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Sample records for boranes

  1. 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.

  2. 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.

  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. Three-dimensional aromaticity of polyhedral boranes

    International Nuclear Information System (INIS)

    Aihara, J.

    1978-01-01

    Resonance energies of typical polyhedral boranes with a general formula of B/sub n/H/sub n/ 2- have been calculated by means of a graph-theoretical theory of aromaticity previously reported by Aihara. Huckel-type molecular orbitals employed are those of Kettle and Tomlinson with three-center BBB localized orbitals as basis functions. Most polyhedral boranes investigated are predicted to be aromatic with positive resonance energies, in general agreement with their chemistry. The present resonance energy is fairly proportional to the logarithm of the number of valence structures allowed for the polyhedral borane

  5. Dirac cones in two-dimensional borane

    Science.gov (United States)

    Martinez-Canales, Miguel; Galeev, Timur R.; Boldyrev, Alexander I.; Pickard, Chris J.

    2017-11-01

    We introduce two-dimensional borane, a single-layered material of BH stoichiometry, with promising electronic properties. We show that, according to density functional theory calculations, two-dimensional borane is semimetallic, with two symmetry-related Dirac cones meeting right at the Fermi energy Ef. The curvature of the cones is lower than in graphene, thus closer to the ideal linear dispersion. Its structure, formed by a puckered trigonal boron network with hydrogen atoms connected to each boron atom, can be understood as distorted, hydrogenated borophene [Mannix et al., Science 350, 1513 (2015), 10.1126/science.aad1080]. Chemical bonding analysis reveals the boron layer in the network being bound by delocalized four-center two-electron σ bonds. Finally, we suggest high pressure could be a feasible route to synthesize two-dimensional borane.

  6. Base metal dehydrogenation of amine-boranes

    Science.gov (United States)

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

    2009-06-09

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

  7. A new luminescent montmorillonite/borane nanocomposite

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

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

  8. Toward (car)borane-based molecular magnets

    Czech Academy of Sciences Publication Activity Database

    Oliva, J. M.; Alcoba, D. R.; Ona, O. B.; Torre, A.; Lain, L.; Michl, Josef

    2015-01-01

    Roč. 134, č. 2 (2015), 9/1-9/8 ISSN 1432-881X Institutional support: RVO:61388963 Keywords : car boranes * spin population * Heisenberg spin Hamiltonian * Heisenberg coupling constatns Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.806, year: 2015

  9. Catalysts for Dehydrogenation of ammonia boranes

    Energy Technology Data Exchange (ETDEWEB)

    Heinekey, Dennis M. [Univ. of Washington, Seattle, WA (United States)

    2009-10-31

    Several effective homogeneous catalysts for the dehydrogenation of amine boranes have been developed. The best catalyst uses an iridium complex, and is capable of dehydrogenating H3NBH3 (AB) and CH3NH2BH3 (MeAB) at comparable rates. Thermodynamic measurements using this catalyst demonstrate that the dehydrogenation of AB and MeAB is substantially exothermic, which has important implications for regeneration.

  10. 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

  11. Development of High-Performance Ammonia Borane Based Rocket Propellants

    Data.gov (United States)

    National Aeronautics and Space Administration — Ammonia borane based fuels for use in hybrid rocket systems have the potential to be high performing while at the same time mitigating many of the issues associated...

  12. Towards chiral diamines as chiral catalytic precursors for the borane ...

    Indian Academy of Sciences (India)

    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% ) ...

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

    Science.gov (United States)

    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.

  14. 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.

  15. Synergistic effects in ambiphilic phosphino-borane catalysts for the hydroboration of CO2.

    Science.gov (United States)

    Tlili, Anis; Voituriez, Arnaud; Marinetti, Angela; Thuéry, Pierre; Cantat, Thibault

    2016-06-18

    The benefit of combining both a Lewis acid and a Lewis base in a catalytic system has been established for the hydroboration of CO2, using ferrocene-based phosphine, borane and phosphino-borane derivatives.

  16. 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.

  17. 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.)

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

    Science.gov (United States)

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

    2012-06-05

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

  19. Genetic parameters for weaning weight of Kenyan Boran cattle ...

    African Journals Online (AJOL)

    Genetic parameters were estimated for weaning weight (WW) in Kenya Boran cattle using animal models that assumed non-zero direct-maternal genetic covariance. In addition to the direct and maternal genetic effects, maternal permanent environmental and sire by herd-year interaction effects were tested. Two datasets ...

  20. Asymmetric borane reduction using mixtures of homochiral amino alcohol ligands

    NARCIS (Netherlands)

    Kaptein, Bernard; Elsenberg, Henk; Minnaard, Adriaan J.; Broxterman, Quirinus B.; Hulshof, Lumbertus A.; Vries, Ton R.

    1999-01-01

    The asymmetric borane reduction of acetophenone is investigated using mixtures of homochiral β-amino alcohol ligands. With stoichiometric amounts of a mixture of two- or three-amino alcohols, the e.e. remains at the level of the best amino alcohol for a wide composition range. A small but

  1. Compositions containing borane or carborane cage compounds and related applications

    Science.gov (United States)

    Bowen, III, Daniel E; Eastwood, Eric A

    2013-05-28

    Compositions comprising a polymer-containing matrix and a filler comprising a cage compound selected from 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. Methods of making and applications for using such compositions are also disclosed.

  2. Towards chiral diamines as chiral catalytic precursors for the borane ...

    Indian Academy of Sciences (India)

    Administrator

    anilinomethylpiperidine (2) have been employed as chiral catalytic sources in the borane-mediated asymmetric reduction of prochiral ketones ..... 7⋅86 min (S) and 8.53 min (R)]. 2.7c (S)-2-Bromo-1-(4-bromophenyl)ethanol [(S)– ... of (a) compound 8 and (b) compound 15-TFA salt (Hydrogen atoms were omitted for clarity).

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

    African Journals Online (AJOL)

    Tuoyo Aghomotsegin

    2016-08-17

    Aug 17, 2016 ... observed and IOI was shorter (P<0.001) for cows with two follicular waves per estrous cycle (n=27; 19.5. ± 0.9 days) than ... Key words: Boran, estrous cycle length, follicular dynamics, follicular waves, dominant follicle. INTRODUCTION ..... advanced reproductive biotechnologies (especially embryo transfer ...

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

    Science.gov (United States)

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

    2015-11-20

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

  5. Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

    Directory of Open Access Journals (Sweden)

    Tetsuo Umegaki

    2