction mixture containing sodium borohydride, at least one ammonium salt, and ammonia; and (b) incubating the reaction mixture at temperatures between about 0.degree. C. to about room temperature in an ambient air environment under conditions sufficient to form ammonia borane. Methods for synthesizing ethylenediamine bisborane, and methods for dehydrogenation of ethylenediamine bisborane are also described.

  10. 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.

  11. Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

    Directory of Open Access Journals (Sweden)

    Romain Moury

    2015-04-01

    Full Text Available Hydrazine borane N2H4BH3 and alkali derivatives (i.e., lithium, sodium and potassium hydrazinidoboranes MN2H3BH3 with M = Li, Na and K have been considered as potential chemical hydrogen storage materials. They belong to the family of boron- and nitrogen-based materials and the present article aims at providing a timely review while focusing on fundamentals so that their effective potential in the field could be appreciated. It stands out that, on the one hand, hydrazine borane, in aqueous solution, would be suitable for full dehydrogenation in hydrolytic conditions; the most attractive feature is the possibility to dehydrogenate, in addition to the BH3 group, the N2H4 moiety in the presence of an active and selective metal-based catalyst but for which further improvements are still necessary. However, the thermolytic dehydrogenation of hydrazine borane should be avoided because of the evolution of significant amounts of hydrazine and the formation of a shock-sensitive solid residue upon heating at >300 °C. On the other hand, the alkali hydrazinidoboranes, obtained by reaction of hydrazine borane with alkali hydrides, would be more suitable to thermolytic dehydrogenation, with improved properties in comparison to the parent borane. All of these aspects are surveyed herein and put into perspective.

  12. In situ Synchrotron X-ray Thermodiffraction of Boranes

    Directory of Open Access Journals (Sweden)

    Pascal G. Yot

    2016-01-01

    Full Text Available Boranes of low molecular weight are crystalline materials that have been much investigated over the past decade in the field of chemical hydrogen storage. In the present work, six of them have been selected to be studied by in situ synchrotron X-ray thermodiffraction. The selected boranes are ammonia borane NH3BH3 (AB, hydrazine borane N2H4BH3 (HB, hydrazine bisborane N2H4(BH32 (HBB, lithium LiN2H3BH3 (LiHB and sodium NaN2H3BH3 (NaHB hydrazinidoboranes, and sodium triborane NaB3H8 (STB. They are first investigated separately over a wide range of temperature (80–300 K, and subsequently compared. Differences in crystal structures, the existence of phase transition, evolutions of unit cell parameters and volumes, and variation of coefficients of thermal expansion can be observed. With respect to AB, HB and HBB, the differences are mainly explained in terms of molecule size, conformation and motion (degree of freedom of the chemical groups (NH3, N2H4, BH3. With respect to LiHB, NaHB and STB, the differences are explained by a stabilization effect favored by the alkali cations via M···H interactions with four to five borane anions. The main results are presented and discussed herein.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-09-01

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

  14. Quantum Monte Carlo calculations of the dimerization energy of borane.

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    Fracchia, Francesco; Bressanini, Dario; Morosi, Gabriele

    2011-09-07

    Accurate thermodynamic data are required to improve the performance of chemical hydrides that are potential hydrogen storage materials. Boron compounds are among the most interesting candidates. However, different experimental measurements of the borane dimerization energy resulted in a rather wide range (-34.3 to -39.1) ± 2 kcal/mol. Diffusion Monte Carlo (DMC) simulations usually recover more than 95% of the correlation energy, so energy differences rely less on error cancellation than other methods. DMC energies of BH(3), B(2)H(6), BH(3)CO, CO, and BH(2)(+) allowed us to predict the borane dimerization energy, both via the direct process and indirect processes such as the dissociation of BH(3)CO. Our D(e) = -43.12(8) kcal/mol, corrected for the zero point energy evaluated by considering the anharmonic contributions, results in a borane dimerization energy of -36.59(8) kcal/mol. The process via the dissociation of BH(3)CO gives -34.5(2) kcal/mol. Overall, our values suggest a slightly less D(e) than the most recent W4 estimate D(e) = -44.47 kcal/mol [A. Karton and J. M. L. Martin, J. Phys. Chem. A 111, 5936 (2007)]. Our results show that reliable thermochemical data for boranes can be predicted by fixed node (FN)-DMC calculations.

  15. Transition metal catalysed ammonia-borane dehydrogenation in ionic liquids.

    Science.gov (United States)

    Wright, William R H; Berkeley, Emily R; Alden, L R; Baker, R Tom; Sneddon, Larry G

    2011-03-21

    Significant advantages result from combining the disparate hydrogen release pathways for ammonia-borane (AB) dehydrogenation using ionic liquids (ILs) and transition metal catalysts. With the RuCl(2)(PMe(3))(4) catalyst precursor, AB dehydrogenation selectivity and extent are maximized in an IL with a moderately coordinating ethylsulfate anion.

  16. Borane-substituted imidazol-2-ylidenes: syntheses in vacuo.

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    Taylor, Alasdair W; Lovelock, Kevin R J; Jones, Robert G; Licence, Peter

    2011-02-21

    The serendipitous discovery of an efficient reactive distillation is reported. Two borane-substituted imidazol-2-ylidenes have been prepared in high yield from precursor tetrafluoroborate derived room temperature ionic liquids by reactive distillation at T > 500 K and p < 1 × 10(-4) mbar.

  17. The roles of dihydrogen bonds in amine borane chemistry.

    Science.gov (United States)

    Chen, Xuenian; Zhao, Ji-Cheng; Shore, Sheldon G

    2013-11-19

    A dihydrogen bond (DHB) is an electrostatic interaction between a protonic hydrogen and a hydridic hydrogen. Over the past two decades, researchers have made significant progress in the identification and characterization of DHBs and their properties. In comparison with conventional hydrogen bonds (HBs), which have been widely used in catalysis, molecular recognition, crystal engineering, and supramolecular synthesis, chemists have only applied DHBs in very limited ways. Considering that DHBs and conventional HBs have comparable strength, DHBs could be more widely applied in chemistry. Over the past several years, we have explored the impact of DHBs on amine borane chemistry and the syntheses and characterization of amine boranes and ammoniated metal borohydrides for hydrogen storage. Through systematic computational and experimental investigations, we found that DHBs play a dominant role in dictating the reaction pathways (and thus different products) of amine boranes where oppositely charged hydrogens coexist for DHB formation. Through careful experiments, we observed, for the first time, a long-postulated reaction intermediate, ammonia diborane (AaDB), whose behavior is essential to mechanistic understanding of the formation of the diammoniate of diborane (DADB) in the reaction of ammonia (NH3) with tetrahydrofuran borane (THF·BH3). The formation of DADB has puzzled the boron chemistry community for decades. Mechanistic insight enabled us to develop facile syntheses of aminodiborane (ADB), ammonia borane (AB), DADB, and an inorganic butane analog NH3BH2NH2BH3 (DDAB). Our examples, together with those in the literature, reinforce the fact that DHB formation and subsequent molecular hydrogen elimination are a viable approach for creating new covalent bonds and synthesizing new materials. We also review the strong effects of DHBs on the stability of conformers and the hydrogen desorption temperatures of boron-nitrogen compounds. We hope that this Account will

  18. 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.

  19. Polymers containing borane or carborane cage compounds and related applications

    Science.gov (United States)

    Bowen, III, Daniel E; Eastwood, Eric A

    2013-04-23

    Polymers comprising residues of cage compound monomers having at least one polyalkoxy silyl substituent are provided. The cage compound monomers are selected from borane cage compound monomers comprising at least 7 cage atoms and/or carborane cage compound monomers comprising 7 to 11 cage compound monomers. Such polymers can further comprise one or more reactive matrices and/or co-monomers covalently bound with the cage compound monomer residues. Articles of manufacture comprising such polymers are also disclosed.

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

    Science.gov (United States)

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

    2016-01-01

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

  1. 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.

  2. Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride.

    Science.gov (United States)

    Rajendran, Kamalraj V; Gilheany, Declan G

    2012-01-21

    A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.

  3. Ruthenium-Catalyzed Ammonia Borane Dehydrogenation: Mechanism and Utility.

    Science.gov (United States)

    Zhang, Xingyue; Kam, Lisa; Trerise, Ryan; Williams, Travis J

    2017-01-17

    One of the greatest challenges in using H2 as a fuel source is finding a safe, efficient, and inexpensive method for its storage. Ammonia borane (AB) is a solid hydrogen storage material that has garnered attention for its high hydrogen weight density (19.6 wt %) and ease of handling and transport. Hydrogen release from ammonia borane is mediated by either hydrolysis, thus giving borate products that are difficult to rereduce, or direct dehydrogenation. Catalytic AB dehydrogenation has thus been a popular topic in recent years, motivated both by applications in hydrogen storage and main group synthetic chemistry. This Account is a complete description of work from our laboratory in ruthenium-catalyzed ammonia borane dehydrogenation over the last 6 years, beginning with the Shvo catalyst and resulting ultimately in the development of optimized, leading catalysts for efficient hydrogen release. We have studied AB dehydrogenation with Shvo's catalyst extensively and generated a detailed understanding of the role that borazine, a dehydrogenation product, plays in the reaction: it is a poison for both Shvo's catalyst and PEM fuel cells. Through independent syntheses of Shvo derivatives, we found a protective mechanism wherein catalyst deactivation by borazine is prevented by coordination of a ligand that might otherwise be a catalytic poison. These studies showed how a bidentate N-N ligand can transform the Shvo into a more reactive species for AB dehydrogenation that minimizes accumulation of borazine. Simultaneously, we designed novel ruthenium catalysts that contain a Lewis acidic boron to replace the Shvo -OH proton, thus offering more flexibility to optimize hydrogen release and take on more general problems in hydride abstraction. Our scorpionate-ligated ruthenium species (12) is a best-of-class catalyst for homogeneous dehydrogenation of ammonia borane in terms of its extent of hydrogen release (4.6 wt %), air tolerance, and reusability. Moreover, a synthetically

  4. Syntheses and structural characterizations of anionic borane-capped ammonia borane oligomers: evidence for ammonia borane H2 release via a base-promoted anionic dehydropolymerization mechanism.

    Science.gov (United States)

    Ewing, William C; Marchione, Allegra; Himmelberger, Daniel W; Carroll, Patrick J; Sneddon, Larry G

    2011-10-26

    Studies of the activating effect of Verkade's base, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (VB), on the rate and extent of H(2) release from ammonia borane (AB) have led to the syntheses and structural characterizations of three anionic aminoborane chain-growth products that provide direct support for anionic dehydropolymerization mechanistic steps in the initial stages of base-promoted AB H(2) release reactions. The salt VBH(+)[H(3)BNH(2)BH(2)NH(2)BH(3)](-) (1) containing a linear five-membered anionic aminoborane chain was produced in 74% yield via the room-temperature reaction of a 3:1 AB/VB mixture in fluorobenzene solvent, while the branched and linear-chain seven-membered anionic aminoborane oligomers VBH(+)[HB(NH(2)BH(3))(3)](-) (2a) and VBH(+)[H(3)BNH(2)BH(2)NH(2)BH(2)NH(2)BH(3)](-) (2b) were obtained from VB/AB reactions carried out at 50 °C for 5 days when the AB/VB ratio was increased to 4:1. X-ray crystal structure determinations confirmed that these compounds are the isoelectronic and isostructural analogues of the hydrocarbons n-pentane, 3-ethylpentane, and n-heptane, respectively. The structural determinations also revealed significant interionic B-H···H-N dihydrogen-bonding interactions in these anions that could enhance dehydrocoupling chain-growth reactions. Such mechanistic pathways for AB H(2) release, involving the initial formation of the previously known [H(3)BNH(2)BH(3)](-) anion followed by sequential dehydrocoupling of B-H and H-N groups of growing borane-capped aminoborane anions with AB, are supported by the fact that 1 was observed to react with an additional AB equivalent to form 2a and 2b.

  5. Ruthenium nanoparticles confined in SBA-15 as highly efficient catalyst for hydrolytic dehydrogenation of ammonia borane and hydrazine borane

    Science.gov (United States)

    Yao, Qilu; Lu, Zhang-Hui; Yang, Kangkang; Chen, Xiangshu; Zhu, Meihua

    2015-10-01

    Ultrafine ruthenium nanoparticles (NPs) within the mesopores of the SBA-15 have been successfully prepared by using a “double solvents” method, in which n-hexane is used as a hydrophobic solvent and RuCl3 aqueous solution is used as a hydrophilic solvent. After the impregnation and reduction processes, the samples were characterized by XRD, TEM, EDX, XPS, N2 adsorption-desorption, and ICP techniques. The TEM images show that small sized Ru NPs with an average size of 3.0 ± 0.8 nm are uniformly dispersed in the mesopores of SBA-15. The as-synthesized Ru@SBA-15 nanocomposites (NCs) display exceptional catalytic activity for hydrogen generation by the hydrolysis of ammonia borane (NH3BH3, AB) and hydrazine borane (N2H4BH3, HB) at room temperature with the turnover frequency (TOF) value of 316 and 706 mol H2 (mol Ru min)-1, respectively, relatively high values reported so far for the same reaction. The activation energies (Ea) for the hydrolysis of AB and HB catalyzed by Ru@SBA-15 NCs are measured to be 34.8 ± 2 and 41.3 ± 2 kJ mol-1, respectively. Moreover, Ru@SBA-15 NCs also show satisfied durable stability for the hydrolytic dehydrogenation of AB and HB, respectively.

  6. Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride

    OpenAIRE

    2012-01-01

    A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.

  7. Kinetics of electroless deposition: the copper-dimethylamine borane system.

    Science.gov (United States)

    Plana, Daniela; Campbell, Andrew I; Patole, Samson N; Shul, Galyna; Dryfe, Robert A W

    2010-06-15

    A kinetic study of the electroless deposition of copper on gold, using dimethylamine borane (DMAB) as a reducing agent, has been carried out. The copper deposition rate in the electroless bath was determined to be 50 nm min(-1), through electrochemical stripping of the copper deposits as well as from direct measurements of the film thickness using atomic force microscopy (AFM). Comparison with a galvanic cell setup, where the two half-reactions were physically separated, yielded a lower deposition rate of 30 nm min(-1). An important kinetic effect of the surface on the oxidation of the reducing agent, and thus on the overall process, was therefore revealed. The efficiency of the process was measured over time, revealing the contribution of side reactions in the cathodic half-cell, particularly during the initial stages of the electroless process.

  8. Efficient regeneration of partially spent ammonia borane fuel

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Benjamin Lee [Los Alamos National Laboratory; Gordon, John C [Los Alamos National Laboratory; Stephens, Frances [Los Alamos National Laboratory; Dixon, David A [UNIV OF ALABAMA; Matus, Myrna H [UNIV OF ALABAMA

    2008-01-01

    A necessary target in realizing a hydrogen (H{sub 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{sub 3}B-NH{sub 3}, AB), due to its high gravimetric capacity of hydrogen (19.6 wt %) and low molecular weight (30.7 g mol{sup -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{sub 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{sub 4} as a H{sub 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{sub 2} depleted AB with a minimum number of steps.

  9. Solid amine-boranes as high performance hypergolic hybrid rocket fuels

    Science.gov (United States)

    Pfeil, Mark A.

    Hypergolic hybrid rockets have the potential of providing systems that are simple, reliable, have high performance, and allow for energy management. Such a propulsion system can be applied to fields that need a single tactical motor with flexible mission requirements of either high speed to target or extended loitering. They also provide the possibility for alternative fast response dynamic altitude control systems if ignition delays are sufficiently short. Amines are the traditional fuel of choice when selecting a hypergolic combination as these tend to react readily with both nitric acid and dinitrogen tertroxide based oxidizers. It has been found that the addition of a borane adduct to an amine fuel tends to reduce the ignition delay by up to an order of magnitude with white fuming nitric acid (WFNA). The borane addition has resulted in fuels with very short ignition delays between 2-10 ms - the fastest times for an amine based fuel reacting with nitric acid based oxidizers. The incorporation of these amine-boranes, specifically ethylenediamine bisborane (EDBB), into various fuel binders has also been found to result in ignition delays between 3-10 ms - the fastest times again for amine based fuels. It was found that the addition of a borane to an amine increased theoretical performance of the amine resulting in high performance fuels. The amine-borane/fuel binder combinations also produced higher theoretical performance values than previously used hypergolic hybrid rockets. Some of the theoretical values are on par or higher than the current toxic liquid hypergolic fuels, making amine boranes an attractive replacement. The higher performing amine-borane/fuel binder combinations also have higher performance values than the traditional rocket fuels, excluding liquid hydrogen. Thus, amine-borane based fuels have the potential to influence various area in the rocket field. An EDBB/ferrocene/epoxy fuel was tested in a hypergolic hybrid with pure nitric acid as the

  10. Hydrogen generation from deliquescence of ammonia borane using Ni-Co/r-GO catalyst

    Science.gov (United States)

    Chou, Chang-Chen; Chen, Bing-Hung

    2015-10-01

    Hydrogen generation from the catalyzed deliquescence/hydrolysis of ammonia borane (AB) using the Ni-Co catalyst supported on the graphene oxide (Ni-Co/r-GO catalyst) under the conditions of limited water supply was studied with the molar feed ratio of water to ammonia borane (denoted as H2O/AB) at 2.02, 3.97 and 5.93, respectively. The conversion efficiency of ammonia borane to hydrogen was estimated both from the cumulative volume of the hydrogen gas generated and the conversion of boron chemistry in the hydrolysates analyzed by the solid-state 11B NMR. The conversion efficiency of ammonia borane could reach nearly 100% under excess water dosage, that is, H2O/AB = 3.97 and 5.93. Notably, the hydrogen storage capacity could reach as high as 6.5 wt.% in the case with H2O/AB = 2.02. The hydrolysates of ammonia borane in the presence of Ni-Co/r-GO catalyst were mainly the mixture of boric acid and metaborate according to XRD, FT-IR and solid-state 11B NMR analyses.

  11. Intracellular disulfide reduction by phosphine-borane complexes: Mechanism of action for neuroprotection.

    Science.gov (United States)

    Niemuth, Nicholas J; Thompson, Alex F; Crowe, Megan E; Lieven, Christopher J; Levin, Leonard A

    2016-10-01

    Phosphine-borane complexes are novel cell-permeable drugs that protect neurons from axonal injury in vitro and in vivo. These drugs activate the extracellular signal-regulated kinases 1/2 (ERK1/2) cell survival pathway and are therefore neuroprotective, but do not scavenge superoxide. In order to understand the interaction between superoxide signaling of neuronal death and the action of phosphine-borane complexes, their biochemical activity in cell-free and in vitro assays was studied by electron paramagnetic resonance (EPR) spectrometry and using an intracellular dithiol reporter that becomes fluorescent when its disulfide bond is cleaved. These studies demonstrated that bis(3-propionic acid methyl ester) phenylphosphine-borane complex (PB1) and (3-propionic acid methyl ester) diphenylphosphine-borane complex (PB2) are potent intracellular disulfide reducing agents which are cell permeable. EPR and pharmacological studies demonstrated reducing activity but not scavenging of superoxide. Given that phosphine-borane complexes reduce cell injury from mitochondrial superoxide generation but do not scavenge superoxide, this implies a mechanism where an intracellular superoxide burst induces downstream formation of protein disulfides. The redox-dependent cleavage of the disulfides is therefore a novel mechanism of neuroprotection.

  12. Hydrogen Generation from Ammonia Borane and Water Through the Combustion Reactions with Mechanically Alloyed Al/Mg Powder

    Science.gov (United States)

    2014-08-11

    synthesis of ammonia -A ‘‘never ending story? " Angewandte...34 # && , (/ -%(/ &$’$) ) ! -( ( !( &" # ( %’ !&% # ’)( (% (" %’% (" ( & *%" # ’)( *! % + 3 HYDROGEN GENERATION FROM AMMONIA BORANE AND WATER THROUGH THE...FROM AMMONIA BORANE AND WATER THROUGH THE COMBUSTION REACTIONS WITH MECHANICALLY ALLOYED AL/MG POWDER by DANIEL RODRIGUEZ THESIS Presented to

  13. Iridium-catalysed dehydrocoupling of aryl phosphine-borane adducts: synthesis and characterisation of high molecular weight poly(phosphinoboranes).

    Science.gov (United States)

    Paul, Ursula S D; Braunschweig, Holger; Radius, Udo

    2016-06-30

    The thermal dehydrogenative coupling of aryl phosphine-borane adducts with iridium complexes bearing a bis(phosphinite) pincer ligand is reported. This catalysis produces high molecular weight poly(phosphinoboranes) [ArPH-BH2]n (Ar = Ph, (p)Tol, Mes). Furthermore, we investigated the reactivity of these pincer complexes towards primary phosphines and their respective borane adducts on a stoichiometric scale.

  14. 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...

  15. Rotational dynamics in ammonia borane: Evidence of strong isotope effects

    Energy Technology Data Exchange (ETDEWEB)

    Cantelli, Rosario; Paolone, Annalisa; Palumbo, Oriele; Leardini, F.; Autrey, Thomas; Karkamkar, Abhijeet J.; Luedtke, Avery T.

    2013-12-15

    This work reports anelastic spectroscopy measurements on the partially deuterated (ND3BH3 and NH3BD3) and perdeuterated (ND3BD3) ammonia borane (NH3BH3) compounds. The relaxations previously reported in NH3BH3 are observed in all the samples, and are ascribed to the rotational and torsional dynamics of NH(D)3BH(D)3 complexes. A new thermally activated peak appears at 70 K (for a vibration frequency of 1 kHz) in the spectrum of NH3BD3 and ND3BD3. The peak is practically a single-time Debye process, indicating absence of interaction between the relaxing units, and has a strikingly high intensity. A secondary relaxation process is also detected around 55 K. The anelastic spectrum of the ND3BH3 only displays this less intense process at 55 K. The analysis of the peaks supplies information about the dynamics of the relaxing species, and the obtained results provide indications on the effect of partial and selective deuteration on the hydrogen (deuterium) dynamics.

  16. Effects of Dimethylamine Borane in Electroless Ni-B Plating.

    Science.gov (United States)

    Rha, Sa-Kyun; Baek, Seung-Deok; Lee, Youn-Seoung

    2015-10-01

    By electroless plating in a pH 7 bath at 50 °C, Ni-B alloy films with nano-crystallite size (3-6 nm) were formed on screen printed Ag paste. According to the addition of DMAB (dimethylamine borane), the boron concentration in the Ni-B alloy films increased systematically from <1 at.% to ~10 at.%, and the crystallite size of the Ni-B alloy films decreased gradually. The crystal/electronic structures of the Ni-B alloys were studied using XAS (X-ray absorption spectroscopy), XRD, etc., with changes of boron contents. In the crystalline structure, the ordering of fcc type was broken upon alloying and then the samples with additions of 0.5 M and 1 M DMAB had amorphous-like structures with decreases of crystallite size. In the electronic structure, the unoccupied d states of the Ni sites were filled as the B concentration increased upon alloying. From the electronegativity rule and the broken orderging upon alloying, we can suggest that an overall charge transfer occurs from the Ni sites toward the alloying B sites with intra-atomic charge redistribution, leading to an increased occupancy of the Ni 3d states in the alloys.

  17. 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.

  18. Ni→B Interactions in Nickel Phosphino-Alkynyl-Borane Complexes

    NARCIS (Netherlands)

    Zhao, Xiaoxi; Otten, Edwin; Song, Datong; Stephan, Douglas W.

    2010-01-01

    The Ni complexes [{tBu2PC≡CB(C6F5)2}Ni(cod)] and [({tBu2PC≡CB(C6F5)2}Ni(NCMe))2] derived from the reaction between the phosphino-alkynyl-borane tBu2PC≡CB(C6F5)2 and [Ni(cod)2] exhibit an unprecedented metal–alkyne interaction in which the borane substituent bends towards the metal affording a Ni→B d

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

    Directory of Open Access Journals (Sweden)

    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.

  20. Intermediates in the Rh-catalysed dehydrocoupling of phosphine-borane.

    Science.gov (United States)

    Huertos, Miguel A; Weller, Andrew S

    2012-07-21

    Active species, product distributions and a suggested catalytic cycle are reported for the dehydrocoupling of the phosphine-borane H(3)B·P(t)Bu(2)H to give HP(t)Bu(2)BH(2)P(t)Bu(2)BH(3) using the [Rh(COD)(2)][BAr(F)(4)] pre-catalyst.

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

    Directory of Open Access Journals (Sweden)

    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.

  2. Tris(pentafluorophenyl)borane-Catalyzed Acceptorless Dehydrogenation of N-Heterocycles.

    Science.gov (United States)

    Kojima, Masahiro; Kanai, Motomu

    2016-09-26

    Catalytic acceptorless dehydrogenation is an environmentally benign way to desaturate organic compounds. This process is traditionally accomplished with transition-metal-based catalysts. Herein, a borane-catalyzed, metal-free acceptorless dehydrogenation of saturated N-heterocycles is disclosed. Tris(pentafluorophenyl)borane was identified as a versatile catalyst, which afforded several synthetically important N-heteroarenes in up to quantitative yield. Specifically, the present metal-free catalytic system exhibited a uniquely high tolerance toward sulfur functionalities, and demonstrated superior reactivity in the synthesis of benzothiazoles compared to conventional metal-catalyzed systems. This protocol can thus be regarded as the first example of metal-free acceptorless dehydrogenation in synthetic organic chemistry.

  3. Density functional study on enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine

    Institute of Scientific and Technical Information of China (English)

    LI; Ming; ZHENG; Wenxu

    2006-01-01

    The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction are optimized completely at the B3LYP/6-31g(d) level, and the transition states are verified by vibrational modes. As shown, the chirality-controlled steps for this reaction are the hydride transfer from borane to carbonyl carbon and oxime carbon of keto oxime ether, and the chirality for the reduced products is determined in these two reaction steps. In all examined reaction paths, the first hydride is transferred via a six-membered ring and the second hydride via a five-membered ring or a four-membered ring.

  4. One-pot synthesis of core-shell Cu@SiO2 nanospheres and their catalysis for hydrolytic dehydrogenation of ammonia borane and hydrazine borane

    Science.gov (United States)

    Yao, Qilu; Lu, Zhang-Hui; Zhang, Zhujun; Chen, Xiangshu; Lan, Yaqian

    2014-12-01

    Ultrafine copper nanoparticles (Cu NPs) within porous silica nanospheres (Cu@SiO2) were prepared via a simple one-pot synthetic route in a reverse micelle system and characterized by SEM, TEM, EDX, XRD, N2 adsorption-desorption, CO-TPD, XPS, and ICP methods. The characterized results show that ultrafine Cu NPs with diameter of around 2 nm are effectively embedded in the center of well-proportioned spherical SiO2 NPs of about 25 nm in diameter. Compared to commercial SiO2 supported Cu NPs, SiO2 nanospheres supported Cu NPs, and free Cu NPs, the synthesized core-shell nanospheres Cu@SiO2 exhibit a superior catalytic activity for the hydrolytic dehydrogenation of ammonia borane (AB, NH3BH3) and hydrazine borane (HB, N2H4BH3) under ambient atmosphere at room temperature. The turnover frequencies (TOF) for the hydrolysis of AB and HB in the presence of Cu@SiO2 nanospheres were measured to be 3.24 and 7.58 mol H2 (mol Cu min)-1, respectively, relatively high values for Cu nanocatalysts in the same reaction. In addition, the recycle tests show that the Cu@SiO2 nanospheres are still highly active in the hydrolysis of AB and HB, preserving 90 and 85% of their initial catalytic activity even after ten recycles, respectively.

  5. 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

  6. Smallpox inoculation (variolation) in East Africa with special reference to the practice among the Boran and Gabra of Northern Kenya.

    Science.gov (United States)

    Imperato, Pascal James; Imperato, Gavin H

    2014-12-01

    Smallpox inoculation (variolation) was widely reported in sub-Sahara Africa before, during, and after the colonial era. The infective smallpox materials and techniques used, as well as the anatomical sites for inoculation, varied widely among different ethnic groups. The practice among the Boran and Gabra pastoralists of northern Kenya resembled that which was prevalent in a number of areas of Ethiopia. This is not surprising as the Boran also live in southern Ethiopia, and Gabra herdsmen frequently cross the border into this region. The Boran and Gabra technique for smallpox inoculation consisted of taking infective material from the vesicles or pustules of those with active smallpox, and scraping it into the skin on the dorsum of the lower forearm. Although the intent was to cause a local reaction and at most a mild form of smallpox, severe cases of the disease not infrequently resulted. Also, variolated individuals were capable of infecting others with smallpox, thereby augmenting outbreaks and sustaining them. The limited known reports of smallpox inoculation among the Boran and Gabra are presented in this communication. The expansion of vaccination with effective heat stable vaccines, the development of medical and public health infrastructures, and educational programs all contributed to the eventual disappearance of the practice among the Boran and Gabra.

  7. 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.

  8. Mechanism of phosphine borane deprotection with amines: the effects of phosphine, solvent and amine on rate and efficiency.

    Science.gov (United States)

    Lloyd-Jones, Guy C; Taylor, Nicholas P

    2015-03-27

    The kinetics of borane transfer from simple tertiary phosphine borane adducts to a wide range of amines have been determined. All data obtained, including second-order kinetics, lack of cross-over, and negative entropies of activation for reaction of triphenylphosphine borane with quinuclidine and triethylamine, are consistent with a direct (SN 2-like) transfer process, rather than a dissociative (SN 1-like) process. The identities of the amine, phosphine, and solvent all impact substantially on the rate (k) and equilibrium (K) of the transfer, which in some cases vary by many orders of magnitude. P-to-N transfer is more efficient with cyclic amines in apolar solvents due to reduced entropic costs and ground-state destabilisation. Taken as a whole, the data allow informed optimisation of the deprotection step from the stand-point of rate, or synthetic convenience. In all cases, both reactants should be present at high initial concentration to gain kinetic benefit from the bimolecularity of the process. Ultimately, the choice of amine is dictated by the identity of the phosphine borane complex. Aryl-rich phosphine boranes are sufficiently reactive to allow use of diethylamine or pyrrolidine as a volatile low polarity solvent and reactant, whereas more alkyl-rich phosphines benefit from the use of more reactive amines, such as 1,4-diaza[2.2.2]bicyclooctane (DABCO), in apolar solvents at higher temperatures.

  9. An Intramolecular Silylene Borane Capable of Facile Activation of Small Molecules, Including Metal-Free Dehydrogenation of Water.

    Science.gov (United States)

    Mo, Zhenbo; Szilvási, Tibor; Zhou, Yu-Peng; Yao, Shenglai; Driess, Matthias

    2017-02-27

    The first single-component N-heterocyclic silylene borane 1 (LSi-R-BMes2 ; L=PhC(N(t) Bu)2 ; R=1,12-xanthendiyl spacer; Mes=2,4,6-Me3 C6 H2 ), acting as a frustrated Lewis pair (FLP) in small-molecule activation, can be synthesized in 65 % yields. Its HOMO is largely localized at the silicon(II) atom and the LUMO has mainly boron 2p character. In small-molecule activation 1 allows access to the intramolecular silanone-borane 3 featuring a Si=O→B interaction through reaction with O2 , N2 O, or CO2 , and formation of silanethione borane 4 from reaction with S8 . The Si(II) center in 1 undergoes immediate hydrogenation if exposed to H2 at 1 atm pressure in benzene, affording the silane borane 5-H2 , L(H2 )Si-R-BMes2 . Remarkably, no H2 activation occurs if the single silylene LSiPh and Mes3 B intermolecularly separated are exposed to dihydrogen. Unexpectedly, the pre-organized Si-B separation in 1 enables a metal-free dehydrogenation of H2 O to give the silanone-borane 3 as reactive intermediate.

  10. Polymer Film Supported Bimetallic Au-Ag Catalysts for Electrocatalytic Oxidation of Ammonia Borane in Alkaline Media

    Institute of Scientific and Technical Information of China (English)

    Şükriye Ulubay Karabiberoglu; ÇagrCeylan Koçak; Süleyman Kocak; Zekerya Dursun

    2016-01-01

    Ammonia borane is widely used in most areas including fuel cell applications. The present paper describes electrochemical behavior of ammonia borane in alkaline media on the poly(p-aminophenol) film modified with Au and Ag bimetallic nanoparticles. The glassy carbon electrode was firstly covered with polymeric film electrochemically and then, Au, Ag, and Au–Ag nanoparticles were deposited on the polymeric film, respectively. The surface morphology and chemical composition of these electrodes were examined by scanning electron microscopy, transmission electron microscopy, electrochemical impedance spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. It was found that alloyed Au–Ag bimetallic nanoparticles are formed. Electrochemical measurements indicate that the developed electrode modified by Au–Ag bimetallic nanoparticles exhibit the highest electrocatalytic activity for ammonia borane oxidation in alkaline media. The rotating disk electrode voltammetry demonstrates that the developed electrode can catalyze almost six-electron oxidation pathway of ammonia borane. Our results may be attractive for anode materials of ammonia borane fuel cells under alkaline conditions.

  11. 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.

  12. The route to a feasible hydrogen-storage material: MOFs versus ammonia borane.

    Science.gov (United States)

    Hügle, Thomas; Hartl, Monika; Lentz, Dieter

    2011-09-05

    The replacement of fossil fuels is one of the greatest challenges that chemistry and material sciences will have to face in the near future. While hydrogen seems to be the most likely candidate for this, a material able to store the hydrogen itself is sorely needed. Intense research in the past decade has narrowed down the field of possible concepts to two materials: ammonia borane with chemically bound hydrogen atoms and metal-organic frameworks with physisorbed hydrogen molecules. Herein we want to give an overview of the strengths and weaknesses of each concept, discuss the challenges that need to be overcome, and try to compare the future capabilities of these two materials.

  13. 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.

  14. Materials for hydrogen storage: structure and dynamics of borane ammonia complex.

    Science.gov (United States)

    Parvanov, Vencislav M; Schenter, Gregory K; Hess, Nancy J; Daemen, Luke L; Hartl, Monika; Stowe, Ashley C; Camaioni, Donald M; Autrey, Tom

    2008-09-07

    The activation energies for rotations in low-temperature orthorhombic ammonia borane were analyzed and characterized in terms of electronic structure theory. The perdeuterated (11)B-enriched ammonia borane, (11)BD(3)ND(3), sample was synthesized, and the structure was refined from neutron powder diffraction data at 175 K. This temperature has been chosen as median of the range of previously reported nuclear magnetic resonance spectroscopy measurements of these rotations. A representative molecular cluster model was assembled from the refined geometry, and the activation energies were calculated and characterized by analysis of the environmental factors that control the rotational dynamics. The barrier for independent NH(3) rotation, E(a) = 12.7 kJ mol(-1), largely depends on the molecular conformational torsion in the solid-state geometry. The barrier for independent BH(3) rotation, E(a) = 38.3 kJ mol(-1), results from the summation of the effect of molecular torsion and large repulsive intermolecular hydrogen-hydrogen interactions. However, a barrier of E(a) = 31.1 kJ mol(-1) was calculated for internally correlated rotation with preserved molecular conformation. Analysis of the barrier heights and the corresponding rotational pathways shows that rotation of the BH(3) group involves strongly correlated rotation of the NH(3) end of the molecule. This observation suggests that the barrier from previously reported measurement of BH(3) rotation corresponds to H(3)B-NH(3) correlated rotation.

  15. 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.

  16. Tris(pentafluorophenyl)borane and Beyond: Modern Advances in Borylation Chemistry.

    Science.gov (United States)

    Lawson, James R; Melen, Rebecca L

    2017-02-03

    As main-group chemistry, in particular boron chemistry, has expanded and developed over the past 20 years, one reagent has risen to prominence as well. Tris(pentafluorophenyl)borane, B(C6F5)3 (commonly known as BCF), has demonstrated extensive applications in a wide variety of reactions, including borylation, hydrogenation, hydrosilylation, frustrated Lewis pair (FLP) chemistry, Lewis acid catalysis, and more. The high Lewis acidity of B(C6F5)3 is derived from the electronic effects of its three C6F5 rings, rendering it a versatile reagent for a great number of reactions. In addition, the steric bulk of these rings also allows it to function as the Lewis acid in a FLP, granting this reagent yet another synthetically useful application. However, as main-group chemistry continues to evolve as a field, new reagents are required that go beyond BCF, increasing not only the range of reactions available but also the breadth of compounds attainable. Great strides have already been made in order to accomplish this task, and this review will highlight modern advances in boron chemistry relating to borylation reactions. Herein, we will show the recent uses of B(C6F5)3 in borylation reactions while also focusing on current advances in novel borane and borocation usage that eclipses that of the stalwart B(C6F5)3.

  17. Towards chiral diamines as chiral catalytic precursors for the borane-mediated enantioselective reduction of prochiral ketones

    Indian Academy of Sciences (India)

    Deevi Basavaiah; Utpal Das; Suparna Roy

    2009-11-01

    Two chiral diamines (3)-3-anilinomethyl-1,2,3,4-tetrahydroisoquinoline (1) and (2)-2-anilinomethylpiperidine (2) have been employed as chiral catalytic sources in the borane-mediated asymmetric reduction of prochiral ketones thus providing the resulting secondary alcohols in good enantiomeric purities (up to 81% ).

  18. On the origin of reversible hydrogen activation by phosphine-boranes.

    Science.gov (United States)

    Rajeev, Ramanan; Sunoj, Raghavan B

    2009-11-23

    Mechanistic insights into the factors responsible for the reversible hydrogen-activation ability exhibited by an aryl phosphine-borane system ((CH(3))(2)P-C(6)F(4)-B(CF(3))(2)) are presented. A detailed evaluation of the energies of various intermediates, generated by the addition of molecular hydrogen, and their interconverting barriers have been carried out using ab initio and DFT methods. Several rearrangement possibilities of the H(2)-phosphino-borane adduct have been investigated so as to unravel the lower energy pathways that convert the initial adduct to a series of other intermediates. The initial adduct formed by the heterolytic addition of a molecular hydrogen across the C-B bond is identified to undergo a series of rearrangement reactions until it terminates at the C-P end of the molecule. Among the possible 1,n-migrations (for which n=1-5), 1,2-proton migrations are found to possess lower energy transition states, whereas 1,2-hydride (in a zwitterionic intermediate) and 1,4-proton-coupled electron transfers exhibited much higher energy transition states. The minimum energy pathway for the transfer of a proton and hydride from the C-B bond to the C-P bond is found to involve a cascade of 1,2-proton transfers followed by a 1,2-hydride migration and finally a 1,4-proton-coupled electron transfer. The higher energy pathways identified for the hydride transfer suggest the possibility of a cascade of reversible proton migrations from a thermodynamically stable intermediate (M(a)). Possible uptake of two hydrogen molecules by the phosphine-borane system is additionally considered in the present study, in which relatively higher barriers than those with one molecule of hydrogen are observed. The computed thermodynamic parameters are found to be in accordance with the experimental observations, in which the uptake and storage of molecular hydrogen are carried out at lower temperatures whereas the liberation demands elevated temperatures.

  19. The structure study of boron carbonitride films obtained by use of trimethylamine borane complex

    CERN Document Server

    Kosinova, M L; Fainer, N I; Maximovski, E A; Kuznetsov, F A

    2001-01-01

    Diffraction of synchrotron radiation (SR) was used to investigate crystalline structure and phase composition of thin films (1500-5000 A) of boron carbonitride. These films were synthesized by plasma-enhanced chemical vapor deposition using nontraditional volatile single source precursor trimethylamine borane complex (CH sub 3) sub 3 N centre dot BH sub 3 and its mixture with ammonia. The effect of the gas ratio and substrate temperature on chemical and phase composition as well as the structure of the films were investigated. The XRD peculiarities of texture films and ways of increasing sensibility of measurements were considered. A possibility of the information density rise of the thin film XRD was shown due to application of different methods for recording diffraction patterns.

  20. Borane catalysed ring opening and closing cascades of furans leading to silicon functionalized synthetic intermediates

    Science.gov (United States)

    Hazra, Chinmoy K.; Gandhamsetty, Narasimhulu; Park, Sehoon; Chang, Sukbok

    2016-11-01

    The conversion of renewable biomass resources to synthetically valuable chemicals is highly desirable, but remains a formidable challenge in regards to the substrate scope and reaction conditions. Here we present the development of tris(pentafluorophenyl)borane-catalysed conversion of furans via ring-opening and closing cascade processes to afford silicon-functionalized synthetic chemicals under transition metal-free conditions. The furan ring-opening with hydrosilanes is highly efficient (TON up to 2,000) and atom-economical without forming any byproduct to give rise to α-silyloxy-(Z)-alkenyl silanes. Additional equivalents of silane smoothly induce a subsequent B(C6F5)3-catalysed cyclization of initially formed olefinic silane compounds to produce anti-(2-alkyl)cyclopropyl silanes, another versatile synthon being potentially applicable in the synthesis of natural products and pharmacophores.

  1. Towards Safer Rocket Fuels: Hypergolic Imidazolylidene-Borane Compounds as Replacements for Hydrazine Derivatives.

    Science.gov (United States)

    Huang, Shi; Qi, Xiujuan; Liu, Tianlin; Wang, Kangcai; Zhang, Wenquan; Li, Jianlin; Zhang, Qinghua

    2016-07-11

    Currently, toxic and volatile hydrazine derivatives are still the main fuel choices for liquid bipropellants, especially in some traditional rocket propulsion systems. Therefore, the search for safer hypergolic fuels as replacements for hydrazine derivatives has been one of the most challenging tasks. In this study, six imidazolylidene-borane compounds with zwitterionic structure have been synthesized and characterized, and their hypergolic reactivity has been studied. As expected, these compounds exhibited fast spontaneous combustion upon contact with white fuming nitric acid (WFNA). Among them, compound 5 showed excellent integrated properties including wide liquid operating range (-70-160 °C), superior loading density (0.99 g cm(-3) ), ultrafast ignition delay times with WFNA (15 ms), and high specific impulse (303.5 s), suggesting promising application potential as safer hypergolic fuels in liquid bipropellant formulations.

  2. Evaluation of F1 calves sired by Brahman, Boran, and Tuli bulls for birth, growth, size, and carcass characteristics.

    Science.gov (United States)

    Herring, A D; Sanders, J O; Knutson, R E; Lunt, D K

    1996-05-01

    Birth (n = 308), weaning (n = 291), feedlot and carcass (n = 142), and yearling heifer traits (n = 139) were evaluated in F1 calves sired by Brahman (BR), Boran (BO), and Tuli (TU) bulls and born to multiparous Hereford and Angus cows. Calves sired by BR were heaviest (P Brahman crosses had larger (P Brahman F1 heifers had larger (P carcass quality traits, but not for carcass yield traits, among these three breeds.

  3. 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.

  4. Decomposition Pathway of Ammonia Borane on the Surface of nano-BN

    Energy Technology Data Exchange (ETDEWEB)

    Neiner, Doinita; Luedtke, Avery T; Karkamkar, Abhijeet J; Shaw, Wendy J; Wang, Julia; Browning, Nigel; Autrey, Thomas; Kauzlarich, Susan M

    2010-08-19

    Ammonia borane (AB) is under significant investigation as a possible hydrogen storage material. While many chemical additives have been demonstrated to have a significant positive effect on hydrogen release from ammonia borane, many provide additional complications in the regeneration cycle. Mechanically alloyed hexagonal BN (nano-BN) has been shown to facilitate the release of hydrogen from AB at lower temperature, with minimal induction time, less exothermically, and inert nano-BN may be easily removed during any regeneration of the spent AB. The samples were prepared by mechanically alloying AB with nano-BN. Raman spectroscopy indicates that the AB:nano-BN samples are physical mixtures of AB and h-BN. The release of hydrogen from AB:nano-BN mixtures as well as the decomposition products were characterized by 11B magic angle spinning (MAS) solid state NMR, TGA/DSC/MS with 15N labeled AB, and solution 11B NMR spectroscopy. The 11B MAS solid state NMR spectrum shows that diammonate of diborane (DADB) is present in the mechanically alloyed mixture, which drastically shortens the induction period for hydrogen release from AB. Analysis of the TGA/DSC/MS spectra using 15N labeled AB shows that all the borazine (BZ) produced in the reaction comes from AB and that increasing nano-BN surface area results in increased amounts of BZ. However, under high temperature, 150°C, isothermal conditions, the amount of BZ released was the same as for neat AB. High resolution transmission electron microscopy (HRTEM), selected area diffraction (SAD), and electron energy loss spectroscopy (EELS) of the initial and final nano-BN additive provide evidence for crystallinity loss but not significant chemical changes. The higher concentration of BZ observed for low temperature dehydrogenation of AB:nano-BN mixtures versus neat AB is attributed to a surface interaction that favors the formation of precursors which ultimately result in BZ

  5. Portable ammonia-borane-based H2 power-pack for unmanned aerial vehicles

    Science.gov (United States)

    Seo, Jung-Eun; Kim, Yujong; Kim, Yongmin; Kim, Kibeom; Lee, Jin Hee; Lee, Dae Hyung; Kim, Yeongcheon; Shin, Seock Jae; Kim, Dong-Min; Kim, Sung-Yug; Kim, Taegyu; Yoon, Chang Won; Nam, Suk Woo

    2014-05-01

    An advanced ammonia borane (AB)-based H2 power-pack is designed to continually drive an unmanned aerial vehicle (UAV) for 57 min using a 200-We polymer electrolyte membrane fuel cell (PEMFC). In a flight test with the UAV platform integrated with the developed power-pack, pure hydrogen with an average flow rate of 3.8 L(H2) min-1 is generated by autothermal H2-release from AB with tetraethylene glycol dimethylether (T4EGDE) as a promoter. During take-off, a hybridized power management system (PMS) consisting of the fuel cell and an auxiliary lithium-ion battery supplies 500 We at full power simultaneously, while the fuel cell alone provides 150-200 We and further recharges the auxiliary battery upon cruising. Gaseous byproducts identified by in situ Fourier transform infrared (FT-IR) spectroscopy during AB dehydrogenation are sequestrated using a mixed absorbent in an H2 purification system. In addition, a real-time monitoring system is employed to determine the remaining filter capacity of the purifier at a ground control system for rapidly responding unpredictable circumstances during flight. Separate experiments are conducted to screen potential materials and methods for enhancing filter capacity in the current H2 refining system. A prospective reactor concept for long-term fuel cell applications is proposed based on the results.

  6. Quantifying the thermodynamic interactions of polyhedral boranes in solution to guide nanocomposite fabrication

    Energy Technology Data Exchange (ETDEWEB)

    Mutz, M. [University of Tennessee, Department of Chemistry (United States); Eastwood, Eric [Honeywell Kansas City Plant (United States); Lee, Mark E. [University of Missouri (United States); Bowen, Daniel E. [Honeywell Kansas City Plant (United States); Dadmun, M. D., E-mail: dad@utk.edu [University of Tennessee, Department of Chemistry (United States)

    2012-11-15

    The solubility of boron containing nanoparticles in a variety of solvents is quantified using static light scattering in conjunction with refractometry. Four polyhedral boranes were tested in this work, using refractometry to obtain dn/dc, while static light scattering quantifies A{sub 2}. A{sub 2} obtained from these measurements was then used to calculate {chi}, the solute-solvent interaction parameter, and the Hildebrand solubility parameter, {delta}, which provides a quantifiable method to identify good solvents. Of the nanoparticles studied, 1,3-di-o-carboranylpropane is thermodynamically stable in toluene, with a {chi} less than 0.5, a solubility limit of 2.47 mg/mL, and all solutions remaining clear with no visible particle settling. For all of the particles tested, there was good correlation between the physical observations of the solutions, {chi}, and {delta}. For instance, lower values of {chi} correspond to a smaller radius of gyration (R{sub g}). A list of suitable solvents based on {delta} is also presented.

  7. Quantifying the thermodynamic interactions of polyhedral boranes in solution to guide nanocomposite fabrication

    Energy Technology Data Exchange (ETDEWEB)

    Mutz, M [The University of Tennessee; Eastwood, Eric Allen [ORNL; LeeJr, Mark E [University of Missouri; BowenIII, Daniel E [Honeywell, Inc.; Dadmun, Mark D [ORNL

    2012-01-01

    The solubility of boron containing nanoparticles in a variety of solvents is quantified using static light scattering in conjunction with refractometry. Four polyhedral boranes were tested in this work, using refractometry to obtain dn/dc, while static light scattering quantifies A2. A2 obtained from these measurements was then used to calculate v, the solute solvent interaction parameter, and the ildebrand solubility parameter, d, which provides a quantifiable method to identify good solvents. Of the nanoparticles studied, 1,3-di-o-carboranylpropane is thermodynamically stable in toluene, with a v less than 0.5, a solubility limit of 2.47 mg/mL, and all solutions remaining clear with no visible particle settling. For all of the particles tested, there was good correlation between the physical observations of the solutions, v, and d. For instance, lower values of v correspond to a smaller radius of gyration (Rg). A list of suitable solvents based on d is also presented.

  8. Highly active metastable ruthenium nanoparticles for hydrogen production through the catalytic hydrolysis of ammonia borane.

    Science.gov (United States)

    Abo-Hamed, Enass K; Pennycook, Timothy; Vaynzof, Yana; Toprakcioglu, Chris; Koutsioubas, Alexandros; Scherman, Oren A

    2014-08-13

    Late transition metal nanoparticles (NPs) with a favorably high surface area to volume ratio have garnered much interest for catalytic applications. Yet, these NPs are prone to aggregation in solution, which has been mitigated through attachment of surface ligands, additives or supports; unfortunately, protective ligands can severely reduce the effective surface area on the NPs available for catalyzing chemical transformations. The preparation of 'metastable' NPs can readily address these challenges. We report herein the first synthesis of monodisperse metastable ruthenium nanoparticles (RuNPs), having sub 5 nm size and an fcc structure, in aqueous media at room temperature, which can be stored for a period of at least 8 months. The RuNPs can subsequently be used for the catalytic, quantitative hydrolysis of ammonia-borane (AB) yielding hydrogen gas with 21.8 turnovers per min at 25 °C. The high surface area available for hydrolysis of AB on the metastable RuNPs translated to an Ea of 27.5 kJ mol(-1) , which is notably lower than previously reported values for RuNP based catalysts.

  9. 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.

  10. 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.

  11. 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.

  12. Birth and weaning traits in crossbred cattle from Hereford, Angus, Brahman, Boran, Tuli, and Belgian Blue sires.

    Science.gov (United States)

    Casas, E; Thallman, R M; Cundiff, L V

    2011-04-01

    The objective of this study was to characterize breeds representing diverse biological types for birth and weaning traits in crossbred cattle. Gestation length, calving difficulty, percentage of unassisted calving, percentage of perinatal survival, percentage of survival from birth to weaning, birth weight, BW at 200 d, and ADG were measured in 2,500 calves born and 2,395 calves weaned. Calves were obtained by mating Hereford, Angus, and MARC III (one-fourth Hereford, one-fourth Angus, one-fourth Pinzgauer, and one-fourth Red Poll) mature cows to Hereford or Angus (British breed), Brahman, Tuli, Boran, and Belgian Blue sires. Calves were born during the spring seasons of 1992, 1993, and 1994. Sire breed was significant for all traits (P gestation length (285 d) when compared with progeny from other sire breeds (average of 291 d). Calving difficulty was greater in offspring from Brahman sires (1.24), whereas the offspring of Tuli sires had the least amount of calving difficulty (1.00). Offspring from all sire breeds had similar perinatal survival and survival from birth to weaning (average of 97.2 and 96.2%, respectively), with the exception of offspring from Brahman sires, which had less (92.8 and 90.4%, respectively). Progeny of Brahman sires were heaviest at birth (45.7 kg), followed by offspring from British breed, Boran, and Belgian Blue sires (average of 42.4 kg). The lightest offspring at birth were from Tuli sires (38.6 kg). Progeny derived from Brahman sires were the heaviest at 200 d (246 kg), and they grew faster (1.00 kg/d) than offspring from any other group. The progeny of British breeds and the Belgian Blue breed had an intermediate BW at 200 d (238 kg) and an intermediate ADG (average of 0.98 kg/d). The progeny of Boran and Tuli sires were the lightest at 200 d (227 kg) and had the least ADG (0.93 kg/d). Male calves had a longer gestation length, had a greater incidence of calving difficulty, had greater mortality to weaning, were heavier, and grew

  13. Effect of the phosphine steric and electronic profile on the Rh-promoted dehydrocoupling of phosphine-boranes.

    Science.gov (United States)

    Hooper, Thomas N; Huertos, Miguel A; Jurca, Titel; Pike, Sebastian D; Weller, Andrew S; Manners, Ian

    2014-04-07

    The electronic and steric effects in the stoichiometric dehydrocoupling of secondary and primary phosphine-boranes H3B·PR2H [R = 3,5-(CF3)2C6H3; p-(CF3)C6H4; p-(OMe)C6H4; adamantyl, Ad] and H3B·PCyH2 to form the metal-bound linear diboraphosphines H3B·PR2BH2·PR2H and H3B·PRHBH2·PRH2, respectively, are reported. Reaction of [Rh(L)(η(6)-FC6H5)][BAr(F)4] [L = Ph2P(CH2)3PPh2, Ar(F) = 3,5-(CF3)2C6H3] with 2 equiv of H3B·PR2H affords [Rh(L)(H)(σ,η-PR2BH3)(η(1)-H3B·PR2H)][BAr(F)4]. These complexes undergo dehydrocoupling to give the diboraphosphine complexes [Rh(L)(H)(σ,η(2)-PR2·BH2PR2·BH3)][BAr(F)4]. With electron-withdrawing groups on the phosphine-borane there is the parallel formation of the products of B-P cleavage, [Rh(L)(PR2H)2][BAr(F)4], while with electron-donating groups no parallel product is formed. For the bulky, electron rich, H3B·P(Ad)2H no dehydrocoupling is observed, but an intermediate Rh(I) σ phosphine-borane complex is formed, [Rh(L){η(2)-H3B·P(Ad)2H}][BAr(F)4], that undergoes B-P bond cleavage to give [Rh(L){η(1)-H3B·P(Ad)2H}{P(Ad)2H}][BAr(F)4]. The relative rates of dehydrocoupling of H3B·PR2H (R = aryl) show that increasingly electron-withdrawing substituents result in faster dehydrocoupling, but also suffer from the formation of the parallel product resulting from P-B bond cleavage. H3B·PCyH2 undergoes a similar dehydrocoupling process, and gives a mixture of stereoisomers of the resulting metal-bound diboraphosphine that arise from activation of the prochiral P-H bonds, with one stereoisomer favored. This diastereomeric mixture may also be biased by use of a chiral phosphine ligand. The selectivity and efficiencies of resulting catalytic dehydrocoupling processes are also briefly discussed.

  14. Dihydrogen activation by frustrated carbene-borane Lewis pairs: an experimental and theoretical study of carbene variation.

    Science.gov (United States)

    Kronig, Sabrina; Theuergarten, Eileen; Holschumacher, Dirk; Bannenberg, Thomas; Daniliuc, Constantin G; Jones, Peter G; Tamm, Matthias

    2011-08-01

    A variety of Lewis acid-base pairs consisting of tris(pentafluorophenyl)borane, B(C(6)F(5))(3), in combination with sterically demanding five- and six-membered N-heterocyclic carbenes (NHCs) of the imidazolin-2-ylidene, imidazolidin-2-ylidene, and tetrahydropyrimidin-2-ylidene types were investigated with respect to their potential to act as frustrated Lewis pairs (FLP) by reaction with dihydrogen (H(2)) and tetrahydrofuran (THF). A sufficient degree of "frustration" was usually established by introduction of a 1,3-di-tert-butyl or 1,3-diadamantyl carbene substitution pattern, which allows an unquenched acid-base reactivity and thus leads to heterolytic dihydrogen activation and ring-opening of THF. In contrast, 1,3-bis(2,6-diisopropylphenyl)-substituted carbenes showed ambiguous behavior, and the corresponding five-membered imidazolin-2-ylidene formed a stable carbene-B(C(6)F(5))(3) adduct, whereas fast C-F activation and formation of a zwitterionic pyrimidinium-fluoroborate was observed for the six-membered tetrahydropyrimidin-2-ylidene. A stable adduct was also isolated for the combination of the acyclic carbene bis(diisopropylamino)methylene with B(C(6)F(5))(3), and consequently no reactivity toward H(2) and THF was observed. To rationalize the reactivity of the carbene-borane Lewis pairs, the thermodynamics of adduct formation with B(C(6)F(5))(3) were calculated for 10 different carbenes; the stability (or instability) of these adducts can be used as a good measure of the degree of "frustration".

  15. Syntheses and structures of dimeric sodium and potassium complexes of 2,6-diisopropyl-anilidophosphine borane ligand

    Indian Academy of Sciences (India)

    Kishor Naktode; Jayeeta Bhattacharjee; Anirban Chakrabarti; Tarun K Panda

    2015-02-01

    We report here the syntheses and structural studies of dimeric sodium and potassium complexes of composition [Na(THF)2{Ph2P(BH3)N(2,6-iPr2C6H6)}]2 (2) and [K(THF)2{Ph2P(BH3)N(2,6-iPr2C6H6)}]2(3). The sodium complex 2 was readily prepared by the reaction of sodium bis(trimethylsilyl)amide with 2,6-diisopropylanilidophosphine-borane ligand [2,6-iPr2C6H3NHP(BH3)Ph2] (1-H) at ambient temperature. The potassium complex 3 was prepared by two synthetic routes: in the first method, the ligand 1-H was made to react with potassium hydride at room temperature to afford the corresponding potassium complex. The potassium bis(trimethylsilyl)amides were made to react with protic ligand 1-H in the second method to eliminate the volatile bis(trimethyl)silyl amine. Solid-state structures of both the new complexes were established by single crystal X-ray diffraction analysis. In the molecular structures of complexes 2, the sodium metal is coordinated by the anilido nitrogen (1) and borane group (1) attached to the phosphorus atom of ligand 1. In contrast, for compound 2, ligand 1 displays 6-arene interaction from 2,6-diisopopylphenyl ring with potassium atom along with 3 interaction of BH3 group due to larger ionic radius of potassium ion.

  16. Use of an accelerometer and a microphone as gas detectors in the online quantitative detection of hydrogen released from ammonia borane by gas chromatography.

    Science.gov (United States)

    He, Yi-San; Chen, Kuan-Fu; Lin, Chien-Hung; Lin, Min-Tsung; Chen, Chien-Chung; Lin, Cheng-Huang

    2013-03-19

    The use of an accelerometer as a gas detector in gas chromatography (GC) is described for the first time. A milli-whistle was connected to the outlet of the GC capillary. When the eluted and GC carrier gases pass through the capillary and milli-whistle, a sound is produced. After a fast Fourier transform (FFT), the sound wave generated from the milli-whistle is picked up by a microphone and the resulting vibration of the milli-whistle body can be recorded by an accelerometer. The release of hydrogen gas, as the result of thermal energy, from ammonia borane (NH3BH3), which has been suggested as a storage medium for hydrogen, was selected as the model sample. The findings show that the frequencies generated, either by sound or by the vibration from the whistle body, were identical. The concentration levels of the released hydrogen gas can be determined online, based on the frequency changes. Ammonia borane was placed in a brass reservoir, heated continually, and the released hydrogen gas was directly injected into the GC inlet at 0.5 min intervals, using a home-built electromagnetic pulse injector. The concentration of hydrogen for each injection can be calculated immediately. When the ammonia borane was encapsulated within a polycarbonate (PC) microtube array membrane, the temperature required for the release of hydrogen can be decreased, which would make such a material more convenient for use. The findings indicate that 1.0 mg of ammonia borane can produce hydrogen in the range of 1.0-1.25 mL, in the temperature range of 85-115 °C.

  17. Determination of Genetic Structure and Signatures of Selection in Three Strains of Tanzania Shorthorn Zebu, Boran and Friesian Cattle by Genome-Wide SNP Analyses

    Science.gov (United States)

    Msalya, George; Kim, Eui-Soo; Laisser, Emmanuel L. K.; Kipanyula, Maulilio J.; Karimuribo, Esron D.; Kusiluka, Lughano J. M.; Chenyambuga, Sebastian W.; Rothschild, Max F.

    2017-01-01

    Background More than 90 percent of cattle in Tanzania belong to the indigenous Tanzania Short Horn Zebu (TSZ) population which has been classified into 12 strains based on historical evidence, morphological characteristics, and geographic distribution. However, specific genetic information of each TSZ population has been lacking and has caused difficulties in designing programs such as selection, crossbreeding, breed improvement or conservation. This study was designed to evaluate the genetic structure, assess genetic relationships, and to identify signatures of selection among cattle of Tanzania with the main goal of understanding genetic relationship, variation and uniqueness among them. Methodology/Principal findings The Illumina Bos indicus SNP 80K BeadChip was used to genotype genome wide SNPs in 168 DNA samples obtained from three strains of TSZ cattle namely Maasai, Tarime and Sukuma as well as two comparative breeds; Boran and Friesian. Population structure and signatures of selection were examined using principal component analysis (PCA), admixture analysis, pairwise distances (FST), integrated haplotype score (iHS), identical by state (IBS) and runs of homozygosity (ROH). There was a low level of inbreeding (F~0.01) in the TSZ population compared to the Boran and Friesian breeds. The analyses of FST, IBS and admixture identified no considerable differentiation between TSZ trains. Importantly, common ancestry in Boran and TSZ were revealed based on admixture and IBD, implying gene flow between two populations. In addition, Friesian ancestry was found in Boran. A few common significant iHS were detected, which may reflect influence of recent selection in each breed or strain. Conclusions Population admixture and selection signatures could be applied to develop conservation plan of TSZ cattle as well as future breeding programs in East African cattle. PMID:28129396

  18. More user-friendly phosphines? Molecular structure of methylphosphine and its adduct with borane, studied by gas-phase electron diffraction and quantum chemical calculations

    OpenAIRE

    2008-01-01

    The molecular structures of methylphosphine (CH3PH2) and methylphosphine-borane (CH3PH2·BH3) have been determined from gas-phase electron diffraction data and rotational constants, employing the SARACEN method. The experimental geometric parameters generally showed a good agreement with those obtained using ab initio calculations and previous microwave spectroscopy studies. In order to assess the accuracy of the calculated structures a range of ab initio methods were used, including the CCSD(...

  19. Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism.

    Science.gov (United States)

    Rossin, Andrea; Bottari, Giovanni; Lozano-Vila, Ana M; Paneque, Margarita; Peruzzini, Maurizio; Rossi, Andrea; Zanobini, Fabrizio

    2013-03-14

    Catalytic dehydrogenation of ammonia-borane (NH(3)·BH(3), AB) and dimethylamine borane (NHMe(2)·BH(3), DMAB) by the Pd(II) complex [((tBu)PCP)Pd(H(2)O)]PF(6) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] leads to oligomerization and formation of spent fuels of general formula cyclo-[BH(2)-NR(2)](n) (n = 2,3; R = H, Me) as reaction byproducts, while one equivalent of H(2) is released per amine-borane equivalent. The processes were followed through multinuclear ((31)P, (1)H, (11)B) variable temperature NMR spectroscopy; kinetic measurements on the hydrogen production rate and the relative rate constants were also carried out. One non-hydridic intermediate could be detected at low temperature, whose chemical nature was explored through a DFT modeling of the reaction mechanism, at the M06//6-31+G(d,p) computational level. The computational output was of help to propose a reliable mechanistic picture of the process.

  20. Studies on the sythesis of c-BN layers with ECWR-PACVD and borane- ammonia as educt material

    CERN Document Server

    Schumacher, A

    2000-01-01

    Boron nitride films were deposited by controlled plasma assisted chemical vapor deposition (PACVD) on the basis of borane-ammonia (BH sub 3 NH sub 3) as B- and N- supplier. Having a high vapor pressure, this white crystalline solid of less toxicity in comparision to generally used boron precursors can easily be transferred into the gas phase by moderate heating. Together with argon as working gas the BH sub 3 NH sub 3 -vapor is led into a two-circuit plasma source utilizing the electron cyclotron wave resonance technique (ECWR) for ionization and dissoziation of the gas mixture by electron impact in the low pressure range (propor to 10 mbar). For a precise adjustment of the energy of the ionic plasma species arriving at the growing film, an r.f.-diode circuit is superimposed to the discharge. Since for a controlled film deposition by PACVD a stationary plasma composition is mandatory, the evaporation characteristics of the reactant source was determined primarily. Therefore the evolution of the plasma and the...

  1. Uptake of [sup 10]B in gliosarcomas following the injection of gluthathione monoethyl ester and sulfhydryl borane

    Energy Technology Data Exchange (ETDEWEB)

    Joel, D.D.; Slatkin, D.N.; Coderre, J.A.

    1992-01-01

    The sulfhydryl borane Na[sub 2][sup 10]B[sub 12]H[sub 11]SH (BSH) was developed as a capture agent for BNCT about 20 years ago and is the compound currently used clinically in Japan for BNCT of malignant brain tumors. Tumor [sup 10]B concentrations following the infusion of the oxidized BSH, a disulfide dimer (Na[sub 4][sup 10]B[sub 24]H[sub 22]S[sub 2]), are nearly twice those obtained following administration of equal amounts of boron as BSH. Also, the rate of decrease of tumor [sup 10]B concentration is slower after dimer infusion than after BSH infusion. When BNCT was administered to rats bearing intracerebral gliosarcomas, the animals infused with dimer had a significant longer median survival time. Dimer, on the other hand, induces a moderately severe, but reversible, hepatotoxicity which may complicate its use in humans. Intracellular glutathione plays an important role in defense against radical-mediated tissue injury. Glutathione monoesters have been reported to have a protective effective on cisplatin toxicity and on radical-induced acute pancreatitis. We investigated the possibility of reducing dimer-induced hepatotoxicity by pre-administration of GSH-ME. The results indicate that not only does the pre-administration of GSH-ME markedly reduce dimer-induced hepatotoxicity, but also results in nearly a doubling of tumor boron concentration. Furthermore, GSH-ME markedly increases tumor boron uptake and retention following administration of BSH.

  2. Uptake of {sup 10}B in gliosarcomas following the injection of gluthathione monoethyl ester and sulfhydryl borane

    Energy Technology Data Exchange (ETDEWEB)

    Joel, D.D.; Slatkin, D.N.; Coderre, J.A.

    1992-12-31

    The sulfhydryl borane Na{sub 2}{sup 10}B{sub 12}H{sub 11}SH (BSH) was developed as a capture agent for BNCT about 20 years ago and is the compound currently used clinically in Japan for BNCT of malignant brain tumors. Tumor {sup 10}B concentrations following the infusion of the oxidized BSH, a disulfide dimer (Na{sub 4}{sup 10}B{sub 24}H{sub 22}S{sub 2}), are nearly twice those obtained following administration of equal amounts of boron as BSH. Also, the rate of decrease of tumor {sup 10}B concentration is slower after dimer infusion than after BSH infusion. When BNCT was administered to rats bearing intracerebral gliosarcomas, the animals infused with dimer had a significant longer median survival time. Dimer, on the other hand, induces a moderately severe, but reversible, hepatotoxicity which may complicate its use in humans. Intracellular glutathione plays an important role in defense against radical-mediated tissue injury. Glutathione monoesters have been reported to have a protective effective on cisplatin toxicity and on radical-induced acute pancreatitis. We investigated the possibility of reducing dimer-induced hepatotoxicity by pre-administration of GSH-ME. The results indicate that not only does the pre-administration of GSH-ME markedly reduce dimer-induced hepatotoxicity, but also results in nearly a doubling of tumor boron concentration. Furthermore, GSH-ME markedly increases tumor boron uptake and retention following administration of BSH.

  3. 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.

  4. From betaines to anionic N-heterocyclic carbenes. Borane, gold, rhodium, and nickel complexes starting from an imidazoliumphenolate and its carbene tautomer

    Directory of Open Access Journals (Sweden)

    Ming Liu

    2016-12-01

    Full Text Available The mesomeric betaine imidazolium-1-ylphenolate forms a borane adduct with tris(pentafluorophenylborane by coordination with the phenolate oxygen, whereas its NHC tautomer 1-(2-phenolimidazol-2-ylidene reacts with (triphenylphosphinegold(I chloride to give the cationic NHC complex [Au(NHC2][Cl] by coordination with the carbene carbon atom. The anionic N-heterocyclic carbene 1-(2-phenolateimidazol-2-ylidene gives the complexes [K][Au(NHC−2], [Rh(NHC−3] and [Ni(NHC−2], respectively. Results of four single crystal analyses are presented.

  5. Synthesis, structure, and reactivity of diazene adducts: isolation of iso-diazene stabilized as a borane adduct.

    Science.gov (United States)

    Reiß, Fabian; Schulz, Axel; Villinger, Alexander

    2014-09-08

    This work describes the synthesis and full characterization of a series of GaCl3 and B(C6 F5 )3 adducts of diazenes R(1) NNR(2) (R(1) =R(2) =Me3 Si, Ph; R(1) =Me3 Si, R(2) =Ph). Trans-PhNNPh forms a stable adduct with GaCl3 , whereas no adduct, but instead a frustrated Lewis acid-base pair is formed with B(C6 F5 )3 . The cis-PhNNPh⋅B(C6 F5 )3 adduct could only be isolated when UV light was used, which triggers the isomerization from trans- to cis-PhNNPh, which provides more space for the bulky borane. Treatment of trans-PhNNSiMe3 with GaCl3 led to the expected trans-PhNNSiMe3 ⋅GaCl3 adduct but the reaction with B(C6 F5 )3 triggered a 1,2-Me3 Si shift, which resulted in the formation of a highly labile iso-diazene, Me3 Si(Ph)NN; stabilized as a B(C6 F5 )3 adduct. Trans-Me3 SiNNSiMe3 forms a labile cis-Me3 SiNNSiMe3 ⋅B(C6 F5 )3 adduct, which isomerizes to give the transient iso-diazene species (Me3 Si)2 NN⋅B(C6 F5 )3 upon heating. Both iso-diazene species insert easily into one BC bond of B(C6 F5 )3 to afford hydrazinoboranes. All new compounds were fully characterized by means of X-ray crystallography, vibrational spectroscopy, CHN analysis, and NMR spectroscopy. All compounds were further investigated by DFT and the bonding situation was assessed by natural bond orbital (NBO) analysis.

  6. Self-supported Cu(OH)2@Co2CO3(OH)2 core-shell nanowire array as a robust catalyst for ammonia-borane hydrolysis

    Science.gov (United States)

    Wang, Jianmei; Ma, Xiao; Yang, Wenrong; Sun, Xuping; Liu, Jingquan

    2017-01-01

    High hydrogen content and long-term stability in aqueous solutions make ammonia-borane (AB) a promising hydrogen-storage material. It is highly attractive but still challenging to develop efficient catalysts for real-time and controllable hydrogen release from AB solution under mild conditions. Herein, we describe the use of a three-dimensional hierarchical Cu(OH)2@Co2CO3(OH)2 core-shell nanowire array on copper foam (denoted as Cu(OH)2@Co2CO3(OH)2/CF) as a highly efficient catalyst for hydrolytic dehydrogenation of AB. The Cu(OH)2@Co2CO3(OH)2/CF works as an on/off switch for on-demand hydrogen generation with a low activation energy of 44.3 KJ mol-1 and a turnover frequency of 39.72 mol(H2)/mol(cat.)/min. It also maintains activity and integration after long-term usage.

  7. Core-shell structured nanospheres with mesoporous silica shell and Ni core as a stable catalyst for hydrolytic dehydrogenation of ammonia borane

    Institute of Scientific and Technical Information of China (English)

    Hua; Liu; Changyan; Cao; Ping; Li; Yu; Yu; Weiguo; Song

    2014-01-01

    Core-shell structured nanospheres with mesoporous silica shell and Ni core(denoted as Ni@meso-SiO2) are prepared through a three-step process. Monodispersed Ni precursors are first prepared, and then coated with mesoporous SiO2. Final Ni@meso-SiO2spheres are obtained after calcination. The products are characterized by X-ray powder diffraction, transmission electron microscopy and N2adsorption-desorption methods. These spheres have a high surface area and are well dispersed in water, showing a high catalytic activity with a TOF value of 18.5,and outstanding stability in hydrolytic dehydrogenation of ammonia borane at room temperature.

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

    Science.gov (United States)

    Zhao, Binhua; Liu, Jinyin; Zhou, Litao; Long, Dan; Feng, Kun; Sun, Xuhui; Zhong, Jun

    2016-01-01

    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, NH3BH3), 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.

  9. 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

    2015-05-01

    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.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. Electronic supplementary information (ESI) available: Magnified TEM images, high resolution TEM images and the particle size distributions of the samples, the STXM results of a thick tube at different positions, XPS results, stability test. See DOI: 10.1039/c5nr01168j

  10. Efficient synthesis of 1,3,5-oxygenated synthons from dimethyl 3-oxoglutarate: first use of borane-dimethyl sulfide complex as a regioselective reducing agent of 3-oxygenated glutarate derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Riatto, Valeria B.; Carneiro, Maria N.M.; Victor, Mauricio M., E-mail: mmvictor@ufba.b [Universidade Federal da Bahia (IQ/UFBA), Salvador, BA (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Carvalho, Venilia B. [Centro Universitario FIB, Salvador, BA (Brazil). Inst. de Ciencias da Saude

    2011-07-01

    The selective reduction of dimethyl 3-oxoglutarate was accomplished in different levels. A high yielding sodium borohydride reduction of the keto group is fully described leading to dimethyl 3-hydroxyglutarate. When borane-dimethyl sulfide (BMS) complex was used, a diol or a triol compound can be obtained by selective or total reduction of 3-hydroxy- or 3-oxoglutarate, respectively, allowing an efficient and practical route to 1,3,5-oxygenated compounds. (author)

  11. 氨硼烷低温和室温结构的第一性原理计算%First-principles Study of Structure of Ammonia Borane

    Institute of Scientific and Technical Information of China (English)

    刘超仁; 胡青苗; 王平

    2011-01-01

    Two kinds of crystal structures (Pmn21 and P42cm) of (ammonia borane) are studied using first-principles plane wave pseudopotential method based on density functional theory in this paper. It was found that the Pmn21 structure is energetically more stable than the P42cm structure at 0 K.This agrees well with the experimental observation, that lower temperature phase is the Pmn21 structure whereas the room temperature phase is P42cm structure. The structure difference between Pmn21 and P42cm phases manifests itself mainly by the variation of intermolecular bond length whereas the intramolecular bond length remains almost unchanged. Electronic state of density was calculated to identify the bonding nature of ammonia borane. The XRD and FTIR patterns of the P42cm structure were calculated, results agree well with the experimental results of AB at room temperature.%采用第-性原理平面波赝暖势方法研究了两种氨硼烷结构(Pmn21及P42cm)的晶格参数、电子结构以及动力学性质.结果表明,Pmn21结构的能量低于P42cm结构,与实验观测结果相符,即低温相为Pmn21结构而室温相为P42cm结构.Pmn21到P42cm相变所引起的结构变化主要体现为氨硼烷分子间双氢键键长显著增加,而分子内部化学键键长变化不大.根据电子态密度分析了氨硼烷的成键状态.氨硼烷室温相的XRD图谱和FTIR图谱的理论预测结果与实验结果符合得较好.

  12. Body composition and energy utilization by steers of diverse genotypes fed a high-concentrate diet during the finishing period: II. Angus, Boran, Brahman, Hereford, and Tuli sires.

    Science.gov (United States)

    Ferrell, C L; Jenkins, T G

    1998-02-01

    Objectives of the study were to determine the influence of Angus (A), Boran (BO), Brahman (BR), Hereford (H), or Tuli (T) sires on body composition, composition of gain, and energy utilization of crossbred steers during the finishing period. Beginning at 300 kg, 96 steers were adjusted to a high-corn diet and individual feeding. Steers were assigned, by sire breed, to be killed as an initial slaughter group or fed either a limited amount or ad libitum for 140 d then killed. Organ weights, carcass traits, and body composition were evaluated. The statistical model included sire breed (S), treatment (Trt), and the S x Trt interaction. Ad libitum feed intake was least for BO- and T-, intermediate for BR- and H-, and greatest for A-sired steers. Rates of weight, fat, and energy gains were similar for A-, H-, and BR-sired steers but less (P .12). Rates of water, fat, and protein gain increased linearly with increased rate of BW gain, but relationships differed (P < .05) among sire breeds. Linear regression analyses indicated energy requirements for maintenance and efficiency of energy use for energy gain differed (P < .05) among sire breeds. Evaluation by nonlinear regression indicated that heat production increased exponentially and energy gain increased asymptotically as feed intake increased above maintenance.

  13. Theoretical approach to the conformational analyses of dithiazinane, thiadiazinane and triazinane, their N-borane adducts and N-H cations

    Science.gov (United States)

    Suárez-Moreno, Galdina V.; Xotlanihua-Flores, Alfonso; Vela, Alberto; Contreras, Rosalinda; Flores-Parra, Angelina

    2016-06-01

    Computational methods were applied to the study of the different nitrogen and chair conformers of [1,3,5]-dithiazinanes, [1,3,5]-thiadiazinanes and [1,3,5]-triazinanes. Optimisation of heterocycles bearing N-H and N-Me were performed by B3LYP density functional and the 6-311++G** basis set methods, and their free energies were correlated. N-Borane adducts and the protonated cations of these heterocycles were also optimized. The relative free energy differences (ΔG) in gas phase of the chair conformers of eighteen heterocycles were calculated. Calculations agree with experimental data and allow to explain the steric and electronic factors that determine the preferred conformations. The distribution of the electronic density and the NBO atomic charges of the optimized structures support the experimental conformational analyses. The bonding and intramolecular interactions were analysed by using critical point search of the electronic density. They were also evaluated by exchange reduced density gradients associated to overlapping, using the PBE functional with the DZUP basis set. Proton-hydride, proton-proton, hydride-hydride, hydride-sulphur, proton-sulphur and hydride-nitrogen stabilising weak interactions were analysed.

  14. Aqueous solution synthesis of Pt-M (M = Fe, Co, Ni) bimetallic nanoparticles and their catalysis for the hydrolytic dehydrogenation of ammonia borane.

    Science.gov (United States)

    Wang, Shuai; Zhang, Duo; Ma, Yanyun; Zhang, Hui; Gao, Jing; Nie, Yuting; Sun, Xuhui

    2014-08-13

    Platinum-based bimetallic nanocatalysts have attracted much attention due to their high-efficiency catalytic performance in energy-related applications such as fuel cell and hydrogen storage, for example, the hydrolytic dehydrogenation of ammonia borane (AB). In this work, a simple and green method has been demonstrated to successfully prepare Pt-M (M = Fe, Co, Ni) NPs with tunable composition (nominal Pt/M atomic ratios of 4:1, 1:1, and 1:4) in aqueous solution under mild conditions. All Pt-M NPs with a small size of 3-5 nm show a Pt fcc structure, suggesting the bimetallic formation (alloy and/or partial core-shell), examined by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray absorption fine structure (XAFS) analysis. The catalytic activities of Pt-M NPs in the hydrolytic dehydrogenation of AB reveal that Pt-Ni NPs with a ratio of 4:1 show the best catalytic activity and even better than that of pure Pt NPs when normalized to Pt molar amount. The Ni oxidation state in Pt-Ni NPs has been suggested to be responsible for the corresponding catalytic activity for hydrolytic dehydrogenation of AB by XAFS study. This strategy for the synthesis of Pt-M NPs is simple and environmentally benign in aqueous solution with the potential for scale-up preparation and the in situ catalytic reaction.

  15. 吡啶硼烷改性对沥青性能及组成的影响%INFLUENCE OF PYRIDINE-BORANE MODIFICATION ON THE PROPERTIES AND COMPONENT OF PITCHES

    Institute of Scientific and Technical Information of China (English)

    张丽芳; 宋进仁; 要立中; 刘朗

    2001-01-01

    以吡啶硼烷为添加剂对煤焦油沥青进行改性,考察了工艺条件(硼添加量,反应温度,反应时间)对改性沥青软化点、残炭值及其族组成的影响。发现吡啶硼烷参与并促进了沥青分子的反应,其结果是随着硼添加量的增加,改性沥青的软化点、残炭值提高,TS组份的含量降低,而PI组份的含量增加。在同一反应条件下,体系有无吡啶硼烷,所得结果有显著差别。吡啶硼烷改性系列的软化点、残炭值及PI组份的含量均明显高于纯沥青系列。%Coal tar pitch was modified by adding pyridine-borane. The effectof reaction conditions on the properties and components of modified pitches was investigated. It was found that pyridine-borane participate in and accelerated the reaction among molecules, but changed the component and structure of pitches. The softening points, carbon yields and PI fraction content increased with the increasing of boron addition and reaction temperature, while TS fraction content of pitches decreased. Compared with the pure pitches, pyridine-borane modified pitches had higher softening points, carbon yields and PI fraction content at the same reaction conditions.

  16. Lithium insertion into boron containing carbons prepared by co-pyrolysis of coal-tar pitch and borane-pyridine complex

    Energy Technology Data Exchange (ETDEWEB)

    Machnikowski, J.; Frackowiak, E.; Kierzek, K.; Waszak, D.; Benoit, R.; Beguin, F. [Wroclaw University of Technology, Wroclaw (Poland)

    2004-03-01

    Carbon materials of boron content ranging from 0.6 to 4 wt.% were synthesized by co-pyrolysis of QI-free coal-tar pitch with the borane-pyridine complex. The growing amount of boron introduced into the carbonaceous material is associated with an increase in nitrogen content and a progressive degradation of structural and textural ordering. The structural variations of the boron-doped materials on heat treatment up to 2500{sup o}C were monitored using X-ray diffraction and X-ray photoelectron spectroscopy. The intrinsic boron acts effectively as a catalyst of graphitization above 2100{sup o}C. The carbonaceous material with boron content of about 1.5 wt% shows the highest degree of structural ordering after thermal treatment. A high amount of oxygen was found in the graphitized boronated carbons, proving that the incorporated boron induces a strong chemisorption activity of the material when exposed to air. For a series of cokes calcined at 1000 {sup o}C, the most striking effect of increasing the boron content is an increase of irreversible capacity X-irr from 0.2 to 0.7. The reversible capacity (X-rev) amounts to about 1, with a slight tendency to decrease with the boron content. Upon increasing the temperature up to 2500{sup o}C, X-irr decreases to about 0.1 in the graphitic carbons, while X-rev reaches a minimum of 0.4-0.5 at 1700{sup o}C and next increases to a value close to 1 at 2500{sup o}C. In the boron doped graphite, X-irr has a slight tendency to increase with the boron content, due to the simultaneous presence of nitrogen in these materials and their strong affinity for oxygen from the atmosphere.

  17. Iron complex-catalyzed ammonia-borane dehydrogenation. A potential route toward B-N-containing polymer motifs using earth-abundant metal catalysts.

    Science.gov (United States)

    Baker, R Tom; Gordon, John C; Hamilton, Charles W; Henson, Neil J; Lin, Po-Heng; Maguire, Steven; Murugesu, Muralee; Scott, Brian L; Smythe, Nathan C

    2012-03-28

    Ammonia-borane (NH(3)BH(3), AB) has garnered interest as a hydrogen storage material due to its high weight percent hydrogen content and ease of H(2) release relative to metal hydrides. As a consequence of dehydrogenation, B-N-containing oligomeric/polymeric materials are formed. The ability to control this process and dictate the identity of the generated polymer opens up the possibility of the targeted synthesis of new materials. While precious metals have been used in this regard, the ability to construct such materials using earth-abundant metals such as Fe presents a more economical approach. Four Fe complexes containing amido and phosphine supporting ligands were synthesized, and their reactivity with AB was examined. Three-coordinate Fe(PCy(3))[N(SiMe(3))(2)](2) (1) and four-coordinate Fe(DEPE)[N(SiMe(3))(2)](2) (2) yield a mixture of (NH(2)BH(2))(n) and (NHBH)(n) products with up to 1.7 equiv of H(2) released per AB but cannot be recycled (DEPE = 1,2-bis(diethylphosphino)ethane). In contrast, Fe supported by a bidentate P-N ligand (4) can be used in a second cycle to afford a similar product mixture. Intriguingly, the symmetric analogue of 4 (Fe(N-N)(P-P), 3), only generates (NH(2)BH(2))(n) and does so in minutes at room temperature. This marked difference in reactivity may be the result of the chemistry of Fe(II) vs Fe(0).

  18. 不同煤焦油沥青与吡啶硼烷反应性能的比较%STUDY OF REACTIVITY BETWEEN DIFFERENT COAL TAR PITCHES AND PYRIDINE-BORANE

    Institute of Scientific and Technical Information of China (English)

    张丽芳; 宋进仁; 要立中; 刘朗

    2001-01-01

    以三种不同的煤焦油沥青为原料,分别与吡啶硼烷反应制备了硼取代中间相沥青。比较了它们的软化点、残炭值、四氢呋喃不溶物(THFI)以及中间相的偏光显微结构。发现煤焦油沥青不同所得结果有显著差别:较高软化点的沥青与吡啶硼烷的反应活性较强,而相同软化点的净化煤焦油沥青与吡啶硼烷具有更强的反应性,所得中间相沥青的软化点、残炭值及四氢呋喃不溶物的含量较高,其偏光显微结构也证实了这一点。%Boron-substituted mesophase pitches were synthesized by co-pyrolysis of different coal tar pitches with pyridine-borane complex.The softing points, coke yields, solubility in tetrahydrofurane (THF) and polarized micrographs were compared. It is found that the results are different. The coal tar pitch with high soffening point after purification had higher reactivity with pyridine-borane, which was proved by the soffening point, coke yield solubitily in THF and polarized microstructure of obtained pitch.

  19. Selective reversible hydrogenation of Mg(B3H8)2/MgH2 to Mg(BH4)2: pathway to reversible borane-based hydrogen storage?

    Science.gov (United States)

    Chong, Marina; Matsuo, Motoaki; Orimo, Shin-ichi; Autrey, Tom; Jensen, Craig M

    2015-04-20

    Mg(B3H8)2·2THF (THF = tetrahydrofuran) was prepared by the addition of BH3·THF to Mg/Hg amalgam. Heating a 1:2 molar mixture of Mg(B3H8)2·2THF and MgH2 to 200 °C under 5 MPa H2 for 2 h leads to nearly quantitative conversion to Mg(BH4)2. The differential scanning calorimetry profile of the reaction measured under 5 MPa H2 shows an initial endothermic feature at ∼65 °C for a phase change of the compound followed by a broad exothermic feature that reaches a maximum at 130 °C corresponding to the hydrogenation of Mg(B3H8)2 to Mg(BH4)2. Heating Mg(B3H8)2·2THF to 200 °C under 5 MPa H2 pressure in the absence of MgH2 gives predominantly MgB12H12 as well as significant amounts of MgB10H10 and Mg(BH4)2. Hydrogenation of a mixture of Mg(B3H8)2·2THF and LiH in a 1:4 molar ratio at 130 °C under 5 MPa H2 yields [B12H12](2-) in addition to [BH4](-), while a 1:4 molar ratio of Mg(B3H8)2·2THF and NaH yields [BH4](-) and a new borane, likely [B2H7](-). Hydrogenation of the NaH-containing mixture at 130 °C gives primarily the alternative borane, indicating it is an intermediate in the two-step conversion of the triborane to [BH4](-). The solvent-free triborane Mg(B3H8)2, derived from the low-temperature dehydrogenation of Mg(BH4)2, also produces Mg(BH4)2, but higher temperature and pressure is required to effect the complete transformation of the Mg(B3H8)2. These results show that the reversible transformation of the triborane depends on the stability of the metal hydride. The more stable the metal hydride, that is, LiH > NaH > MgH2, the lower is the "regeneration" efficiency.

  20. Reduction of Nitroarenes into Aryl Amines and N-Aryl hydroxylamines via Activation of NaBH4 and Ammonia-Borane Complexes by Ag/TiO2 Catalyst

    Directory of Open Access Journals (Sweden)

    Dimitrios Andreou

    2016-03-01

    Full Text Available In this study, we report the fabrication of mesoporous assemblies of silver and TiO2 nanoparticles (Ag/MTA and demonstrate their catalytic efficiency for the selective reduction of nitroarenes. The Ag/TiO2 assemblies, which show large surface areas (119–128 m2·g−1 and narrow-sized mesopores (ca. 7.1–7.4 nm, perform as highly active catalysts for the reduction of nitroarenes, giving the corresponding aryl amines and N-aryl hydroxylamines with NaBH4 and ammonia-borane (NH3BH3, respectively, in moderate to high yields, even in large scale reactions (up to 5 mmol. Kinetic studies indicate that nitroarenes substituted with electron-withdrawing groups reduced faster than those with electron-donating groups. The measured positive ρ values from the formal Hammett-type kinetic analysis of X-substituted nitroarenes are consistent with the proposed mechanism that include the formation of possible [Ag]-H hybrid species, which are responsible for the reduction process. Because of the high observed chemo selectivities and the clean reaction processes, the present catalytic systems, i.e., Ag/MTA-NaBH4 and Ag/MTA-NH3BH3, show promise for the efficient synthesis of aryl amines and N-aryl hydroxylamines at industrial levels.

  1. 2-(Methylamido)pyridine-Borane: A Tripod κ(3)-N,H,H Ligand in Trigonal Bipyramidal Rhodium(I) and Iridium(I) Complexes with an Asymmetric Coordination of Its BH3 Group.

    Science.gov (United States)

    Brugos, Javier; Cabeza, Javier A; García-Álvarez, Pablo; Kennedy, Alan R; Pérez-Carreño, Enrique; Van der Maelen, Juan F

    2016-09-06

    The complexes [M(κ(3)-N,H,H-mapyBH3)(cod)] (M = Rh, Ir; HmapyBH3 = 2-(methylamino)pyridine-borane; cod = 1,5-cyclooctadiene), which contain a novel anionic tripod ligand coordinated to the metal atom through the amido N atom and through two H atoms of the BH3 group, were prepared by treating the corresponding [M2(μ-Cl)2(cod)2] (M = Rh, Ir) precursor with K[mapyBH3]. X-ray diffraction studies and a theoretical Quantum Theory of Atoms in Molecules analysis of their electron density confirmed that the metal atoms of both complexes are in a very distorted trigonal bipyramidal coordination environment, in which two equatorial sites are asymmetrically spanned by the H-B-H fragment. While both 3c-2e BH-M interactions are more κ(1)-H (terminal σ coordination of the B-H bond) than κ(2)-H,B (agostic-type coordination of the B-H bond), one BH-M interaction is more agostic than the other, and this difference is more marked in the iridium complex than in the rhodium one. This asymmetry is not evident in solution, where the cod ligand and the BH3 group of these molecules participate in two concurrent dynamic processes of low activation energies (variable-temperature NMR and density functional theory studies), namely, a rotation of the cod ligand that interchanges its two alkene fragments (through a square pyramidal transition state) and a rotation of the BH3 group about the B-N bond that equilibrates the three B-H bonds (through a square planar transition state). While the cod rotation has similar activation energy in 2 and 3, the barrier to the BH3 group rotation is higher in the iridium complex than in the rhodium one.

  2. 氨基络合物制备氨硼烷及放氢性能研究%Preparation of Ammonia Borane with Ammonia Complex and the Study of Hydrogen Desorption Performance

    Institute of Scientific and Technical Information of China (English)

    邹少爽; 陶占良; 陈军

    2011-01-01

    This paper reports on the synthesis of ammonia borane(NH3BH3,AB) from sodium borohydride and ammonia complex Ni(NH3)6?Cl2 and the dehydrogenation of the as-synthesized AB.The composition and purity of the products have been tested by instrumental analyses of XRD,FTIR,11B NMR and ICP.The effects of raw materials molar ratio,reaction temperature,reaction time and solvent on the synthesis of AB have been systematically investigated.At the same time,a thermal decomposition process has also been ex-plored on the as-prepared AB with different raw material ratios.The results show that a pure phase AB(pu-rity99%) can be obtained with the molar ratio of NaBH4∶Ni(NH3)6Cl2=2∶1 and the reaction time of 10 h.Thermal analysis displays that the hydrogen gas is released in the first step from AB with raw material molar ratio of NaBH4∶Ni(NH3)6Cl2=3∶1,and impurities of diborane(m/e=27),borazine(m/e=80) are effectively inhibited at the heating rate of 2 ℃/min.In addition,a certain amount of Ni nanoparticles with the size of about 10 nm exist in the products,which would be used as a catalyst for the hydrolysis of AB.%以NaBH4为硼源、氨基络合物Ni(NH3)6Cl2为氨源制备高储氢容量的氨硼烷(NH3BH3,Ammonia Borane,AB)及其放氢性能研究.通过XRD,FTIR,11B NMR,ICP等手段分析表征了所制备产物的组成和纯度,在此基础上探究了原料比例、反应温度、时间和溶剂等因素对产物的影响.同时,对不同原料比制得氨硼烷的热解放氢性能进行了研究.实验结果表明:当物质的量NaBH4∶Ni(NH3)6Cl2=2∶1经过10 h的反应,得到了纯度非常高的氨硼烷(纯度〉99%);以NaBH4∶Ni(NH3)6Cl2=3∶1得到的氨硼烷,当以2℃/min进行升温时,氢气释放主要集中在第一步,并且没有硼烷和硼嗪等杂质气体的产生.另外,在产物中得到了金属Ni纳米颗粒,经洗涤干燥后其粒径大小可控制在10 nm左右,在催化氨硼烷等

  3. Difluoro[2-(quinolin-2-ylphenolato]borane

    Directory of Open Access Journals (Sweden)

    Xi Yang

    2011-05-01

    Full Text Available The title compound, C15H10BF2NO, was synthesized by the reaction of 2-(quinolin-2-ylphenol and boron trifluoride etherate. The quinoline ring system and the benzene ring are twisted, making a dihedral angle of 8.3 (2°. In the crystal, π–π interactions between the aromatic rings [centroid–centroid distance = 3.638 (9 Å] link the molecules into chains propagating in [100].

  4. Relations Between Stabilities and Structures of Closo Borane Dianions

    Institute of Scientific and Technical Information of China (English)

    LI Ping

    2006-01-01

    An effective method to investigate the stabilities of a series of new closo-BnHn2-(n = 12, 14, 16, 18, 20, 22, 24, 30) was put forward with the aid of G96PW91/SHC calculations. Stabilities are related to the relative stabilized energies (RSE) and the 2e3c bound geometries of closo-BnHn2-. The structures in which a boron atom connects to four atoms up to seven are stable and appear in many borides because of the lower relative stabilized energy. In geometries, both triangular and quadrangular faces are in favor of forming the structures of closo-BnHn2-. The energies of optimized geometries support the existence of these new compounds. By employing both RSE and ▲E per boron atom in cage, the stabilities were studied to predict the probabilities of unknown clusters in existence. The electron-deficient clusters can be understood that the positive holes should be disperse to every triangular face and lead to share the holes, wherever there are not enough electrons to occupy them. The negative charges which anions carry distribute to 2e3c bonds to increase the stabilities.

  5. HIDEF Igniter Technology Program. Phase I. Final Report. Appendix A. Polyhedral Boranes in Pyrotechnic Applications

    Science.gov (United States)

    1980-06-15

    Fluorine gas, diluted with 5-15% nitrogen, is bubbled into the aqueous solution until it is present in excess. An aqueous solution of Nt^ PFe is then added...stirred and aqueous te’ramethylammonium hydroxide is added until the color changes abruptly to a light hue. At this point an audition :.] 5-10 g. of

  6. High and rapid hydrogen release from thermolysis of ammonia borane near PEM fuel cell operating temperature

    Energy Technology Data Exchange (ETDEWEB)

    Varma, Arvind; Hwang, Hyun Tae; Al-Kukhun, Ahmad

    2016-11-15

    A system for generating and purifying hydrogen. To generate hydrogen, the system includes inlets configured to receive a hydrogen carrier and an inert insulator, a mixing chamber configured to combine the hydrogen carrier and the inert insulator, a heat exchanger configured to apply heat to the mixture of hydrogen carrier and the inert insulator, wherein the applied heat results in the generation of hydrogen from the hydrogen carrier, and an outlet configured to release the generated hydrogen. To purify hydrogen, the system includes a primary inlet to receive a starting material and an ammonia filtration subassembly, which may include an absorption column configured to absorb the ammonia into water for providing purified hydrogen at a first purity level. The ammonia filtration subassembly may also include an adsorbent member configured to adsorb ammonia from the starting material into an adsorbent for providing purified hydrogen at a second purity level.

  7. Asymmetric synthesis of trans-disubstituted cyclopropanes using phosphine oxides and phosphine boranes

    DEFF Research Database (Denmark)

    Clarke, Celia; Foussat, Stéphanie; Fox, David J;

    2009-01-01

    The stereocontrolled synthesis of trans-disubstituted cyclopropylketones has been achieved from beta-alkyl, gamma-benzoyl phosphine oxides via a three-step cascade reaction incorporating an acyl transfer, phosphinoyl transfer and cyclisation to form the cyclopropane. Using Evans' chiral oxazolidi...

  8. Dehydrocoupling of dimethylamine borane catalyzed by Rh(PCy3)2H2Cl.

    Science.gov (United States)

    Sewell, Laura J; Huertos, Miguel A; Dickinson, Molly E; Weller, Andrew S; Lloyd-Jones, Guy C

    2013-04-15

    The Rh(III) species Rh(PCy3)2H2Cl is an effective catalyst (2 mol %, 298 K) for the dehydrogenation of H3B·NMe2H (0.072 M in 1,2-F2C6H4 solvent) to ultimately afford the dimeric aminoborane [H2BNMe2]2. Mechanistic studies on the early stages in the consumption of H3B·NMe2H, using initial rate and H/D exchange experiments, indicate possible dehydrogenation mechanisms that invoke turnover-limiting N-H activation, which either precedes or follows B-H activation, to form H2B═NMe2, which then dimerizes to give [H2BNMe2]2. An additional detail is that the active catalyst Rh(PCy3)2H2Cl is in rapid equilibrium with an inactive dimeric species, [Rh(PCy3)H2Cl]2. The reaction of Rh(PCy3)2H2Cl with [Rh(PCy3)H2(H2)2][BAr(F)4] forms the halide-bridged adduct [Rh(PCy3)2H2(μ-Cl)H2(PCy3)2Rh][BAr(F)4] (Ar(F) = 3,5-(CF3)2C6H3), which has been crystallographically characterized. This dinuclear cation dissociates on addition of H3B·NMe2H to re-form Rh(PCy3)2H2Cl and generate [Rh(PCy3)2H2(η(2)-H3B·NMe2H)][BAr(F)4]. The fate of the catalyst at low catalyst loadings (0.5 mol %) is also addressed, with the formation of an inactive borohydride species, Rh(PCy3)2H2(η(2)-H2BH2), observed. On addition of H3B·NMe2H to Ir(PCy3)2H2Cl, the Ir congener Ir(PCy3)2H2(η(2)-H2BH2) is formed, with concomitant generation of the salt [H2B(NMe2H)2]Cl.

  9. Synthesis and Reactivity of Novel Boranes Derived from Bulky Salicylaldimines: The Molecular Structure of a Maltolato Compound

    Directory of Open Access Journals (Sweden)

    Jeremy L. Bourque

    2015-02-01

    Full Text Available Reductive amination of salicylaldehyde or 3,5-di-tert-butylsalicylaldehyde and 1-adamantylamine using NaBH4 gave the corresponding aminoalcohols in high yields. Subsequent addition of one equivalent of H3B·SMe2 to the aminoalcohols, with loss of two equivalents of dihydrogen, resulted in the formation of adamantanyl oxazaborinanes (1a,b. The molecular structure of 1b was studied by a single crystal X-ray diffraction study. Crystals were obtained from a saturated Et2O solution and belong to the triclinic space group Pī with unit cell parameters a = 9.1267(4 Å; b = 11.676(2 Å; c = 12.240(3 Å; α = 66.840(3°; β = 78.529(3°; and γ = 67.354(3°. The molecular structure of the addition product (2a arising from maltol and 1a was also confirmed by single crystal X-ray diffraction. Crystals were obtained from a saturated 1:2 mixture of toluene/Et2O and belong to the orthorhombic space group Pna2(1 with unit cell parameters a = 18.519(6 Å; b = 17.315(5 Å; and c = 12.680(4 Å. The asymmetric unit contains two molecules that differ slightly in some of the dihedral angles.

  10. Birth and weaning traits in crossbred cattle from Hereford, Angus, Brahman, Boran, Tuli, and Belgian Blue sires

    Science.gov (United States)

    The objective of this study was to characterize breeds representing diverse biological types for birth and weaning traits in crossbred cattle. Gestation length, calving difficulty, percentage of unassisted calving, percentage of perinatal survival, percentage of survival from birth to weaning, birt...

  11. Silver and Copper Complexes with closo-Polyhedral Borane, Carborane and Metallacarborane Anions: Synthesis and X-ray Structure

    Directory of Open Access Journals (Sweden)

    Varvara V. Avdeeva

    2016-05-01

    Full Text Available Synthesis and structure of silver and copper salts and complexes with polyhedral boron hydride anions, including closo-decaborate [B10H10]2−, closo-dodecaborate [B12H12]2−, 1-carba-closo- decaborate [1-CB9H10]−, carba-closo-dodecaborate [CB11H12]−, and cobalt bis(dicarbollide [3,3′-Co(1,2-C2B9H112]− anions and their derivatives, are reviewed. The complexes demonstrate a wide variety of structural types, relating to both the metal coordination environment and coordination modes of boron hydride anions. The latter can range from strong coordination via the polyhedron triangular face including formation of 3c-2e MHB bonds in the case of the [B10H10]2− dianion, the structure of which contains two four-coordinated boron atoms, to very weak M…H interactions with the hydride atoms in the case of bulky [3,3′-Co(1,2-C2B9H112]− monoanion.

  12. Screening of reducing agents for the PEGylation of recombinant human IL-10.

    Science.gov (United States)

    Ambrogelly, Alexandre; Cutler, Collette; Paporello, Brittany

    2013-06-01

    PEGylation is a technology commonly used to enhance the bioavailability of therapeutic proteins in patients. Reductive alkylation of a protein amino terminal alpha amine in the presence of a polyethylene glycol (PEG) chain derivatized with propionaldehyde and a reducing agent, typically sodium cyanoborohydride, is one of the technologies available to achieve quantitative and site specific PEGylation. While cyanoborohydride has proven to be a robust and efficient reagent for this type of reaction, it generates aqueous cyanide as a reaction by-product (and its corollary, the very volatile hydrogen cyanide). We report here the screening of reducing agents such as dimethylamine borane, trimethylamine borane, triethylamine borane, tert-butylamine borane, morpholine borane, pyridine borane, 2-picoline borane, and 5-ethyl-2-methyl-pyridine borane as alternatives to cyanoborohydride for the PEGylation of recombinant human IL-10. The results of our study show that pyridine borane and 2-picoline borane promote rhIL-10 PEGylation at levels comparable to those observed with cyanoborohydride.

  13. Efficient and Safe Chemical Gas Generators with Nanocomposite Reactive Materials

    Science.gov (United States)

    2015-11-30

    ammonia borane has been developed that involves the reaction of mechanically alloyed Al·Mg powder with water as a source of heat for ammonia borane...Edward L. Dreizin, Evgeny Shafirovich. Hydrogen generation from ammonia borane and water through combustion reactions with mechanically alloyed... Synthesis , 21 - 24 October 2013, South Padre Island, TX, p. 211. Rodriguez, D., Machado, M., Shafirovich, E., and Dreizin, E.L., “Gas Generating

  14. Metal nanoparticles via the atom-economy green approach.

    Science.gov (United States)

    Kalidindi, Suresh Babu; Sanyal, Udishnu; Jagirdar, Balaji R

    2010-05-03

    Metal nanoparticles (NPs) of Cu (air-stable), Ag, and Au have been prepared using an atom-economy green approach. Simple mechanical stirring of solid mixtures (no solvent) of a metal salt and ammonia borane at 60 degrees C resulted in the formation of metal NPs. In this reaction, ammonia borane is transformed into a BNH(x) polymer, which protects the NPs formed and halts their growth. This results in the formation of the BNH(x) polymer protected monodisperse NPs. Thus, ammonia borane used in these reactions plays a dual role (reducing agent and precursor for the stabilizing agent).

  15. Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides.

    Science.gov (United States)

    Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

    2011-01-01

    Trialkylborane additives promote reduction of CO(2) to formate by bis(diphosphine) Ni(II) and Rh(III) hydride complexes. The late transition metal hydrides, which can be formed from dihydrogen, transfer hydride to CO(2) to give a formate-borane adduct. The borane must be of appropriate Lewis acidity: weaker acids do not show significant hydride transfer enhancement, while stronger acids abstract hydride without CO(2) reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formate-borane adduct.

  16. Disease: H01186 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available XH, Abdullah MS, Lado-Abeal J, Majed FA, Moeller LC, Boran G, Schomburg L, Weiss RE, Refeto...05) PMID:19769464 (description, gene) Dumitrescu AM, Di Cosmo C, Liao XH, Weiss RE, Refetoff S The syndrome

  17. Fuel Cells and Other Emerging Manportable Power Technologies for the NATO Warfighter. Part 1: Power Sources for Manportable/Manwearable Applications (Piles a combustible et autres technologies portatives d’alimentation en energie pour les combattants de l’OTAN - Partie 1: Sources d’alimentation pour les applications transportables/portables par l’homme)

    Science.gov (United States)

    2014-10-01

    experimentation and a range of related scientific activities that include systems engineering, operational research and analysis, synthesis , integration... Ammonia Borane, Ethylene Diamine Borane and Aluminium Hydride (AlH3). To design a system, challenges of reaction control (hydrolysis, thermolysis...mol H2 [1] It should also be noted that as a result of the fuel’s synthesis process and low volume requirements, the cost of AlH3 must be lowered

  18. Synthèse de mono et diphosphines dérivées d'amino acides ou de peptides, appliquées en chimie de coordination et pour le greffage de fullerène C60

    OpenAIRE

    Minois, Pauline,

    2013-01-01

    The synthesis of secondary phosphine borane amino acids or dipeptides and their applications for the preparation of chiral ligands or for the grafting of fullerene, is described. These compounds were synthesized in good yield (up to 98%) without racemization. The principle of the synthesis is based on the alkylation of primary phosphine borane with a γ-iodo amino acid using phase transfer conditions. Tertiary diphosphine amino acids are obtained with 70% yield after a second alkylation. These...

  19. In vivo comparison of susceptibility between Bos indicus and Bos taurus cattle types to Theileria parva infection

    Directory of Open Access Journals (Sweden)

    S.G. Ndungu

    2005-09-01

    Full Text Available The objective of this study was to determine whether Bos taurus cattle differ form Bos indicus in their susceptibility to infection with the Muguga stabilate of Theileria parva and in their resistance to the resultant disease. Ten Friesians (B. taurus, ten improved Borans (B. indicus, ten unimproved Borans (B. indicus and ten Zebus (B. indicus born to dams from an East Coast fever (ECF endemic area were inoculated with an infective dose50 dilution of T. parva Muguga stabilate 147. All the animals except one Friesian and one Zebu developed schizont parasitosis. All the improved Borans, nine of the Friesians, eight of the unimproved Borans and six of the Zebus developed a febrile response. Four of the improved Borans, four of the Friesians and three of the unimproved Borans died of theileriosis. No significant difference (P > 0.05 in the prepatent period occurred between the groups, but the Zebus had a significantly shorter duration of schizont parasitosis (P > 0.05 and took a significantly shorter time to recover (P > 0.05 than the other three groups. There was no significant difference in the two parameters between the other three groups. The study showed that three B. indicus breds and a B. taurus breed are equally susceptible to T. parva infection. However, Zebus born to dams from an ECF endemic area showed a better ability to control the course of disease than cattle from ECF free areas.

  20. Quantum chemical study on the mechanism of enantioselective reduction of prochiral ketones catalyzed by oxazaborolidines

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The ab initio molecular orbital study on the mechanism of enantioselective reduction of 3,3-dimethyl butanone-2 with borane catalyzed by chiral oxazaborolidine is performed. As illus trated, this enantioselective reduction is exothermic and goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-3,3-dimethyl butanone-2 adduct, and the cata lyst-alkoxyborane adduct with a B-O-B-N 4-member ring and through the decomposition of the catalyst-alkoxyborane adduct with the regeneration of the catalyst. During the hydride transfer in the catalyst-borane-3,3-dimethyl butanone-2 adduct to form the catalyst-alkoxyborane adduct, the hydride transfer and the formation of the B-O-B-N 4-member ring in the catalyst-alkoxyborane ad duct happen simultaneously. The controlling step for the reduction is the transfer of hydride from the borane moiety to the carbonyl carbon of 3,3-dimethyl butanone-2. The transition state for the hydride transfer is a twisted chair structure and the reduction leads to R-chiral alcohols.

  1. Stoichiometric and Catalytic Synthesis of Alkynylphosphines

    Directory of Open Access Journals (Sweden)

    Annie-Claude Gaumont

    2012-12-01

    Full Text Available Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent scope and structure complexity.

  2. Quantum chemical study on asymmetric catalysis reduction of imine

    Institute of Scientific and Technical Information of China (English)

    LI; Ming; (李明); TIAN; Anmin; (田安民)

    2003-01-01

    The quantum chemical method is employed to study the enantioselective reduction of imine with borane catalyzed by chiral oxazaborolidine. All the structures are optimized completely at the B3LYP/6-31G(d) level. The catalysis property of oxazaborolidine is notable. The reduction goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-imine adduct, and the catalyst-amidoborane adduct and the dissociation of the catalyst-amidoborane adduct with the regeneration of the catalyst. The controlling step for the reduction is the dissociation of the catalyst-amidoborane adduct. The main reduced product predicted theoretically is (R )-sec- ondary amine, which is in agreement with the experiment.

  3. A Density Functional Study of α-Mg(BH4)2

    NARCIS (Netherlands)

    Setten, van Michiel J.; Wijs, de Gilles A.; Fichtner, Maximilian; Brocks, Geert

    2008-01-01

    Boranates (tetrahydroborates) are studied intensively because of their potential use as hydrogen storage materials. In this Article, we present a first-principles study of α-Mg(BH4)2 at the level of density functional theory. We optimize the complex structure of α-Mg(BH4)2, starting from the experim

  4. Synthesis of Novel Derivatives of (R)-Cysteine and Their Application in Asymmetric Reduction of Prochiral Ketones

    Institute of Scientific and Technical Information of China (English)

    WANG Hui; PEI Wei-wei; YE Wei-ping

    2005-01-01

    Novel chiral β-amino alcohols containing sulfide or sulfonyl groups were synthesized from (R)-cysteine. Their chiral induction in the asymmetric borane reduction of prochiral ketones was investigated. Optically active secondary alcohols with moderate or high e.e. values were obtained, and the causes of different enantioselectivities between these two sulfur-containing chiral β-amino alcohols were researched.

  5. Gold Cleaning Methods for Electrochemical Detection Applications

    DEFF Research Database (Denmark)

    Fischer, Lee MacKenzie; Tenje, Maria; Heiskanen, Arto

    2009-01-01

    ; hydrochloric acid potential cycling; dimethylamine borane reducing agent solutions at 25 and 65 degrees C; and a dilute form of Aqua Regia. Peak-current potential-differences obtained from cyclic voltammetry and charge transfer resistance obtained from electrochemical impedance spectroscopy, as well as X...

  6. Cooperative redox activation for carbon dioxide conversion

    DEFF Research Database (Denmark)

    Lian, Zhong; Nielsen, Dennis U.; Lindhardt, Anders T.

    2016-01-01

    A longstanding challenge in production chemistry is the development of catalytic methods for the transformation of carbon dioxide into useful chemicals. Silane and borane promoted reductions can be fined-tuned to provide a number of C1-building blocks under mild conditions, but these approaches...

  7. Synthesis of Bis-N-squaramidoacids and their Applications to Asymmetric Reduction of Prochiral Ketone and Diketones

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A series of novel bis-squaramidoacid ligands were prepared. Prochiral ketone and diketones were direct reduced by borane in the presence of these ligands giving secondary alcohol products with enantiomeric excesses up to 64.2% for ω-bromoacetophenone and 90.0% for 1, 6-diphenyl-1, 6-hexanedione.

  8. Recent Developments in the Field of Energetic Ionic Liquids

    Science.gov (United States)

    2014-10-07

    properties of ILs comes from Shreeve et al. (Fig. 17), whom employed ILs to solubilise various boranes. In preliminary tests, the solids: ammonia ... Synthesis , 1977, 1, 1. 91 C. D. Hurd, L. F. Audrieth and L. A. Nalefski, Inorganic Syntheses, ed. H. S. Booth, McGraw-Hill Book Company Inc., New York

  9. Anionic polymerization and polyhomologation: An ideal combination to synthesize polyethylene-based block copolymers

    KAUST Repository

    Zhang, H.

    2013-08-07

    A novel one-pot methodology combining anionic polymerization and polyhomologation, through a "bridge" molecule (BF3OEt 2), was developed for the synthesis of polyethylene (PE)-based block copolymers. The anionically synthesized macroanion reacts with the "bridge" molecule to afford a 3-arm star (trimacromolecular borane) which serves as an initiator for the polyhomologation. 2013 The Royal Society of Chemistry.

  10. STIR: Redox-Switchable Olefin Polymerization Catalysis: Electronically Tunable Ligands for Controlled Polymer Synthesis

    Science.gov (United States)

    2013-03-28

    frameworks and metallated using organometallic reagents so as to produce precatalysts that could be activated using methylaluminoxane, borane, or...capable functionalities were incorporated into specifically chosen ligand frameworks and metallated using organometallic reagents so as to produce...Polymerization Catalysis: Electronically Tunable Ligands for Controlled Polymer Synthesis Brian K. Long Department of Chemistry University of Tennessee

  11. Effects of grazing and feedlot finishing duration on the performance of three beef cattle genotypes in Uganda

    DEFF Research Database (Denmark)

    Asizua, Denis; Mpairwe, Denis; Kabi, Fred

    2017-01-01

    stover, 300 maize bran, 447 brewers’ spent grain, 50 molasses and 3 salt (NaCl) as g/kg on dry matter (DM) basis. The three durations were 60, 90 and 120 days excluding 14 days of adaptation period. Data was collected on feed intake, growth, slaughter and carcass characteristics. The Boran consumed less...

  12. Novel baculovirus-derived p67 subunit vaccines efficacious against East Coast fever in cattle

    NARCIS (Netherlands)

    Kaba, S.A.; Musoke, A.J.; Schaap, D.; Schetters, T.; Rowlands, J.; Vermeulen, A.J.; Nene, V.; Vlak, J.M.; Oers, van M.M.

    2005-01-01

    Two novel baculovirus-derived recombinant Theileria parva p67 constructs were tested for their vaccine potential against East Coast fever. Boran calves were immunized with a his-GFP-p67 fusion protein (GFP:p67¿SS) or with GP64:p67C, a protein fusion between a C-terminal domain of p67 and the baculov

  13. Some preliminary observations on the susceptibility and resistance of different cattle breeds to Theileria parva infection

    Directory of Open Access Journals (Sweden)

    S.G. Ndungu

    2005-09-01

    Full Text Available Theileria parva-naïve Friesian (Bos taurus, Boran (Bos indicus and Maasai Zebu steers (B. indicus were infected with a T. parva sporozoite stabilate dose which had previously been shown to induce an estimated 50 % mortality rate in Boran cattle. All the cattle developed patent infections with no significant differences in the length of the prepatent period to development of macroschizonts (P > 0.05 between the three groups. Clinical theileriosis occurred in all eight the Friesians (100 %, five out of nine Borans (55.6 % and two out of five Zebus (40 %. Three of the Friesians (37.5 %, and two of the Borans (22.2 % died of theileriosis. The different cattle types were equally susceptible to the infective dose used as indicated by the length of the prepatent periods, but there was a marked difference in their development of clinical theileriosis. The gradation in resistance to disease confirms the findings of earlier less critical studies and identifies these cattle breeds as suitable for investigations into the mechanisms of resistance to theileriosis.

  14. An Efficient Method for Catalytic Asymmetric Reduction of Diketones and Application of Synthesis to Chiral 2,5-Diphenylpyrrolidine and 2,5-Diphenylthiolane

    Institute of Scientific and Technical Information of China (English)

    LI Xiang; ZHAO Gang; CAO Wei-Guo

    2006-01-01

    Asymmetric reduction of diketones with borane reagents generated in situ using cheap and available NaBH4 and SnCl2 in the presence of (S)-(-)-α,α-diphenyl-2-pyrrolidinemethanol was successfully achieved to yield the corresponding chiral diols with excellent stereoselectivity and enantioselectivity. And the chiral diol was transformed into optically pure C2-symmetricl chiral amine or thioether.

  15. De Novo Design of Boron-Based Host Materials for Highly Efficient Blue and White Phosphorescent OLEDs with Low Efficiency Roll-Off.

    Science.gov (United States)

    Xue, Miao-Miao; Huang, Chen-Chao; Yuan, Yi; Cui, Lin-Song; Li, Yong-Xi; Wang, Bo; Jiang, Zuo-Quan; Fung, Man-Keung; Liao, Liang-Sheng

    2016-08-10

    Borane is an excellent electron-accepting species, and its derivatives have been widely used in a variety of fields. However, the use of borane derivatives as host materials in OLEDs has rarely reported because the device performance is generally not satisfactory. In this work, two novel spiro-bipolar hosts with incorporated borane were designed and synthesized. The strategies used in preparing these materials were to increase the spatial separation of the highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) in the molecules, tune the connecting positions of functional groups, and incorporate specific functional groups with desirable thermal stability. Based on these designs, phosphorescent OLEDs with borane derivatives as hosts and with outstanding device performances were obtained. In particular, devices based on SAF-3-DMB/FIrpic exhibited an external quantum efficiency (EQE) of >25%. More encouragingly, the device was found to have quite a low efficiency roll-off, giving an efficiency of >20% even at a high brightness of 10000 cd/m(2). Furthermore, the EQE of the three-color-based (R + G + B) white OLED employing SAF-3-DMB as a host was also as high as 22.9% with CIE coordinates of (x, y) = (0.40, 0.48). At a brightness of 5000 cd/m(2), there was only a 3% decrease in EQE from its maximum value, implying a very low efficiency roll-off.

  16. Reductive Amination of Aldehydes and Ketones with Primary Amines by Using Lithium Amidoborane as Reducing Reagent

    Institute of Scientific and Technical Information of China (English)

    徐维亮; 郑学丽; 吴国涛; 陈萍

    2012-01-01

    A variety of secondary amines were obtained in high isolated yields in the reductive amination of aldehydes and ketones by using lithium amidoborane as reducing agent. Compared to ammonia borane, lithium amidoborane has higher reducibility, and thus, exhibits faster reaction rate.

  17. Solid-phase synthesis of rigid acylpolyamines using temporary N-4,4'-dimethoxytrityl protection in the presence of trityl linkers

    DEFF Research Database (Denmark)

    Olsen, Christian A; Witt, Matthias; Jaroszewski, Jerzy W;

    2004-01-01

    An N-protection protocol employing the 4,4'-dimethoxytrityl (Dmt) group in combination with borane reduction of resin-bound polyamides was shown to be an efficient methodology that enables synthesis of novel analogues of natural acylpolyamine toxins. Thus, three philanthotoxins containing polyami...

  18. New Chiral Pyridine Prolinol Derivatives and Preliminary Study on Asymmetric Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

    Two new chiral pyridine prolinol derivatives have been synthesized from N-alkylation of (S)-α,α-diphenyl-2-pyrrolidinemethanol with 2-bromomethylpyridine and 2, 6-dibromo-methyl-pyridine. The catalytic asymmetric borane reduction of prochiral ketones and the asymmetric addition of diethylzinc to benzaldehyde were investigated.

  19. Boron-Based Hydrogen Storage: Ternary Borides and Beyond

    Energy Technology Data Exchange (ETDEWEB)

    Vajo, John

    2016-09-22

    DOE continues to seek reversible solid-state hydrogen materials with hydrogen densities of ³11 wt% and ³80 g/L that can deliver hydrogen and be recharged at moderate temperatures (£100 °C) and pressures (£100 bar) enabling incorporation into hydrogen storage systems suitable for transportation applications. Boron-based hydrogen storage materials have the potential to meet the density requirements given boron’s low atomic weight, high chemical valance, and versatile chemistry. However, the rates of hydrogen exchange in boron based compounds are thus far much too slow for practical applications. Although contributing to the high hydrogen densities, the high valance of boron also leads to slow rates of hydrogen exchange due to extensive boron-boron atom rearrangements during hydrogen cycling. This rearrangement often leads to multiple solid phases occurring over hydrogen release and recharge cycles. These phases must nucleate and react with each other across solid-solid phase boundaries leading to energy barriers that slow the rates of hydrogen exchange. This project sought to overcome the slow rates of hydrogen exchange in boron-based hydrogen storage materials by minimizing the number of solid phases and the boron atom rearrangement over a hydrogen release and recharge cycle. Two novel approaches were explored: 1) developing matched pairs of ternary borides and mixed-metal borohydrides that could exchange hydrogen with only one hydrogenated phase (the mixed-metal borohydride) and only one dehydrogenated phase (the ternary boride); and 2) developing boranes that could release hydrogen by being lithiated using lithium hydride with no boron-boron atom rearrangement. For the first approach, possible pairs of ternary borides and mixed-metal borohydrides based on Mg with various first row transition metals were investigated both experimentally and theoretically. In particular, the Mg/Mn ternary boride and mixed-metal borohydride were found to be a suitable pair and

  20. Combined crossed molecular beam and ab initio investigation of the multichannel reaction of boron monoxide (BO; X2Σ+) with Propylene (CH3CHCH2; X1A'): competing atomic hydrogen and methyl loss pathways.

    Science.gov (United States)

    Maity, Surajit; Dangi, Beni B; Parker, Dorian S N; Kaiser, Ralf I; An, Yi; Sun, Bing-Jian; Chang, A H H

    2014-10-16

    The reaction dynamics of boron monoxide ((11)BO; X(2)Σ(+)) with propylene (CH(3)CHCH(2); X(1)A') were investigated under single collision conditions at a collision energy of 22.5 ± 1.3 kJ mol(-1). The crossed molecular beam investigation combined with ab initio electronic structure and statistical (RRKM) calculations reveals that the reaction follows indirect scattering dynamics and proceeds via the barrierless addition of boron monoxide radical with its radical center located at the boron atom. This addition takes place to either the terminal carbon atom (C1) and/or the central carbon atom (C2) of propylene reactant forming (11)BOC(3)H(6) intermediate(s). The long-lived (11)BOC(3)H(6) doublet intermediate(s) underwent unimolecular decomposition involving at least three competing reaction mechanisms via an atomic hydrogen loss from the vinyl group, an atomic hydrogen loss from the methyl group, and a methyl group elimination to form cis-/trans-1-propenyl-oxo-borane (CH(3)CHCH(11)BO), 3-propenyl-oxo-borane (CH(2)CHCH(2)(11)BO), and ethenyl-oxo-borane (CH(2)CH(11)BO), respectively. Utilizing partially deuterated propylene (CD(3)CHCH(2) and CH(3)CDCD(2)), we reveal that the loss of a vinyl hydrogen atom is the dominant hydrogen elimination pathway (85 ± 10%) forming cis-/trans-1-propenyl-oxo-borane, compared to the loss of a methyl hydrogen atom (15 ± 10%) leading to 3-propenyl-oxo-borane. The branching ratios for an atomic hydrogen loss from the vinyl group, an atomic hydrogen loss from the methyl group, and a methyl group loss are experimentally derived to be 26 ± 8%:5 ± 3%:69 ± 15%, respectively; these data correlate nicely with the branching ratios calculated via RRKM theory of 19%:5%:75%, respectively.

  1. Postweaning performance and carcass merit of F1 steers sired by Brahman and alternative subtropically adapted breeds.

    Science.gov (United States)

    Franke, D E

    1997-10-01

    Comparisons were made among F1 steers sired by Brahman and alternative subtropically adapted breeds of bulls for feedlot and carcass traits when steers were produced from Angus- and Hereford-type dams. Brahman-derivative breeds included Brangus, Beefmaster, and Santa Gertrudis. Brangus- and Beefmaster-sired steers weighed less at slaughter, whereas carcasses of Brangus- and Santa Gertrudis-sired steers had more marbling than those of Brahman-sired steers. Brahman-sired steer carcasses had greater longissimus muscle area than carcasses of Santa Gertrudis-sired steers. Other Zebu breeds compared to Brahman were Boran, Gir, Indu-Brazil, Nellore, Red Brahman, and Sahiwal. Steers by Brahman sires had higher slaughter weights than steers by Boran, Gir, Nellore, or Sahiwal sires. Hot carcass weights of Brahman-sired steers were also higher than those of Boran- and Sahiwal-sired steers. Steer carcasses by Brahman sires had greater longissimus muscle area than those of steers by Sahiwal sires. Non-Zebu breeds included Tuli and Senepol. Steers by Tuli sires grew slower, had lower slaughter weights, and their carcasses weighed less than those of Brahman-sired steers. Brahman-sired steer carcasses had greater longissimus muscle area but less marbling than carcasses of Tuli-sired steers. These data suggest that steers by Brahman sires have an advantage for slaughter weight over steers by Brangus, Beefmaster, Boran, Gir, Nellore, Sahiwal, and Tuli sires, but their carcasses are at a disadvantage for marbling score compared with those by Brangus, Boran, Nellore, and Tuli sires.

  2. Phosphine-boranes as bidentate ligands: formation of [8,8-eta(2)-(eta(2)-(BH(3)).dppm)-nido-8,7-RhSB(9)H(10)] and [9,9-eta(2)-(eta(2)-(BH(3)).dppm)-nido-9,7,8-RhC(2)B(8)H(11)] from [8,8-(eta(2)-dppm)-8-(eta(1)-dppm)-nido-8,7-RhSB(9)H(10)] and [9,9-(eta(2)-dppm)-9-(eta(1)-dppm)-nido-9,7,8-RhC(2)B(8)H(11)], respectively.

    Science.gov (United States)

    Volkov, Oleg; Macías, Ramón; Rath, Nigam P; Barton, Lawrence

    2002-11-04

    The two clusters [8,8-(eta(2)-dppm)-8-(eta(1)-dppm)-nido-8,7-RhSB(9)H(10)] (1) and [9,9-(eta(2)-dppm)-9-(eta(1)-dppm)-nido-9,7,8-RhC(2)B(8)H(11)] (2) (dppm = PPh(2)CH(2)PPh(2)), both of which contain pendant PPh(2) groups, react with BH(3).thf to afford the species [8,8-eta(2)-(eta(2)-(BH(3)).dppm)-nido-8,7-RhSB(9)H(10)] (3) and [9,9-eta(2)-(eta(2)-(BH(3)).dppm))-nido-9,7,8-RhC(2)B(8)H(11)] (4), respectively. These two species are very similar in that they both contain the bidentate ligand [(BH(3)).dppm], which coordinates to the Rh center via a PPh(2) group and also via a eta(2)-BH(3) group. Thus, the B atom in the BH(3) group is four-coordinate, bonded to Rh by two bridging hydrogen atoms, to a terminal H atom, and to a PPh(2) group. At room temperature, the BH(3) group is fluxional; the two bridging H atoms and the terminal H atom are equivalent on the NMR time scale. The motion is arrested at low temperature with DeltaG++ = ca. 37 and 42 kJ mol(-1), respectively, for 3 and 4. Both species are characterized completely by NMR and mass spectral measurements as well as by elemental analysis and single-crystal structure determinations.

  3. Boron-Based (Nano-Materials: Fundamentals and Applications

    Directory of Open Access Journals (Sweden)

    Umit B. Demirci

    2016-09-01

    Full Text Available The boron (Z = 5 element is unique. Boron-based (nano-materials are equally unique. Accordingly, the present special issue is dedicated to crystalline boron-based (nano-materials and gathers a series of nine review and research articles dealing with different boron-based compounds. Boranes, borohydrides, polyhedral boranes and carboranes, boronate anions/ligands, boron nitride (hexagonal structure, and elemental boron are considered. Importantly, large sections are dedicated to fundamentals, with a special focus on crystal structures. The application potentials are widely discussed on the basis of the materials’ physical and chemical properties. It stands out that crystalline boron-based (nano-materials have many technological opportunities in fields such as energy storage, gas sorption (depollution, medicine, and optical and electronic devices. The present special issue is further evidence of the wealth of boron science, especially in terms of crystalline (nano-materials.

  4. Preparation of polypropylene/montmorillonite nanocomposites by intercalative polymerization: Effect of in situ polymer matrix functionalization on the stability of the nanocomposite structure

    Institute of Scientific and Technical Information of China (English)

    YANG KeFang; HUANG YingJuan; DONG JinYong

    2007-01-01

    The copolymerization of propylene and 5-hexenyl-9-borabicyclo[3.3.1]nonane (5-hexenyl-9-BBN) has been conducted with an MgCl2/TiCl4 catalyst intercalated in an organically modified montmorillonite (OMMT) with triethylaluminum (AlEt3) cocatalyst and diphenyldimethoxysilane (DDS) external donor. This polymerization process simultaneously results in both the exfoliation of MMT layers to realize the preparation of polypropylene (PP)/MMT nanocomposites and the implantation of reactive borane groups in the formed PP matrix. The polymer-borne borane groups have been able to undergo an efficient hydrolysis process under very mild reaction conditions (40℃, 3 h, in THF), introducing hydroxy groups into PP without sacrificing the polymerization-formed nanocomposite structure (the exfoliation of MMT). The resultant hydroxyl-functionalized PP/MMT nanocomposites exhibit enhanced structural stability against processing compared with those based on unfunctionalized PP matrix.

  5. A novel route to synthesize diphenylene by the catalytic effect of GaP nanocrystals

    Institute of Scientific and Technical Information of China (English)

    CU; I; Deliang

    2001-01-01

    [1]Corey, E. J., Bakshi, R. K., Shibata, S., Highly enantioselective borane reduction ketones catalyzed by chiral oxazaborolidines, J. Am. Chem. Soc., 1987, 109:5551-5553.[2]Wallbaum, S., Martens, J., Asymmetric syntheses with chiral oxazaborolidines, Tetrahedron Asymmetry, 1992, 3: 1475-1504.[3]Deloux, L., Srebnik, M., Asymmetric borane-catalyzed reactions, Chem. Rev., 1993, 93: 763-784.[4]Togni, A., Venanzi, L. M., Nitrogen donors in organometallic chemistry and in homogeneous catalysis, Angew Chem. Int. Ed. Engl., 1994, 33: 497-562.[5]Ager, D. J., Prakash, I., Schaad, D. R., 1,2-amino alcohols and their heterocyclic derivatives as chiral auxiliaries in asymmetric synthesis, Chem. Rev., 1996, 96: 835-875.[6]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 4. On the hydride transfer in ketone complexes of borane adducts of oxazaborolidines and regeneration of catalyst, Tetrahedron Asymmetry, 1991, 2:1133-1155.[7]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 8. On the conformational freedom of the ketone of ketone-borane complexes of oxazaborolidines used as catalysts in the enantioselective reduction of ketones, Tetrahedron Asymmetry. 1992, 3: 1563-1572.[8]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 7. On the effects controlling the coordination of borane to chiral oxazaborolidines used as catalysts in the enantioselective reduction of ketones, Tetrahedron Asymmetry,1992, 3: 1441-1453.[9]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 12. On the influence of the nature of the ring system on binding in ketone-borane complexes of chiral oxazaborolidines used as catalysts in the enantioselective reduction of ketones. Tetrahedron Asymmetry, 1993, 4: 1597-1602.[10]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 19. Strain and stability-oxazadiboretanes potentially involved in the enantioselective reduction of ketones promoted

  6. Quantum chemical study on the mechanism of enantioselective reduction of prochiral ketones catalyzed by oxazaborolidines

    Institute of Scientific and Technical Information of China (English)

    LI; Ming

    2001-01-01

    [1]Corey, E. J., Bakshi, R. K., Shibata, S., Highly enantioselective borane reduction ketones catalyzed by chiral oxazaborolidines, J. Am. Chem. Soc., 1987, 109:5551-5553.[2]Wallbaum, S., Martens, J., Asymmetric syntheses with chiral oxazaborolidines, Tetrahedron Asymmetry, 1992, 3: 1475-1504.[3]Deloux, L., Srebnik, M., Asymmetric borane-catalyzed reactions, Chem. Rev., 1993, 93: 763-784.[4]Togni, A., Venanzi, L. M., Nitrogen donors in organometallic chemistry and in homogeneous catalysis, Angew Chem. Int. Ed. Engl., 1994, 33: 497-562.[5]Ager, D. J., Prakash, I., Schaad, D. R., 1,2-amino alcohols and their heterocyclic derivatives as chiral auxiliaries in asymmetric synthesis, Chem. Rev., 1996, 96: 835-875.[6]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 4. On the hydride transfer in ketone complexes of borane adducts of oxazaborolidines and regeneration of catalyst, Tetrahedron Asymmetry, 1991, 2:1133-1155.[7]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 8. On the conformational freedom of the ketone of ketone-borane complexes of oxazaborolidines used as catalysts in the enantioselective reduction of ketones, Tetrahedron Asymmetry. 1992, 3: 1563-1572.[8]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 7. On the effects controlling the coordination of borane to chiral oxazaborolidines used as catalysts in the enantioselective reduction of ketones, Tetrahedron Asymmetry,1992, 3: 1441-1453.[9]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 12. On the influence of the nature of the ring system on binding in ketone-borane complexes of chiral oxazaborolidines used as catalysts in the enantioselective reduction of ketones. Tetrahedron Asymmetry, 1993, 4: 1597-1602.[10]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 19. Strain and stability-oxazadiboretanes potentially involved in the enantioselective reduction of ketones promoted

  7. Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

    Directory of Open Access Journals (Sweden)

    Morten B. Ley

    2015-09-01

    Full Text Available This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability.

  8. Liquid-phase chemical hydrogen storage: catalytic hydrogen generation under ambient conditions.

    Science.gov (United States)

    Jiang, Hai-Long; Singh, Sanjay Kumar; Yan, Jun-Min; Zhang, Xin-Bo; Xu, Qiang

    2010-05-25

    There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

  9. B(C6F5)3 catalyzed one-pot three-component Biginelli reaction: An efficient and environmentally benign protocol for the synthesis of 3,4-dihydropyrimidin-2(1)-ones/thiones

    Indian Academy of Sciences (India)

    Santosh Kumar Prajapti; Keshav Kumar Gupta; Bathini Nagendra Babu

    2015-06-01

    Tris(pentafluorophenyl)borane catalyzed, one-pot, simple, efficient and environmentally benign protocol for the synthesis of dihydropyrimidinones/thiones via Biginelli reaction has been described. The main highlights of the present protocol is low catalyst loading, low toxicity, compatibility with acid-labile-protecting groups, short reaction time, consistently excellent yields and simple reaction/workup procedure. Moreover, the applicability of the present methodology for large-scale synthesis of monastrol highlights its potential for bulk synthesis.

  10. Use of Li.sub.2[B.sub.12H.sub.12] salt to absorb water into polymers

    Energy Technology Data Exchange (ETDEWEB)

    Eastwood, Eric A.; Bowen, III, Daniel E.

    2016-08-30

    Methods of adjusting the properties of a composition are provided. The compositions comprise a polymer-containing matrix and a filler comprising a hygroscopic salt. Preferred such salts comprise a cage compound selected from the group consisting of borane cage compounds, carborane cage compounds, metal complexes thereof, residues thereof, mixtures thereof, and/or agglomerations thereof, where the cage compound is not covalently bound to the matrix polymer.

  11. Boron Nanoparticles with High Hydrogen Loading: Mechanism for B-H Binding, Size Reduction, and Potential for Improved Combustibility and Specific Impulse

    Science.gov (United States)

    2014-05-01

    reaction . The relative enthalpies of the fully optimized stationary points in Figures S3-S12 and S14 include scaled harmonic zero point vibrational energy...distribution unlimited. 3  ignitability of diesel fuel,14 and the effects of hydrogen loading on conventional hydrocarbon fuels such as gasoline,15 jet...structures and reaction coordinates are shown in Figures 2 and S3 – S10. Dissociative adsorption of hydrogen to form borane-like B−H bonds on adjacent B

  12. Production of Nanopowders of Platinum Metals Using the Chemical Reduction Method

    Institute of Scientific and Technical Information of China (English)

    PYATAKHINA E. S.; BUSLAYEVA T. M.; VOLCHKOVA E. V.; KHRISTICH E. A.; SERGEYEVA T. Yu.

    2012-01-01

    The literary data on the application of various methods for the production of nanopowders of platinum metals and alloys have been summarized,and the selection of the method of chemical reduction from salt solutions has been substantiated as the simplest and most affordable.The optimum conditions for the production of nanoparticles of metal palladium and platinum/cobalt alloy,using the effect of boranes with various structures,have been selected.

  13. Catalytic Activation of Small Molecules. Development and Characterisation of Ruthenium Complexes for Application in Catalysis

    OpenAIRE

    Choi, Jong-Hoo

    2016-01-01

    In this work, the synthesis, characterisation and catalytic application of ruthenium pincer complexes is presented. In this context, new synthetic strategies are discussed to obtain novel ruthenium pincer dihydrogen complexes. Furthermore, the reactivity of the complexes towards small molecules (e.g. alcohols, boranes, ammonia, amines, nitriles and hydrogen) was observed, delivering fundamental insights into catalytic applications. With the reactivity testing, new borylated B-H-σ-complexes we...

  14. An efficient synthesis of S-[gamma]-[(4-trifluoromethyl)phenoxy] benzenepropanamine-[1-[sup 14]C]maleate, an important metabolite of fluoxetine hydrochloride. [Antidepressant, serotonin uptake inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    Wheeler, W.J. (Lilly (Eli) and Co., Indianapolis, IN (United States). Lilly Research Labs.)

    1992-02-01

    S-[gamma]-[(4-Trifluoromethyl)phenoxy]benzenepropanamine-[1-[sup 14]C] maleate has been prepared in six steps from R-(-)1-phenyl-1,2-ethanediol. The isotope was incorporated by the reaction of NaCN-[[sup 14]C] with the tert. butyldimethylsilyl ether of R-(-)1-phenyl-1,2-ethane-diol 2-tosylate. Borane reduction and arylation, followed by salt formation yielded S-[gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[1-[sup 14]C] maleate. (Author).

  15. Boron in nuclear medicine: New synthetic approaches to PET and SPECT. Final report, May 1, 1986--April 30, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Kabalka, G.W.

    1997-08-01

    Research is described in the development of organometallic reagents in which the boron was attached to a nonreactive organic or inorganic matrix such as polystyrene, silica, or alumina. We developed the synthesis of oxygen-15 labelled butanol, which has been found to be a valuable blood flow agent in humans. We have also developed a series of polymeric borane derivatives which were used to prepare nitrogen-13 labelled amines.

  16. Improved Performance of Protected Catecholic Polysiloxanes for Bioinspired Wet Adhesion to Surface Oxides

    Science.gov (United States)

    2012-11-26

    materials based on a readily available precursor ( eugenol ) and efficient chemistries [tris- (pentafluorophenyl)borane-catalyzed silation and thiol−ene...polymer adhesion.25,26 Our strategy overcomes these issues by employing a common building block, eugenol (the active ingredient of clove oil, which is...reactivity of TPFPB allows the facile one-step transformation of eugenol into a reactive, bis-silyl- protected DOPA mimic. The silyl protecting groups

  17. Program and Abstracts, Boron Americas IX Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Feakes, Debra A.

    2006-08-09

    The Scientific and Technical Information (STI) submitted includes the final report and a collection of abstracts for the Ninth Boron in the Americas Conference which was held May 19-22, 2004, in San Marcos, Texas. The topics covered in the abstracts include: Application in Medicine, Application in Organic Synthesis and Catalysis, Boranes and Carboranes, Materials and Polymers, Metallaboranes and Metallacarboranes, Organoboron Compounds, Synthesis and Catalysis, and Theoretical Studies. Attendees represented researchers from government, industry, and academia.

  18. An Organometallic Future in Green and Energy Chemistry?

    Energy Technology Data Exchange (ETDEWEB)

    Crabtree, Robert H

    2011-01-10

    The title topic is reviewed with selected examples taken from recent work, such as: the 'hydrogen borrowing' amine alkylation by alcohols; the dehydrogenative coupling of amine and alcohol to give amide; Ru complexes as solar cell photosensitizers; Ir organometallics as water oxidation catalyst precursors and as OLED emitters; as well as recent hydrogen storage strategies involving catalytic dehydrogenation of ammonia-borane and of organic heterocycles.

  19. US Army Power Overview

    Science.gov (United States)

    2010-09-01

    Cells (DMFC, RMFC, SOFC ), Batteries & Stirl ing (LFP, Kinemat ic) * Packaged & Reformed Fuels : Methanol, Propane, NaBH4, Ammonia Borane * Direct JP-8... Fuel Goal - SOFC , Stirl ing Burner ~ RENEWABLES/ALTERNATIVE ENERGY * Solar, Wind Energy Storage Systems * Bio- Fuels , Hydrogen Generation ~ MOBILE...ENVIRONMENTAL CONTROL UNITS * Advanced C02 Cooling * Co-Gen Systems (HAC & Stir ling I Fuel Cell ) Soldier Power Existing Situation: • Batteries

  20. Blending materials composed of boron, nitrogen and carbon to transform approaches to liquid hydrogen stores

    Energy Technology Data Exchange (ETDEWEB)

    Whittemore, Sean M.; Bowden, Mark; Karkamkar, Abhijeet; Parab, Kshitij; Neiner, Doinita; Autrey, Tom; Ishibashi, Jacob S. A.; Chen, Gang; Liu, Shih-Yuan; Dixon, David A.

    2015-12-02

    Energy storage remains a key challenge for the advancement of fuel cell applications. Because of this, hydrogen has garnered much research attention for its potential as an energy carrier. This can be attributed to its abundance from non-petroleum sources, and its energy conversion efficiency. Our group, among others, has been studying the use of ammonia borane as a chemical hydrogen storage material for the past several years. Ammonia borane (AB, NH3BH3), a solid state complex composed of the light weight main group elements of nitrogen and boron, is isoelectronic with ethane and as such is an attractive hydrogen storage material with a high gravimetric capacity of H2 (19.6 wt%). However, the widespread use of AB as a chemical hydrogen storage material has been stalled by some undesirable properties and reactivity. Most notably, AB is a solid and this presents compatibility issues with the existing liquid fuel infrastructure. The thermal release of H2 from AB also results in the formation of volatile impurities (borazine and ammonia) that are detrimental to operation of the fuel cell. Additionally, the major products in the spent fuel are polyborazylene and amine borane oligomers that present challenges in regenerating AB. This research was funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  1. Electrochemical hydrogen Storage Systems

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Digby Macdonald

    2010-08-09

    described in the previous literature for electrochemical reduction of spent fuels, have been attempted. A quantitative analytical method for measuring the concentration of sodium borohydride in alkaline aqueous solution has been developed as part of this work and is described herein. Finally, findings from stability tests for sodium borohydride in aqueous solutions of several different compositions are reported. For aminoborane, other research institutes have developed regeneration schemes involving tributyltin hydride. In this report, electrochemical reduction experiments attempting to regenerate tributyltin hydride from tributyltin chloride (a representative by-product of the regeneration scheme) are described. These experiments were performed in the non-aqueous solvents acetonitrile and 1,2-dimethoxyethane. A non-aqueous reference electrode for electrolysis experiments in acetonitrile was developed and is described. One class of boron hydrides, called polyhedral boranes, became of interest to the DOE due to their ability to contain a sufficient amount of hydrogen to meet program goals and because of their physical and chemical safety attributes. Unfortunately, the research performed here has shown that polyhedral boranes do not react in such a way as to allow enough hydrogen to be released, nor do they appear to undergo hydrogenation from the spent fuel form back to the original hydride. After the polyhedral boranes were investigated, the project goals remained the same but the hydrogen storage material was switched by the DOE to ammonia borane. Ammonia borane was found to undergo an irreversible hydrogen release process, so a direct hydrogenation was not able to occur. To achieve the hydrogenation of the spent ammonia borane fuel, an indirect hydrogenation reaction is possible by using compounds called organotin hydrides. In this process, the organotin hydrides will hydrogenate the spent ammonia borane fuel at the cost of their own oxidation, which forms organotin

  2. Facile synthesis and regeneration of Mg(BH4)2 by high energy reactive ball milling of MgB2.

    Science.gov (United States)

    Gupta, Shalabh; Hlova, Ihor Z; Kobayashi, Takeshi; Denys, Roman V; Chen, Fu; Zavaliy, Ihor Y; Pruski, Marek; Pecharsky, Vitalij K

    2013-01-28

    We report direct hydrogenation of MgB(2) in a planetary ball mill. Magnesium borohydride, Mg(BH(4))(2), and various polyhedral borane anion salts have been synthesized at pressures between 50 and 350 bar H(2) without the need for subsequent isothermal hydrogenation at elevated temperature and pressure. The obtained products release ∼4 wt% H(2) below 390 °C, and a major portion of Mg(BH(4))(2) transforms back to MgB(2) at around 300 °C, demonstrating the possibility of reversible hydrogen storage in an Mg(BH(4))(2)-MgB(2) system.

  3. The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters

    Science.gov (United States)

    2016-01-04

    diborane, hydrogen, and a white solid. Whatley et al.8 studied the products of diborane oxidation. Roth and co-workers9 found HOBO to be the main...product during the oxidation of diborane. Roth and Bauer10 proposed that the formation of HOBO severely inhibits the oxidation of boranes by breaking...Whatley and R. N . Pease, J. Am. Chem. Soc, 76, 1997 (1954). 9 W. Roth and W. H. Bauer, J. Phys. Chem, 60, 639 (1956). 10 W. Roth , and W. H. Bauer

  4. The mechanism of asymmetric reduction catalyzed by a C2 symmetric bis-amino alcohol catalyst——In situ NMR study of the structure of new type of dual-centered catalyst

    Institute of Scientific and Technical Information of China (English)

    赵金铠; 韩秀文; 刘秀梅; 包信和; 杭剑峰; 姜标

    2000-01-01

    By means of 1H, 13C, 11B NMR, polar transfer DEPT135, DEPT90 and 2D NMR experiments, IR, etc, the structure of the diaminodihydroxyl ligand and its derivatives used in the asymmetric reduction of prochiral ketones were detected. The catalysts derived from the ligand and bo-rane formed in situ were also studied and the structure transformations in solution were monitored.The structure of the catalyst was proved to be a new type of dual-centered catalyst——bis-oxazaborolidine.

  5. Deoxyiminoalditols from Aldonolactones - V. Preparation of the Four Stereoisomers of 1,5-Dideoxy-1,5-iminopentitols. Evaluation of these Iminopentitols and Three 1,5-Dideoxy-1,5-iminoheptitols as Glycosidase Inhibitors

    DEFF Research Database (Denmark)

    Godskesen, Michael Anders; Lundt, Inge; Madsen, Robert

    1996-01-01

    The four stereoisomeric 1,5-dideoxy-1,5-iminopentitols with D-arabino - (D-lyxo-) (3), ribo- (9), L-lyxo- (L-arabino-) (13) and xylo-(18) configurations were synthesized. The corresponding aldonolactones (1, 7 and 11) or aldonic acid ester (150) having a leaving group at C-5 gave by reaction...... with aqueous ammonia, the 5-amino-5-deoxy-1,5-lactams, 2, 8, 12 and 17, respectively. Reduction of the lactam function using sodium borohydride/acetic or trifluoroacetic acid, or borane dimethyl sulfide complex yielded the iminopentitols. The compounds 3, 9, 13 and 18, together with the three 1,5-dideoxy-1...

  6. Olefin Hydroborations with Diamidocarbene–BH3 Adducts at Room Temperature

    Directory of Open Access Journals (Sweden)

    Dominika N. Lastovickova

    2016-09-01

    Full Text Available An isolable N,N’-diamidocarbene (DAC was previously shown to promote the B–H bond activation of various BH3 complexes. The resultant DAC–BH3 adducts facilitated olefin hydroborations under mild conditions and in the absence of exogenous initiators. The substrate scope for such transformations was further explored and is described herein. While organoboranes were obtained in quantitative yields from various terminal and internal olefins, use of the latter substrates resulted in intramolecular ring-expansion of the newly formed DAC–borane adducts.

  7. Reduktive Synthese zu neuartigen cyclischen und acyclischen Borverbindungen

    OpenAIRE

    Claes, Christina

    2016-01-01

    Ein Teil der hier vorliegenden Arbeit beschäftigte sich mit der Synthese und Charakterisierung neuer Boran-Addukte. Dabei wurden neben den NHCs IMe und IMeMe die Phosphane PEt3 und PMe3 als stabilisierende Lewisbasen eingesetzt. Neben dem Liganden wurde auch der borgebundene organische Rest variiert (Phenyl und n-Butyl), um deren Einfluss auf die Eigenschaften der Addukte zu untersuchen. Die NHC-stabilisierten Monoborane IMe∙B(nBu)Cl2 (99) und IMeMe∙B(Ph)Cl2 (100) konnten in guten Ausbeuten i...

  8. Phosphine-directed C-H borylation reactions: facile and selective access to ambiphilic phosphine boronate esters.

    Science.gov (United States)

    Crawford, Kristina M; Ramseyer, Timothy R; Daley, Christopher J A; Clark, Timothy B

    2014-07-14

    Ambiphilic ligands have received considerable attention over the last two decades due to their unique reactivity as organocatalysts and ligands. The iridium-catalyzed C-H borylation of phosphines is described in which the phosphine is used as a directing group to provide selective formation of arylboronate esters with unique scaffolds of ambiphilic compounds. A variety of aryl and benzylic phosphines were subjected to the reaction conditions, selectively providing stable, isolable boronate esters upon protection of the phosphine as the borane complex. After purification, the phosphine-substituted boronate esters could be deprotected and isolated in pure form.

  9. An enantioselective synthesis of S-[gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride, an important metabolite of fluoxetine hydrochloride

    Energy Technology Data Exchange (ETDEWEB)

    Wheeler, W.J. (Lilly (Eli) and Co., Indianapolis, IN (United States). Lilly Research Labs.)

    1992-06-01

    The S-enantiomer of [gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride has been prepared in eight steps from acetophenone-[carbonyl-[sup 14]C]. The key step in the synthesis involved the enantioselective reduction of R-2-chloroacetophenone-[1-[sup 14]C]with (-)-diisopinocampheyl-chloroborane in an 86.5% yield. The chlorohydrin was converted to R-phenyloxirane-[1-[sup 14]C], which was subsequently converted to the corresponding R-cyanohydrin by reaction with TMS-CN/CaO. Borane reduction and arylation, followed by salt formation yielded S-[gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride. (author).

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

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

  11. NaBH4/NaNO3/H2O: A Convenient System for Selective Reduction of Aldehydes VS. Ketones to their Corresponding Alcohols

    Directory of Open Access Journals (Sweden)

    Soheila Ghaderi

    2014-12-01

    Full Text Available NaBH4 (1.25 equivalents & NaNO3 (3 equivalents reduce a variety of aldehydes in the presence of ketones to their corresponding alcohols. Also, regioselectivity and exclusive 1,2-reduction enals to their corresponding allylic alcohols in high to excellent yields was achieved successfully with this reducing system. The reduction reactions were carried out in water as green solvent in high to excellent yields of the products. A nitrate-borane complex [H3B-NO3]Na is possibly the active reductant in the reaction mixture.

  12. NaBH4/Na2C2O4/H2O: An efficient System for Selective Reduction of Aldehydes in the presence of Ketones

    Directory of Open Access Journals (Sweden)

    Maghsoud Azimzadeh

    2015-06-01

    Full Text Available Selective reduction of a variety of aldehydes (1 equivalents in the presence of ketones to their corresponding alcohols has been carried out by NaBH4 (1.5 equivalents & Na2C2O4 (3 equivalents in water as green solvent in high to excellent yields of the products. An oxalate-borane complex Na2[(H3B2C2O4] is possibly the active reductant in the reaction mixture. Also, Chemoselective, regioselectivity and exclusive 1,2-reduction enals to their corresponding allylic alcohols in high to excellent yields was achieved successfully with this reducing system.

  13. Influence of Experimental Conditions on Deposition of Silver Nanoparticles Onto Surface of Graphene Oxide / Wpływ Warunków Eksperymentalnych Na Proces Osadzania Nanocząstek Srebra Na Powierzchni Tlenku Grafenu

    Directory of Open Access Journals (Sweden)

    Wojnicki M.

    2015-12-01

    Full Text Available Present work describes the influence of silver nanoparticles precursor form as well as the impact of graphene oxide initial concentration on deposition of the silver nanoparticles onto graphene oxide. Borane dimethylamine complex (DMAB was used as the reducing agent. It was observed that application of silver ammonia complexes as the silver nanoparticles precursor as well as alkaline solution effect in higher quantity of deposited AgNPs in comparison to deposition process with the use of silver(I nitrate in acidic solution.

  14. Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

    KAUST Repository

    Dong, G.

    2011-09-15

    Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.

  15. New method for synthesis of unsymmetrical bis-organoelemental (Si, B) ketenes

    Energy Technology Data Exchange (ETDEWEB)

    Ponomarev, S.V.; Nikolaeva, S.N.; Molchanova, G.N.; Kostyuk, A.S.; Grishin, Yu.K. (Moskovskij Gosudarstvennyj Univ. (USSR))

    1984-08-01

    To develop a new general method of synthesis of boronorganic (Si, B) ketenes the interaction of trialkylsilyletoxyacetylenes with BCl/sub 3/, BBr/sub 3/ and (Me/sub 2/N)/sub 2/BBr has been studied. Reaction with boron halides proceeds at - 50 deg C with the formation of trialkylsilylhalogenborylketenes, and with bromine-bis(dimethylamino)borane - at 80 deg C in the medium of dibutyl ether. The ketenes synthesized are stable compounds, distilled in argon atmosphere. Their structure and the presence of the direct bond B-C are confirmed by the data of IR, NMR /sup 1/H, /sup 11/B, /sup 13/C spectra.

  16. Asymmetric synthesis of nonracemic primary amines via spiroborate-catalyzed reduction of pure (E)- and (Z)-O-benzyloximes: applications toward the synthesis of calcimimetic agents.

    Science.gov (United States)

    Ou, Wenhua; Espinosa, Sandraliz; Meléndez, Héctor J; Farré, Silvia M; Alvarez, Jaime L; Torres, Valerie; Martínez, Ileanne; Santiago, Kiara M; Ortiz-Marciales, Margarita

    2013-06-07

    Highly enantiopure (1-aryl)- and (1-naphthyl)-1-ethylamines were synthesized by the borane-mediated reduction of single-isomeric (E)- and (Z)-O-benzyloxime ethers using the stable spiroborate ester derived from (S)-diphenyl valinol and ethylene glycol as the chiral catalyst. Primary (R)-arylethylamines were prepared by the reduction of pure (Z)-ethanone oxime ethers in up to 99% ee using 15% of catalyst. Two convenient and facile approaches to the synthesis of new and known calcimimetic analogues employing enantiopure (1-naphthalen-1-yl)ethylamine as chiral precursor are described.

  17. B-H bond activation using an electrophilic metal complex: insights into the reaction pathway.

    Science.gov (United States)

    Kumar, Rahul; Jagirdar, Balaji R

    2013-01-07

    A highly electrophilic ruthenium center in the [RuCl(dppe)(2)][OTf] complex brings about the activation of the B-H bond in ammonia borane (H(3)N·BH(3), AB) and dimethylamine borane (Me(2)HN·BH(3), DMAB). At room temperature, the reaction between [RuCl(dppe)(2)][OTf] and AB or DMAB results in trans-[RuH(η(2)-H(2))(dppe)(2)][OTf], trans-[RuCl(η(2)-H(2))(dppe)(2)][OTf], and trans-[RuH(Cl)(dppe)(2)], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B-H bond activation were obtained. In both cases, the reaction proceeds via an η(1)-B-H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.

  18. Syntese af amino/hydroxypyrrolidines og -piperidiner fra kulhydratderivater

    DEFF Research Database (Denmark)

    Godskesen, Michael Anders

    lactams were reduced with sodium acetoxyborohydride or borane dimethyl sulfide to the 1,5-imino-1,5-pentitols.1,2,5-Trideoxy-1,5-imino-D-erythro-pentito l and 1,2,5-trideoxy-1,5-imino-D-threo-pentitol were synthesised from 2,5-difunctionalised aldonolactones by reduction of the 2-functionality......Two aldonolactones and an aldonic acid methylester were used in the synthesis of three stereoisomeric 1,5-dideoxy-1,5-imino-pentitols with ribo-, L-lyxo- (L-arabino-), and xylo-configuration. The aldonic acid derivatives were mesylated at C-5 and subsequently reacted with ammonia. The corresponding...... with hydrazin. The hereby formed 5-functionalsed 2-deoxy-lactones were then reacted with ammonia to give the corresponding lactams. The lactams were reduced by borane dimethyl sulfid or lithium aluminium hydride to the 1,2,5-trideoxy-1,5-imino-pentitols.2,5-Difunctionalised aldonolactones were also used...

  19. Increasing Hydrogen Density with the Cation-Anion Pair BH4−-NH4+ in Perovskite-Type NH4Ca(BH43

    Directory of Open Access Journals (Sweden)

    Pascal Schouwink

    2015-08-01

    Full Text Available A novel metal borohydride ammonia-borane complex Ca(BH42·NH3BH3 is characterized as the decomposition product of the recently reported perovskite-type metal borohydride NH4Ca(BH43, suggesting that ammonium-based metal borohydrides release hydrogen gas via ammonia-borane-complexes. For the first time the concept of proton-hydride interactions to promote hydrogen release is applied to a cation-anion pair in a complex metal hydride. NH4Ca(BH43 is prepared mechanochemically from Ca(BH42 and NH4Cl as well as NH4BH4 following two different protocols, where the synthesis procedures are modified in the latter to solvent-based ball-milling using diethyl ether to maximize the phase yield in chlorine-free samples. During decomposition of NH4Ca(BH43 pure H2 is released, prior to the decomposition of the complex to its constituents. As opposed to a previously reported adduct between Ca(BH42 and NH3BH3, the present complex is described as NH3BH3-stuffed α-Ca(BH42.

  20. Theoretical investigation on the chemistry of entrapment of the elusive aminoborane (H2 N=BH2 ) molecule.

    Science.gov (United States)

    Malakar, Tanmay; Bhunya, Sourav; Paul, Ankan

    2015-04-20

    Aminoborane (H2 N=BH2 ) is an elusive entity and is thought to be produced during dehydropolymerization of ammonia borane, a molecule of prime interest in the field of chemical hydrogen storage. The entrapment of H2 N=BH2 through hydroboration of exogenous cyclohexene has emerged as a routine technique to infer if free H2 N=BH2 is produced or not during metal-catalyzed ammonia borane dehydrogenation reactions. But to date, the underlying mechanism of this trapping reaction remains unexplored. Herein, by using DFT calculations, we have investigated the mechanism of trapping of H2 N=BH2 by cyclohexene. Contrary to conventional wisdom, our study revealed that the trapping of H2 N=BH2 does not occur through direct hydroboration of H2 N=BH2 on the double bond of cyclohexene. We found that autocatalysis by H2 N=BH2 is crucial for the entrapment of another H2 N=BH2 molecule by cyclohexene. Additionally, nucleophilic assistance from the solvent is also implicated for the entrapment reaction carried out in nucleophilic solvents. In THF, the rate-determining barrier for formation of the trapping product was predicted to be 16.7 kcal mol(-1) at M06 L(CPCM) level of theory.

  1. A comprehensive investigation on CVD growth thermokinetics of h-BN white graphene

    Science.gov (United States)

    Song, Xiufeng; Li, Qiguang; Ji, Jianping; Yan, Zhong; Gu, Yu; Huo, Chengxue; Zou, Yousheng; Zhi, Chunyi; Zeng, Haibo

    2016-09-01

    As an isomorph of graphene, monolayer hexagonal boron nitride (h-BN), so-called white graphene, has been in the spotlight of two-dimensional materials due to its outstanding properties. However, the growth of large and uniform white graphene monocrystalline with low density of defects is still a great challenge. Here, we present a comprehensive investigation on the growth thermokinetics of white graphene monocrystalline domains via atmospheric pressure chemical vapor deposition with the solid ammonia borane as precursors, which will be more suitable for future industrial production due to the handy process and precursor. The single domain size, coverage on substrate, and thickness of white graphene were taken as targeted parameters of products. And then, their dependences on the flow rate of carrier gas, heating temperature of ammonia borane, growth temperature and time were studied in details. Finally, after optimizing the above conditions, both white graphene monocrystalline domains as large as 80 μm2 and polycrystalline ultrathin film with coverage ratio of 95%-100% can be achieved facilely without using vacuum technique. Such white graphene products would be of great significance for the tunnel barrier for the tunneling transistor and the dielectric layers for nanocapacitor with the graphene based heterostructures.

  2. Technical Analysis of Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Ali T-Raissi

    2005-01-14

    The aim of this work was to assess issues of cost, and performance associated with the production and storage of hydrogen via following three feedstocks: sub-quality natural gas (SQNG), ammonia (NH{sub 3}), and water. Three technology areas were considered: (1) Hydrogen production utilizing SQNG resources, (2) Hydrogen storage in ammonia and amine-borane complexes for fuel cell applications, and (3) Hydrogen from solar thermochemical cycles for splitting water. This report summarizes our findings with the following objectives: Technoeconomic analysis of the feasibility of the technology areas 1-3; Evaluation of the hydrogen production cost by technology areas 1; and Feasibility of ammonia and/or amine-borane complexes (technology areas 2) as a means of hydrogen storage on-board fuel cell powered vehicles. For each technology area, we reviewed the open literature with respect to the following criteria: process efficiency, cost, safety, and ease of implementation and impact of the latest materials innovations, if any. We employed various process analysis platforms including FactSage chemical equilibrium software and Aspen Technologies AspenPlus and HYSYS chemical process simulation programs for determining the performance of the prospective hydrogen production processes.

  3. Analysis of boron carbides' electronic structure

    Science.gov (United States)

    Howard, Iris A.; Beckel, Charles L.

    1986-01-01

    The electronic properties of boron-rich icosahedral clusters were studied as a means of understanding the electronic structure of the icosahedral borides such as boron carbide. A lower bound was estimated on bipolaron formation energies in B12 and B11C icosahedra, and the associated distortions. While the magnitude of the distortion associated with bipolaron formation is similar in both cases, the calculated formation energies differ greatly, formation being much more favorable on B11C icosahedra. The stable positions of a divalent atom relative to an icosahedral borane was also investigated, with the result that a stable energy minimum was found when the atom is at the center of the borane, internal to the B12 cage. If incorporation of dopant atoms into B12 cages in icosahedral boride solids is feasible, novel materials might result. In addition, the normal modes of a B12H12 cluster, of the C2B10 cage in para-carborane, and of a B12 icosahedron of reduced (D sub 3d) symmetry, such as is found in the icosahedral borides, were calculated. The nature of these vibrational modes will be important in determining, for instance, the character of the electron-lattice coupling in the borides, and in analyzing the lattice contribution to the thermal conductivity.

  4. Synthesis of Ternary Borocarbonitrides by High Temperature Pyrolysis of Ethane 1,2-Diamineborane

    Directory of Open Access Journals (Sweden)

    Fabrice Leardini

    2015-09-01

    Full Text Available Ethane 1,2-diamineborane (EDAB is an alkyl-containing amine-borane adduct with improved hydrogen desorption properties as compared to ammonia borane. In this work, it is reported the high temperature thermolytic decomposition of EDAB. Thermolysis of EDAB has been investigated by concomitant thermogravimetry-differential thermal analysis-mass spectrometry experiments. EDAB shows up to four H2 desorption events below 1000 °C. Small fractions of CH4, C2H4 and CO/CO2 are also observed at moderate-high temperatures. The solid-state thermolysis product has been characterized by means of different structural and chemical methods, such as X-ray diffraction, Raman spectroscopy, Scanning electron microscopy, Elemental analysis, and X-ray photoelectron spectroscopy (XPS. The obtained results indicate the formation of a ternary borocarbonitride compound with a poorly-crystalline graphitic-like structure. By contrast, XPS measurements show that the surface is rich in carbon and nitrogen oxides, which is quite different to the bulk of the material.

  5. ENVIRONMENTAL REACTIVITY OF SOLID-STATE HYDROGEN SYSTEMS: FUNDAMENTAL TESTING AND EVALUATION

    Energy Technology Data Exchange (ETDEWEB)

    James, C.; Cortes-Concepcion., J; Anton, D.; Tamburello, D.

    2010-12-13

    In order to enable the commercial acceptance of solid state hydrogen storage materials and systems it is important to understand the risks associated with the environmental exposure of various materials. In some instances, these materials are sensitive to the environment surrounding the material and the behavior is unique and independent to each material. The development of testing procedures to evaluate a material's behavior with different environmental exposures is a critical need. In some cases material modifications may be needed in order to reduce the risk of environmental exposure. We have redesigned two standardized UN tests for clarity and exactness; the burn rate and self-heating tests. The results of these and other UN tests are shown for ammonia borane, NH{sub 3}BH{sub 3}, and alane, AlH{sub 3}. The burn rate test showed a strong dependence on the preparation method of aluminum hydride as the particle size and trace amounts of solvent greatly influence the test results. The self-heating test for ammonia borane showed a failed test as low as 70 C in a modified cylindrical form. Finally, gas phase calorimetry was performed and resulted in an exothermic behavior within an air and 30%RH environment.

  6. Electrochemical hydrogen Storage Systems

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Digby Macdonald

    2010-08-09

    described in the previous literature for electrochemical reduction of spent fuels, have been attempted. A quantitative analytical method for measuring the concentration of sodium borohydride in alkaline aqueous solution has been developed as part of this work and is described herein. Finally, findings from stability tests for sodium borohydride in aqueous solutions of several different compositions are reported. For aminoborane, other research institutes have developed regeneration schemes involving tributyltin hydride. In this report, electrochemical reduction experiments attempting to regenerate tributyltin hydride from tributyltin chloride (a representative by-product of the regeneration scheme) are described. These experiments were performed in the non-aqueous solvents acetonitrile and 1,2-dimethoxyethane. A non-aqueous reference electrode for electrolysis experiments in acetonitrile was developed and is described. One class of boron hydrides, called polyhedral boranes, became of interest to the DOE due to their ability to contain a sufficient amount of hydrogen to meet program goals and because of their physical and chemical safety attributes. Unfortunately, the research performed here has shown that polyhedral boranes do not react in such a way as to allow enough hydrogen to be released, nor do they appear to undergo hydrogenation from the spent fuel form back to the original hydride. After the polyhedral boranes were investigated, the project goals remained the same but the hydrogen storage material was switched by the DOE to ammonia borane. Ammonia borane was found to undergo an irreversible hydrogen release process, so a direct hydrogenation was not able to occur. To achieve the hydrogenation of the spent ammonia borane fuel, an indirect hydrogenation reaction is possible by using compounds called organotin hydrides. In this process, the organotin hydrides will hydrogenate the spent ammonia borane fuel at the cost of their own oxidation, which forms organotin

  7. Bis(phosphine)boronium salts. Synthesis, structures and coordination chemistry.

    Science.gov (United States)

    Shuttleworth, Timothy A; Huertos, Miguel A; Pernik, Indrek; Young, Rowan D; Weller, Andrew S

    2013-09-28

    The synthesis of a range of bis(phosphine)boronium salts is reported [(R2HP)2BH2][X] (R = Ph, (t)Bu, Cy) in which the counter anion is also varied (X(-) = Br(-), [OTf](-), [BAr(F)4](-), Ar(F) = 3,5-(CF3)2C6H3). Characterization in the solid-state by X-ray diffraction suggests there are weak hydrogen bonds between the PH units of the boronium cation and the anion (X(-) = Br(-), [OTf](-)), while solution NMR spectroscopy also reveals hydrogen bonding occurs in the order [BAr(F)4](-) < [OTf](-) < Br(-). [(Ph2HP)2BH2][BAr(F)4] reacts with RhH(PPh3)3, by elimination of H2, forming [Rh(κ(1),η-PPh2BH2·PPh2H)(PPh3)2][BAr(F)4] which shows a β-B-agostic interaction from the resulting base stabilised phosphino-borane ligand. Alternatively such ligands can be assembled directly on the metal centre by reaction of in situ generated {Rh(PPh3)3}(+) and Ph2HP·BH3 to afford [Rh(κ(1),η-PPh2BH2·PPh3)(PPh3)2][BAr(F)4], which was characterised by X-ray crystallography. Addition of H3B·PPh2H to the well-defined 16-electron "T-shaped" complex [Rh(P(i)Bu3)2(PPh3)][BAr(F)4] (characterised by X-ray crystallography) formed of a mixture of base-stabilised phosphino borane ligated complexes [Rh(κ(1),η-PR2BH2·PR3)(PR3)2][BAr(F)4] (R = (i)Bu or Ph). These last observations may lend clues to the formation of bis(phosphine)boronium salts in the catalytic dehydrocoupling reaction of phosphine boranes as mediated by Rh(I) compounds.

  8. Hydroboration-oxidation: A chemoselective route to cellulose ω-hydroxyalkanoate esters.

    Science.gov (United States)

    Meng, Xiangtao; York, Emily A; Liu, Shu; Edgar, Kevin J

    2015-11-20

    We describe the first synthesis of hydroxy-functionalized polysaccharide esters via chemoselective olefin hydroboration-oxidation in the presence of ester groups. Cellulose esters with terminally olefinic side chains were first synthesized by esterification of commercially available cellulose esters (e.g., cellulose acetate) with undec-10-enoyl chloride or pent-4-enoyl chloride. Subsequent two-step, one-pot hydroboration-oxidation reactions of the cellulose esters were performed, using 9-borabicyclo[3.3.1]nonane as hydroboration agent, followed by oxidizing the intermediate borane to a hydroxyl group using mildly alkaline H2O2. Sodium acetate was used as a weak base to catalyze the oxidation, thereby minimizing undesired ester hydrolysis. Characterization methods including FTIR, (1)H, and (13)C NMR proved the selectivity of the hydroboration-oxidation pathway, providing a family of novel cellulose ω-hydroxyalkanoyl esters that were previously difficult to access.

  9. Weak-link capacitor

    Science.gov (United States)

    Dirk, Shawn M.; Johnson, Ross S.; Wheeler, David R.; Bogart, Gregory R.

    2013-04-23

    A process for making a dielectric material where a precursor polymer selected from poly(phenylene vinylene)polyacetylene, poly(p-phenylene), poly(thienylene vinylene), poly(1,4-naphthylene vinylene), and poly(p-pyridine vinylene) is energized said by exposure by radiation or increase in temperature to a level sufficient to eliminate said leaving groups contained within the precursor polymer, thereby transforming the dielectric material into a conductive polymer. The leaving group in the precursor polymer can be a chloride, a bromide, an iodide, a fluoride, an ester, an xanthate, a nitrile, an amine, a nitro group, a carbonate, a dithiocarbamate, a sulfonium group, an oxonium group, an iodonium group, a pyridinium group, an ammonium group, a borate group, a borane group, a sulphinyl group, or a sulfonyl group.

  10. Weak-link capacitor

    Energy Technology Data Exchange (ETDEWEB)

    Dirk, Shawn M. (Albuquerque, NM); Johnson, Ross S. (Albuquerque, NM); Wheeler, David R. (Albuquerque, NM); Bogart, Gregory R. (Corrales, NM)

    2011-06-07

    A process for making a dielectric material where a precursor polymer selected from poly(phenylene vinylene) polyacetylene, poly(p-phenylene), poly(thienylene vinylene), poly(1,4-naphthylene vinylene), and poly(p-pyridine vinylene) is energized said by exposure by radiation or increase in temperature to a level sufficient to eliminate said leaving groups contained within the precursor polymer, thereby transforming the dielectric material into a conductive polymer. The leaving group in the precursor polymer can be a chloride, a bromide, an iodide, a fluoride, an ester, an xanthate, a nitrile, an amine, a nitro group, a carbonate, a dithiocarbamate, a sulfonium group, an oxonium group, an iodonium group, a pyridinium group, an ammonium group, a borate group, a borane group, a sulphinyl group, or a sulfonyl group.

  11. Mechanism of Solid-State Thermolysis of Ammonia Boraine: 15N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Takeshi [Ames Laboratory; Gupta, Shalabh [Ames Laboratory; Caporini, Marc A [Bruker BioSpin Corporation; Pecharsky, Vitalij K [Ames Laboratory; Pruski, Marek [Ames Laboratory

    2014-08-28

    The solid-state thermolysis of ammonia borane (NH3BH3, AB) was explored using state-of-the-art 15N solid-state NMR spectroscopy, including 2D indirectly detected 1H{15N} heteronuclear correlation and dynamic nuclear polarization (DNP)-enhanced 15N{1H} cross-polarization experiments as well as 11B NMR. The complementary use of 15N and 11B NMR experiments, supported by density functional theory calculations of the chemical shift tensors, provided insights into the dehydrogenation mechanism of AB—insights that have not been available by 11B NMR alone. Specifically, highly branched polyaminoborane derivatives were shown to form from AB via oligomerization in the “head-to-tail” manner, which then transform directly into hexagonal boron nitride analog through the dehydrocyclization reaction, bypassing the formation of polyiminoborane.

  12. Boronated mesophase pitch coke for lithium insertion

    Science.gov (United States)

    Frackowiak, E.; Machnikowski, J.; Kaczmarska, H.; Béguin, F.

    Boronated carbons from mesophase pitch have been used as materials for lithium storage in Li/carbon cells. Doping by boron has been realized by co-pyrolysis of coal tar pitch with the pyridine-borane complex. Amount of boron in mesocarbon microbeads (MCMB) varied from 1.4 to 1.8 wt.% affecting the texture of carbon. Optical microscopy and X-ray diffractograms have shown tendency to more disordered structure for boron-doped carbon. The values of specific reversible capacity ( x) varied from 0.7 to 1.1 depending significantly on the final temperature of pyrolysis (700-1150°C). The optimal charge/discharge performance was observed for boronated carbon heated at 1000°C.

  13. Pressure-induced transformations of molecular boron hydride

    CERN Document Server

    Nakano, S; Gregoryanz, E A; Goncharov, A F; Mao Ho Kwang

    2002-01-01

    Decaborane, a molecular boron hydride, was compressed to 131 GPa at room temperature to explore possible non-molecular phases in this system and their physical properties. Decaborane changed its colour from transparent yellow to orange/red above 50 GPa and then to black above 100 GPa, suggesting some transformations. Raman scattering and infrared (IR) absorption spectroscopy reveal significant structural changes. Above 100 GPa, B-B skeletal, B-H and B-H-B Raman/IR peaks gradually disappeared, which implies a transformation into a non-molecular phase in which conventional borane-type bonding is lost. The optical band gap of the material at 100 GPa was estimated to be about 1.0 eV.

  14. P-Stereogenic Phosphines for the Stabilisation of Metal Nanoparticles. A Surface State Study

    Directory of Open Access Journals (Sweden)

    Eva Raluy

    2016-12-01

    Full Text Available Palladium and ruthenium nanoparticles have been prepared following the organometallic precursor decomposition methodology, under dihydrogen pressure and in the presence of borane protected P-stereogenic phosphines. NMR (Nuclear Magnetic Resonance monitoring of the corresponding syntheses has permitted to determine the optimal metal/ligand ratio for leading to small and well-dispersed nanoparticles. Exchange ligand reactions of the as-prepared materials have proven the strong interaction of the phosphines with the metal surface; only oxidative treatment using hydrogen peroxide could release the phosphine-based stabiliser from the metal surface. Pd and Ru nanoparticles have been evaluated in hydrogenation reactions, confirming the robustness of the stabilisers, which selectively permitted the hydrogenation of exocyclic C=C bonds, preventing the coordination of the aromatic rings and as a result, their hydrogenation.

  15. Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification.

    Science.gov (United States)

    Mason, Christopher R; Maynard-Atem, Louise; Heard, Kane W J; Satilmis, Bekir; Budd, Peter M; Friess, Karel; Lanc̆, Marek; Bernardo, Paola; Clarizia, Gabriele; Jansen, Johannes C

    2014-02-11

    Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine-PIM-1 showed higher CO2 uptake and higher CO2/N2 sorption selectivity than the parent polymer, with very evident dual-mode sorption behavior. In gas permeation with six light gases, the individual contributions of solubility and diffusion to the overall permeability was determined via time-lag analysis. The high CO2 affinity drastically restricts diffusion at low pressures and lowers CO2 permeability compared to the parent PIM-1. Furthermore, the size-sieving properties of the polymer are increased, which can be attributed to a higher stiffness of the system arising from hydrogen bonding of the amine groups. Thus, for the H2/CO2 gas pair, whereas PIM-1 favors CO2, amine-PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.

  16. Citrus bergamia Risso Elevates Intracellular Ca2+ in Human Vascular Endothelial Cells due to Release of Ca2+ from Primary Intracellular Stores

    Directory of Open Access Journals (Sweden)

    Purum Kang

    2013-01-01

    , which was partially inhibited by a nonselective Ca2+ channel blocker La3+. In Ca2+-free extracellular solutions, BEO increased [Ca2+]i in a concentration-dependent manner, suggesting that BEO mobilizes intracellular Ca2+. BEO-induced [Ca2+]i increase was partially inhibited by a Ca2+-induced Ca2+ release inhibitor dantrolene, a phospholipase C inhibitor U73122, and an inositol 1,4,5-triphosphate (IP3-gated Ca2+ channel blocker, 2-aminoethoxydiphenyl borane (2-APB. BEO also increased [Ca2+]i in the presence of carbonyl cyanide m-chlorophenylhydrazone, an inhibitor of mitochondrial Ca2+ uptake. In addition, store-operated Ca2+ entry (SOC was potentiated by BEO. These results suggest that BEO mobilizes Ca2+ from primary intracellular stores via Ca2+-induced and IP3-mediated Ca2+ release and affect promotion of Ca2+ influx, likely via an SOC mechanism.

  17. Orbital deletion procedure and its applications

    Institute of Scientific and Technical Information of China (English)

    莫亦荣; 林梦海; 吴玮; 张乾二

    1999-01-01

    The orbital deletion procedure is introduced, which is suited to quantitatively investigating the electronic delocalization effiect in earboeations and boranes. While the routine, ab initio molecular orbital methods can generate wavefunetions for real systems where all electrons are delocalized, the present orbital deletion procedure can generate wavefunctions for hypothetical reference molecules where electronic delocalization effect is deactivated. The latter wavefunetion normlly corresponds In the most stable resonance structure in terms of the resonance theory. By comparing and analyzing the delocalized and the localized wavefunetions, one can obtain a quantitative and instinct pieture to show how electronic deloealizalion inside a molecule affects the molecular structure, energy as well as other physical properties. Two examples are detailedly discussed. The first is related to the hypercoujugation of alkyl groups in carbocations and a comparison of the order of stability of carbocations is made, T

  18. Elusive silane-alane complex [Si-H⋅⋅⋅Al]: isolation, characterization, and multifaceted frustrated Lewis pair type catalysis.

    Science.gov (United States)

    Chen, Jiawei; Chen, Eugene Y-X

    2015-06-01

    The super acidity of the unsolvated Al(C6F5)3 enabled isolation of the elusive silane-alane complex [Si-H⋅⋅⋅Al], which was structurally characterized by spectroscopic and X-ray diffraction methods. The Janus-like nature of this adduct, coupled with strong silane activation, effects multifaceted frustrated-Lewis-pair-type catalysis. When compared with the silane-borane system, the silane-alane system offers unique features or clear advantages in the four types of catalytic transformations examined in this study, including: ligand redistribution of tertiary silanes into secondary and quaternary silanes, polymerization of conjugated polar alkenes, hydrosilylation of unactivated alkenes, and hydrodefluorination of fluoroalkanes.

  19. The 2-(Triphenylsilylethoxycarbonyl-(“Tpseoc”- Group: A New Silicon-Based, Fluoride Cleavable Oxycarbonyl Protecting Group Highly Orthogonal to the Boc-, Fmoc- and Cbz-Groups

    Directory of Open Access Journals (Sweden)

    Martin Golkowski

    2011-06-01

    Full Text Available Starting from 2-(triphenylsilylethanol a new oxycarbonyl protecting group cleavable by fluoride ion induced Peterson-elimination has been developed. Known 2-(triphenylsilylethanol has been prepared from commercially available triphenylvinyl-silane by a hydroboration-oxidation sequence using the sterically hindered borane reagent 9-BBN. The silyl alcohol was subsequently transformed into its chloroformate, imidazolylcarboxylic acid ester and p-nitrophenyl carbonate and used in standard protocols for the formation of carbamates and carbonates. The Tpseoc group proved to be highly resistant against acidic conditions applied in removal of tert-butyl esters and the t-Boc-group. It also withstood catalytic hydrogenation, treatment with morpholine, methylhydrazine and Pd-reagents/allyl-scavanger combinations, conditions required to cleave Cbz-, Fmoc-, phthalimide- and Alloc-groups. The Tpseoc-group is cleaved upon treatment with TBAF/CsF at 0 °C or r.t. with cleavage times reaching from

  20. Cooperative redox activation for carbon dioxide conversion

    Science.gov (United States)

    Lian, Zhong; Nielsen, Dennis U.; Lindhardt, Anders T.; Daasbjerg, Kim; Skrydstrup, Troels

    2016-12-01

    A longstanding challenge in production chemistry is the development of catalytic methods for the transformation of carbon dioxide into useful chemicals. Silane and borane promoted reductions can be fined-tuned to provide a number of C1-building blocks under mild conditions, but these approaches are limited because of the production of stoichiometric waste compounds. Here we report on the conversion of CO2 with diaryldisilanes, which through cooperative redox activation generate carbon monoxide and a diaryldisiloxane that actively participate in a palladium-catalysed carbonylative Hiyama-Denmark coupling for the synthesis of an array of pharmaceutically relevant diarylketones. Thus the disilane reagent not only serves as the oxygen abstracting agent from CO2, but the silicon-containing `waste', produced through oxygen insertion into the Si-Si bond, participates as a reagent for the transmetalation step in the carbonylative coupling. Hence this concept of cooperative redox activation opens up for new avenues in the conversion of CO2.

  1. Direct access to primary amines and particle morphology control in nanoporous CO2 sorbents.

    Science.gov (United States)

    Dogan, Nesibe A; Ozdemir, Ercan; Yavuz, Cafer T

    2017-03-13

    Chemical tuning of nanoporous, solid sorbents for an ideal CO2 binding requires unhindered amine functional groups on the pore walls. Although common for soluble organics, post-synthetic reduction of nitriles in porous networks often fail due to the insufficient and irreversible metal hydride penetration. Here, we synthesized a nanoporous network with pendant nitrile groups, microsphere morphology and in large scale. The hollow microspheres were easily decorated with primary amines through in situ reduction by widely available boranes. CO2 capture capacity of the modified sorbent was increased up to an eight times of the starting nanoporous network with a high heat of adsorption (98 kJ/mol). Surface area can be easily tuned between 1 and 354 m2/g. Average particle size (~50 µm) is also quite suitable for CO2 capture applications where processes like fluidized bed require spheres of micron sizes.

  2. Chelation-Assisted Substrate-Controlled Asymmetric Lithiation-Allylboration of Chiral Carbamate 1,2,4-Butanetriol Acetonide

    Directory of Open Access Journals (Sweden)

    Adeem Mahmood

    2015-05-01

    Full Text Available The lithiation of 2-(2,2-dimethyl-1,3-dioxolan-4-ylethyl diisopropylcarbamate (1 is achieved freely by sec-butyllithium in diethylether with high lk-diastereoselectivity: the bicyclic chelate complexes 3a and 3b are reacted with electrophiles to form optically active precursors 4a and 4b with >95% diastereoselectivity. In addition, tertiary diamines can undergo an external complexation in contest with the internal oxygen ligand, leading to improved stereoselectivities. The further reactions of lithiated carbamates with trans alkenyl-9-BBN derivatives after 1,2 metallate rearrangements, gave the key intermediate α-substituted allylic boranes 7. Subsequent allylboration of aldehydes gave (Z-anti-homoallylic alcohols 8 in good yield and excellent d.r.

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

    Institute of Scientific and Technical Information of China (English)

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

    2003-01-01

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

  4. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    Science.gov (United States)

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect.

  5. Formation Process of Eosin Y-Adsorbing ZnO Particles by Electroless Deposition and Their Photoelectric Conversion Properties.

    Science.gov (United States)

    Nagaya, Satoshi; Nishikiori, Hiromasa; Mizusaki, Hideaki; Wagata, Hajime; Teshima, Katsuya

    2015-06-03

    The thin films consisting of crystalline ZnO particles were prepared on fluorine-doped tin oxide electrodes by electroless deposition. The particles were deposited from an aqueous solution containing zinc nitrate, dimethyamine-borane, and eosin Y at 328 K. As the Pd particles were adsorbed on the substrate, not only the eosin Y monomer but also the dimer and debrominated species were rapidly adsorbed on the spherical ZnO particles, which were aggregated and formed secondary particles. On the other hand, in the absence of the Pd particles, the monomer was adsorbed on the flake-shaped ZnO particles, which vertically grew on the substrate surface and had a high crystallinity. The photoelectric conversion efficiency was higher for the ZnO electrodes containing a higher amount of the monomer during light irradiation.

  6. Preparation of dye-adsorbing ZnO thin films by electroless deposition and their photoelectrochemical properties.

    Science.gov (United States)

    Nagaya, Satoshi; Nishikiori, Hiromasa

    2013-09-25

    Dye-adsorbing ZnO thin films were prepared on ITO films by electroless deposition. The films were formed in an aqueous solution containing zinc nitrate, dimethylamine-borane, and eosin Y at 328 K. The film thickness was 1.2-2.0 μm. Thinner and larger-plane hexagonal columns were produced from the solution containing a higher concentration of eosin Y. A photocurrent was observed in the electrodes containing such ZnO films during light irradiation. The photoelectrochemical performance of the film was improved by increasing the concentration of eosin Y because of increases in the amount of absorbed photons and the electronic conductivity of ZnO.

  7. Direct tandem mass spectrometric analysis of amino acids in plasma using fluorous derivatization and monolithic solid-phase purification.

    Science.gov (United States)

    Tamashima, Erina; Hayama, Tadashi; Yoshida, Hideyuki; Imakyure, Osamu; Yamaguchi, Masatoshi; Nohta, Hitoshi

    2015-11-10

    In this study, we developed a novel direct tandem mass spectrometric method for rapid and accurate analysis of amino acids utilizing a fluorous derivatization and purification technique. Amino acids were perfluoroalkylated with 2H,2H,3H,3H-perfluoroundecan-1-al in the presence of 2-picoline borane via reductive amination. The derivatives were purified by perfluoroalkyl-modified silica-based monolithic solid-phase extraction (monolithic F-SPE), and directly analyzed by tandem mass spectrometry using electrospray ionization without liquid chromatographic separation. The perfluoroalkyl derivatives could be sufficiently distinguished from non-fluorous compounds, i.e. the biological matrix, due to their fluorous interaction. Thus, rapid and accurate determination of amino acids was accomplished. The method was validated with human plasma samples and applied to the analysis of amino acids in the plasma of mice with maple syrup urine disease or phenylketonuria.

  8. Polymethylene-based copolymers by polyhomologation or by its combination with controlled/living and living polymerizations

    KAUST Repository

    Zhang, Hefeng

    2014-01-20

    Polyhomologation, recently developed by Shea, is a borane-initiated living polymerization of ylides leading to linear polymethylenes (C1 polymerization) with controlled molecular weight, low polydispersity, and well-defined structures. In this Review, the copolyhomologation of different ylides as well as the combination of polyhomologation with controlled/living (nitroxide-mediated, atom transfer radical, reversible addition-fragmentation chain-transfer) and living (ring opening, anionic) polymerizations is discussed. Polyhomologation of ylides, in combination with living and controlled/living polymerizations, leads to a plethora novel well-defined polymethylene (polyethylene)-based polymeric materials, which are very important for understanding/improving the behavior of industrial polyethylenes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    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.

  10. Graphitized boron-doped carbon foams: Performance as anodes in lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, Elena; Camean, Ignacio; Garcia, Roberto [Instituto Nacional del Carbon (CSIC), C/Francisco Pintado Fe 26, 33011 Oviedo (Spain); Garcia, Ana B., E-mail: anabgs@incar.csic.es [Instituto Nacional del Carbon (CSIC), C/Francisco Pintado Fe 26, 33011 Oviedo (Spain)

    2011-05-30

    Highlights: > Because of the catalytic effect of boron, graphite-like foams were prepared. > The presence of substitutional boron in carbon foams improves their anodic performance. > The graphitized boron-doped foams provide reversible capacities of 310 mA h g{sup -1}. - Abstract: The electrochemical performance as potential anodes in lithium-ion batteries of several boron-doped and non-doped graphitic foams with different degree of structural order was investigated by galvanostatic cycling. The boron-doped foams were prepared by the co-pyrolysis of a coal and two boron sources (boron oxide and a borane-pyridine complex), followed by heat treatment in the 2400-2800 deg. C temperature interval. The extent of the graphitization process of the carbon foams depends on boron concentration and source. Because of the catalytic effect of boron, lightweight graphite-like foams were prepared. Boron in the foams was found to be present as carbide (B{sub 4}C), in substitutional positions in the carbon lattice (B-C), bonded to nitrogen (B-N) and forming clusters. Larger reversible lithium storage capacities with values up to {approx}310 mA h g{sup -1} were achieved by using the boron oxide-based carbon foams. Moreover, since the electrochemical anodic performance of these boron-doped foams with different degree of structural order is similar, the beneficial effect of the presence of the B-C boron phase was inferred. However, the bonding of boron with nitrogen in the pyridine borane-based has a negative effect on lithium intercalation.

  11. Synthesis of a TREN in which the aryl substituents are part of a 45 atom macrocycle.

    Science.gov (United States)

    Cain, Matthew F; Forrest, William P; Peryshkov, Dmitry V; Schrock, Richard R; Müller, Peter

    2013-10-16

    A substituted TREN has been prepared in which the aryl groups in (ArylNHCH2CH2)3N are substituted at the 3- and 5-positions with a total of six OCH2(CH2)nCH═CH2 groups (n = 1, 2, 3). Molybdenum nitride complexes, [(ArylNCH2CH2)3N]Mo(N), have been isolated as adducts that contain B(C6F5)3 bound to the nitride. Two of these [(ArylNCH2CH2)3N]Mo(NB(C6F5)3) complexes (n = 1 and 3) were crystallographically characterized. After removal of the borane from [(ArylNCH2CH2)3N]Mo(NB(C6F5)3) with PMe3, ring-closing olefin metathesis (RCM) was employed to join the aryl rings with OCH2(CH2)nCH═CH(CH2)nCH2O links (n = 1-3) between them. RCM worked best with a W(O)(CHCMe3)(Me2Pyr)(OHMT)(PMe2Ph) catalyst (OHMT = hexamethylterphenoxide, Me2Pyr = 2,5-dimethylpyrrolide) and n = 3. The macrocyclic ligand was removed from the metal through hydrolysis and isolated in 70-75% yields relative to the borane adducts. Crystallographic characterization showed that the macrocyclic TREN ligand in which n = 3 contains three cis double bonds. Hydrogenation produced a TREN in which the three links are saturated, i.e., O(CH2)10O.

  12. Transcriptional profiling of cattle infected with Trypanosoma congolense highlights gene expression signatures underlying trypanotolerance and trypanosusceptibility

    Directory of Open Access Journals (Sweden)

    Naessens Jan

    2009-05-01

    Full Text Available Abstract Background African animal trypanosomiasis (AAT caused by tsetse fly-transmitted protozoa of the genus Trypanosoma is a major constraint on livestock and agricultural production in Africa and is among the top ten global cattle diseases impacting on the poor. Here we show that a functional genomics approach can be used to identify temporal changes in host peripheral blood mononuclear cell (PBMC gene expression due to disease progression. We also show that major gene expression differences exist between cattle from trypanotolerant and trypanosusceptible breeds. Using bovine long oligonucleotide microarrays and real time quantitative reverse transcription PCR (qRT-PCR validation we analysed PBMC gene expression in naïve trypanotolerant and trypanosusceptible cattle experimentally challenged with Trypanosoma congolense across a 34-day infection time course. Results Trypanotolerant N'Dama cattle displayed a rapid and distinct transcriptional response to infection, with a ten-fold higher number of genes differentially expressed at day 14 post-infection compared to trypanosusceptible Boran cattle. These analyses identified coordinated temporal gene expression changes for both breeds in response to trypanosome infection. In addition, a panel of genes were identified that showed pronounced differences in gene expression between the two breeds, which may underlie the phenomena of trypanotolerance and trypanosusceptibility. Gene ontology (GO analysis demonstrate that the products of these genes may contribute to increased mitochondrial mRNA translational efficiency, a more pronounced B cell response, an elevated activation status and a heightened response to stress in trypanotolerant cattle. Conclusion This study has revealed an extensive and diverse range of cellular processes that are altered temporally in response to trypanosome infection in African cattle. Results indicate that the trypanotolerant N'Dama cattle respond more rapidly and with a

  13. Hydrogen Release Studies of Alkali Metal Amidoboranes

    Energy Technology Data Exchange (ETDEWEB)

    Luedtke, Avery T.; Autrey, Thomas

    2010-04-19

    A series of metal amido boranes LiNH2BH3 (LAB), NaNH2BH3 (SAB), LiNH(Me)BH3 (LMAB), NaNH(Me)BH3 (SMAB), KNH(Me)BH3 (PMAB), and KNH(tBu)BH3 (PBAB) were synthesized, by solution phase methods, and the thermal release of H2 in the solid state was studied. Based on the observed trends in reaction rates of H > Me > tBu and the kinetic isotope effect, the mechanism of hydrogen release from MAB compounds was found to proceed through a bimolecular mechanism involving the intermediacy of a MH (M = Li, Na, or K). The mechanism of hydrogen release from metal amidoboranes, a metal ion assisted hydride transfer, is very different than the mechanism of hydrogen release from the parent compound ammonia borane (AB). The non-volatile products formed from MAB’s are significantly different than the products formed after hydrogen release from AB. The boron containing resulting from the release of one equivalent of hydrogen from the metal amidoboranes were characterized by MAS 11B NMR spectroscopy and found to contain both BH3 and sp2 hybridized BH groups, consistent with a general structural feature MN(R)=BHN(R)MBH3. This work was funded by the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy as part of the Chemical Hydrogen Storage CoE at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. DOE by Battelle. MAS NMR studies were performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL.

  14. Predicting impurity gases and phases during hydrogen evolution from complex metal hydrides using free energy minimization enabled by first-principles calculations.

    Science.gov (United States)

    Kim, Ki Chul; Allendorf, Mark D; Stavila, Vitalie; Sholl, David S

    2010-09-07

    First-principles calculations represent a potent tool for screening metal hydride mixtures that can reversibly store hydrogen. A number of promising new hydride systems with high hydrogen capacity and favorable thermodynamics have been predicted this way. An important limitation of these studies, however, is the assumption that H(2) is the only gas-phase product of the reaction, which is not always the case. This paper summarizes new theoretical and numerical approaches that can be used to predict thermodynamic equilibria in complex metal hydride systems with competing reaction pathways. We report thermochemical equilibrium calculations using data obtained from density functional theory (DFT) computations to describe the possible occurrence of gas-phase products other than H(2) in three complex hydrides, LiNH(2), LiBH(4), and Mg(BH(4))(2), and mixtures of these with the destabilizing compounds LiH, MgH(2), and C. The systems under investigation contain N, C, and/or B and thus have the potential to evolve N(2), NH(3), hydrocarbons, and/or boranes as well as H(2). Equilibria as a function of both temperature and total pressure are predicted. The results indicate that significant amounts of these species can form under some conditions. In particular, the thermodynamic model predicts formation of N(2) and NH(3) as products of LiNH(2) decomposition. Comparison with published experimental data indicates that N(2) formation must be kinetically limited. Our examination of C-containing systems indicates that methane is the stable gas-phase species at low temperatures, not H(2). On the other hand, very low amounts of boranes (primarily BH(3)) are predicted to form in B-containing systems.

  15. Amineborane Based Chemical Hydrogen Storage - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sneddon, Larry G.

    2011-04-21

    The development of efficient and safe methods for hydrogen storage is a major hurdle that must be overcome to enable the use of hydrogen as an alternative energy carrier. The objectives of this project in the DOE Center of Excellence in Chemical Hydride Storage were both to develop new methods for on-demand, low temperature hydrogen release from chemical hydrides and to design high-conversion off-board methods for chemical hydride regeneration. Because of their reactive protic (N-H) and hydridic (B-H) hydrogens and high hydrogen contents, amineboranes such as ammonia borane, NH3BH3 (AB), 19.6-wt% H2, and ammonia triborane NH3B3H7 (AT), 17.7-wt% H2, were initially identified by the Center as promising, high-capacity chemical hydrogen storage materials with the potential to store and deliver molecular hydrogen through dehydrogenation and hydrolysis reactions. In collaboration with other Center partners, the Penn project focused both on new methods to induce amineborane H2-release and on new strategies for the regeneration the amineborane spent-fuel materials. The Penn approach to improving amineborane H2-release focused on the use of ionic liquids, base additives and metal catalysts to activate AB dehydrogenation and these studies successfully demonstrated that in ionic liquids the AB induction period that had been observed in the solid-state was eliminated and both the rate and extent of AB H2-release were significantly increased. These results have clearly shown that, while improvements are still necessary, many of these systems have the potential to achieve DOE hydrogen-storage goals. The high extent of their H2­-release, the tunability of both their H2 materials weight-percents and release rates, and their product control that is attained by either trapping or suppressing unwanted volatile side products, such as borazine, continue to make AB/ionic­-liquid based systems attractive candidates for chemical hydrogen storage applications. These studies also

  16. Catalysts for portable, solid state hydrogen genration systems

    Science.gov (United States)

    Gabl, Jason Robert

    Hydrogen and air powered proton exchange membrane fuel cells are a potential alternative to batteries. In portable power systems, the design requirements often focus on cost efficiency, energy density, storability, as well as safety. Ammonia borane (AB), a chemical hydride containing 19.6 wt. % hydrogen, has a high hydrogen capacity and is a stable and non-toxic candidate for storing hydrogen in portable systems. Throughout this work, Department of Energy guidelines for low power portable hydrogen power systems were used as a baseline and comparison with commercially available systems. In order to make this comparison, the system parameters of a system using AB hydrolysis were estimated by developing capacity and cost correlations from the commercial systems and applying them to this work. Supporting experiments were designed to evaluate a system that would use a premixed solid storage bed of AB and a catalyst. This configuration would only require a user input of water in order to initiate the hydrogen production. Using ammonia borane hydrolysis, the hydrogen yield is ˜9 wt. %, when all reactants are considered. In addition to the simplicity of initiating the reaction, hydrolysis of AB has the advantage of suppressing the production of some toxic borazines that are present when AB is thermally decomposed. However, ammonia gas will be formed and this problem must be addressed, as ammonia is damaging to PEM fuel cells. The catalyst focused on throughout this work was Amberlyst - 15; an ion exchange resin with an acid capacity of 4.7 eq/kg and ammonia adsorbent. At less than 0.30/g, this is a cost effective alternative to precious metal catalysts. The testing with this catalyst was compared to a traditional catalyst in literature, 20% platinum in carbon, costing more than 40/g. The Amberlyst catalyst was found to reduce the formation of ammonia in the gas products from ˜3.71 wt. % with the Pt/C catalyst to 90 % to cost effective, energy dense, and safe option for

  17. Studies of Molecular Dynamics by Solid State Deuterium NMR Spectroscopy

    Science.gov (United States)

    Zhao, Baiyi

    The rotational dynamics of molecules in a number of solid systems were followed by variable temperature deuterium (^2H), nuclear magnetic resonance (NMR) spectroscopy via changes in the spectral lineshapes and spin-lattice relaxation times (T _1). First the pure solid trimethylamine-borane adduct, (CH_3)_3NBH_3, was studied. For a methyl deuterated sample, T _1 measurements yielded two T_1 minima, 6.9 ms and 4.3 ms corresponding to the slowing of methyl and trimethyl rotation, respectively, with decreasing temperature. Activation energies for methyl and trimethyl rotation, obtained from fitting the T _1 curve as a function of temperature, were 32.8 and 15.0 kJ/mol, respectively; simulations of the spectral lineshapes gave 26.6 and 18.9 kT/mol, respectively. Fitting of the ^2H T_1 curve for the borane deuterated sample gave a BH _3 rotation activation energy of 14.1 kT/mol and a ^2H quadrupolar coupling constant, chi, of 101 kHz. The activation energy for BH_3 rotation obtained from the spectral lineshape simulations gave 12.6 kT/mol. A series of deuterated organic chalcogen cations: (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, were ion exchanged into the cavities of sodium Mordenite LZ-M5 and the dynamics of these guests within the hydrated zeolite were followed by ^2H NMR. All three undergo isotropic motion above about -80 to -90^circC. Below this temperature two superimposed ^2H powder spectra appear; the broad lineshape is consistent with only methyl rotation in a hindered, coordinated site, and the other narrow lineshape is due to both methyl and trimethyl rotation in a less hindered, uncoordinated site. As the temperature is lowered the population of the lower energy coordinated site increases. Relative peak areas yield adsorption enthalpies of 6.7, 7.8 and 10.0 kJ/mol for (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, respectively. The series of methyl deuterated ammonium and phosphonium cations: (CH_3)NH_3^+ , (CH_3)_2NH^+ , (CH_3)_3NH^+ and (CH_3)_4P^+ , were

  18. Dynamics and fragmentation of van der Waals and hydrogen bonded cluster cations: (NH3)n and (NH3BH3)n ionized at 10.51 eV

    Science.gov (United States)

    Yuan, Bing; Shin, Joong-Won; Bernstein, Elliot R.

    2016-04-01

    A 118 nm laser is employed as a high energy, single photon (10.51 eV/photon) source for study of the dynamics and fragmentation of the ammonia borane (NH3BH3) cation and its cluster ions through time of flight mass spectrometry. The behavior of ammonia ion and its cluster ions is also investigated under identical conditions in order to explicate the ammonia borane results. Charge distributions, molecular orbitals, and spin densities for (NH3BH3)n and its cations are explored at both the second-order perturbation theory (MP2) and complete active space self-consistent field (CASSCF) theory levels. Initial dissociation mechanisms and potential energy surfaces for ionized NH3BH3, NH3, and their clusters are calculated at the MP2/6-311++G(d,p) level. Protonated clusters (NH3)xH+ dominate ammonia cluster mass spectra: our calculations show that formation of (NH3)n-1H+ and NH2 from the nascent (NH3)n+ has the lowest energy barrier for the system. The only common features for the (NH3)n+ and (NH3BH3)n+ mass spectra under these conditions are found to be NHy+ (y = 0,…,4) at m/z = 14-18. Molecular ions with both 11B and 10B isotopes are observed, and therefore, product ions observed for the (NH3BH3)n cluster system derive from (NH3BH3)n clusters themselves, not from the NH3 moiety of NH3BH3 alone. NH3BH2+ is the most abundant ionization product in the (NH3BH3)n+ cluster spectra: calculations support that for NH3BH3+, an H atom is lost from the BH3 moiety with an energy barrier of 0.67 eV. For (NH3BH3)2+ and (NH3BH3)3+ clusters, a Bδ+⋯Hδ-⋯δ-H⋯δ+B bond can form in the respective cluster ions, generating a lower energy, more stable ion structure. The first step in the (NH3BH3)n+ (n = 2, 3) dissociation is the breaking of the Bδ+⋯Hδ-⋯δ-H⋯δ+B moiety, leading to the subsequent release of H2 from the latter cluster ion. The overall reaction mechanisms calculated are best represented and understood employing a CASSCF natural bond orbital

  19. U.S. Department of Energy Hydrogen Storage Cost Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Law, Karen; Rosenfeld, Jeffrey; Han, Vickie; Chan, Michael; Chiang, Helena; Leonard, Jon

    2013-03-11

    The overall objective of this project is to conduct cost analyses and estimate costs for on- and off-board hydrogen storage technologies under development by the U.S. Department of Energy (DOE) on a consistent, independent basis. This can help guide DOE and stakeholders toward the most-promising research, development and commercialization pathways for hydrogen-fueled vehicles. A specific focus of the project is to estimate hydrogen storage system cost in high-volume production scenarios relative to the DOE target that was in place when this cost analysis was initiated. This report and its results reflect work conducted by TIAX between 2004 and 2012, including recent refinements and updates. The report provides a system-level evaluation of costs and performance for four broad categories of on-board hydrogen storage: (1) reversible on-board metal hydrides (e.g., magnesium hydride, sodium alanate); (2) regenerable off-board chemical hydrogen storage materials(e.g., hydrolysis of sodium borohydride, ammonia borane); (3) high surface area sorbents (e.g., carbon-based materials); and 4) advanced physical storage (e.g., 700-bar compressed, cryo-compressed and liquid hydrogen). Additionally, the off-board efficiency and processing costs of several hydrogen storage systems were evaluated and reported, including: (1) liquid carrier, (2) sodium borohydride, (3) ammonia borane, and (4) magnesium hydride. TIAX applied a bottom-up costing methodology customized to analyze and quantify the processes used in the manufacture of hydrogen storage systems. This methodology, used in conjunction with ® software and other tools, developed costs for all major tank components, balance-of-tank, tank assembly, and system assembly. Based on this methodology, the figure below shows the projected on-board high-volume factory costs of the various analyzed hydrogen storage systems, as designed. Reductions in the key cost drivers may bring hydrogen storage system costs closer to this DOE target

  20. Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

    Energy Technology Data Exchange (ETDEWEB)

    Sadikin, Yolanda [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Stare, Katarina [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana (Slovenia); Schouwink, Pascal [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Brix Ley, Morten; Jensen, Torben R. [Center for Materials Crystallography (CMC), Interdisciplinary Nanoscience Center (iNANO), and Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Århus C (Denmark); Meden, Anton [Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana (Slovenia); Černý, Radovan, E-mail: radovan.cerny@unige.ch [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland)

    2015-05-15

    The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y{sup 3+} is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH{sub 4} both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A{sub 3}Y(BH{sub 4}){sub 6} or c-A{sub 2}LiY(BH{sub 4}){sub 6} (A=Rb, Cs) form in all the investigated systems, with the exception of the Li–K–Y system. The compounds with the stoichiometry AY(BH{sub 4}){sub 4} crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride – closo-borane is observed during decomposition of all double perovskites. - Graphical abstract: The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five novel compounds and four further ones previously reported. Significant coordination flexibility of Y{sup 3+} is revealed, which can be employed to form both octahedral frameworks and tetrahedral complex anions, very different structural topologies. Versatility is also manifested in three different simultaneously occurring coordination modes of borohydrides for one metal cation, as proposed by DFT optimization of the monoclinic KY(BH{sub 4}){sub 4} structural model observed by powder diffraction. - Highlights: • The system Li-A-Y-BH{sub 4} (A=K, Rb, Cs) contains nine compounds in total. • Y{sup 3+} forms octahedral frameworks and tetrahedral complex anions. • Bi- and trimetallic double-perovskites crystallize in most systems. • Various AY(BH{sub 4}){sub 4} crystallize with

  1. Full phosphorescent white-light organic light-emitting diodes with improved color stability and efficiency by fine tuning primary emission contributions

    Directory of Open Access Journals (Sweden)

    Wang Hua

    2014-02-01

    Full Text Available In this paper, a novel type of white-light organic light emitting diode (OLED with high color stability was reported, in which the yellow-light emission layer of (4,4′-N,N′-dicarbazolebiphenyl (CBP : tris(2-phenylquinoline-C2,N′iridium(III (Ir(2-phq3 was sandwiched by double blue-light emission layers of 1,1-bis-[(di-4-tolylaminopheny1]cyclohexane (TAPC : bis[4,6-(di-fluorophenyl-pyridinato-N,C2′]picolinate (FIrpic and tris[3-(3-pyridylmesityl]borane (3TPYMB:FIrpic. And, it exhibited the maximum current efficiency of 33.1 cd/A, the turn-on voltage at about 3 V and the maximum luminance in excess of 20000 cd/m2. More important, it realized very stable white-light emission, and its CIE(x, y coordinates only shift from (0.34, 0.37 to (0.33, 0.37 as applied voltage increased from 5 V to 12 V. It is believed that the new scheme in emission layer of white-light OLED can fine tune the contribution of primary emission with applied voltage changed, resulting in high quality white-light OLED.

  2. Characterisation of the acidity and the basicity of transition alumina by NMR and FTIR spectroscopy of adsorption of probe molecules; Caracterisation par RMN et infrarouge de molecules sondes adsorbees, de l'acidite et de la basicite d'alumines de transition

    Energy Technology Data Exchange (ETDEWEB)

    Mathonneau, E.

    2003-04-01

    This work has been devoted to characterization of the acidity and the basicity of the surface of transition alumina. Three different alumina (Alumina-{gamma}, -{delta} et -{theta} ({gamma}-Al, {delta}-Al, {theta}-Al)) have been studied by adsorption of probe molecules such trimethyl phosphine and carbon monoxide (acidity study); and tri-ethyl borane (basicity study). We emphasized that the acidity increases with an increasing pretreatment temperature where as the basicity decreases. Comparing quantitative results from the different probe molecules we could show an increasing strength acidity following: {gamma}-Al > {theta}-Al > {delta}-Al, and basicity following: {delta}-Al > {gamma}-Al > {theta}-Al. We could evaluate on a qualitative (nature and repartition) and on a quantitative point of view the impact of the transformations {gamma}-Al {yields} {delta}-Al and {gamma}-Al > {theta}-Al on the acid-basicity of the surface. We could also explain catalytic reactivity differences between alumina for the position isomerization of butene-1. (author)

  3. Hydrogen for automotive applications and beyond

    Energy Technology Data Exchange (ETDEWEB)

    Eberle, U. [Adam Opel GmbH, Ruesselsheim (Germany)

    2010-12-30

    The energy storage system is of decisive importance for all types of electric vehicles, in contrast to the case of vehicles powered by a conventional fossil fuel or bio-fuel based internal combustion engine. Two major alternatives exist and need to be discussed: on the one hand, there is the possibility of electrical energy storage using batteries, whilst on the other hand there is the storage of energy in chemical form as hydrogen and the application of a fuel cell as energy converter. Considering the latter concept, hydrogen is a promising energy carrier in future energy systems. However, storage of hydrogen is a substantial challenge, especially for applications in vehicles with fuel cells that use proton-exchange membranes (PEMs). Different methods for hydrogen storage are discussed, including high-pressure and cryogenic-liquid storage, adsorptive storage on high-surface-area adsorbents, chemical storage in metal hydrides and complex hydrides, and storage in boranes. For the latter chemical solutions, reversible options and hydrolytic release of hydrogen with off-board regeneration are both possible. Reforming of liquid hydrogen-containing compounds is also a possible means of hydrogen generation. The advantages and disadvantages of the different systems are compared. (orig.)

  4. Electrochemical behavior and microstructural characterization of 1026 Ni-B coated steel

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, A. [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas Norte 152, Col. San Bartolo Atepehuacan, Mexico D.F. 07730 (Mexico)]. E-mail: acontrer@imp.mx; Leon, C. [Programa de investigacion en Ductos, Materiales y Corrosion, Universidad Michoacana de San Nicolas de Hidalgo, Apdo. Postal 888, Morelia Mich. 58000 (Mexico); Jimenez, O. [Programa de investigacion en Ductos, Materiales y Corrosion, Universidad Michoacana de San Nicolas de Hidalgo, Apdo. Postal 888, Morelia Mich. 58000 (Mexico); Sosa, E. [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas Norte 152, Col. San Bartolo Atepehuacan, Mexico D.F. 07730 (Mexico); Perez, R. [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas Norte 152, Col. San Bartolo Atepehuacan, Mexico D.F. 07730 (Mexico)

    2006-11-15

    Ni-B coatings have been deposited on the surfaces of commercial steels (SAE-1026). The depositions were carried out using the electroless plating technique employing a nickel chloride solution with borane-dimethylamine as the reducing agent. These specimens were subsequently heat treated at different temperatures (300-500 deg. C) and different periods of time. The obtained coating thickness was in the order of approximately 1.5 {mu}m. X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques were used to characterize the structure and superficial morphology of the coatings. Phases like Ni, Ni{sub 3}B and Ni{sub 4}B{sub 3} were observed through X-ray diffraction and confirmed by differential scanning calorimeter (DSC) studies. Some of the precipitated phases have been structurally characterized. The corrosion behavior of the coated surfaces was carried out by electrochemical impedance spectroscopy (EIS) using electrolytic sodium chlorine solutions with pH 2 and 7. The EIS results showed an active corrosion mechanism in acid solution while diffusion-reaction phenomena are predominant in neutral solution.

  5. Diastereoselective and enantioselective reduction of tetralin-1,4-dione

    Directory of Open Access Journals (Sweden)

    2008-10-01

    Full Text Available BackgroundThe chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis.ResultsThe title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16. Red-Al gave preferentially the trans-diol (d.r. 13 : 87. NaBH4, LiAlH4, and BH3 gave lower diastereoselectivities (yields: 76–98%. Fractional crystallization allowed isolation of the cis-diol and the trans-diol (55% and 66% yield, respectively. Borane was used to cleanly give the mono-reduction product. Highly enantioselective CBS reductions afforded the trans-diol (72% yield, 99% ee and the mono-reduction product (81%, 95% ee.ConclusionDiastereoselective and enantioselective reductions of the unexplored tetralin-1,4-dione provides a very convenient entry into a number of synthetically highly attractive 1,4-tetralindiols and 4-hydroxy-1-tetralone.

  6. Development and Validation of a Slurry Model for Chemical Hydrogen Storage in Fuel Cell Applications

    Energy Technology Data Exchange (ETDEWEB)

    Brooks, Kriston P.; Pires, Richard P.; Simmons, Kevin L.

    2014-07-25

    The US Department of Energy's (DOE) Hydrogen Storage Engineering Center of Excellence (HSECoE) is developing models for hydrogen storage systems for fuel cell-based light duty vehicle applications for a variety of promising materials. These transient models simulate the performance of the storage system for comparison to the DOE’s Technical Targets and a set of four drive cycles. The purpose of this research is to describe the models developed for slurry-based chemical hydrogen storage materials. The storage systems of both a representative exothermic system based on ammonia borane and endothermic system based on alane were developed and modeled in Simulink®. Once complete the reactor and radiator components of the model were validated with experimental data. The model was then run using a highway cycle, an aggressive cycle, cold-start cycle and hot drive cycle. The system design was adjusted to meet these drive cycles. A sensitivity analysis was then performed to identify the range of material properties where these DOE targets and drive cycles could be met. Materials with a heat of reaction greater than 11 kJ/mol H2 generated and a slurry hydrogen capacity of greater than 11.4% will meet the on-board efficiency and gravimetric capacity targets, respectively.

  7. Development and validation of a slurry model for chemical hydrogen storage in fuel cell vehicle applications

    Science.gov (United States)

    Brooks, Kriston P.; Pires, Richard P.; Simmons, Kevin L.

    2014-12-01

    The U.S. Department of Energy's (DOE) Hydrogen Storage Engineering Center of Excellence (HSECoE) is developing models for hydrogen storage systems for fuel cell-based light duty vehicle applications for a variety of promising materials. These transient models simulate the performance of the storage system for comparison to the DOE's Technical Targets and a set of four drive cycles. PNNL developed models to simulate the performance and suitability of slurry-based chemical hydrogen storage materials. The storage systems of both a representative exothermic system based on ammonia borane and an endothermic system based on alane were developed and modeled in Simulink®. Once complete, the reactor and radiator components of the model were validated with experimental data. The system design parameters were adjusted to allow the model to successfully meet a highway cycle, an aggressive cycle, a cold-start cycle, and a hot drive cycle. Finally, a sensitivity analysis was performed to identify the range of material properties where these DOE targets and drive cycles could be met. Materials with a heat of reaction >11 kJ mol-1 H2 generated and a slurry hydrogen capacity of >11.4% will meet the on-board efficiency and gravimetric capacity targets, respectively.

  8. Organic Monolayers by B(C6F5)3-Catalyzed Siloxanation of Oxidized Silicon Surfaces

    Science.gov (United States)

    2017-01-01

    Inspired by the homogeneous catalyst tris(pentafluorophenyl) borane [B(C6F5)3], which acts as a promotor of Si–H bond activation, we developed and studied a method of modifying silicon oxide surfaces using hydrosilanes with B(C6F5)3 as the catalyst. This dedihydrosiloxanation reaction yields complete surface coverage within 10 min at room temperature. Organic monolayers derived from hydrosilanes with varying carbon chain lengths (C8–C18) were prepared on oxidized Si(111) surfaces, and the thermal and hydrolytic stabilities of the obtained monolayers were investigated in acidic (pH 3) medium, basic (pH 11) medium, phosphate-buffered saline (PBS), and deionized water (neutral conditions) for up to 30 days. DFT calculations were carried out to gain insight into the mechanism, and the computational results support a mechanism involving silane activation with B(C6F5)3. This catalyzed reaction path proceeds through a low-barrier-height transition state compared to the noncatalyzed reaction path. PMID:28230381

  9. Regeneration of the periodontium for preservation of the damaged tooth.

    Science.gov (United States)

    Maeda, Hidefumi; Tomokiyo, Atsushi; Wada, Naohisa; Koori, Katsuaki; Kawachi, Giichiro; Akamine, Akifumi

    2014-10-01

    The population of the world grows every year, and life expectancy tends to increase. Thus, long-term preservation of teeth in aged individuals is an urgent issue. The main causes of tooth loss are well known to be periodontitis, caries, fractures, and orthodontic conditions. Although implant placement is a widely accepted treatment for tooth loss, most patients desire to preserve their own teeth. Many clinicians and researchers are therefore challenged to treat and preserve teeth that are irreversibly affected by deep caries, periodontitis, fractures, and trauma. Tissue engineering techniques are beneficial in addressing this issue; stem cells, signal molecules, and scaffolds are the main elements of such techniques. In this review, we describe these three elements with respect to their validation for regeneration of the periodontium and focus particularly on the potency of diverse scaffolds. In addition, we provide a short overview of the ongoing studies of 4-methacryloxyethyl trimellitate anhydride/methyl methacrylate-tri-n-butyl-borane resin including calcium chloride or hydroxyapatite for periodontium regeneration.

  10. Large-scale fabrication and utilization of novel hexagonal/turbostratic composite boron nitride nanosheets

    KAUST Repository

    Zhong, Bo

    2017-02-15

    In this report, we have developed a scalable approach to massive synthesis of hexagonal/turbostratic composite boron nitride nanosheets (h/t-BNNSs). The strikingly effective, reliable, and high-throughput (grams) synthesis is performed via a facile chemical foaming process at 1400°C utilizing ammonia borane (AB) as precursor. The characterization results demonstrate that high quality of h/t-BNNSs with lateral size of tens of micrometers and thickness of tens of nanometers are obtained. The growth mechanism of h/t-BNNSs is also discussed based on the thermogravimetric analysis of AB which clearly shows two step weight loss. The h/t-BNNSs are further used for making thermoconductive h/t-BNNSs/epoxy resin composites. The thermal conductivity of the composites is obviously improved due to the introduction of h/t-BNNSs. Consideration of the unique properties of boron nitride, these novel h/t-BNNSs are envisaged to be very valuable for future high performance polymer based material fabrication.

  11. New syntheses and structural characterization of NH3BH2Cl and (BH2NH2)3 and thermal decomposition behavior of NH3BH2Cl.

    Science.gov (United States)

    Lingam, Hima K; Wang, Cong; Gallucci, Judith C; Chen, Xuenian; Shore, Sheldon G

    2012-12-17

    New convenient procedures for the preparation of ammonia monochloroborane (NH(3)BH(2)Cl) and cyclotriborazane [(BH(2)NH(2))(3)] are described. Crystal structures have been determined by single-crystal X-ray diffraction. Strong H···Cl···H bifurcated hydrogen bonding and weak N-H···H dihydrogen bonding are observed in the crystal structure of ammonia monochloroborane. When heated at 50 °C or under vacuum, ammonia monochloroborane decomposes to (NH(2)BHCl)(x), which was characterized by NMR, elemental analysis, and powder X-ray diffraction. Redetermination of the crystal structure of cyclotriborazane at low temperature by single-crystal X-ray diffraction analysis provides accurate hydrogen positions. Similar to ammonia borane, cyclotriborazane shows extensive dihydrogen bonding of N-H···H and B-H···H bonds with H(δ+)···H(δ-) interactions in the range of 2.00-2.34 Å.

  12. Synthesis of monolayer hexagonal boron nitride on Cu foil using chemical vapor deposition.

    Science.gov (United States)

    Kim, Ki Kang; Hsu, Allen; Jia, Xiaoting; Kim, Soo Min; Shi, Yumeng; Hofmann, Mario; Nezich, Daniel; Rodriguez-Nieva, Joaquin F; Dresselhaus, Mildred; Palacios, Tomas; Kong, Jing

    2012-01-11

    Hexagonal boron nitride (h-BN) is very attractive for many applications, particularly, as protective coating, dielectric layer/substrate, transparent membrane, or deep ultraviolet emitter. In this work, we carried out a detailed investigation of h-BN synthesis on Cu substrate using chemical vapor deposition (CVD) with two heating zones under low pressure (LP). Previous atmospheric pressure (AP) CVD syntheses were only able to obtain few layer h-BN without a good control on the number of layers. In contrast, under LPCVD growth, monolayer h-BN was synthesized and time-dependent growth was investigated. It was also observed that the morphology of the Cu surface affects the location and density of the h-BN nucleation. Ammonia borane is used as a BN precursor, which is easily accessible and more stable under ambient conditions than borazine. The h-BN films are characterized by atomic force microscopy, transmission electron microscopy, and electron energy loss spectroscopy analyses. Our results suggest that the growth here occurs via surface-mediated growth, which is similar to graphene growth on Cu under low pressure. These atomically thin layers are particularly attractive for use as atomic membranes or dielectric layers/substrates for graphene devices.

  13. Adipose tissue partitioning of limit-fed beef cattle and beef cattle with ad libitum access to feed differing in adaptation to heat.

    Science.gov (United States)

    Sprinkle, J E; Ferrell, C L; Holloway, J W; Warrington, B G; Greene, L W; Wu, G; Stuth, J W

    1998-03-01

    We compared fat distribution and lipoprotein lipase (LPL) activity in steers differing in adaptability to the subtropics. Steers were fed a grain diet (3.13 Mcal ME/kg DM) at limited (150 kcal ME x kg[-.75] x d[-1]; .23 kg ADG) or ad libitum levels for 140 d, then slaughtered. Sixteen British- (8 Angus, 8 Hereford; S), 16 Boran- (R), 16 Brahman- (B), and 16 Tuli- (T) cross steers from MARC III composite cows were used. Adipose tissue samples from perirenal, omental, and subcutaneous depots were analyzed for LPL activity. Carcass measurements including omental, external, and seam fat trim from 1/ 2 of the carcass were measured. Subcutaneous fat had greater (P .05) in fat distribution for steers fed at limited levels. Means for ADG, slaughter weights, carcass weights, yield grades, and carcass lipid weights for S and B fed for ad libitum intake were greater (P .05) for the other breeds with ad libitum intake. Factor analysis of fat depots for animals with ad libitum intake indicated that Bos taurus cattle differing in adaptation to heat deposited fat differently; S deposited greater (P carcass fat and T deposited greater (P < .05) proportions of internal fat. It seems that accumulation of internal fat is detrimental for ADG for Bos taurus cattle.

  14. Maternal grandsire, granddam, and sire breed effects on growth and carcass traits of crossbred cattle.

    Science.gov (United States)

    Casas, E; Cundiff, L V

    2003-04-01

    Postweaning growth, feed efficiency, and carcass traits were analyzed on 1,422 animals obtained by mating F1 cows to F1 (Belgian Blue x British breeds) or Charolais sires. Cows were obtained from mating Hereford, Angus, and MARC IIIHereford, 1/4 Angus, 1/4 Pinzgauer, and 1/4 Red Poll) dams to Hereford or Angus (British breeds), Tuli, Boran, Brahman, or Belgian Blue sires. Breed groups were fed in replicated pens and slaughtered serially in each of 2 yr. Postweaning average daily gain; live weight; hot carcass weight; fat depth; longissimus area; estimated kidney, pelvic, and heart fat (percentage); percentage Choice; marbling score; USDA yield grade; retail product yield (percentage); retail product weight; fat yield (percentage); fat weight; bone yield (percentage); and bone weight were analyzed in this population. Quadratic regressions of pen mean weight on days fed and of cumulative ME consumption on days fed were used to estimate gain, ME consumption and efficiency (Mcal of ME/kg of gain) over time (0 to 200 d on feed), and weight (300 to 550 kg) intervals. Maternal grandsire breed was significant (P carcass weight, longissimus area, and bone weight. Sex class was a significant (P < 0.001) source of variation for all traits except for percentage Choice, marbling score, retail product yield, and fat yield. Interactions between maternal grandsire and sire breed were nonexistent. Sire and grandsire breed effects can be optimized by selection and use of appropriate crossbreeding systems.

  15. Characterization of biological types of cattle (Cycle V): carcass traits and longissimus palatability.

    Science.gov (United States)

    Wheeler, T L; Cundiff, L V; Shackelford, S D; Koohmaraie, M

    2001-05-01

    Carcass (n = 854) and longissimus thoracis palatability (n = 802) traits from F1 steers obtained from mating Hereford, Angus, and MARC III cows to Hereford or Angus (HA), Tuli (Tu), Boran (Bo), Brahman (Br), Piedmontese (Pm), or Belgian Blue (BB) sires were compared. Data were adjusted to constant age (444 d), carcass weight (333 kg), fat thickness (1.0 cm), fat trim percentage (21%), and marbling (Small00) end points. Results presented in this abstract are for age-constant data. Carcasses from BB- and HA-sired steers were heaviest (P carcass traits but had little effect on palatability traits. Carcasses from BB- and Pm-sired steers provided the most desirable combination of yield grade and longissimus palatability, but carcasses from HA-cross steers provided the most desirable combination of quality grade and longissimus palatability. Tuli, a breed shown to be heat-tolerant, had longissimus tenderness similar to that of the non-heat-tolerant breeds and more tender longissimus than the heat-tolerant breeds in this study.

  16. Regioselective immobilization of short oligonucleotides to acrylic copolymer gels.

    Science.gov (United States)

    Timofeev, E; Kochetkova, S V; Mirzabekov, A D; Florentiev, V L

    1996-01-01

    Four types of polyacrylamide or polydimethyl-acrylamide gels for regioselective (by immobilization at the 3' end) of short oligonucleotides have been designed for use in manufacturing oligonucleotide microchips. Two of these supports contain amino or aldehyde groups in the gel, allowing coupling with oligonucleotides bearing aldehyde or amino groups, respectively, in the presence of a reducing agent. The aldehyde gel support showed a higher immobilization efficiency relative to the amino gel. Of all reducing agents tested, the best results were obtained with a pyridine-borane complex. The other supports are based on an acrylamide gel activated with glutaraldehyde or a hydroxyalkyl-functionalized gel treated with mesyl chloride. The use of dimethylacrylamide instead of acrylamide allows subsequent gel modifications in organic solvents. All the immobilization methods are easy and simple to perform, give high and reproducible yields, allow long durations of storage of the activated support, and provide high stability of attachment and low non-specific binding. Although these gel supports have been developed for preparing oligonucleotide microchips, they may be used for other purposes as well. PMID:8774893

  17. Comparative Studies of the Electrochemical and Thermal Stability of Composite Electrolytes for Lithium Battery Using Two Types of Boron-Based Anion Receptors

    Energy Technology Data Exchange (ETDEWEB)

    Yang, X. Q.; Lee, H. S.; Sun, X.; McBreen, J.

    1999-10-17

    Comparative studies were done on two new types of boron based anion receptors, tris(pentafluorophenyl) borane (TFPB) and tris(pentafluorophenyl) borate (TFPBO), regarding conductivity enhancement electrochemical and thermal stability when used as additives in composite electrolytes for lithium batteries. Both additives enhance the ionic conductivity of electrolytes of simple lithium salts, LiF, CF{sub 3}CO{sub 2}Li and C{sub 2}F{sub 5}CO{sub 2}Li in several organic solvents. The electrochemical windows of TPFB based electrolytes in ethylene carbonate (EC)-propylene carbonate (PC)-dmethyl carbonate (DMC) (1:1:3, v/v) are up to 5, 4.76 and 4.96 V for LiF, CF{sub 3}CO{sub 2}Li and C{sub 2}F{sub 5}CO{sub 2}Li respectively. TPFBO has lower electrochemical stability compared to TPFB. The thermal stability of pure TFPB is better than TFPBO. The lithium salt complexes have higher thermal stability than these two compounds. TPFB based electrolytes showed high cycling efficiencies and good cycleability when they were tested in Li/LiMn{sub 2}O{sub 4} cells. The capacity retention of the cells using TFPB based electrolytes during multiple cycling is better than those using TFPBO based electrolytes.

  18. Reproductive performance of cows mated to and preweaning performance of calves sired by Brahman vs alternative subtropically adapted breeds.

    Science.gov (United States)

    Thrift, F A

    1997-10-01

    Comparisons involving Brahman and Brahman-derivative (Brangus, Santa Gertrudis, Beef-master, Simbrah, Braford) sires indicate the following: 1) cows mated to Brangus and Santa Gertrudis bulls had a shorter gestation length than cows mated to Brahman bulls, 2) calves sired by Brangus and Beefmaster bulls were lighter at birth and weaning than calves sired by Brahman bulls, and 3) birth and weaning weights were similar for calves sired by Santa Gertrudis and Brahman bulls and for calves sired by Simbrah and Brahman bulls. Comparisons involving Brahman and other Zebu (Sahiwal, Nellore, Gir, Indu-Brazil, Boran, Romana Red) sires indicate that gestation length was slightly longer for cows mated to Sahiwal and Nellore bulls and that, relative to the Brahman, birth and weaning weights were similar to or lighter for calves sired by bulls of the other Zebu breeds. The only exception to this pattern was birth weight of Indu-Brazil-sired calves, which were heavier than calves sired by Brahman bulls. Comparisons involving Brahman and non-Zebu subtropically adapted (Tuli, Senepol) sires indicate that cows mated to Tuli bulls had a slightly shorter gestation length than cows mated to Brahman bulls and that birth and weaning weights of calves sired by Tuli and Senepol bulls were lighter than those of calves sired by Brahman bulls.

  19. Regulated-stereoselective construction of thirteen stereogenic centers necessary for the frame of (+)-discodermolide, based on iterative Lewis acid-promoted aldol reactions.

    Science.gov (United States)

    Kiyooka, Syun-ichi; Shahid, Kazi Abdus; Goto, Fumitaka; Okazaki, Momotoshi; Shuto, Yoshihiro

    2003-10-17

    The segments C(1)-C(13) and C(15)-C(21) containing the 13 stereogenic centers required for the frame of (+)-discodermolide were synthesized in good to excellent enantio- and diastereoselectivities from a common racemic aldehyde, derived from 2-methyl-1,3-propanediol. The enantioselective aldol reactions of the racemic aldehyde with a silylketene acetal, derived from ethyl 2-bromopropionate, in the presence of chiral oxazaborolidinones, prepared in situ with N-p-toluenesulfonyl-(R)- and -(S)-valine and BH(3).THF, proceeded under kinetic control to give the stereotriads with a high degree of enantioselectivity. Enantioselective (chiral borane) and diastereoselective (BF(3).OEt(2) and TiCl(4)) aldol reactions with the silylketene acetal, coupled with diastereoselective radical debrominations (Bu(3)SnH, Et(3)B, with or without MgBr(2)), were used iteratively. This aldol reaction strategy for the construction of the polypropionate frame dramatically shortened the steps needed for the construction of the final segments.

  20. Silver nanoparticles supported on CeO2-SBA-15 by microwave irradiation possess metal-support interactions and enhanced catalytic activity.

    Science.gov (United States)

    Qian, Xufang; Kuwahara, Yasutaka; Mori, Kohsuke; Yamashita, Hiromi

    2014-11-24

    Metal-support interactions (MSIs) and particle size play important roles in catalytic reactions. For the first time, silver nanoparticles supported on CeO2-SBA-15 supports are reported that possess tunable particle size and MSIs, as prepared by microwave (MW) irradiation, owing to strong charge polarization of CeO2 clusters (i.e., MW absorption). Characterizations, including TEM, X-ray photoelectron spectroscopy, and extended X-ray absorption fine structure, were carried out to disclose the influence of CeO2 contents on the Ag particle size, MSI effect between Ag nanoparticles and CeO2-SBA-15 supports, and the strong MW absorption of CeO2 clusters that contribute to the MSIs during Ag deposition. The Ag particle sizes were controllably tuned from 1.9 to 3.9 nm by changing the loading amounts of CeO2 from 0.5 to 2.0 wt%. The Ag nanoparticle size was predominantly responsible for the high turnover frequency (TOF) of 0.41 min(-1) in ammonia borane dehydrogenation, whereas both particle size and MSIs contributed to the high TOF of 555 min(-1) in 4-nitrophenol reduction for Ag/0.5CeO2-SBA-15, which were twice as large as those of Ag/SBA-15 without CeO2 and Ag/CeO2-SBA-15 prepared by conventional oil-bath heating.

  1. Chemo-Enzymatic Synthesis of Chiral Epoxides Ethyl and Methyl (S-3-(Oxiran-2-ylpropanoates from Renewable Levoglucosenone: An Access to Enantiopure (S-Dairy Lactone

    Directory of Open Access Journals (Sweden)

    Aurélien A. M. Peru

    2016-07-01

    Full Text Available Chiral epoxides—such as ethyl and methyl (S-3-(oxiran-2-ylpropanoates ((S-1a/1b—are valuable precursors in many chemical syntheses. Until recently, these compounds were synthesized from glutamic acid in four steps (deamination, reduction, tosylation and epoxide formation in low to moderate overall yield (20%–50%. Moreover, this procedure requires some harmful reagents such as sodium nitrite ((ecotoxic and borane (carcinogen. Herein, starting from levoglucosenone (LGO, a biobased chiral compound obtained through the flash pyrolysis of acidified cellulose, we propose a safer and more sustainable chemo-enzymatic synthetic pathway involving lipase-mediated Baeyer-Villiger oxidation, palladium-catalyzed hydrogenation, tosylation and treatment with sodium ethoxide/methoxide as key steps. This route afforded ethyl and methyl (S-3-(oxiran-2-ylpropanoates in 57% overall yield, respectively. To demonstrate the potentiality of this new synthetic pathway from LGO, the synthesis of high value-added (S-dairy lactone was undertaken from these epoxides and provided the target in 37% overall yield from LGO.

  2. Quartic canonical force field in curvilinear internal coordinates for XY3 (D3h) molecules. The case of the BH3 molecule.

    Science.gov (United States)

    Ródenas, Consuelo Rosales; Quesada, Juana Vázquez; Torres, Emilio Martínez; González, Juan Jesús López

    2014-06-01

    Using the canonical force field theory, expressions of quadratic, cubic, and quartic canonical force constants are obtained for XY3 (D3h) molecules in curvilinear redundant coordinates, i.e., simple valence internal coordinates (VICs), in terms of force constants in normal coordinates and in independent symmetry coordinates. To carry out this task, it was previously necessary to obtain for the first time the non-linear redundancy relation and the corresponding orthogonal projection onto the pure vibrational manifold for XY3 (D3h) molecules corresponding to a set of seven VICs. As an application, the quartic canonical force field in curvilinear redundant internal coordinates of BH3 is determined from ab initio force fields in normal coordinates calculated at the coupled-cluster singles and doubles level with perturbative treatment of the triples in conjunction with a triple- and quadruple-ζ size basis set. This anharmonic force field so obtained for the borane molecule, and in general for XY3 (D3h) molecules, is uniquely defined (therefore in an unambiguous form) and depending on the same number of parameters, i.e., force constants, when independent coordinates (natural or symmetry) are used in its description.

  3. Synthesis, Hydrolysis, and Protonation-Promoted Intramolecular Reductive Breakdown of Potential NRTIs: Stavudine α-P-Borano-γ-P-N-l-tryptophanyltriphosphates

    Directory of Open Access Journals (Sweden)

    Zhihong Xu

    2015-10-01

    Full Text Available Phosphorus-modified prodrugs of dideoxynucleoside triphosphates (ddNTPs have shown promise as pronucleotide strategies for improving antiviral activity compared to their parent dideoxynucleosides. Borane modified NTPs offer a promising choice as nucleoside/nucleotide reverse transcriptase inhibitors (NRTIs. However, the availability of α-P-borano-γ-P-substituted NTP analogs remains limited due to challenges with synthesis and purification. Here, we report the chemical synthesis and stability of a new potential class of NRTI prodrugs: stavudine (d4T 5′-α-P-borano-γ-P-N-L-tryptophanyltriphosphates. One-pot synthesis of these compounds was achieved via a modified cyclic trimetaphosphate approach. Pure Rp and Sp diastereomers were obtained after HPLC separation. Based on LC-MS analysis, we report degradation pathways, half-lives (5–36 days and mechanisms arising from structural differences to generate the corresponding borano tri- and di-phosphates, and H-phosphonate, via several parallel routes in buffer at physiologically relevant pH and temperature. Here, the major hydrolysis products, d4T α-P-boranotriphosphate Rp and Sp isomers, were isolated by HPLC and identified with spectral data. We first propose that one of the major degradation products, d4T H-phosphonate, was generated from the d4T pronucleotides via a protonation-promoted intramolecular reduction followed by a second step nucleophilic attack. This report could provide valuable information for pronucleotide-based drug design in terms of selective release of target nucleotides.

  4. Hydrothermal Synthesis and Catalytic Application of Ultrathin Rhodium Nanosheet Nanoassemblies.

    Science.gov (United States)

    Bai, Juan; Xu, Guang-Rui; Xing, Shi-Hui; Zeng, Jing-Hui; Jiang, Jia-Xing; Chen, Yu

    2016-12-14

    Ultrathin noble metal nanosheets with atomic thickness exhibit abnormal electronic, surfacial, and photonic properties due to the unique two-dimensional (2D) confinement effect, which have attracted intensive research attention in catalysis/electrocatalysis. In this work, the well-defined ultrathin Rh nanosheet nanoassemblies with dendritic morphology are synthesized by a facile hydrothermal method with assistance of poly(allylamine hydrochloride) (PAH), where PAH effectively acts as the complexant and shape-directing agent. Transmission electron microscopy and atomic force microscopy images reveal the thickness of 2D Rh nanosheet with (111) planes is only ca. 0.8-1.1 nm. Nitrogen adsorption-desorption measurement displays the specific surface area of the as-prepared ultrathin Rh nanosheet nanoassemblies is 139.4 m(2) g(-1), which is much bigger than that of homemade Rh black (19.8 m(2) g(-1)). Detailed catalytic investigations display the as-prepared ultrathin Rh nanosheet nanoassemblies have nearly 20.4-fold enhancement in mass-activity for the hydrolysis of ammonia borane as compared with homemade Rh black.

  5. A biotemplated nickel nanostructure: Synthesis, characterization and antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Ashtari, Khadijeh [Department of Nanobiotechnology, Faculty of Biological Science, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Fasihi, Javad [Department of Analytical Chemistry, Faculty of Science, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Mollania, Nasrin [Department of Biochemistry, Faculty of Biological Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Khajeh, Khosro, E-mail: khajeh@modares.ac.ir [Department of Nanobiotechnology, Faculty of Biological Science, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Department of Biochemistry, Faculty of Biological Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2014-02-01

    Highlights: • Nickel nanostructure-encapsulated bacteria were prepared using electroless deposition. • Bacterium surface was activated by red-ox reaction of its surface amino acids. • Interfacial changes at cell surfaces were investigated using fluorescence spectroscopy. • TEM and AFM depicted morphological changes. • Antibacterial activity of nanostructure was examined against different bacteria strains. - Abstract: Nickel nanostructure-encapsulated bacteria were prepared using the electroless deposition procedure and activation of bacterium cell surface by red-ox reaction of surface amino acids. The electroless deposition step occurred in the presence of Ni(II) and dimethyl amine boran (DMAB). Interfacial changes at bacteria cell surfaces during the coating process were investigated using fluorescence spectroscopy. Fluorescence of tryptophan residues was completely quenched after the deposition of nickel onto bacteria surfaces. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) depicted morphological changes on the surface of the bacterium. It was found that the Ni coated nanostructure was mechanically stable after ultrasonication for 20 min. Significant increase in surface roughness of bacteria was also observed after deposition of Ni clusters. The amount of coated Ni on the bacteria surface was calculated as 36% w/w. The antibacterial activity of fabricated nanostructure in culture media was examined against three different bacteria strains; Escherichia coli, Bacillus subtilis and Xantomonas campestris. The minimum inhibitory concentrations (MIC) were determined as 500 mg/L, 350 mg/L and 200 mg/L against bacteria, respectively.

  6. AUTOCATALYTIC REDUCTION AND CHARACTERISTICS OF BORON-CONTAINING COATINGS

    Directory of Open Access Journals (Sweden)

    V. Covaliov

    2013-06-01

    Full Text Available The research results of the plating conditions, chemical composition and properties of Ni-B coatings and Ni-Re-B, Ni-Mo-B and Ni-W-B alloys are given. It was shown that introduction of alloying elements (Re, Мо and W in the composition of Ni-containing coatings modifies the catalytic activity of the alloys’ surface, with regard to the parallel reactions of dimethylamino-borane (DMAB heterogeneous hydrolysis, Ni reduction and evolving of the molecular hydrogen. It was found that with the increase in concentration of alloying element, boron content in the coatings is decreased to the trace amounts. The effect of alloys composition on hydrogen evolving overvoltage was studied. Due to the low overvoltage of hydrogen evolving (HE on the alloy Ni-Re-B surface (11 at.% Re, it can be used as electrode for hydrogen generation from water in the electrolytic cell with novel design and improved technical-economic indicators.

  7. Materials Engineering and Scale Up of Fluid Phase Chemical Hydrogen Storage for Automotive Applications

    Energy Technology Data Exchange (ETDEWEB)

    Westman, Matthew P.; Chun, Jaehun; Choi, Young Joon; Ronnebro, Ewa

    2016-01-25

    Among candidates for chemical hydrogen storage in PEM fuel cell automotive applications, ammonia borane (AB, NH3BH3) is considered to be one of the most promising materials due to its high hydrogen content of 14-16 wt% below 200°C and high volumetric density. In our previous paper, we selected AB in silicone oil as a role model for a slurry hydrogen storage system. Materials engineering properties were optimized by increasing solid loading by using an ultra-sonic process. In this paper, we proceeded to scale up to liter size batches with solid loadings up to 50 wt% (8 wt% H2) with dynamic viscosities less than 1000cP at 25°C. The use of a non-ionic surfactant, Triton X-15, shows significant promise in controlling the level of foaming produced during the thermal dehydrogenation of the AB. Through the development of new and efficient processing techniques and the ability to adequately control the foaming, stable homogenous slurries of high solid loading have been demonstrated as a viable hydrogen delivery source.

  8. Feed intake and production parameters of lactating crossbred cows fed maize-based diets of stover, silage or quality protein silage.

    Science.gov (United States)

    Gebrehawariat, Efrem; Tamir, Berhan; Tegegne, Azage

    2010-12-01

    Thirty-six Boran × Friesian dairy cows (392 ± 12 kg; mean ± SD) in early parity were used in a randomised complete block design. Cows were blocked by parity into three blocks of 12 animals and offered normal maize (NM) stover (T1), NM silage (T2) or quality protein maize (QPM) silage (T3) basal diets supplemented with a similar concentrate mix. Feed intake, body weight and condition changes and milk yield and composition were assessed. The daily intake of DM, OM, NDF and ADF for cows fed the NM stover-based diet was higher (Psilage and QPM silage-based diets. However, the daily intake of DOM (9.3 kg) and ME (140.8 MJ) for cows on QPM silage-based diet was higher (Psilage-based diet (7.9 kg and 119.1 MJ). Body weight of cows was affected (P0.05) on body condition score, milk yield and milk composition. The digestible organic matter in the NM stover-based diet (724 g/kg DM) was lower (Psilage-based diet (762 g/kg DM). It was concluded that the performances of the cows on the NM silage and QPM silage diets were similar and were not superior to that of the NM stover-based diet.

  9. Morphosyntactic Aspects of Ocaina: Between Genetic Features (Witotoan family and Areal Influences

    Directory of Open Access Journals (Sweden)

    Doris Fagua Rincón

    2010-02-01

    Full Text Available This paper presents some morphosyntactic features of Ocaina, a seriously endangered, underdescribed language of the Colombian-Peruvian Amazon region. Ocaina has an extensive nominal classification system and number markers—dual  and plural—suffixed to both nouns and person markers on verbs. Grammatical relations follow a nominative-accusative pattern and are coded by a relatively rigid constituent order SOV (Subject-Object-Verb; by verbal prefixes (o-s-V and enclitics (o-V=s, with just one prefix for objects of monotransitive and ditransitive verbs; and by the marking of oblique objects of certain verbs by case suffixes and postpositions. Most of the Ocaina features described are shared with Uitoto of the Witotoan family; many are also shared with Bora (Boran family, whose genetic link to the Witotoan family is still hypothetical. All these languages share certain features with neighboring languages, such as those of the Vaupés region, e.g. nominal classification and nominative-accusative alignment. We suggest that some aspects of Ocaina morphosyntax are probably inherited from the Witotoan family while others are better explained by areal diffusion.

  10. Syntheses and characterizations of linear triborazanes.

    Science.gov (United States)

    Ewing, William C; Carroll, Patrick J; Sneddon, Larry G

    2013-09-16

    Reaction of the amine boranes NH2(R)BH3, where R = H, Me, and Bz, with 1/3 equiv of sodium hexamethyldisilazane produced the five-membered, linear aminoborane anions Na(+)[BH3N(R)HBH2N(R)HBH3(-)], where R = H (1), Me (1Me), and benzyl (1Bz). Reactions of 1 and 1Me with ammonium chloride and methylammonium chloride, respectively, resulted in elimination of NaCl and H2 to produce the linear triborazanes BH3(RNHBH2)2N(R)H2, where R = H (2) and Me (2Me), with the structure of 2 crystallographically confirmed. The reactions of 1 and 1Me with pyridine-HCl produced the pyridine-capped aminoboranes H3B(RNHBH2)2(NC5H5), where R = H (3) and Me (3Me). 2 and 2Me proved to be stable up to 90 °C but produced a mixture of products when heated above 90 °C. 2 was selectively monochlorinated at the terminal boron when treated with 1 equiv of HCl and dichlorinated when reacted with a second 1 equiv of HCl.

  11. Superhalogens as Building Blocks of Complex Hydrides for Hydrogen Storage

    CERN Document Server

    Srivastava, Ambrish Kumar

    2016-01-01

    Superhalogens are species whose electron affinity (EA) or vertical detachment energy (VDE) exceed to those of halogen. These species typically consist of a central electropositive atom with electronegative ligands. The EA or VDE of species can be further increased by using superhalogen as ligands, which are termed as hyperhalogen. Having established BH4- as a superhalogen, we have studied BH4-x(BH4)x- (x = 1 to 4) hyperhalogen anions and their Li-complexes, LiBH4-x(BH4)x using density functional theory. The VDE of these anions is larger than that of BH4-, which increases with the increase in the number of peripheral BH4 moieties (x). The hydrogen storage capacity of LiBH4-x(BH4)x complexes is higher but binding energy is smaller than that of LiBH4, a typical complex hydride. The linear correlation between dehydrogenation energy of LiBH4-x(BH4)x complexes and VDE of BH4-x(BH4)x- anions is established. These complexes are found to be thermodynamically stable against dissociation into LiBH4 and borane. This stud...

  12. Iridium(I) complexes with anionic N-heterocyclic carbene ligands as catalysts for the hydrogenation of alkenes in nonpolar media.

    Science.gov (United States)

    Kolychev, Eugene L; Kronig, Sabrina; Brandhorst, Kai; Freytag, Matthias; Jones, Peter G; Tamm, Matthias

    2013-08-21

    A series of lithium complexes of anionic N-heterocyclic carbenes that contain a weakly coordinating borate moiety (WCA-NHC) was prepared in one step from free N-heterocyclic carbenes by deprotonation with n-butyl lithium followed by borane addition. The reaction of the resulting lithium-carbene adducts with [M(COD)Cl]2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) afforded zwitterionic rhodium(I) and iridium(I) complexes of the type [(WCA-NHC)M(COD)], in which the metal atoms exhibit an intramolecular interaction with the N-aryl groups of the carbene ligands. For M = Rh, the neutral complex [(WCA-NHC)Rh(CO)2] and the ate complex (NEt4)[(WCA-NHC)Rh(CO)2Cl] were prepared, with the latter allowing an assessment of the donor ability of the ligand by IR spectroscopy. The zwitterionic iridium-COD complexes were tested as catalysts for the homogeneous hydrogenation of alkenes, which can be performed in the presence of nonpolar solvents or in the neat alkene substrate. Thereby, the most active complex showed excellent stability and activity in hydrogenation of alkenes at low catalyst loadings (down to 10 ppm).

  13. DFT Predictions on Structures and Stabilities of Eleven-vertex nido-and cioso-Heteroboranes

    Institute of Scientific and Technical Information of China (English)

    LI Ping

    2009-01-01

    Based on the octadecahedron of eleven-vertex closo-borane,the eleven-vertex closo-heteroborane was suggested with nonmetallic atoms instead of the different nonequivalent boron,and the stabilities were predicted at G96PW91/6-31+G(3d,2p) level.The small heteroatoms,C,N,O,preferentially occupy vertex 2 with the absolutely lowest relative energy to form the high stabilization closo-heteroboranes.They cap four-membered rings to satisfy the geometrical demand of short B-Z bonds.The electron attractions from the vicinal boron atoms make the frameworks shrink.Differently,Si and Ge preferentially substitute for boron at vertex 1 with six tight B-Z bonds and form stabilized molecules.P,As,S,and Se tend to occupy vertex 4 and the optimized structures belong to the nido configurations,in contrast to high electronegative heteroatoms,S and Se transfer less negative charges to framework and the electropositive heteroatoms,Si and Ge transfer more negative charges to framework to form the delocalization structures.The HOMO-LUMO gaps show that most of predicted clusters possess chemical stabilities.The substitutions of heteroatoms for boron atoms in eleven-vertex closo-hcteroboranes are consistent with the topological charge stabilization rule proposed by Gimarc.

  14. Sodium hydrazinidoborane: a chemical hydrogen-storage material.

    Science.gov (United States)

    Moury, Romain; Demirci, Umit B; Ichikawa, Takayuki; Filinchuk, Yaroslav; Chiriac, Rodica; van der Lee, Arie; Miele, Philippe

    2013-04-01

    Herein, we present the successful synthesis and full characterization (by (11) B magic-angle-spinning nuclear magnetic resonance spectroscopy, infrared spectroscopy, powder X-ray diffraction) of sodium hydrazinidoborane (NaN2 H3 BH3 , with a hydrogen content of 8.85 wt %), a new material for chemical hydrogen storage. Using lab-prepared pure hydrazine borane (N2 H4 BH3 ) and commercial sodium hydride as precursors, sodium hydrazinidoborane was synthesized by ball-milling at low temperature (-30 °C) under an argon atmosphere. Its thermal stability was assessed by thermogravimetric analysis and differential scanning calorimetry. It was found that under heating sodium hydrazinidoborane starts to liberate hydrogen below 60 °C. Within the range of 60-150 °C, the overall mass loss is as high as 7.6 wt %. Relative to the parent N2 H4 BH3 , sodium hydrazinidoborane shows improved dehydrogenation properties, further confirmed by dehydrogenation experiments under prolonged heating at constant temperatures of 80, 90, 95, 100, and 110 °C. Hence, sodium hydrazinidoborane appears to be more suitable for chemical hydrogen storage than N2 H4 BH3 .

  15. Evaluation of on-board hydrogen storage methods f or high-speed aircraft

    Science.gov (United States)

    Akyurtlu, Ates; Akyurtlu, Jale F.

    1991-01-01

    Hydrogen is the fuel of choice for hypersonic vehicles. Its main disadvantage is its low liquid and solid density. This increases the vehicle volume and hence the drag losses during atmospheric flight. In addition, the dry mass of the vehicle is larger due to larger vehicle structure and fuel tankage. Therefore it is very desirable to find a fuel system with smaller fuel storage requirements without deteriorating the vehicle performance substantially. To evaluate various candidate fuel systems, they were first screened thermodynamically with respect to their energy content and cooling capacities. To evaluate the vehicle performance with different fuel systems, a simple computer model is developed to compute the vehicle parameters such as the vehicle volume, dry mass, effective specific impulse, and payload capacity. The results indicate that if the payload capacity (or the gross lift-off mass) is the most important criterion, only slush hydrogen and liquid hydrogen - liquid methane gel shows better performance than the liquid hydrogen vehicle. If all the advantages of a smaller vehicle are considered and a more accurate mass analysis can be performed, other systems using endothermic fuels such as cyclohexane, and some boranes may prove to be worthy of further consideration.

  16. Functionalization of metal-organic frameworks through the postsynthetic transformation of olefin side groups.

    Science.gov (United States)

    Hindelang, Konrad; Kronast, Alexander; Vagin, Sergei I; Rieger, Bernhard

    2013-06-17

    For the first time, the adaptability of the C=C double bond as a versatile precursor for the postsynthetic modification (PSM) of microporous materials was extensively investigated and evaluated. Therefore, an olefin-tagged 4,4'-bipyridine linker was synthesized and successfully introduced as pillar linker within a 9,10-triptycenedicarboxylate (TDC) zinc paddle-wheel metal-organic framework (MOF) through microwave-assisted synthesis. Different reactions, predominately used in organic chemistry, were tested, leading to the development of new postsynthetic reactions for the functionalization of solid materials. The postsynthetic oxidation of the olefin side groups applying osmium tetroxide (OsO₄) as a catalyst led to the formation of a microporous material with free vicinal diol functionalities. The epoxidation with dimethyldioxirane (DMDO) enabled the synthesis of epoxy-functionalized MOFs. In addition to that, reaction procedures for a postsynthetic hydroboration with borane dimethyl sulfide as well as a photoinduced thiol-ene click reaction with ethyl mercaptan were developed. For all of these PSMs, yields of more than 90% were obtained, entirely maintaining the crystallinity of the MOFs. Since the direct introduction of the corresponding groups by means of pre-synthetic approaches is hardly possible, these new PSMs are useful tools for the functionalization of porous solids towards applications such as selective adsorption, separation, and catalysis.

  17. Spontaneous reduction and C-H borylation of arenes mediated by uranium(III) disproportionation.

    Science.gov (United States)

    Arnold, Polly L; Mansell, Stephen M; Maron, Laurent; McKay, David

    2012-07-15

    Transition-metal-arene complexes such as bis(benzene)chromium Cr(η(6)-C(6)H(6))(2) are historically important to d-orbital bonding theory and have modern importance in organic synthesis, catalysis and organic spintronics. In investigations of f-block chemistry, however, arenes are invariably used as solvents rather than ligands. Here, we show that simple uranium complexes UX(3) (X = aryloxide, amide) spontaneously disproportionate, transferring an electron and X-ligand, allowing the resulting UX(2) to bind and reduce arenes, forming inverse sandwich molecules [X(2)U(µ-η(6):η(6)-arene)UX(2)] and a UX(4) by-product. Calculations and kinetic studies suggest a 'cooperative small-molecule activation' mechanism involving spontaneous arene reduction as an X-ligand is transferred. These mild reaction conditions allow functionalized arenes such as arylsilanes to be incorporated. The bulky UX(3) are also inert to reagents such as boranes that would react with the traditional harsh reaction conditions, allowing the development of a new in situ arene C-H bond functionalization methodology converting C-H to C-B bonds.

  18. Ru Nanoframes with an fcc Structure and Enhanced Catalytic Properties.

    Science.gov (United States)

    Ye, Haihang; Wang, Qingxiao; Catalano, Massimo; Lu, Ning; Vermeylen, Joseph; Kim, Moon J; Liu, Yuzi; Sun, Yugang; Xia, Xiaohu

    2016-04-13

    Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd-Ru core-frame octahedra could be easily converted to Ru octahedral nanoframes of ∼2 nm in thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. The fcc Ru nanoframes showed higher catalytic activities toward the reduction of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.

  19. Spontaneous reduction and C-H borylation of arenes mediated by uranium(III) disproportionation

    Science.gov (United States)

    Arnold, Polly L.; Mansell, Stephen M.; Maron, Laurent; McKay, David

    2012-08-01

    Transition-metal-arene complexes such as bis(benzene)chromium Cr(η6-C6H6)2 are historically important to d-orbital bonding theory and have modern importance in organic synthesis, catalysis and organic spintronics. In investigations of f-block chemistry, however, arenes are invariably used as solvents rather than ligands. Here, we show that simple uranium complexes UX3 (X = aryloxide, amide) spontaneously disproportionate, transferring an electron and X-ligand, allowing the resulting UX2 to bind and reduce arenes, forming inverse sandwich molecules [X2U(µ-η6:η6-arene)UX2] and a UX4 by-product. Calculations and kinetic studies suggest a ‘cooperative small-molecule activation’ mechanism involving spontaneous arene reduction as an X-ligand is transferred. These mild reaction conditions allow functionalized arenes such as arylsilanes to be incorporated. The bulky UX3 are also inert to reagents such as boranes that would react with the traditional harsh reaction conditions, allowing the development of a new in situ arene C-H bond functionalization methodology converting C-H to C-B bonds.

  20. Kinetic and Thermodynamic Investigation of Hydrogen Release from Ethane 1,2-di-amineborane

    Energy Technology Data Exchange (ETDEWEB)

    Neiner, Doinita; Karkamkar, Abhijeet J.; Bowden, Mark; Choi, Young Joon; Luedtke, Avery T.; Holladay, Jamelyn D.; Fisher, Allison M.; Szymczak, Nathaniel; Autrey, Thomas

    2011-07-18

    The thermodynamics and kinetics of hydrogen (H2) release from ethane 1,2-di-amineborane (EDAB, BH3NH2CH2CH2NH2BH3) were measured using Calvet and differential scanning calorimetry (DSC), pressure-composition isotherms, and volumetric gas-burette experiments. The results presented here indicate that EDAB releases ~ 9 wt.% H2 at temperatures ranging from 100 °C to 200 °C in two moderately exothermic steps, approximately -10±1 kJ/mol H2 and -3.8±1 kJ/mol H2. Isothermal kinetic analysis shows that EDAB is more stable than ammonia borane (AB) at temperatures lower than 100°C; however, the rates of hydrogen release are faster for EDAB than for AB at temperatures higher than 120°C. In addition, no volatile impurities in the H2 released by EDAB were detected by mass spectrometry upon heating with 1°C/min to 200°C in a calorimeter.

  1. Checklist of butterfly (Insecta: Lepidoptera fauna of Tehsil Tangi, Khyber Pakhtunkhwa, Pakistan

    Directory of Open Access Journals (Sweden)

    Farzana Khan Perveen

    2015-12-01

    Full Text Available The butterflies (Insecta: Lepidopteraare well known insects, play an important role in the ecosystem as bioindicators and pollinators. They have bright colours, remarkable shapes and supple flight. The present study was conducted to prepare the checklist of butterfly fauna of Tehsil Tangi during August, 2014 to May, 2015. A total of 506 specimens were collected belong to 3 families with 18 genera and 23 species. The collected species are the common or lemon emigrant, Catopsila ponoma Fabricius; mottled emigrant, Catopsilia pyranthe Linnaeus; clouded yellow, Colias fieldii Fabricius; common grass yellow, Eurema hecabe Linnaeus; eastern pale clouded yellow butterfly, Colias erate Esper; Indian cabbage white, Pieris canidia Sparrman; Indian little orange tip, Colotis etrida Boisduval; pioneer white or African caper white, Belonias aurota Fabricius; plain tiger, Danaua chrysippus Linnaeus; blue tiger, Tirumala liminniace Cramer; peacock pansy, Junonia almanac Linnaeus; Indian fritillary, Argyreus hyperbius Linnaeus; Indian red admiral, Venesa indica Herbst; yellow pansy, Junonia hierta Fabricius; blue pansy, Junonia orytha Linnaeus; white edged rock brown, Hipparchia parisatis Kollar; banded tree brwon, Lethe confuse Aurivillius; common castor, Ariadne merione Cramer; painted lady, Caynthia cardui Linnaeus; Himalayan sailer, Neptis mahendra Moore; common boran, Euthalia garuda Hewitson; lime butterfly, Papilio demoleus Linnaeus and great black mormon butterfly, Papilio polytes Linnaeus. It was concluded that the family Nymphalidae has the highest numbers of individuals in the present checklist. It is recommended that butterfly fauna of the study area should be conserved and their habitat should be protected.

  2. From Nanowires to Nanopores: A Versatile Method for Electroless Deposition of Nanostructures on Micropatterned Organic Substrates.

    Science.gov (United States)

    Ellsworth, Ashley A; Walker, Amy V

    2016-03-22

    We demonstrate a fast, flexible, parallel, and highly controllable method by which to synthesize a variety of nanoscale and mesoscale structures. This method addresses one of the most significant challenges in nanoscience: the in situ parallel placement and synthesis of nano-objects over the mesoscale. The method is based on electroless nanowire deposition on micropatterned substrates (ENDOM). In ENDOM nanostructures are produced at the boundary between two unlike materials if two conditions are met: (a) deposition is kinetically preferred on one of the materials while (b) transport of reactants is favored on the other. In this study, copper structures were deposited on patterned -OH/-CH3-terminated alkanethiolate self-assembled monolayers (SAMs) by exploiting the different reaction rates of electroless deposition on these using the reducing agent dimethylamine borane (DMAB). We demonstrate production of nanowires (width < 100 nm), mesowires (100 nm < width < ∼3000 nm), nanorings, nanopores, and nanochannels. We show that a variety of experimental conditions can be employed, making this method compatible with many substrates. We have also studied the nucleation and growth kinetics of the ENDOM process. The width of the deposit grows exponentially with deposition time and can be modeled using classical nucleation theory. Although the deposit width increases, the height and grain size of the copper deposit is constant (to within experimental uncertainty) with deposition time. These observations indicate that the minimum deposit width is controlled by the nanoparticle dimensions and so can be controlled using the reaction conditions.

  3. High-purity Ni electroless plating on screen-printed anodized Al substrates

    Science.gov (United States)

    Park, Sang-Geon; Lee, Youn-Seoung; Rha, Sa-Kyun

    2016-07-01

    By using an electroless plating process with a Ni source solution including dimethylamine borane (DMAB) at pH 6.5 and 65 ◦ C, we obtained a higher purity Ni film (< 1 at.% boron) without damage to the anodized Al substrate. With increasing plating time, the thickness of the film increased gradually, although the average deposition rate of the Ni films decreased steadily. We can infer that the abrupt decrease in sheet resistance (Rs) at the interface region is due to the change in the boron concentration caused by surface reactions, and the gradual decrease in Rs in the bulk region is due mainly to the effect of the saturation of boron's concentration on the thickness. From a boron-distribution viewpoint, this result indicates that the B concentration in the Ni film increases gradually with increasing plating time for plating times ≤ 60 s as a kind of initial stage (that is, interface region), and then saturates uniformly for plating times ≥ 300 s as a kind of bulk region. On the other hand, from an electronic structure viewpoint, this result implies that Ni gains 3d electrons with respect to elemental Ni. The increase in the number of electrons gained by the Ni 3d states may result in an enhancement of the electrical conductivity.

  4. Reactions of Ni-B on printed Ag pattern by using nearly neutral electroless bath.

    Science.gov (United States)

    Rha, Sa-Kyun; Kim, Hyung Chul; Lee, Youn-Seoung

    2014-11-01

    In this study, we investigated the characteristics of a nearly neutral Ni source solution including dimethylamine borane (DMAB) used to develop the metal PCB (printed circuit board) of high power LED (light-emitting diode) package. In accordance with the bath temperature ranging from 50 degrees C to 75 degrees C, an electroless Ni-B plating on a screen-printed Ag pattern with an anodized Al substrate was carried out. The depositon rate of the electroless plated Ni-B film at bath temperature ranging from 50 degrees C to 75 degrees C was estimated by measurements of the thickness and the mass. The deposition rates by change of thickness and mass of the electroless plated Ni-B film at 50 degrees C were - 58 nm/min and 0.113 mg/min respectively. The activation energy obtained from slope of Arrhenius plot using these deposition rates was - 59 kJ/mol. Finally, selectively the film growth was achieved at all plating temperatures, without a damage of anodized Al substrate.

  5. Feed intake and production parameters of lactating crossbred cows fed maize-based diets of stover, silage or quality protein silage

    Science.gov (United States)

    Gebrehawariat, Efrem; Tegegne, Azage

    2010-01-01

    Thirty-six Boran × Friesian dairy cows (392 ± 12 kg; mean ± SD) in early parity were used in a randomised complete block design. Cows were blocked by parity into three blocks of 12 animals and offered normal maize (NM) stover (T1), NM silage (T2) or quality protein maize (QPM) silage (T3) basal diets supplemented with a similar concentrate mix. Feed intake, body weight and condition changes and milk yield and composition were assessed. The daily intake of DM, OM, NDF and ADF for cows fed the NM stover-based diet was higher (P  0.05) on body condition score, milk yield and milk composition. The digestible organic matter in the NM stover-based diet (724 g/kg DM) was lower (P < 0.05) than that in the NM (770 g/kg DM) and QPM silage-based diet (762 g/kg DM). It was concluded that the performances of the cows on the NM silage and QPM silage diets were similar and were not superior to that of the NM stover-based diet. PMID:20577806

  6. Well-defined Polymethylene-Based Co/Terpolymers by Combining Anthracene/Maleimide Diels-Alder Reaction with Polyhomologation

    KAUST Repository

    Hadjichristidis, Nikolaos

    2015-05-26

    A novel strategy towards well-defined polymethylene-based co/terpolymers, by combining anthracene/maleimide Diels-Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: a) synthesis of α-anthracene-ω-hydroxy- polymethylene by polyhomologation using tri (9-anthracene-methyl propyl ether) borane as initiator, b) synthesis of furan-protected-maleimide-terminated poly (ε-caprolactone) or polyethylene glycol and c). Diels-Alder reaction between the anthracene and maleimide-terminated polymers. In the case of triblock terpolymers the α-anthracene-ω-hydroxy-polymethylene was used as macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by Diels-Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. All intermediate and final products were characterized by SEC, 1H NMR, UV-VIS spectroscopy and DSC.

  7. Mechanisms of chemical vapor generation by aqueous tetrahydridoborate. Recent developments toward the definition of a more general reaction model

    Science.gov (United States)

    D'Ulivo, Alessandro

    2016-05-01

    A reaction model describing the reactivity of metal and semimetal species with aqueous tetrahydridoborate (THB) has been drawn taking into account the mechanism of chemical vapor generation (CVG) of hydrides, recent evidences on the mechanism of interference and formation of byproducts in arsane generation, and other evidences in the field of the synthesis of nanoparticles and catalytic hydrolysis of THB by metal nanoparticles. The new "non-analytical" reaction model is of more general validity than the previously described "analytical" reaction model for CVG. The non-analytical model is valid for reaction of a single analyte with THB and for conditions approaching those typically encountered in the synthesis of nanoparticles and macroprecipitates. It reduces to the previously proposed analytical model under conditions typically employed in CVG for trace analysis (analyte below the μM level, borane/analyte ≫ 103 mol/mol, no interference). The non-analytical reaction model is not able to explain all the interference effects observed in CVG, which can be achieved only by assuming the interaction among the species of reaction pathways of different analytical substrates. The reunification of CVG, the synthesis of nanoparticles by aqueous THB and the catalytic hydrolysis of THB inside a common frame contribute to rationalization of the complex reactivity of aqueous THB with metal and semimetal species.

  8. Synthesis and Electrochemical Evaluation of Carbon Supported Pt-Co Bimetallic Catalysts Prepared by Electroless Deposition and Modified Charge Enhanced Dry Impregnation

    Directory of Open Access Journals (Sweden)

    John Meynard M. Tengco

    2016-06-01

    Full Text Available Carbon-supported bimetallic Pt-Co cathode catalysts have been previously identified as higher activity alternatives to conventional Pt/C catalysts for fuel cells. In this work, a series of Pt-Co/C catalysts were synthesized using electroless deposition (ED of Pt on a Co/C catalyst prepared by modified charge enhanced dry impregnation. X-ray diffraction (XRD and scanning transmission electron microscopy (STEM characterization of the base catalyst showed highly dispersed particles. A basic ED bath containing PtCl62− as the Pt precursor, dimethylamine borane as reducing agent, and ethylenediamine as stabilizing agent successfully targeted deposition of Pt on Co particles. Simultaneous action of galvanic displacement and ED resulted in Pt-Co alloy formation observed in XRD and energy dispersive X-ray spectroscopy (XEDS mapping. In addition, fast deposition kinetics resulted in hollow shell Pt-Co alloy particles while particles with Pt-rich shell and Co-rich cores formed with controlled Pt deposition. Electrochemical evaluation of the Pt-Co/C catalysts showed lower active surface but much higher mass and surface activities for oxygen reduction reaction compared to a commercial Pt/C fuel cell catalyst.

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

    Science.gov (United States)

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

    2016-03-03

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

  10. The Concept about the Regeneration of Spent Borohydrides and Used Catalysts from Green Electricity

    Directory of Open Access Journals (Sweden)

    Cheng-Hong Liu

    2015-06-01

    Full Text Available Currently, the Brown-Schlesinger process is still regarded as the most common and mature method for the commercial production of sodium borohydride (NaBH4. However, the metallic sodium, currently produced from the electrolysis of molten NaCl that is mass-produced by evaporation of seawater or brine, is probably the most costly raw material. Recently, several reports have demonstrated the feasibility of utilizing green electricity such as offshore wind power to produce metallic sodium through electrolysis of seawater. Based on this concept, we have made improvements and modified our previously proposed life cycle of sodium borohydride (NaBH4 and ammonia borane (NH3BH3, in order to further reduce costs in the conventional Brown-Schlesinger process. In summary, the revision in the concept combining the regeneration of the spent borohydrides and the used catalysts with the green electricity is reflected in (1 that metallic sodium could be produced from NaCl of high purity obtained from the conversion of the byproduct in the synthesis of NH3BH3 to devoid the complicated purification procedures if produced from seawater; and (2 that the recycling and the regeneration processes of the spent NaBH4 and NH3BH3 as well as the used catalysts could be simultaneously carried out and combined with the proposed life cycle of borohydrides.

  11. Novel developments in hydrogen storage, hydrogen activation and ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Doroodian, Amir

    2010-12-03

    This dissertation is divided into three chapters. Recently, metal-free hydrogen activation using phosphorous compounds has been reported in science magazine. We have investigated the interaction between hydrogen and phosphorous compounds in presence of strong Lewis acids (chapter one). A new generation of metal-free hydrogen activation, using amines and strong Lewis acids with sterically demanding nature, was already developed in our group. Shortage of high storage capacity using large substitution to improve sterical effect led us to explore the amine borane derivatives, which are explained in chapter two. Due to the high storage capacity of hydrogen in aminoborane derivatives, we have explored these materials to extend hydrogen release. These compounds store hydrogen as proton and hydride on adjacent atoms or ions. These investigations resulted in developing hydrogen storage based on ionic liquids containing methyl guanidinium cation. Then we have continued to develop ionic liquids based on methyl guanidinium cation with different anions, such as tetrafluoro borate (chapter three). We have replaced these anions with transition metal anions to investigate hydrogen bonding and catalytic activity of ionic liquids. This chapter illustrates the world of ionic liquid as a green solvent for organic, inorganic and catalytic reactions and combines the concept of catalysts and solvents based on ionic liquids. The catalytic activity is investigated particularly with respect to the interaction with CO{sub 2}. (orig.)

  12. Hydrogen Storage Properties of New Hydrogen-Rich BH3NH3-Metal Hydride (TiH2, ZrH2, MgH2, and/or CaH2) Composite Systems

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Young Joon; Xu, Yimin; Shaw, Wendy J.; Ronnebro, Ewa

    2012-04-19

    Ammonia borane (AB = NH3BH3) is one of the most attractive materials for chemical hydrogen storage due to its high hydrogen contents of 19.6 wt.%, however, impurity levels of borazine, ammonia and diborane in conjunction with foaming and exothermic hydrogen release calls for finding ways to mitigate the decomposition reactions. In this paper we present a solution by mixing AB with metal hydrides (TiH2, ZrH2, MgH2 and CaH2) which have endothermic hydrogen release in order to control the heat release and impurity levels from AB upon decomposition. The composite materials were prepared by mechanical ball milling, and their H2 release properties were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The formation of volatile products from decomposition side reactions, such as borazine (N3B3H6) was determined by mass spectrometry (MS). Sieverts type pressure-composition-temperature (PCT) gas-solid reaction instrument was adopted to observe the kinetics of the H2 release reactions of the combined systems and neat AB. In situ 11B MAS-NMR revealed a destabilized decomposition pathway. We found that by adding specific metal hydrides to AB we can eliminate the impurities and mitigate the heat release.

  13. Metal-Free Alternating Copolymerization of CO2with Epoxides: Fulfilling “Green” Synthesis and Activity

    KAUST Repository

    Zhang, Dongyue

    2016-08-16

    Polycarbonates were successfully synthesized for the first time through the anionic copolymerization of epoxides with CO2, under metal-free conditions. Using an approach based on the activation of epoxides by Lewis acids and of CO, by appropriate cations, well-defined alternating copolymers made of CO, and propylene oxide (PO) or cyclohexene oxide (CHO) were indeed obtained. Triethyl borane was the Lewis acid chosen to activate the epoxides, and onium halides or onium alkoxides involving either ammonium, phosphonium, or phosphazenium cations were selected to initiate the copolymerization. In the case of PO, the carbonate content of the poly(propylene carbonate) formed was in the range of 92-99% and turnover numbers (TON) were close to 500; in the case of CHO perfectly alternating poly(cyclohexene carbonate) were obtained and TON values were close to 4000. The advantages of such a copolymerization system are manifold: (i) no need for multistep catalyst/ligand synthesis as in previous works; (ii) no transition metal involved in the copolymer synthesis and therefore no coloration of the samples isolated; and (iii) no necessity for postsynthesis purification.

  14. Synthesis of octahedral, truncated octahedral, and cubic Rh2Ni nanocrystals and their structure-activity relationship for the decomposition of hydrazine in aqueous solution to hydrogen

    Science.gov (United States)

    Li, Chun; Wang, Tao; Chu, Wei; Wu, Ping; Tong, Dong Ge

    2016-03-01

    We developed a co-reduction method to synthesize octahedral, truncated octahedral, and cubic Rh2Ni nanocrystals. The shape/size distribution, structural characteristics, and composition of the Rh2Ni nanocrystals are investigated, and their possible formation mechanism at high temperatures in margaric acid/1-aminoheptadecane solution in the presence of tetraethylgermanium and borane trimethylamine complexes is proposed. A preliminary probing of the structure-activity dependence of the surface ``clean'' Rh2Ni nanocrystals supported on carbon towards hydrazine (N2H4) in aqueous solution dehydrogenation revealed that the higher the percentage of {111} facets, the higher is the activity and H2 selectivity of the nanocrystals. This result was attributed to the {111} facets not only introducing more basic sites, but also weakening the interaction between the produced adspecies (including H2 and NHx) and surface metal atoms in comparison with those of {100} facets. Furthermore, the as-prepared Rh2Ni nanooctahedra exhibited 100% H2 selectivity and high activity at room temperature for H2 generation via N2H4 decomposition. The activation energy of the Rh2Ni nanooctahedra was 41.6 +/- 1.2 kJ mol-1. The Rh2Ni nanooctahedra were stable catalysts for the hydrolytic dehydrogenation of N2H4, providing 27 723 total turnovers in 30 h. Our work provides a new perspective concerning the possibility of constructing hydrogen-producing systems based on N2H4 and surface ``clean'' Rh2Ni nanocrystal catalysts with defined shapes supported on carbon that possess a competitive performance in comparison with NaBH4 and NH3BH3 hydrogen-producing systems for fuel cell applications.We developed a co-reduction method to synthesize octahedral, truncated octahedral, and cubic Rh2Ni nanocrystals. The shape/size distribution, structural characteristics, and composition of the Rh2Ni nanocrystals are investigated, and their possible formation mechanism at high temperatures in margaric acid/1

  15. Mechanistic Insights into Homogeneous and Heterogeneous Asymmetric Iron Catalysis

    Science.gov (United States)

    Sonnenberg, Jessica

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

  16. Boron-Based Hydrogen Storage: Ternary Borides and Beyond

    Energy Technology Data Exchange (ETDEWEB)

    Vajo, John J. [HRL Laboratories, LLC, Malibu, CA (United States)

    2016-04-28

    DOE continues to seek reversible solid-state hydrogen materials with hydrogen densities of ≥11 wt% and ≥80 g/L that can deliver hydrogen and be recharged at moderate temperatures (≤100 °C) and pressures (≤100 bar) enabling incorporation into hydrogen storage systems suitable for transportation applications. Boron-based hydrogen storage materials have the potential to meet the density requirements given boron’s low atomic weight, high chemical valance, and versatile chemistry. However, the rates of hydrogen exchange in boron-based compounds are thus far much too slow for practical applications. Although contributing to the high hydrogen densities, the high valance of boron also leads to slow rates of hydrogen exchange due to extensive boron-boron atom rearrangements during hydrogen cycling. This rearrangement often leads to multiple solid phases occurring over hydrogen release and recharge cycles. These phases must nucleate and react with each other across solid-solid phase boundaries leading to energy barriers that slow the rates of hydrogen exchange. This project sought to overcome the slow rates of hydrogen exchange in boron-based hydrogen storage materials by minimizing the number of solid phases and the boron atom rearrangement over a hydrogen release and recharge cycle. Two novel approaches were explored: 1) developing matched pairs of ternary borides and mixed-metal borohydrides that could exchange hydrogen with only one hydrogenated phase (the mixed-metal borohydride) and only one dehydrogenated phase (the ternary boride); and 2) developing boranes that could release hydrogen by being lithiated using lithium hydride with no boron-boron atom rearrangement.

  17. Reactions of (CF3)3BCO with amines and phosphines.

    Science.gov (United States)

    Finze, Maik; Bernhardt, Eduard; Willner, Helge; Lehmann, Christian W

    2006-01-23

    Reactions of tris(trifluoromethyl)borane carbonyl, (CF(3))(3)BCO, with ammonia yielded either a mixture of [NH(4)][(CF(3))(3)BC(O)NH(2)], [NH(4)][(CF(3))(3)BCN], and [NH(4)](2)[{(CF(3))(3)BC(O)}(2)NH] or neat [NH(4)](2)[{(CF(3))(3)BC(O)}(2)NH] depending on the reaction conditions. The salt K[(CF(3))(3)BC(O)NH(2)] was obtained as the sole product from the reaction of NH(3) with K[(CF(3))(3)BC(O)F]. A simple synthesis for cyanotris(trifluoromethyl)borates, M[(CF(3))(3)BCN], was developed by dehydration of M[(CF(3))(3)BC(O)NH(2)] (M = [NH(4)], K) using phosgene. In addition, syntheses of the tris(trifluoromethyl)boron species [(CF(3))(3)BC(O)NH(n)()Pr](-), [(CF(3))(3)BC(O)NMe(2)](-), and (CF(3))(3)BC(O)NMe(3), as well as of (CF(3))(3)BC(O)PMe(3), were performed. All species were characterized by multinuclear NMR spectroscopy. As far as neat substances resulted, IR and Raman spectra were recorded and their thermal behaviors were studied by differential scanning calorimetry. The interpretation of reaction pathways, structures, and vibrational spectra are supported by DFT calculations. The solid-state structure of K(2)[{(CF(3))(3)BC(O)}(2)NH].2MeCN was determined by single-crystal X-ray diffraction.

  18. Evaluation of biological, physical and chemical properties of mineral trioxide aggregate mixed with 4-META/MMA-TBB

    Directory of Open Access Journals (Sweden)

    Rudra Kaul

    2013-01-01

    Full Text Available Aim: To evaluate the change in physical, chemical and biological properties when mineral trioxide aggregate (MTA is mixed with a resin 4-methacryloxyethyl trimellitate anhydride (4-META/methyl methacrylate-tri-n-butyl-borane (MMA-TBB. Materials and Methods: For biological evaluation MTA was inoculated in Wistar rat′s subcutaneous tissue and peripheral tissue response was checked after 72 h, 7 days, 15 days and 30 days. Setting time was evaluated using Gillmore needle. The Ca++ release at the end of 24 h was checked using ethylenediaminetetraacetic acid titration method. For all the trials MTA mixed with water was kept as a control and the ratio of MTA with resin was 1:1 by weight. Results: The biological reaction was verified by two observers and their readings were matched using kappa test and there was an excellent relevance. There was no significant difference in the tissue reaction at the end of 30 days where both the groups seemed to show healing. Setting time of MTA with 4-META/MMA-TBB was coming to a mean of 26 min (approx., which is almost 6 times lesser than that of MTA with water. After applying t test, the difference in Ca++ release was found significant (P = 0.00, with mean of 0.044 and 0.031 mol/L of MTA with water and MTA with 4-META/MMA-TBB respectively. Conclusion: Under the parameters of this study, this new experimental cement has better handling, physical and chemical properties. Even its subcutaneous tissue reaction is comparable to MTA mixed with water.

  19. Foeniculum vulgare Mill. increases cytosolic Ca(2+) concentration and inhibits store-operated Ca(2+) entry in vascular endothelial cells.

    Science.gov (United States)

    Han, A Young; Lee, Hui Su; Seol, Geun Hee

    2016-12-01

    This study assessed the effects of essential oil of Foeniculum vulgare Mill. (fennel oil) and of trans-anethole, the main component of fennel oil, on extracellular Ca(2+)-induced store-operated Ca(2+) entry (SOCE) into vascular endothelial (EA) cells and their mechanisms of action. Components of fennel oil were analyzed by gas chromatography-mass spectrometry. Cytosolic Ca(2+) concentration ([Ca(2+)]c) in EA cells was determined using Fura-2 fluorescence. In the presence of extracellular Ca(2+), fennel oil significantly increased [Ca(2+)]c in EA cells; this increase was significantly inhibited by the Ca(2+) channel blockers La(3+) and nifedipine. In contrast, fennel oil induced [Ca(2+)]c was significantly lower in Ca(2+)-free solution, suggesting that fennel oil increases [Ca(2+)]c mainly by enhancing Ca(2+) influx into EA cells. [Ca(2+)]c mobilization by trans-anethole was similar to that of fennel oil. Moreover, SOCE was suppressed by fennel oil and trans-anethole. SOCE was also attenuated by lanthanum (La(3+)), a non-selective cation channel (NSC) blocker; 2-aminoethoxydiphenyl borane (2-APB), an inositol 1,4,5-triphosphate (IP3) receptor inhibitor and SOCE blocker; and U73122, an inhibitor of phospholipase C (PLC). Further, SOCE was more strongly inhibited by La(3+) plus fennel oil or trans-anethole than by La(3+) alone. These findings suggest that fennel oil and trans-anethole significantly inhibit SOCE-induced [Ca(2+)]c increase in vascular endothelial cells and that these reactions may be mediated by NSC, IP3-dependent Ca(2+) mobilization, and PLC activation.

  20. Nanostructured Boron Nitride: From Molecular Design to Hydrogen Storage Application

    Directory of Open Access Journals (Sweden)

    Georges Moussa

    2014-07-01

    Full Text Available The spray-pyrolysis of borazine at 1400 °C under nitrogen generates boron nitride (BN nanoparticles (NPs. The as-prepared samples form elementary blocks containing slightly agglomerated NPs with sizes ranging from 55 to 120 nm, a Brunauer-Emmett-Teller (BET-specific surface area of 34.6 m2 g−1 and a helium density of 1.95 g cm−3. They are relatively stable in air below 850 °C in which only oxidation of the NP surface proceeds, whereas under nitrogen, their lower size affects their high temperature thermal behavior in the temperature range of 1450–2000 °C. Nitrogen heat-treated nanostructures have been carefully analyzed using X-ray diffraction, electron microscopy and energy-dispersive X-ray spectroscopy. The high temperature treatment (2000 °C gives hollow-cored BN-NPs that are strongly facetted, and after ball-milling, hollow core-mesoporous shell NPs displaying a BET-specific surface area of 200.5 m2·g−1 and a total pore volume of 0.287 cm3·g−1 were produced. They have been used as host material to confine, then destabilize ammonia borane (AB, thus improving its dehydrogenation properties. The as-formed AB@BN nanocomposites liberated H2 at 40 °C, and H2 is pure in the temperature range 40–80 °C, leading to a safe and practical hydrogen storage composite material.

  1. Synthesis, X-ray Opacity, and Biological Compatibility of Ultra-High Payload Elemental Bismuth Nanoparticle X-ray Contrast Agents.

    Science.gov (United States)

    Brown, Anna L; Naha, Pratap C; Benavides-Montes, Victor; Litt, Harold I; Goforth, Andrea M; Cormode, David P

    2014-04-01

    Inorganic nanoscale X-ray contrast agents (XCAs) offer many potential advantages over currently used intravascular molecular contrast agents, including longer circulation and retention times, lower administration volumes, and greater potential for site directed imaging. Elemental bismuth nanoparticles (BiNPs) are particularly attractive candidate XCAs due to the low cost, the high atomic number and high density of bismuth, and the likelihood that BiNPs will oxidatively decompose to biocompatible bismuth(III) ions at controlled rates for renal excretion. Herein we describe the synthesis of ultrahigh payload BiNPs in 1,2-propanediol using a borane reducing agent and glucose as a biocompatible surface stabilizer. Both synthetic solvent (1,2-propanediol) and surfactant (glucose) are evident on the BiNP surfaces when analyzed by (1)H NMR and FT-IR spectroscopies. These particles contain ∼6 million Bi atoms per NP and have large inorganic cores (74 nm by TEM) compared to their hydrodynamic size (86 nm by DLS). Thus, the dense BiNP core constitutes the majority (∼60%) of each particle's volume, a necessary property to realize the full potential of nanoscale XCAs. Using quantitative computed tomography in phantom and in vitro imaging studies, we demonstrate that these BiNPs have greater X-ray opacity than clinical small molecule iodinated contrast agents at the same concentrations. We furthermore demonstrate a favorable biocompatibility profile for these BiNPs in vitro. Altogether, these studies indicate that these ultrahigh payload BiNPs, synthesized from known biocompatible components, have promising physical and cytotoxicological properties for use as XCAs.

  2. Therapeutic efficacy of boron neutron capture therapy mediated by boron-rich liposomes for oral cancer in the hamster cheek pouch model.

    Science.gov (United States)

    Heber, Elisa M; Hawthorne, M Frederick; Kueffer, Peter J; Garabalino, Marcela A; Thorp, Silvia I; Pozzi, Emiliano C C; Monti Hughes, Andrea; Maitz, Charles A; Jalisatgi, Satish S; Nigg, David W; Curotto, Paula; Trivillin, Verónica A; Schwint, Amanda E

    2014-11-11

    The application of boron neutron capture therapy (BNCT) mediated by liposomes containing (10)B-enriched polyhedral borane and carborane derivatives for the treatment of head and neck cancer in the hamster cheek pouch oral cancer model is presented. These liposomes are composed of an equimolar ratio of cholesterol and 1,2-distearoyl-sn-glycero-3-phosphocholine, incorporating K[nido-7-CH3(CH2)15-7,8-C2B9H11] (MAC) in the bilayer membrane while encapsulating the hydrophilic species Na3[ae-B20H17NH3] (TAC) in the aqueous core. Unilamellar liposomes with a mean diameter of 83 nm were administered i.v. in hamsters. After 48 h, the boron concentration in tumors was 67 ± 16 ppm whereas the precancerous tissue contained 11 ± 6 ppm, and the tumor/normal pouch tissue boron concentration ratio was 10:1. Neutron irradiation giving a 5-Gy dose to precancerous tissue (corresponding to 21 Gy in tumor) resulted in an overall tumor response (OR) of 70% after a 4-wk posttreatment period. In contrast, the beam-only protocol gave an OR rate of only 28%. Once-repeated BNCT treatment with readministration of liposomes at an interval of 4, 6, or 8 wk resulted in OR rates of 70-88%, of which the complete response ranged from 37% to 52%. Because of the good therapeutic outcome, it was possible to extend the follow-up of BNCT treatment groups to 16 wk after the first treatment. No radiotoxicity to normal tissue was observed. A salient advantage of these liposomes was that only mild mucositis was observed in dose-limiting precancerous tissue with a sustained tumor response of 70-88%.

  3. Fyn kinase controls Fc{epsilon}RI receptor-operated calcium entry necessary for full degranulation in mast cells

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez-Miranda, Elizabeth; Ibarra-Sanchez, Alfredo [Departamento de Farmacobiologia, Centro de Investigacion y de Estudios Avanzados (Cinvestav), Sede Sur, Calzada de los Tenorios 235, Col. Granjas Coapa, CP 14330 Mexico City (Mexico); Gonzalez-Espinosa, Claudia, E-mail: cgonzal@cinvestav.mx [Departamento de Farmacobiologia, Centro de Investigacion y de Estudios Avanzados (Cinvestav), Sede Sur, Calzada de los Tenorios 235, Col. Granjas Coapa, CP 14330 Mexico City (Mexico)

    2010-01-22

    IgE-antigen-dependent crosslinking of the high affinity IgE receptor (Fc{epsilon}RI) on mast cells leads to degranulation, leukotriene synthesis and cytokine production. Calcium (Ca{sup 2+}) mobilization is a sine qua non requisite for degranulation, allowing the rapid secretion of stored pro-inflammatory mediators responsible for allergy symptoms. Fyn is a Src-family kinase that positively controls Fc{epsilon}RI-induced mast cell degranulation. However, our understanding of the mechanism connecting Fyn activation to secretion of pre-synthesized mediators is very limited. We analyzed Fc{epsilon}RI-dependent Ca{sup 2+} mobilization in bone marrow-derived mast cells (BMMCs) differentiated from WT and Fyn -/- knock out mice. Fyn -/- BMMCs showed a marked defect in extracellular Ca{sup 2+} influx after Fc{epsilon}RI crosslinking but not after thapsigargin addition. High concentrations of Gadolinium (Gd{sup 3+}) partially blocked Fc{epsilon}RI-induced Ca{sup 2+} influx in WT cells but, in contrast, completely inhibited Ca{sup 2+} mobilization in Fyn -/- cells. Low concentrations of an inhibitor of the canonical transient receptor potential (TRPC) Ca{sup 2+} channels (2-aminoethoxyphenyl-borane, 2-APB) blocked Fc{epsilon}RI-induced maximal Ca{sup 2+} rise in WT but not in Fyn -/- cells. Ca{sup 2+} entry through Fyn-controlled, 2-APB sensitive channels was found to be important for full degranulation and IL-2 mRNA accumulation in WT cells. Immunoprecipitation assays showed that Fyn kinase interacts with TRPC 3/6/7 channels after IgE-antigen stimulation, but its association is not related to protein tyrosine phosphorylation. Results indicate Fyn kinase mediates the receptor-dependent activation of TRPC channels that contribute to degranulation in Fc{epsilon}RI-stimulated mast cells.

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

    Science.gov (United States)

    Raabe, Ines; Himmel, Daniel; Krossing, Ingo

    2007-12-20

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

  5. Rumen degradability characteristics of normal maize stover and silage, and quality protein maize silage-based diets offered to cows.

    Science.gov (United States)

    Tamir, Berhan; Gebrehawariat, Ephrem; Tegegne, Azage; Kortu, Mohammed Y

    2012-10-01

    Rumen degradability characteristics of dry matter (DM), organic matter (OM) and crude protein (CP) of normal maize (NM) stover (T1)-, NM silage (T2)- and quality protein maize (QPM) silage (T3)-based diets were studied using three rumen-fistulated Boran × Friesian non-lactating cows (371 ± 32.00 kg) in 3 × 3 Latin Square Design. Cows were supplemented with a similar concentrate mix. In sacco degradability of DM and OM indicated that the (a) values of DM (128) and OM (114) for NM stover were lower (P silage (268 and 253) and for QPM silage (323 and 303), respectively. The (a) value for CP was lower (P silage (286) than for NM stover (404) and NM silage (326). The (b) values of DM in NM stover (597) and NM silage (535) were higher (P silage (499). The (b) value of CP in NM stover (372) was lower (P silage (655) and in QPM silage (608). Rate of degradation of OM in NM stover and NM silage, each with 0.03, was faster (P silage (0.02). Moreover, QPM silage had higher potentially degradable fraction for DM (821) (P silage was higher (P silage (170 mg/l). The average rumen pH (6.1) in cows fed QPM silage was lowest (P silage. The concentration of total volatile fatty acids (116 mmol/l) in the rumen of cows incubated with QPM silage was higher (P silage (110 mmol/l). It was concluded that QPM silage-based diet was superior in DM and OM degradability, and had higher ammonia and VFA concentration than NM stover-based diet. No differences have been observed in all parameters measured between QPM and NM silages.

  6. A Stannyl-Decorated Zintl Ion [Ge18Pd3(Sn(i)Pr3)6](2-): Twinned Icosahedron with a Common Pd3-Face or 18-Vertex Hypho-Deltahedron with a Pd3-Triangle Inside.

    Science.gov (United States)

    Perla, Luis G; Sevov, Slavi C

    2016-08-10

    We report the synthesis and characterization of the title anion which has a germanium/palladium cluster core of [Ge18Pd3] and six tri-isopropyl tin substituents. Its two Ge9-halves are the first examples of germanium deltahedra with three nonsilyl substituents, tri-isopropyl tin in this case. The new cluster is made by a reaction of an acetonitrile suspension of K4Ge9 with (i)Pr3SnCl that generates primarily tristannylated 9-atom clusters [Ge9{Sn(i)Pr3}3](-), followed by addition of Pd(PPh3)4 to the reaction mixture. It was structurally characterized by single-crystal X-ray diffraction in [K(222crypt)]2[Ge18Pd3{Sn(i)Pr3}6]·(i)Pr2O and was also confirmed in solution by ESI-MS and NMR. The new anion can be viewed both as a dimer of face-fused icosahedra (twinned icosahedron) with a common Pd3-face, i.e., [((i)Pr3Sn)3Ge9Pd3Ge9(Sn(i)Pr3)3](2-) that resembles but is not isoelectronic with the known borane version B21H18(-) or as a large hypho-deltahedron of 18 Ge-atoms with a triangle of Pd3 inside, i.e., [Pd3@Ge18(Sn(i)Pr3)6](2-). DFT calculations show a very large HOMO-LUMO gap of 2.42 eV.

  7. Applying an electron counting rule to screen prospective thermoelectric alloys: The thermoelectric properties of YCrB{sub 4} and Er{sub 3}CrB{sub 7}-type phases

    Energy Technology Data Exchange (ETDEWEB)

    Simonson, J.W., E-mail: jws9n@virginia.ed [Department of Physics, University of Virginia, 382 McCormick Rd., Charlottesville, VA 22904-4714 (United States); Poon, S.J. [Department of Physics, University of Virginia, 382 McCormick Rd., Charlottesville, VA 22904-4714 (United States)

    2010-08-13

    An electron counting rule, which was recently expanded to study molecular organometallics, boranes, and metallocenes, is utilized herein to predict the formation of a semiconducting gap or pseudo-gap in the density of states of deltahedral crystalline solids at or near the Fermi energy. It is suggested that this rule may be exploited to screen intermetallic compounds for prospective thermoelectric materials. The rule was applied to several structure types of known deltahedral boride and borocarbide compounds, and its predictions were compared to those of first principles electronic structure calculations when such were available in the literature or to published reports of transport properties. In addition, the rule has been used to predict the properties of several materials for which the electronic structure and properties have not hitherto been reported. In accordance with these predictions, layered ternary boride intermetallic compounds with structure types YCrB{sub 4} and Er{sub 3}CrB{sub 7} were synthesized, and the electrical resistivity and Seebeck coefficients of these alloys were measured from room temperature to 1100 K. Alloys of composition RMB{sub 4} (R = Y, Gd, Ho; M = Cr, Mo, W) were found to be n-type semiconductors and to exhibit thermopower up to {approx}70-115 {mu}V/K; the band gap was estimated to range from 0.17 to 0.28 eV, depending on composition. Undoped YCrB{sub 4} was measured to have a maximum power factor of 6.0 {mu}W/cm K{sup 2} at 500 K and Fe-doped YMoB{sub 4} of 2.4 {mu}W/cm K{sup 2} near 1000 K.

  8. Transparent, biocompatible nanostructured surfaces for cancer cell capture and culture

    Directory of Open Access Journals (Sweden)

    Cheng BR

    2014-05-01

    Full Text Available Boran Cheng,1,* Zhaobo He,2,* Libo Zhao,2,* Yuan Fang,1 Yuanyuan Chen,1 Rongxiang He,2 Fangfang Chen,1 Haibin Song,1 Yuliang Deng,2 Xingzhong Zhao,2 Bin Xiong1 1Department of Oncology, Zhongnan Hospital of Wuhan University, Hubei Key Laboratory of Tumor Biological Behaviors, Hubei Cancer Clinical Study Center, Wuhan, Hubei, People’s Republic of China; 2Key Laboratory of Artificial Micro- and Nano-Structures of Ministry of Education, School of Physics and Technology, Wuhan University, Wuhan, Hubei, People’s Republic of China *These authors contributed equally to this work Abstract: Circulating tumor cells (CTCs in the blood which have detached from both the primary tumor and any metastases may be considered as a “liquid biopsy” and are expected to replace tumor biopsies in the monitoring of treatment response and determining patient prognosis. Here, we introduce a facile and efficient CTC detection material made of hydroxyapatite/chitosan (HA/CTS, which is beneficial because of its transparency and excellent biological compatibility. Atomic force microscopy images show that the roughness of the HA/CTS nanofilm (HA/CTSNF substrates can be controlled by changing the HA:CTS ratio. Enhanced local topographic interactions between nano-components on cancer cell membranes, and the antibody coated nanostructured substrate lead to improved CTC capture and separation. This remarkable nanostructured substrate has the potential for CTC culture in situ and merits further analysis. CTCs captured from artificial blood samples were observed in culture on HA/CTSNF substrates over a period of 14 days by using conventional staining methods (hematoxylin eosin and Wright’s stain. We conclude that these substrates are multifunctional materials capable of isolating and culturing CTCs for subsequent studies. Keywords: cell capture, cell culture, nanofilms, hydroxyapatite/chitosan

  9. A Practical Computational Approach to Study Molecular Instability Using the Pseudo-Jahn-Teller Effect.

    Science.gov (United States)

    García-Fernández, Pablo; Aramburu, Jose Antonio; Moreno, Miguel; Zlatar, Matija; Gruden-Pavlović, Maja

    2014-04-08

    Vibronic coupling theory shows that the cause for spontaneous instability in systems presenting a nondegenerate ground state is the so-called pseudo-Jahn-Teller effect, and thus its study can be extremely helpful to understand the structure of many molecules. While this theory, based on the mixing of the ground and excited states with a distortion, has been long studied, there are two obscure points that we try to clarify in the present work. First, the operators involved in both the vibronic and nonvibronic parts of the force constant take only into account electron-nuclear and nuclear-nuclear interactions, apparently leaving electron-electron repulsions and the electron's kinetic energy out of the chemical picture. Second, a fully quantitative computational appraisal of this effect has been up to now problematic. Here, we present a reformulation of the pseudo-Jahn-Teller theory that explicitly shows the contributions of all operators in the molecular Hamiltonian and allows connecting the results obtained with this model to other chemical theories relating electron distribution and geometry. Moreover, we develop a practical approach based on Hartree-Fock and density functional theory that allows quantification of the pseudo-Jahn-Teller effect. We demonstrate the usefulness of our method studying the pyramidal distortion in ammonia and its absence in borane, revealing the strong importance of the kinetic energy of the electrons in the lowest a2″ orbital to trigger this instability. The present tool opens a window for exploring in detail the actual microscopic origin of structural instabilities in molecules and solids.

  10. Well-Defined Bilayered Molecular Cobrushes with Internal Polyethylene Blocks and ω-Hydroxyl-Functionalized Polyethylene Homobrushes

    KAUST Repository

    Zhang, Hefeng

    2016-02-15

    Novel well-defined bilayered molecular cobrushes with internal polyethylene blocks, P(PEcore-b-PScorona) (PE: polyethylene; PS: polystyrene), and ω-hydroxyl-functionalized polyethylene homobrushes, P(PE-OH), were synthesized through the macromonomer strategy. Two main steps were involved in the synthesis of the P(PEcore-b-PScorona) bilayered cobrushes: (i) formation of norbornyl-terminated macromonomer (Nor-PE-b-PS) by esterification of PS-b-PE-OH (combination of anionic polymerization, hydroboration, and polyhomologation) with 5-norbornene-2-carboxylic acid and (ii) ring-opening metathesis polymerization (ROMP) of Nor-PE-b-PS. The synthesis of P(PE-OH) was achieved by (i) hydroboration of tert-butyldimethylsilyl-protected allyl alcohol, followed by polyhomologation of dimethylsulfoxoniun methylide with the formed tri[3-(tert-butyldimethylsilyloxyl)propyl]borane initiator, oxidation/hydrolysis, and esterification of the TBDMS-O-PE-OH with 5-norbornene-2-carboxylic acid to afford the macromonomer TBDMS-O-PE-Nor, and (ii) ROMP of TBDMS-O-PE-Nor, followed by deprotection. Nuclear magnetic resonance spectroscopy (1H and 13C NMR) and high temperature gel permeation chromatography (HT-GPC) were used to characterize all macromonomers/molecular brushes and differential scanning calorimetry (DSC) to study the thermal properties. The molecular brush P(PE-b-PS) showed lower melting point (Tm) and better solubility in toluene than the corresponding macromonomer PS-b-PE-Nor. In the case of homobrushes, the thermal properties were strongly affected by the presence of the PE end-groups. © 2016 American Chemical Society.

  11. Platinum-ruthenium bimetallic clusters on graphite: a comparison of vapor deposition and electroless deposition methods.

    Science.gov (United States)

    Galhenage, Randima P; Xie, Kangmin; Diao, Weijian; Tengco, John Meynard M; Seuser, Grant S; Monnier, John R; Chen, Donna A

    2015-11-14

    Bimetallic Pt-Ru clusters have been grown on highly ordered pyrolytic graphite (HOPG) surfaces by vapor deposition and by electroless deposition. These studies help to bridge the material gap between well-characterized vapor deposited clusters and electrolessly deposited clusters, which are better suited for industrial catalyst preparation. In the vapor deposition experiments, bimetallic clusters were formed by the sequential deposition of Pt on Ru or Ru on Pt. Seed clusters of the first metal were grown on HOPG surfaces that were sputtered with Ar(+) to introduce defects, which act as nucleation sites for Pt or Ru. On the unmodified HOPG surface, both Pt and Ru clusters preferentially nucleated at the step edges, whereas on the sputtered surface, clusters with relatively uniform sizes and spatial distributions were formed. Low energy ion scattering experiments showed that the surface compositions of the bimetallic clusters are Pt-rich, regardless of the order of deposition, indicating that the interdiffusion of metals within the clusters is facile at room temperature. Bimetallic clusters on sputtered HOPG were prepared by the electroless deposition of Pt on Ru seed clusters from a Pt(+2) solution using dimethylamine borane as the reducing agent at pH 11 and 40 °C. After exposure to the electroless deposition bath, Pt was selectively deposited on Ru, as demonstrated by the detection of Pt on the surface by XPS, and the increase in the average cluster height without an increase in the number of clusters, indicating that Pt atoms are incorporated into the Ru seed clusters. Electroless deposition of Ru on Pt seed clusters was also achieved, but it should be noted that this deposition method is extremely sensitive to the presence of other metal ions in solution that have a higher reduction potential than the metal ion targeted for deposition.

  12. Books Noted

    Science.gov (United States)

    1999-01-01

    Combinatorial Chemistry and Molecular Diversity in Drug Discovery E. M. Gordon and J. F. Kerwin Jr. Wiley-Liss: New York, 1998. xxiv + 516 pp. ISBN 0-471-15518-7. 89.95. Advances in Atomic Spectroscopy, Volume 4 J. Sneddon. JAI: Stamford, CT, 1998. x + 232 pp. ISBN 0-7623-0342-5. 109.50. Organic Synthesis, Collective Volume IX J. P. Freeman, Ed. Wiley: New York, 1998. xxi + 840 pp. ISBN 0-471-24248-9. 89.95. Advances in Theoretically Interesting Molecules R. P. Thummel. JAI: Stamford, CT, 1998. x + 350 pp. ISBN 0-7623-00070-1. 109.50. Organic Syntheses, Volume 75 A. B. Smith III, Ed. Wiley: New York, 1998. xxxvi + 257 pp. ISBN 0-471-18372-5. 39.95. Teaching American Students, 2nd Revised Edition E. Sarksian. Harvard University Publishing: Cambridge, MA, 1997. 109 pp. ISBN 0966246802. 11.95. Advances in Photochemistry, Volume 24 D. C. Neckers, D. H. Volman, and G. Von Bunau. Wiley-Interscience: New York, 1998. ix + 352 pp. ISBN 0-471-28723-1. 95.00. Inorganic Synthesis, Volume 32 M. Y. Darensbourg. Wiley-Interscience: New York, 1998. xxiii + 331 pp. ISBN 0-471-24921-1. 80.00. The Borane, Carborane, Carbocation Continuum J. Casanova, Ed. Wiley-Interscience: New York, 1998. xxi + 437 pp. ISBN 0-471-18075-0. 89.95. Inorganic Reactions and Methods, Volume 14 J. J. Zuckerman and J. D. Atwood, Eds. Wiley-VCH: New York, 1998. xxiii + 688 pp. ISBN 0-471-19201-5. 250.00. Advances in Molecular Vibrations and Collision Dynamics, Volume 3 J. M. Bowman. JAI: Stamford, CT, 1998. xi + 460 pp. ISBN 1-55938-790-4. $109.50.

  13. Hybrids of Reduced Graphene Oxide and Hexagonal Boron Nitride: Lightweight Absorbers with Tunable and Highly Efficient Microwave Attenuation Properties.

    Science.gov (United States)

    Kang, Yue; Jiang, Zhenhua; Ma, Tian; Chu, Zengyong; Li, Gongyi

    2016-11-30

    Sandwichlike hybrids of reduced graphene oxide (rGO) and hexagonal boron nitride (h-BN) were prepared via heat treatment of the self-assemblies of graphene oxide (GO) and ammonia borane (AB). TG-DSC-QMS analysis indicate a mutually promoted redox reaction between GO and AB; 900 °C is a proper temperature to transfer the hybrids into inorganic sandwiches. XRD, XPS, and Raman spectra reveal the existence of h-BN embedded into the rGO frameworks. High-resolution SEM and TEM indicate the layer-by-layer structure of the hybrids. The content of h-BN can be increased with increase of the mass ratio of AB and the highest heat treatment temperature. The complex permittivity and the microwave absorption are tunable with the variation of the content of h-BN. When the mass ratio of GO/AB is 1:1, the microwave absorption of the hybrid treated at 900 °C is preferable in the range of 6-18 GHz. A minimum reflection loss, -40.5 dB, was observed at 15.3 GHz for the wax composite filled with 25 wt % hybrids at the thickness of 1.6 mm. The qualified frequency bandwidth reaches 5 GHz at this thickness with a low surface density close to 1.68 kg/m(2). The layer-by-layer structure of the hybrid makes great contributions to the increased approaches and possibilities of electron migrating and hopping, which has both highly efficient dielectric loss and excellent impedance matching for microwave consumption.

  14. Synthesis and radiofluorination of putative NMDA receptor ligands

    Energy Technology Data Exchange (ETDEWEB)

    Kronenberg, U.

    2011-01-15

    In the course of this work on the synthesis of radioligands for the NMDA receptor the authentic standards and labeling precursors of four compounds with an amidine structure was performed. Synthesis of the precursors followed reaction conditions given in the literature and was successful. The imidoesters used for the synthesis were obtained from their nitriles in a Pinner synthesis, while 2-hydroxybenzylamine was synthesized in a reduction of 2-hydroxybenzonitrile using borane as a reducing agent. After a coupling reaction of the amine and the imidoester in DMF using triethylamine as base the precursors were obtained in good yields and purified by crystallization from methanol. The cyclic standard compound was synthesized directly from 2-(bromomethyl)- benzonitrile and 2-hydroxybenzylamine in a ring closing reaction. Similar to the other precursors, crystallization from methanol produced a pure compound. The authentic standards were synthesized starting from salicylaldehyde. In a four step synthesis the desired ortho-fluoroethoxybenzylamine was obtained in good yield. Coupling of the amine with the respective imidoester or in the case of the cyclic compound 2-(bromomethyl)-benzonitrile gave the desired product which was then purified by column chromatography or by crystallization from ethanol and water. For the labeling procedure 1-bromo-2-[{sub 18}F]fluoroethane was synthesized following a previously published pathway starting from 1,2-dibromoethane. An alternative route of radiosynthesis for this prosthetic group was tested using ethyleneglycole- 1,2-ditosylate. The labeling reaction was performed on one of the precursors testing both DMF and DMSO as solvents and using NaOH as base. Yields of N-(2-fluoroethoxybenzyl)- cinnamamidine were about 78 % at 80 C after 30 minutes in DMSO. The desired product can now be synthesized in sufficient yields for in vitro and in vivo evaluation studies. Labeling on the cyclic precursor was attempted utilizing DMSO as solvent

  15. Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fischbach, Andreas; Bazinet, Patrick R.; Waterman, Rory; Tilley, T. Don

    2007-10-28

    The ambiphilic {beta}-phosphinoethylboranes Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2} (BR{sub 2} = BCy{sub 2} (1a), BBN (1b)), which feature a ethano spacer CH{sub 2}CH{sub 2} between the Lewis acidic boryl and Lewis basic phosphino groups, were synthesized in nearly quantitative yields via the hydroboration of vinyldiphenylphosphine. Compounds 1a and 1b were fully characterized by elemental analysis, and by NMR and IR spectroscopy. X-ray crystallographic studies of compound 1b revealed infinite helical chains of the molecules connected through P{hor_ellipsis}B donor-acceptor interactions. The ability of these ambiphilic ligands to concurrently act as donors and acceptors was highlighted by their reactions with (dmpe)NiMe{sub 2}. Zwitterionic complexes (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}BCy{sub 2}Me) (2a) and (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}[BBN]Me) (2b) were generated via the abstraction of one of the methyl groups, forming a borate, and intramolecular coordination of the phosphine moiety to the resulting cationic metal center. Compound 2b was characterized by X-ray crystallography. Furthermore, B(C{sub 6}F{sub 5}){sub 3} abstracts the methyl group of a coordinated borate ligand to generate a free, 3-coordinate borane center in [(dmpe)NiMe(1a)]{sup +}[MeB(C{sub 6}F{sub 5}){sub 3}]{sup -} (3).

  16. The information compliance indexes. The illustrative case of income taxes

    Directory of Open Access Journals (Sweden)

    Ilídio Tomás Lopes

    2014-01-01

    Full Text Available La adopción de las normas del IASB ha representado, en la Unión Europea, un importanteesfuerzo de armonización hacia la integración de los informes financieros, la confiabilidad,la relevancia y la comparabilidad. En este trabajo se pretende dar a conocer la importanciade los índices de cumplimiento de la información (ICI, con base en las normas contables,como un proxy para la presentación de informes útiles. Este enfoque se pone de manifiestoa través de un ejemplo ilustrativo acerca de las revelaciones sobre los impuestos diferidos,como requiere la NIC 12. Esta norma prescribe el tratamiento contable de los impuestoscorrientes e impuestos por activos y pasivos diferidos. Estos problemas suelen ser percibi-dos por los interesadoscomo indicadores de la continuidad de las empresas y los posiblesrendimientos futuros. Sobre la base de las empresas no financieras cotizadas en el mercadoreguladoEuronext Lisboa, con referencia a finales de los años fiscales 2008 y 2012, serealizó un índice de cumplimiento de la información, sobre la base de la norma contable.Este índice integra una regresión con un conjunto de indicadores de desempeño y control.La evidencia empírica ha proporcionado importantes conocimientos estadísticos que corro-boran los hallazgos de que los niveles de cumplimiento de la información y de divulgacióndependen de varios indicadores de desempeño y control.

  17. Role of lysine and acidic amino acid residues on the insecticidal activity of Jackbean urease.

    Science.gov (United States)

    Real-Guerra, Rafael; Carlini, Célia Regina; Stanisçuaski, Fernanda

    2013-09-01

    Canavalia ensiformis has three isoforms of urease: Jackbean urease (JBU), Jackbean urease II and canatoxin. These isoforms present several biological activities, independent from the enzymatic property, such as entomotoxicity and antifungal properties. The entomotoxic activity is a property of the whole protein, as well as of a 10 kDa peptide released by insect digestive enzymes. Here we have used chemical modification to observe the influence of lysines and acidic residues on JBU enzymatic and insecticidal activities. Chemical modification of lysine residues was performed with dimethylamine-borane complex and formaldehyde, and acidic residues were modified by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and ethylenediamine. Derivatized ureases, called JBU-Lys (lysine-modified) and JBU-Ac (acidic residues-modified), were assayed for their biochemical and insecticidal properties. Neither modification altered significantly the kinetic parameters analyzed, indicating that no residue critical for the enzyme activity was affected and that the modifications did not incur in any significant structural alteration. On the other hand, both modifications reduced the toxic activity of the native protein fed to Dysdercus peruvianus. The changes observed in the entomotoxic property of the derivatized proteins reflect alterations in different steps of JBU's toxicity towards insects. JBU-Ac is not susceptible to hydrolysis by insect digestive enzymes, hence impairing the release of toxic peptide(s), while JBU-Lys is processed as the native protein. On the other hand, the antidiuretic effect of JBU on Rhodnius prolixus is altered in JBU-Lys, but not in JBU-Ac. Altogether, these data emphasize the role of lysine and acidic residues on the insecticidal properties of ureases.

  18. Effect of Solar Radiation on Viscoelastic Properties of Bovine Leather: Temperature and Frequency Scans

    Science.gov (United States)

    Nalyanya, Kallen Mulilo; Rop, Ronald K.; Onyuka, Arthur S.

    2017-04-01

    This work presents both analytical and experimental results of the effect of unfiltered natural solar radiation on the thermal and dynamic mechanical properties of Boran bovine leather at both pickling and tanning stages of preparation. Samples cut from both pickled and tanned pieces of leather of appropriate dimensions were exposed to unfiltered natural solar radiation for time intervals ranging from 0 h (non-irradiated) to 24 h. The temperature of the dynamic mechanical analyzer was equilibrated at 30°C and increased to 240°C at a heating rate of 5°C \\cdot Min^{-1}, while its oscillation frequency varied from 0.1 Hz to 100 Hz. With the help of thermal analysis (TA) control software which analyzes and generates parameter means/averages at temperature/frequency range, the graphs were created by Microsoft Excel 2013 from the means. The viscoelastic properties showed linear frequency dependence within 0.1 Hz to 30 Hz followed by negligible frequency dependence above 30 Hz. Storage modulus (E') and shear stress (σ ) increased with frequency, while loss modulus (E''), complex viscosity (η ^{*}) and dynamic shear viscosity (η) decreased linearly with frequency. The effect of solar radiation was evident as the properties increased initially from 0 h to 6 h of irradiation followed by a steady decline to a minimum at 18 h before a drastic increase to a maximum at 24 h. Hence, tanning industry can consider the time duration of 24 h for sun-drying of leather to enhance the mechanical properties and hence the quality of the leather. At frequencies higher than 30 Hz, the dynamic mechanical properties are independent of the frequency. The frequency of 30 Hz was observed to be a critical value in the behavior in the mechanical properties of bovine hide.

  19. New nanomaterials for hydrogen storage. A new class of aluminum hydrides; Neue Nanomaterialien zur Wasserstoffspeicherung. Eine neue Klasse von Aluminiumhydriden

    Energy Technology Data Exchange (ETDEWEB)

    Cordes, Joern

    2009-02-13

    In this work, Aluminum was vaporized in a PACIS cluster source, while molecular Hydrogen was also provided, thus producing Aluminum hydride clusters. These clusters were mass selected and investigated via Photoelectron Spectroscopy with anions in order to determine their electronic structure. In a cooperation with Puru Jena et al. at the Virginia Commonwealth University, electronic and geometric structures of the clusters were also calculated using Density Functional Theory. A group of clusters, specifically Al{sub 4}H{sub 4}, Al{sub 4}H{sub 6} and a series of clusters Al{sub n}H{sub n+2} (5 {<=} n {<=} 8) showed large HOMO-LUMO-Gaps and relatively small adiabatic electron affinities, hinting towards an increased stability of these clusters. The resemblance of the structures of already known and stable Boranes (BnHm) led to investigations whether ''Wade's Rules'' could also be applied to the new Alanes Al{sub n}H{sub m}. Comparison of the experimentally found values for the HOMO-LUMO-Gap, Adiabatic electron Affinity and Vertical Detachment Energy with the calculated values led to geometric structures of the ground states that, in case of the clusters Al{sub n}H{sub n+2} (5 {<=} n {<=} 8) follow Wade's (n+1) rule: They adopt hollow, cage-like closo-structures with one terminal Hydrogen atom per Aluminum atom and two additional Hydrogen atoms on bridge-sites. The clusters Al{sub 4}H{sub 4} and Al{sub 4}H{sub 6} have tetrahedron-shaped structures. While Al{sub 4}H{sub 4} is a perfect tetrahedron, Al{sub 4}H{sub 6} adopts a slightly distorted tetrahedral geometry with D{sub 2d} symmetry and two Hydrogen atoms on bridge sites. Furthermore, Al{sub 4}H{sub 6} showed the biggest HOMO-LUMO-Gap of all investigated clusters with a value of 1.9 {+-} 0.1 eV. These findings seem to contradict Wade's (n+1) rule, but can be understood in terms of the Polyhedral Skeletal Electron Pair Theory (PSEPT). The molecular orbitals predicted by the PSEPT

  20. Corrosion resistance of electrodeposited Ni-B and Ni-B-Si{sub 3}N{sub 4} composite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Krishnaveni, K. [National Metallurgical Laboratory, Madras Centre CSIR Complex, Taramani, Chennai 600 113 (India); Narayanan, T.S.N. Sankara [National Metallurgical Laboratory, Madras Centre CSIR Complex, Taramani, Chennai 600 113 (India)], E-mail: tsnsn@rediffmail.com; Seshadri, S.K. [Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Chennai 600 036 (India)

    2009-07-08

    Corrosion resistance of electrodeposited (ED) and electroless (EL) composite coatings have been a debatable issue in the published literature. The present paper aims to compare the corrosion resistance of ED Ni-B-Si{sub 3}N{sub 4} composite coating with its plain counter part. The ED Ni-B coatings were prepared using Watt's nickel bath modified with the addition of dimethylamine borane and the ED Ni-B-Si{sub 3}N{sub 4} composite coatings were prepared using the same bath in which Si{sub 3}N{sub 4} particles (mean diameter: 0.80 {mu}m) were dispersed in it. The structural and morphological characteristics of ED Ni-B and Ni-B-Si{sub 3}N{sub 4} composite coatings were determined using X-ray diffraction (XRD) measurements and scanning electron microscopy (SEM). The corrosion resistances of ED Ni-B and Ni-B-Si{sub 3}N{sub 4} composite coatings, both in as-plated and heat treated conditions, in 3.5% NaCl, were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies. The study reveals that the extent of shift in corrosion potential (E{sub corr}) towards the noble direction, decrease in corrosion current density (i{sub corr}), increase in charge transfer resistance (R{sub ct}) and decrease in double layer capacitance (C{sub dl}) values with the incorporation of Si{sub 3}N{sub 4} particles in the ED Ni-B matrix is not appreciable, both in as-plated and heat-treated conditions. The occurrence of the second phase angle maximum suggests penetration of the electrolyte via the pores/micro-pores in these coating to create another interface, namely, the electrolyte/substrate. Unlike the nanosized particles, the micron size Si{sub 3}N{sub 4} particles (mean diameter: 0.80 {mu}m) used in this study is not capable of completely filling all the pores in the coating and allowed diffusion of chloride ions along the interface. The marginal improvement in corrosion resistance observed for ED Ni-B-Si{sub 3}N{sub 4} composite coatings compared

  1. Comparison of B{sub 2}O{sub 3} and BN deposited by atomic layer deposition for forming ultrashallow dopant regions by solid state diffusion

    Energy Technology Data Exchange (ETDEWEB)

    Consiglio, Steven, E-mail: steve.consiglio@us.tel.com; Clark, Robert D.; O' Meara, David; Wajda, Cory S.; Tapily, Kandabara; Leusink, Gert J. [TEL Technology Center, America, LLC, 255 Fuller Rd., Albany, New York 12203 (United States)

    2016-01-15

    In this study, the authors investigated atomic layer deposition (ALD) of B{sub 2}O{sub 3} and BN for conformal, ultrashallow B doping applications and compared the effect of dopant-containing overlayers on sheet resistance (R{sub s}) and B profiles for both types of films subjected to a drive-in thermal anneal. For the deposition of B{sub 2}O{sub 3}, tris(dimethylamido)borane and O{sub 3} were used as coreactants and for the deposition of BN, BCl{sub 3} and NH{sub 3} were used as coreactants. Due to the extreme air instability of B{sub 2}O{sub 3} films, physical analysis was performed on B{sub 2}O{sub 3} films, which were capped in-situ with ∼30 Å ALD grown Al{sub 2}O{sub 3} layers. For the BN films, in-situ ALD grown Si{sub 3}N{sub 4} capping layers (∼30 Å) were used for comparison. From spectroscopic ellipsometry, a thickness decrease was observed after 1000 °C, 30 s anneal for the B{sub 2}O{sub 3} containing stack with 60 ALD cycles of B{sub 2}O{sub 3}, whereas the BN containing stacks showed negligible thickness decrease after the annealing step, regardless of the number of BN cycles tested. The postanneal reduction in film thickness as well as decrease in R{sub s} for the B{sub 2}O{sub 3} containing stack suggests that the solid state diffusion dopant mechanism is effective, whereas for the BN containing stacks this phenomenon seems to be suppressed. Further clarification of the effectiveness of the B{sub 2}O{sub 3} containing layer compared to the film stacks with BN was evidenced in backside secondary ion mass spectrometry profiling of B atoms. Thus, B{sub 2}O{sub 3} formed by an ALD process and subsequently capped in-situ followed by a drive-in anneal offers promise as a dopant source for ultrashallow doping, whereas the same method using BN seems ineffective. An integrated approach for B{sub 2}O{sub 3} deposition and annealing on a clustered tool also demonstrated controllable R{sub s} reduction without the use of a capping layer.

  2. Association of myostatin on early calf mortality, growth, and carcass composition traits in crossbred cattle.

    Science.gov (United States)

    Casas, E; Bennett, G L; Smith, T P L; Cundiff, L V

    2004-10-01

    The objective of this study was to investigate a potential association of an inactive myostatin allele with early calf mortality, and evaluate its effect on growth and carcass traits in a crossbred population. Animals were obtained by mating F1 cows to F1 (Belgian Blue x British Breed) or Charolais sires. Cows were obtained from mating Hereford, Angus, and MARC III (1/4 Hereford, 1/4 Angus, 1/4 Pinzgauer, and 1/4 Red Poll) dams to Hereford, Angus, Tuli, Boran, Brahman, or Belgian Blue sires. Belgian Blue was the source of the inactive myostatin allele. Myostatin genotypes were determined for all animals including those that died before weaning. Early calf mortality was examined in the F2 subpopulation (n = 154), derived from the F1 sires mated to F1 cows from Belgian Blue sires, to evaluate animals with zero, one, or two copies of inactive myostatin allele. An overall 1:2:1 ratio (homozygous active myostatin allele:heterozygous:homozygous inactive myostatin allele) was observed in the population; however, a comparison between calves dying before weaning and those alive at slaughter showed an unequal distribution across genotypes (P Carcass composition traits analyzed were hot carcass weight, fat thickness, LM area, marbling score, USDA yield grade, estimated kidney, pelvic, and heart fat, retail product yield and weight, fat yield and weight, bone yield and weight, and percentage of carcasses classified as Choice. Charolais lack the inactive myostatin allele segregating in Belgian Blue; thus, in the population sired by Charolais (n = 645), only animals with zero or one copy of the inactive myostatin allele were evaluated. Animals carrying one copy were heavier at birth and at weaning, and their carcasses were leaner and more muscled. In the population sired by Belgian Blue x British Breed (n = 725), animals with two copies of inactive myostatin allele were heavier at birth, leaner, and had a higher proportion of muscle mass than animals with zero or one copies

  3. Novel Tc-99m radiotracers for brain imaging

    Directory of Open Access Journals (Sweden)

    Alessandra Boschi

    2007-09-01

    Full Text Available A novel class of Tc-99m complexes able to cross the blood brain barrier has been investigated and described here. These compounds are formed by reacting the bis-substituted nitrido precusors [99mTc(N(PS2] (PS = phosphino-thiol ligand with triethylborane (BEt3 under strictly anhydrous conditions and using non-aqueous solvents. The molecular structure of these tracers was not fully established, but preliminary experimental evidence suggests that they result from the interaction of the Lewis base [99mTc(N(PS2] with the Lewis acid BEt3, which leads to the formation of the novel -B-Nº Tc- adduct. After purification and recovery in a physiological solution, the new borane-nitrido Tc-99m derivatives were injected in rats for evaluating their in vivo biological behavior. Results showed a significant accumulation in brain tissue, thus indicating that these complexes are capable of penetrating the intact blood brain barrier. Uptake in the central nervous system was confirmed by imaging the distribution of activity on the integrated living animal using a YAP(SSPECT small animal scanner.Uma nova classe de complexos de Tc-99m capazes de atravessar a barreira hemato-encefálica foi investigada e descrita neste trabalho. Estes compostos são formados reagindo os precursores bissubstituídos do nitrido [99mTc(N(PS2] (PS = phosphino-tiol ligante com trietillborano (BEt3 sob restritas condições anidras e usando solventes não aquosos. A estrutura molecular desses traçadores não foi totalmente estabelecida, mas evidências experimentais preliminares sugerem que eles resultam da interação da base de Lewis [99mTc(N(PS2] com o ácido de Lewis BEt3, levando a formação do novo aducto -B-Nº Tc-. Após purificação e recuperação em uma solução fisiológica, os novos derivados borano-nitrido-Tc-99m foram injetados em ratos para avaliação de seu comportamento biológico in vivo. Os resultados mostraram uma acumulação significativa no tecido cerebral

  4. Improving rock phosphate availability through feeding, mixing and processing with composting manure.

    Science.gov (United States)

    Odongo, Nicholas E; Hyoung-Ho, K; Choi, Hee-Chul; van Straaten, Peter; McBride, Brian W; Romney, Dannie L

    2007-11-01

    The objective of this study was to improve the availability of phosphorus (P) from rock phosphate (RP) through feeding, mixing and composting manure. The experiment was conducted as a 3 x 2 split-plot design. Manure was collected from 12 Boran steers (200+/-4.5 kg live weight) fed a basal diet of Napier grass (Pennisetum purpureum) at 2.5% body weight on a dry matter (DM) basis. The main plot treatments were (i) manure from steers supplemented with 113 g Busumbu rock phosphate (BRP) per day (FBRP), (ii) manure from steers not supplemented with BRP, feces mixed with 113 g BRP per day (MBRP) and (iii) manure from steers not supplemented with BRP and feces not mixed with BRP (CONT). The sub-plots comprised composting the manure either (i) mixed with 440 g of wheat (Triticum aestivum L.) straw per kg fresh feces (WS) or (ii) without straw (WOS). The manure was composted in 200 L plastic bins for 90 days. After 90 days, P availability was evaluated (i) by aerobic laboratory incubation at 25 degrees C for 1, 2, 4, 8, 12, and 16 weeks and (ii) by greenhouse agronomic evaluation study using maize (Zea Mays L.) as the test crop in either a humic Nitosol or an Andosol. In the laboratory incubation study, resin P was higher (pFBRP-WS, Nitosol>MBRP-WS, Andosol>MBRP-WS, Nitosol>FBRP-WOS, Andosol>FBRP-WOS, Nitosol. In the greenhouse evaluation, maize crops in the WS compost had higher (psuper phosphate, (173% versus 196%; Andosol and Nitosol, respectively). The biomass yield and P uptake relative agronomic effectiveness (RAE) for WS compost was also higher (p<0.05) than that of WOS compost (184 versus 3+/-0.8 and 242 versus 162+/-0.2, WS and WOS, biomass yield and P uptake, respectively). Nitosol biomass yield and P uptake RAE were also higher (p<0.05) than for the Andosol (99 versus 88+/-0.8 and 332 versus 72+/-0.2, Nitosol and Andosol, biomass yield and P uptake, respectively). The results show that P-enriched composting in the presence of wheat straw significantly increased P

  5. Beads,Necklaces, Chains and Strings in Capping Carbonyl Clusters

    Directory of Open Access Journals (Sweden)

    Enos Masheija Kiremire

    2015-09-01

    Full Text Available The paper attempts to explain at length the close relationship between transition metal carbonyl clusters with main group clusters especially the boranes using the 14n and 4n rules. When the ‘shielding’ electrons are removed from a transition metal carbonyl cluster and becomes ‘naked’, it resembles a corresponding one in the main group elements. A an expanded table of osmium carbonyl clusters was constructed using the capping fragment Os(CO2(14n-2 and the fragment Os(CO3 (14n+0. The table reveals the fact that the known series such closo, nido and arachno are part and parcel of a wide range of series especially the capping series 14n+q, where q takes up negative multiple integers of two including 0 such as such = 0, -2,-4, -6, and so on. The linkage between capping series in transition metal carbonyl clusters has also been identified. Apart from the capping series generated in the table, there is another type of series where the skeletal cluster elements remained the same but the number of carbonyl ligands successively decreased. These types of series are referred to as stripping series. Mapping generating functions were also derived which produces any cluster formula or series required. Also the table shows that many clusters form utilizing some of its atoms as closo nucleus around which the larger ones are built and thus forming clusters within larger clusters. The table may be used to categorize a given cluster formula that falls within its range. Otherwise, using the 14n rule or 4n rule can be used for cluster classification. Furthermore, the table indicated that atoms, fragments and molecules can be classified into series. Through this approach of using series, Hoffmann’s important isolobal relationship of chemical species can splendidly be explained.Using the 14n rule and 4n rules creates a framework under which chemical species such as atoms, fragments, molecules and ions some of which may appear unrelated from main group

  6. A divergent asymmetric approach to aza-spiropyran derivative and (1S,8aR-1-hydroxyindolizidine

    Directory of Open Access Journals (Sweden)

    Huang Pei-Qiang

    2007-11-01

    Full Text Available Abstract Background Spiroketals and the corresponding aza-spiroketals are the structural features found in a number of bioactive natural products, and in compounds possessing photochromic properties for use in the area of photochemical erasable memory, self-development photography, actinometry, displays, filters, lenses of variable optical density, and photomechanical biomaterials etc. And (1R,8aS-1-hydroxyindolizidine (3 has been postulated to be a biosynthetic precursor of hydroxylated indolizidines such as (+-lentiginosine 1, (--2-epilentiginosine 2 and (--swainsonine, which are potentially useful antimetastasis drugs for the treatment of cancer. In continuation of a project aimed at the development of enantiomeric malimide-based synthetic methodology, we now report a divergent, concise and highly diastereoselective approach for the asymmetric syntheses of an aza-spiropyran derivative 7 and (1S,8aR-1-hydroxyindolizidine (ent-3. Results The synthesis of aza-spiropyran 7 started from the Grignard addition of malimide 4. Treatment of the THP-protected 4-hydroxybutyl magnesium bromide with malimide 4 at -20°C afforded N,O-acetal 5a as an epimeric mixture in a combined yield of 89%. Subjection of the diastereomeric mixture of N,O-acetal 5a to acidic conditions for 0.5 h resulted in the formation of the desired functionalized aza-spiropyran 7 as a single diastereomer in quantitative yield. The stereochemistry of the aza-spiropyran 7 was determined by NOESY experiment. For the synthesis of ent-3, aza-spiropyran 7, or more conveniently, N,O-acetal 5a, was converted to lactam 6a under standard reductive dehydroxylation conditions in 78% or 77% yield. Reduction of lactam 6a with borane-dimethylsulfide provided pyrrolidine 8 in 95% yield. Compound 8 was then converted to 1-hydroxyindolizidine ent-3 via a four-step procedure, namely, N-debenzylation/O-mesylation/Boc-cleavage/cyclization, and O-debenzylation. Alternatively, amino alcohol 8 was mesylated

  7. Zintl cluster chemistry in the alkali-metal-gallium systems

    Energy Technology Data Exchange (ETDEWEB)

    Henning, Robert [Iowa State Univ., Ames, IA (United States)

    1998-03-27

    Previous research into the alkali-metal-gallium systems has revealed a large variety of networked gallium deltahedra. The clusters are analogues to borane clusters and follow the same electronic requirements of 2n+2 skeletal electrons for closo-deltahedra. This work has focused on compounds that do not follow the typical electron counting rules. The first isolated gallium cluster was found in Cs8Ga11. The geometry of the Ga117- unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga1113- to Ga117- is believed to be the driving force of the distortion. The compound is paramagnetic because of an extra electron but incorporation of a halide atom into the structure captures the unpaired electron and forms a diamagnetic compound. A second isolated cluster has been found in Na10Ga10Ni where the tetra-capped trigonal prismatic gallium is centered by nickel. Stabilization of the cluster occurs through Ni-Ga bonding. A simple two-dimensional network occurs in the binary K2Ga3 Octahedra are connected through four waist atoms to form a layered structure with the potassium atoms sitting between the layers. Na30.5Ga60-xAgx is nonstoichiometric and needs only a small amount of silver to form (x ~ 2-6). The structure is composed of three different clusters which are interconnected to form a three-dimensional structure. The RbGa3-xAux system is also nonstoichiometric with a three-dimensional structure composed of Ga8 dodecahedra and four-bonded gallium atoms. Unlike Na30.5Ga60-xAgx, the RbGa3 binary is also stable. The binary is formally a Zintl phase but the ternary is not. Some chemistry in the alkali-metal-indium system also has been explored. A new potassium-indium binary

  8. Hydrogen-fluorine exchange in NaBH4-NaBF4.

    Science.gov (United States)

    Rude, L H; Filsø, U; D'Anna, V; Spyratou, A; Richter, B; Hino, S; Zavorotynska, O; Baricco, M; Sørby, M H; Hauback, B C; Hagemann, H; Besenbacher, F; Skibsted, J; Jensen, T R

    2013-11-07

    Hydrogen-fluorine exchange in the NaBH4-NaBF4 system is investigated using a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed using in situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF2H2 in the temperature range T = 200 to 215 °C. Combined use of solid-state (19)F MAS NMR, FT-IR and DFT calculations supports the formation of a BF2H2(-) complex ion, reproducing the observation of a (19)F chemical shift at -144.2 ppm, which is different from that of NaBF4 at -159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ~310 °C. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF and BF3 or amorphous products such as closo-boranes, e.g. Na2B12H12. The NaBH4-NaBF4 composite decomposes at lower temperatures (300 °C) compared to NaBH4 (476 °C), as observed by thermogravimetric analysis. NaBH4-NaBF4 (1:0.5) preserves 30% of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8% for NaBH4 as measured using Sievert's method under identical conditions, but more than 50% using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na2B12H12. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH4-NaF.

  9. Low-Cost Precursors to Novel Hydrogen Storage Materials

    Energy Technology Data Exchange (ETDEWEB)

    Suzanne W. Linehan; Arthur A. Chin; Nathan T. Allen; Robert Butterick; Nathan T. Kendall; I. Leo Klawiter; Francis J. Lipiecki; Dean M. Millar; David C. Molzahn; Samuel J. November; Puja Jain; Sara Nadeau; Scott Mancroni

    2010-12-31

    From 2005 to 2010, The Dow Chemical Company (formerly Rohm and Haas Company) was a member of the Department of Energy Center of Excellence on Chemical Hydrogen Storage, which conducted research to identify and develop chemical hydrogen storage materials having the potential to achieve DOE performance targets established for on-board vehicular application. In collaboration with Center co-leads Los Alamos National Laboratory (LANL) and Pacific Northwest National Laboratory (PNNL), and other Center partners, Dow's efforts were directed towards defining and evaluating novel chemistries for producing chemical hydrides and processes for spent fuel regeneration. In Phase 1 of this project, emphasis was placed on sodium borohydride (NaBH{sub 4}), long considered a strong candidate for hydrogen storage because of its high hydrogen storage capacity, well characterized hydrogen release chemistry, safety, and functionality. Various chemical pathways for regenerating NaBH{sub 4} from spent sodium borate solution were investigated, with the objective of meeting the 2010/2015 DOE targets of $2-3/gal gasoline equivalent at the pump ($2-3/kg H{sub 2}) for on-board hydrogen storage systems and an overall 60% energy efficiency. With the September 2007 No-Go decision for NaBH{sub 4} as an on-board hydrogen storage medium, focus was shifted to ammonia borane (AB) for on-board hydrogen storage and delivery. However, NaBH{sub 4} is a key building block to most boron-based fuels, and the ability to produce NaBH{sub 4} in an energy-efficient, cost-effective, and environmentally sound manner is critical to the viability of AB, as well as many leading materials under consideration by the Metal Hydride Center of Excellence. Therefore, in Phase 2, research continued towards identifying and developing a single low-cost NaBH4 synthetic route for cost-efficient AB first fill, and conducting baseline cost estimates for first fill and regenerated AB using a variety of synthetic routes. This

  10. Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal [Ames Lab., Ames, IA (United States)

    2012-12-17

    The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C5H5)(OxR)2] [OxR = Ox4S-iPr,Me2, Ox4R-iPr,Me2, Ox4S-tBu]. These optically active proligands react with an equivalent of M(NMe2)4 (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C5H4)(OxR)2}M(NMe2)2 in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C-N/C-H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C5H4)(Ox4S-iPr,Me2)2}Zr(NMe2)2 ({S-2}Zr(NMe2)2) displays highest activity and enantioselectivity. Interestingly, S-2

  11. From Fundamental Understanding To Predicting New Nanomaterials For High Capacity Hydrogen/Methane Storage and Carbon Capture

    Energy Technology Data Exchange (ETDEWEB)

    Yildirim, Taner [Univ. of Pennsylvania, Philadelphia, PA (United States)

    2015-03-03

    On-board hydrogen/methane storage in fuel cell-powered vehicles is a major component of the national need to achieve energy independence and protect the environment. The main obstacles in hydrogen storage are slow kinetics, poor reversibility and high dehydrogenation temperatures for the chemical hydrides; and very low desorption temperatures/energies for the physisorption materials (MOF’s, porous carbons). Similarly, the current methane storage technologies are mainly based on physisorption in porous materials but the gravimetric and volumetric storage capacities are below the target values. Finally, carbon capture, a critical component of the mitigation of CO2 emissions from industrial plants, also suffers from similar problems. The solid-absorbers such as MOFs are either not stable against real flue-gas conditions and/or do not have large enough CO2 capture capacity to be practical and cost effective. In this project, we addressed these challenges using a unique combination of computational, synthetic and experimental methods. The main scope of our research was to achieve fundamental understanding of the chemical and structural interactions governing the storage and release of hydrogen/methane and carbon capture in a wide spectrum of candidate materials. We studied the effect of scaffolding and doping of the candidate materials on their storage and dynamics properties. We reviewed current progress, challenges and prospect in closely related fields of hydrogen/methane storage and carbon capture.[1-5] For example, for physisorption based storage materials, we show that tap-densities or simply pressing MOFs into pellet forms reduce the uptake capacities by half and therefore packing MOFs is one of the most important challenges going forward. For room temperature hydrogen storage application of MOFs, we argue that MOFs are the most promising scaffold materials for Ammonia-Borane (AB) because of their unique interior active metal-centers for AB binding and well

  12. B═B and B≡E (E = N and o) multiple bonds in the coordination sphere of late transition metals.

    Science.gov (United States)

    Brand, Johannes; Braunschweig, Holger; Sen, Sakya S

    2014-01-21

    Because of their unusual structural and bonding motifs, multiply bonded boron compounds are fundamentally important to chemists, leading to enormous research interest. To access these compounds, researchers have introduced sterically demanding ligands that provide kinetic as well as electronic stability. A conceptually different approach to the synthesis of such compounds involves the use of an electron-rich, coordinatively unsaturated transition metal fragment. To isolate the plethora of borane, boryl, and borylene complexes, chemists have also used the coordination sphere of transition metals to stabilize reactive motifs in these molecules. In this Account, we summarize our results showing that increasingly synthetically challenging targets such as iminoboryl (B≡N), oxoboryl (B≡O), and diborene (B═B) fragments can be stabilized in the coordination sphere of late transition metals. This journey began with the isolation of two new iminoboryl ligands trans-[(Cy3P)2(Br)M(B≡N(SiMe3))] (M = Pd, Pt) attached to palladium and platinum fragments. The synthesis involved oxidative addition of the B-Br bond in (Me3Si)2N═BBr2 to [M(PCy3)2] (M = Pt, Pd) and the subsequent elimination of Me3SiBr at room temperature. Variation of the metal, the metal-bound coligands, and the substituent at the nitrogen atom afforded a series of analogous iminoboryl complexes. Following the same synthetic strategy, we also synthesized the first oxoboryl complex trans-[(Cy3P)2BrPt(BO)]. The labile bromide ligand adjacent to platinum makes the complex a viable candidate for further substitution reactions, which led to a number of new oxoboryl complexes. In addition to allowing us to isolate these fundamental compounds, the synthetic strategy is very convenient and minimizes byproducts. We also discuss the reaction chemistry of these types of compounds. In addition to facilitating the isolation of compounds with B≡E (E = N, O) triple bonds, the platinum fragment can also stabilize a

  13. Coordination- and Redox-Noninnocent Behavior of Ambiphilic Ligands Containing Antimony.

    Science.gov (United States)

    Jones, J Stuart; Gabbaï, François P

    2016-05-17

    Stimulated by applications in catalysis, the chemistry of ambiphilic ligands featuring both donor and acceptor functionalities has experienced substantial growth in the past several years. The unique opportunities in catalysis offered by ambiphilic ligands stem from the ability of their acceptor functionalities to play key roles via metal-ligand cooperation or modulation of the reactivity of the metal center. Ligands featuring group 13 centers, most notably boranes, as their acceptor functionalities have undoubtedly spearheaded these developments, with remarkable results having been achieved in catalytic hydrogenation and hydrosilylation. Motivated by these developments as well as by our fundamental interest in the chemistry of heavy group 15 elements, we became fascinated by the possibility of employing antimony centers as Lewis acids within ambiphilic ligands. The chemistry of antimony-based ligands, most often encountered as trivalent stibines, has historically been considered to mirror that of their lighter phosphorus-based congeners. There is growing evidence, however, that antimony-based ligands may display unique coordination behavior and reactivity. Additionally, despite the diverse Lewis acid and redox chemistry that antimony exhibits, there have been only limited efforts to explore this chemistry within the coordination sphere of a transition metal. By incorporation of antimony into the framework of polydentate ligands in order to enforce the main group metal-transition metal interaction, the effect of redox and coordination events at the antimony center on the structure, electronics, and reactivity of the metal complex may be investigated. This Account describes our group's continuing efforts to probe the coordination behavior, reactivity, and application of ambiphilic ligands incorporating antimony centers. Structural and theoretical studies have established that both Sb(III) and Sb(V) centers in polydentate ligands may act as Z-type ligands toward late

  14. Lewis acid adducts of narrow band gap conjugated polymers.

    Science.gov (United States)

    Welch, Gregory C; Bazan, Guillermo C

    2011-03-30

    We report on the interaction of Lewis acids with narrow band gap conjugated copolymers containing donor and acceptor units. Examination of the widely used poly[(4,4-bis(2-ethylhexyl)cyclopenta-[2,1-b:3,4-b']dithiophene)-2,6-(diyl-alt-benzo[2,1,3]thiadiazole)-4,7-diyl] (1) shows weaker binding with B(C(6)F(5))(3) when compared with a small molecule that contains a cyclopenta-[2,1-b:3,4-b']dithiophene (CDT) unit flanked by two benzo[2,1,3]thiadiazole (BT) fragments. Studies on model compounds representative of 1, together with a comparison between B(C(6)F(5))(3) and BBr(3), indicate that the propensity for Lewis acid coordination is decreased because of steric encumbrance surrounding the BT nitrogen sites. These observations led to the design of chromophores that incorporate an acceptor unit with a more basic nitrogen site, namely pyridal[2,1,3]thiadiazole (PT). That this strategy leads to a stronger B-N interaction was demonstrated through the examination of the reaction of B(C(6)F(5))(3) with two small molecules bis(4,4-bis(hexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-4,7-pyridal[2,1,3]thiadiazole (8) and bis{2-thienyl-(4,4-bis(hexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)}-4,7-pyridal[2,1,3]thiadiazole (9) and two polymer systems (poly[(4,4-bis(2-ethylhexyl)cyclopenta-[2,1-b:3,4-b']dithiophene)-2,6-diyl-alt-([1,2,5]thiadiazolo[3,4-c]pyridine)-4,7-diyl] (10) and poly[(4,4-bis(2-ethylhexyl)cyclopenta-[2,1-b:3,4-b']dithiophene)-2,6-diyl-alt-(4',7'-bis(2-thienyl)-[1,2,5]thiadiazolo[3,4-c]pyridine)-5,5-diyl] (11). From a materials perspective, it is worth pointing out that through the binding of B(C(6)F(5))(3), new NIR-absorbing polymers can be generated with band gaps from 1.31 to 0.89 eV. A combination of studies involving ultraviolet photoemission spectroscopy and density functional theory shows that the narrowing of the band gap upon borane coordination to the pyridal nitrogen on PT is a result of lowering the energies of both the highest occupied molecular

  15. Structural and Electronic Investigations of Complex Intermetallic Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ko, Hyunjin [Iowa State Univ., Ames, IA (United States)

    2008-01-01

    structures of these and related materials. Such calculations allow us to examine various interactions at the atomic scale, interactions which include orbital overlap, two-electron interactions, and Madelung terms. Moreover, these electronic studies also provide links between the angstrom-scale atomic interactions and the macro-scale physical properties, such as magnetism. Over the past few decades, there have been many significant developments toward understanding structure-bonding-property relationships in extended solids in terms of variables including atomic size, valence electron concentration, and electronegativity. However, many simple approaches based on electron counting, e.g., the octet rule, the 18-electron rule, or Wade's rules for boranes, cannot be applied adequately or universally to many of the more complex intermetallic compounds. For intermetallic phases that include late transition metals and post transition main group elements as their constituents, one classification scheme has been developed and effectively applied by using their valence electron count per atom (vec). These compounds are known as Hume-Rothery electron phases, and they have a variety of structure types with vec < 2.0 as shown in Table 1.

  16. Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal [Ames Lab., Ames, IA (United States)

    2012-12-17

    The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C5H5)(OxR)2] [OxR = Ox4S-iPr,Me2, Ox4R-iPr,Me2, Ox4S-tBu]. These optically active proligands react with an equivalent of M(NMe2)4 (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C5H4)(OxR)2}M(NMe2)2 in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C-N/C-H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C5H4)(Ox4S-iPr,Me2)2}Zr(NMe2)2 ({S-2}Zr(NMe2)2) displays highest activity and enantioselectivity. Interestingly, S-2

  17. One-Step PCR Sequencing. Final Technical Progress Report for February 15, 1997 - November 30, 2001

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, B. R.

    2004-04-16

    We investigated new chemistries and alternate approaches for direct gene sequencing and detection based on the properties of boron-substituted nucleotides as chain delimiters in lieu of conventional chain terminators. Chain terminators, such as the widely used Sanger dideoxynucleotide truncators, stop DNA synthesis during replication and hence are incompatible with further PCR amplification. Chain delimiters, on the other hand, are chemically-modified, ''stealth'' nucleotides that act like normal nucleotides in DNA synthesis and PCR amplification, but can be unmasked following chain extension and exponential amplification. Specifically, chain delimiters give rise to an alternative sequencing strategy based on selective degradation of DNA chains generated by PCR amplification with modified nucleotides. The method as originally devised employed template-directed enzymatic, random incorporation of small amounts of boron-modified nucleotides (e.g., 2'-deoxynucleoside 5'-alpha-[P-borano]- triphosphates) during PCR amplification. Rather than incorporation of dideoxy chain terminators, which are less efficiently incorporated in PCR-based amplification than natural deoxynucleotides, our method is based on selective incorporation and exonuclease degradation of DNA chains generated by efficient PCR amplification of chemically-modified ''stealth'' nucleotides. The stealth nucleotides have a boranophosphate group instead of a normal phosphate, yet behave like normal nucleotides during PCR-amplification. The unique feature of our method is that the position of the stealth nucleotide, and hence DNA sequencing fragments, are revealed at the desired, appropriate moment following PCR amplification. During the current grant period, a variety of new boron-modified nucleotides were synthesized, and new chemistries and enzymatic methods and combinations thereof were explored to improve the method and study the effects of borane modified

  18. Boron-Containing Compounds for Liposome-Mediated Tumor Localization and Application to Neutron Capture Therapy

    Energy Technology Data Exchange (ETDEWEB)

    Hawthorne, M. Frederick [Univ. of California, Los Angeles, CA (United States)

    2005-04-07

    Medical application of boron neutron capture therapy (BNCT) has been significantly hindered by the slow development of boron drug-targeting methodologies for the selective delivery of high boron concentration sto malignant cells. We have successfully sought to fill this need by creating liposomes suitable as in vivo boron delivery vehicles for BNCT. Delivery of therapeutic quantities of boron to tumors in murine models has been achieved with small unilamellar boron-rich liposomes. Subsequently, attempts have been made to improve delivery efficiency of liposomes encapsulating boron-containing water-soluble species into their hollow core by incorporating lipophilic boron compounds as addenda to the liposome bilayer, incorporating boron compounds as structural components of the bilayer (which however, poses the risk of sacrificing some stability), and combinations thereof. Regardless of the method, approximately 90% of the total liposome mass remains therapeutically inactive and comprised of the vehicle's construction materials, while less than 5% is boron for neutron targeting. Following this laboratory's intensive study, the observed tumor specificity of certain liposomes has been attributed to their diminutive size of these liposomes (30-150 nm), which enables these small vesicles to pass through the porous, immature vasculature of rapidly growing tumor tissue. We surmised that any amphiphilic nanoparticle of suitable size could possess some tumor selectivity. Consequently, the discovery of a very boron-rich nanoparticle delivery agent with biodistribution performance similar to unilamellar liposomes became one of our goals. Closomers, a new class of polyhedral borane derivatives, attracted us as an alternative BNCT drug-delivery system. We specifically envisioned dodeca (nido-carboranyl)-substituted closomers as possibly having a great potential role in BNCT drug delivery. They could function as extraordinarily boron-rich BNCT drugs since they are

  19. 高压下典型小分子晶体的结构和行为%Structures and Properties in Typical Small-Molecule Crystals under High Pressure

    Institute of Scientific and Technical Information of China (English)

    靳锡联; 崔田

    2013-01-01

    高压能够引起凝聚态物质中原子微观结构的重新排列,形成新的电子分布状态,从而产生新材料和新特性.高压下典型分子体系呈现出了丰富的物理现象和物理性质,探索和发现这些高压下典型分子体系中的新结构及其行为,是高压物理研究重要且有意义的课题.通过对单质和小分子化合物两类体系的研究,说明了高压下典型分子单质I2、N2的结构和金属化行为;高压下典型分子化合物中碘仿、溴仿晶体的氢键和卤键的键合行为,以及氨硼烷晶体中存在的双氢键对分子集团转动动力学行为的影响等.高压下典型分子体系不同于常压下所表现出来的解离、重构和金属化等行为,为新结构的产生、新材料的探索以及新物理性质的发现提供了重要源泉.%High pressure can cause rearrangement of atoms in microstructure,and arouses reconfigurations of electronic states,which often brings new materials and new properties.The rich and colorful new phenomena and properties in the typical molecule system have been observed under high pressure.Studies of these new phases and behaviors in typical molecular system under high pressure are very important and significative.Two types of substance,i.e.elementary crystals and small-molecule compounds,are investigated thoroughly on structures and properties under high pressure,and demonstrate various features.In the elementary crystals,such as pressure-induced phase transition and metallization in I2 (solid iodine) and N2 (polymeric nitrogen),and in the small-molecule compounds,such as the hydrogen-bond and halogen-bond interactions in crystalline iodoform and bromoform under high pressure,the effects from dihydrogen bonds in ammonia borane which determining the complex dynamics behavior of rotations of the NH3 and BH3 groups under high pressure,etc.are discussed deeply.The distinct behaviors of molecular dissociation,reconstruction of crystal structures

  20. Stereoselective formation and catalytic activity of hydrido(acylphosphane)(chlorido)(pyrazole)rhodium(III) complexes. Experimental and DFT studies.

    Science.gov (United States)

    San Nacianceno, Virginia; Azpeitia, Susan; Ibarlucea, Lourdes; Mendicute-Fierro, Claudio; Rodríguez-Diéguez, Antonio; Seco, José M; San Sebastian, Eider; Garralda, María A

    2015-08-07

    The reaction of [{RhCl(COD)}2] (COD = 1,5-cyclooctadiene) with L = pyrazole (Hpz), 3(5)-methylpyrazole (Hmpz) or 3,5-dimethylpyrazole (Hdmpz) and PPh2(o-C6H4CHO) (Rh : L : P = 1 : 2 : 1) gives hydridoacyl complexes [RhHCl{PPh2(o-C6H4CO)}(L)2] (). Stereoselective formation of and with pyrazoles trans to hydrido and phosphorus and hydrogen bond formation with O-acyl and chlorido occur. is a mixture of two linkage isomers in a 9 : 1 ratio, with two 5-methylpyrazole ligands or with one 3- and one 5-methylpyrazole ligand, respectively. Fluxional undergoes metallotropic tautomerization and is a mixture of equal amounts of and , with hydrido trans to pyrazole or chlorido, respectively. Complexes readily exchange hydrido by chlorido to afford [RhCl2{PPh2(o-C6H4CO)}(L)2] (, and ) as single isomers with cis chloridos and two N-HCl hydrogen bonds. The reaction of with PPh3 or PPh2OH affords static [RhHCl{PPh2(o-C6H4CO)}(PPh3)L] () or [RhHCl{PPh2(o-C6H4CO)}(PPh2OH)L] () respectively with trans P-atoms and pyrazoles forming N-HCl hydrogen bonds. and contain single species with hydrido cis to chlorido, while is a mixture of equal amounts of and . Complexes , with an additional O-HO hydrogen bond, selectively contain only the cis-H,Cl species with all the three ligands. The reaction of [{RhCl(COD)}2] with L and PPh2(o-C6H4CHO) (Rh : L : P = 1 : 1 : 2) led to complexes with trans P-atoms, [RhHCl{PPh2(o-C6H4CO)}{PPh2(o-C6H4CHO)-κP}L] (, and ), at room temperature, and to [RhCl{PPh2(o-C6H4CO)}{PPh2(o-C6H4CHOH)}(Hmpz)] () or [RhCl{PPh2(o-C6H4CO)}2L] () with hydrogen evolution in refluxing benzene. DFT calculations were used to predict the correct isomers, their ratios and the particular intramolecular hydrogen bonds in these complexes. Single crystal X-ray diffraction analysis was performed on , and . Complexes are efficient homogeneous catalysts (0.5 mol% loading) in the hydrolysis of amine- or ammonia-borane (AB) to generate up to 3 equivalents

  1. Advancement of Systems Designs and Key Engineering Technologies for Materials Based Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    van Hassel, Bart A. [United Technologies Research Center, East Hartford, CT (United States)

    2015-09-18

    UTRC lead the development of the Simulink Framework model that enables a comparison of different hydrogen storage systems on a common basis. The Simulink Framework model was disseminated on the www.HSECoE.org website that is hosted by NREL. UTRC contributed to a better understanding of the safety aspects of the proposed hydrogen storage systems. UTRC also participated in the Failure Mode and Effect Analysis of both the chemical- and the adsorbent-based hydrogen storage system during Phase 2 of the Hydrogen Storage Engineering Center of Excellence. UTRC designed a hydrogen storage system with a reversible metal hydride material in a compacted form for light-duty vehicles with a 5.6 kg H2 storage capacity, giving it a 300 miles range. It contains a heat exchanger that enables efficient cooling of the metal hydride material during hydrogen absorption in order to meet the 3.3 minute refueling time target. It has been shown through computation that the kinetics of hydrogen absorption of Ti-catalyzed NaAlH4 was ultimately limiting the rate of hydrogen absorption to 85% of the material capacity in 3.3 minutes. An inverse analysis was performed in order to determine the material property requirements in order for a metal hydride based hydrogen storage system to meet the DOE targets. Work on metal hydride storage systems was halted after the Phase 1 to Phase 2 review due to the lack of metal hydride materials with the required material properties. UTRC contributed to the design of a chemical hydrogen storage system by developing an adsorbent for removing the impurity ammonia from the hydrogen gas, by developing a system to meter the transport of Ammonia Borane (AB) powder to a thermolysis reactor, and by developing a gas-liquid-separator (GLS) for the separation of hydrogen gas from AB slurry in silicone oil. Stripping impurities from hydrogen gas is essential for a long life of the fuel cell system on board of a vehicle. Work on solid transport of AB was halted after the

  2. An analysis of Socio-economic and physical aspects of Slum areas in Ahar city

    Directory of Open Access Journals (Sweden)

    N. Zali

    2013-01-01

    these districts shows that economic, social and physical situation of these districts aren’t in a good condition. Due to poor sanitary condition and free flow of sewages, keeping animals in some residential units, the possibility of infectious diseases and their development to other parts of the city are increasing. 4– ConclusionThe results show that more than 90% of the residents of these neighborhoods immigrated from near villages which in Shileh-boran involves nearly 95% of residents. Furthermore, more than 80% of the immigrations are of familial form and individual immigration is rare in these areas. Considering the occupational status of these immigrants, 45% are workers with the average salary of 100-150 thousands tomans. In addition, results show that Shileh-boran and Nirougah neighborhoods have poorer economic, social and physical conditions. The problems of ownership, poor housing situation, sewage system and access can be regarded as the important problems in these areas.The analysis of the results of the SWOT show that despite the serious threats and fundamental weaknesses such as high percentage of workers in primary jobs, hidden and seasonal unemployment, high dependency ratio, limited role of women in economy of the family, poor intensity, lack of financial facilities in improving neighborhoods, disorder of streets margin space, lack of balance in void and solid spaces, narrow passages, compression of texture, inefficiency of network access, weak and inappropriate studding, facade and form, low educated ratio, migration of majority of residents, bad sanitary condition, high rate of crime between young people, there are some opportunities for empowerment of the residents and improvement in neighborhood. These opportunities can be the inclination of the municipality in improving neighborhood, government's attention to organizing the informal habitat, international aids for empowerment activities, the existence of the sense of public participation of the

  3. Design, Synthesis and Characterization of Polyethylene-Based Macromolecular Architectures by Combining Polyhomologation with Powerful Linking Chemistry

    KAUST Repository

    Alkayal, Nazeeha

    2016-09-05

    Polyhomologation is a powerful method to prepare polyethylene-based materials with controlled molecular weight, topology and composition. This dissertation focuses on the discovery of new synthetic routes to prepare polyethylene-based macromolecular architectures by combining polyhomologation with highly orthogonal and efficient linking reactions such as Diels Alder, copper-catalyzed azide-alkyne cycloaddition (CuAAC), and Glaser. Taking advantage of functionalized polyhomologation initiators, as well as of the efficient coupling chemistry, we were able to synthesize various types of polymethylene (polyethylene)-based materials with complex architectures including linear co/terpolymers, graft terpolymers, and tadpole copolymers. In the first project, a facile synthetic route towards well-defined polymethylene-based co/terpolymers, by combining the anthracene/maleimide Diels–Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: (a) synthesis of α-anthracene-ω-hydroxy-polymethylene by polyhomologation using tri (9 anthracene-methyl propyl ether) borane as the initiator, (b) synthesis of furan-protected-maleimide-terminated poly(ε-caprolactone) or polyethylene glycol and (c) Diels–Alder reaction between anthracene and maleimide-terminated polymers. In the case of triblock terpolymers, the α-anthracene-ω-hydroxy polymethylene was used as a macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by the Diels–Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. The synthetic methodology is general and potentially applicable to a range of polymers. The coupling reaction applied in the second project of this dissertation was copper-catalyzed “click” cycloaddition of azides and alkynes (CuAAC). Novel well-defined polyethylene

  4. Application of molecular calcium compounds in catalysis and hydrogen storage; Anwendung von molekularen Calcium-Verbindungen in der Katalyse und der Wasserstoffspeicherung

    Energy Technology Data Exchange (ETDEWEB)

    Spielmann, Jan

    2010-07-20

    structurally characterized. Depending on the metal and the sterical bulk of the substituent R the decomposition resulted in the clean formation of complexes with either a central dianionic [N(R)-BH-N(R)-BH3]2--unit (R = H, Me, i-Pr), a compound containing a borylamide [N(R)=BH2]- (R = 2,6-(i Pr)-C6H3) or a metal hydride complex. For the observed products mechanisms of their formation have been proposed and experimentally confirmed. In these mechanisms metal hydride species play a key role. The favoured decomposition pathway leads to formation of compounds with the central dianionic [N(R)-BH-N(R)-BH3]2--unit. Additionally a magnesium-catalyzed synthetic route to a bis(amino)borane HB[NH(DIPP)]2 has been developed which can form a novel boramidinate ligand {l_brace}HB[N(2,6-(i-Pr)-C6H3)]2{r_brace}2- by double deprotonation. Furthermore a preparative useful synthetic route to zinc and aluminium hydride complexes based on the use of amidoborane compounds has been described. By using novel bis({beta}-diketiminate) ligands it has been possible to prepare dinuclear magnesium amidoborane complexes. The investigation of their thermal decomposition gave important information on aggregation effects of the complexes during the dehydrogenation. As a decomposition product of a N-substituted, dinuclear magnesium amidoborane complex a tetranuclear magnesium hydride complex has been isolated in low yields. Alternatively such compounds have been prepared in good yields by reaction of a n butylmagnesium precursor with phenylsilane. This synthetic approach allowed also the preparation of an octanuclear magnesium hydride complex with a central paddle-wheel shaped [Mg8H10]-unit. These multinuclear magnesium hydride complexes could be considered as ligand-stabilized forms of MgH2 and could be valuable model systems for investigations on MgxHy-hydrogen storage materials. (orig.)

  5. Complex Hydride Compounds with Enhanced Hydrogen Storage Capacity

    Energy Technology Data Exchange (ETDEWEB)

    Mosher, Daniel A.; Opalka, Susanne M.; Tang, Xia; Laube, Bruce L.; Brown, Ronald J.; Vanderspurt, Thomas H.; Arsenault, Sarah; Wu, Robert; Strickler, Jamie; Anton, Donald L.; Zidan, Ragaiy; Berseth, Polly

    2008-02-18

    between alkaline metal hydrides (AmH), Alkaline earth metal hydrides (AeH2), alane (AlH3), transition metal (Tm) hydrides (TmHz, where z=1-3) and molecular hydrogen (H2). The effort started first with variations of known alanates and subsequently extended the search to unknown compounds. In this stage, the FPM techniques were developed and validated on known alanate materials such as NaAlH4 and Na2LiAlH6. The coupled predictive methodologies were used to survey over 200 proposed phases in six quaternary spaces, formed from various combinations of Na, Li Mg and/or Ti with Al and H. A wide range of alanate compounds was examined using SSP having additions of Ti, Cr, Co, Ni and Fe. A number of compositions and reaction paths were identified having H weight fractions up to 5.6 wt %, but none meeting the 7.5 wt%H reversible goal. Similarly, MSP of alanates produced a number of interesting compounds and general conclusions regarding reaction behavior of mixtures during processing, but no alanate based candidates meeting the 7.5 wt% goal. A novel alanate, LiMg(AlH4)3, was synthesized using SBP that demonstrated a 7.0 wt% capacity with a desorption temperature of 150°C. The deuteride form was synthesized and characterized by the Institute for Energy (IFE) in Norway to determine its crystalline structure for related FPM studies. However, the reaction exhibited exothermicity and therefore was not reversible under acceptable hydrogen gas pressures for on-board recharging. After the extensive studies of alanates, the material class of emphasis was shifted to borohydrides. Through SBP, several ligand-stabilized Mg(BH4)2 complexes were synthesized. The Mg(BH4)2*2NH3 complex was found to change behavior with slightly different synthesis conditions and/or aging. One of the two mechanisms was an amine-borane (NH3BH3) like dissociation reaction which released up to 16 wt %H and more conservatively 9 wt%H when not including H2 released from the NH3. From FPM, the stability of the Mg(BH4

  6. "承载丸"对股骨头坏死大鼠细胞黏附分子基因的影响%Effect of Chengzai pill on the genes of cell adhesion molecules in rats with femoral head necrosis

    Institute of Scientific and Technical Information of China (English)

    黄克勤; 陈燕平; 薛延; 郎风萍; 黄宏; 黄辉; 黄永勋; 张景辰

    2009-01-01

    strength and rigidity, it also reverses the low levels of estrogen. OBJECTIVE: To explore the effect of Chengzai pill on the genes of cell adhesion molecules on bone cells of steroid-induced ostaonecrotic rats, and to understand the role to resume normal blood transport in femoral head of steroid-induced osteonecrosis. DESIGN, TIME AND SETTING: Grouping controlled observation was performed in the Pharmacological Laboratory of Wangjing Hospital of China Academy of Chinese Medical Sciences and laboratory of CapitalBio Corporation between March and August in 2006. MATERIALS: Six male SD rats of 6 months old and weighing (280:1:20) g were used in this study. Chengzai pill was consisted of 22 Chinese medicines, such as Chinese Angelica, Eucommia Bark, Milkvetch Root, Barbary Wolfberry Fruit, Degelatined Deer-hom, Desertliving Cistanche, Eupolyphaga seu Steleophaga, Leech, Danshen Root and Himalayan Teasel Root, which were offered by Beijing Boran Pharmaceutical Co., Ltd. METHODS: The lipopolysaccharide and methylprednisolone were applied to prepare a rat model of steroid-induced osteonecrosis of femoral head. Six rats were divided into model group and Chengzai pill group at random with 3 rats in each group. The rats in the Chengzai pill group were administrated with methylprednisolone for the first time and then 1.5 g/kg Chengzai pill solution, once a day, totally for 6 weeks. The total RNA was extracted from femoral head in all rata 6 weeks later and then gene expression profiling was analyzed. MAIN OUTCOME MEASURES: Gene action pathway of cell adhesion molecules in gene expression profile. RESULTS: Compared with model rats, there were totally 8 downregulated genes of cell adhesion molecules which changed by a minimum of 1.5 folds in cell adhesion molecules pathway of Chengzai pill group, three rats were present with 633 genes (506 down-regulated and 127 up-regulated), 883 genes (640 down-regulated and 243 up-regulated) and 593 genes (408 down-regulated and 185 up

  7. Obituary: Hakki Ogelman (1940-2011)

    Science.gov (United States)

    Orio, Marina

    2011-12-01

    Hakki Boran Ögelman died in Austin, Texas, on September 4, 2011, after battling esophageal cancer for several months. Hakki was born in Ankara, Turkey, on July 8, 1940, and was the son of Salehettin Ögelman, a lawyer, and Vedya Özlem Ögelman, a schoolteacher. He had a sister, older by three years, the late Esen Yerliçi. Soon after his birth, the family moved to Istanbul, where Hakki attended the Robert College from sixth grade and obtained an international baccalaureate at age 17. In the same year, he moved to the United States to further his education at DePaw University in Indiana, where he obtained a Bachelor's Degree in three years and developed a strong passion for physics. He was accepted as a graduate student in physics at Cornell University, where he was fortunate to have such professors as Hans Bethe and Ed Salpeter, among others. Hakki's advisor, Kenneth Greisen, had worked on the Manhattan Project and was a leading expert in the study of charged particles from space and gamma rays from astronomical sources. For his Ph.D., Hakki flew a balloon experiment to measure gamma rays at the highest energy, deriving from the radioactive decay of elementary particles from space. Hakki received his Ph.D. from Cornell in February of 1966. After a postdoctoral year working on gamma ray astrophysics at the University of Sydney in Australia, Hakki accepted a fellowship at NASA's Goddard Space Flight Center where he became an expert on pulsars and wrote a series of articles published by Nature on astronomical sources of gamma rays. At age 30, Hakki declined the offer of a civil service position at NASA and left for Turkey, feeling he wanted to give back to his home country, which had given him a strong education and instilled in him core values. After a period in the military as an officer, he was offered a position at the Middle East Technical University (METU) of Ankara, an English speaking university. After becoming a full professor at METU and spending a

  8. Changes in the composition of aroma components in blue honeysuckle fruit at different developmental stages%蓝果忍冬果实不同发育期香气成分构成及对比分析

    Institute of Scientific and Technical Information of China (English)

    刘朋; 赵毅; 赵利娟; 辛秀兰; 娄爽; 霍俊伟; 秦栋; 马旿晛; 刘煜池

    2016-01-01

    were identified from the two cultivars.During fruit ripening,the total relative content of hydrocarbons rose,and aldehydes decreased first and then increased,while alcohol content displayed an opposite pattern with aldehydes.Butylated hydroxytoluene,(E)-2-hexenal,hexanal,alpha-4-trimethyl,1-butanol,trimethylamine,compd with borane (1:1) and eucalyptol were the major aroma components in ripe fruit.Composition of aroma components differed in different periods of fruit.developments.In ‘Berel' fruit,a total of 20 species of compounds were detected at fruit setting stage,and aldehydes [(E)-2-hexenal and hexanal] and alcohols (3,7-dimethyl-1,6-octadien-3-ol) were prevailing compounds.19 aroma components were identified at color break including alcohols such as 1-butanol,(E)-3-hexen-1-ol,2-ethyl-1-hexanol,3,7-dimethyl-1,6-octadien-3-ol,and 2-hexen-1-ol.A total of 24 aroma components were identified in the mature fruit,and aldehydes such as hexanal and (E)-2-hexenal) and hydrocarbons such as butylated hydroxytoluene were the dominant.In ‘ C-1' fruit,25 aroma components were detected in fruit at setting period,and the main components were aldehydes such as (E)-2-hexenal and hexanal.A total of 25 aroma components,chiefly alcohols (1-Butanol,(Z)-3-hexen-1-ol,3,7-dimethyl-1,6-octadien-5-ol,α-4-trimethyl,α-3-cyclohexene-1-methano) and hydrocarbons (butylated,hydroxytoluene,eucalyptol) were identified at color break stage.In ripe fruit,25 aroma compounds were indentified including chiefly alcohols (3,7-dimethyl-1,6-octadien-3-ol,α-4-trimethyl,α-3-cyclohexene-1-methanol),aldehydes [(E)-2-hexenal and hexanal],hydrocarbons (butylated hydroxytoluene,eucalyptol) and others (1-methoxy-1-propene).There were 11 compounds detected in mature fruit of both cultivars.They were 1-butanol,3-methylpenta-1,4-diene-3-ol,alpha-4-trimethyl,hexanal,(E)-2-hexenal,nonanal,eucalyptol,tridecane,tetradecane,butylatcd hydroxytoluene and 2-(1,1-dimethylethyl)-4-methyl-phenol.The contents of aroma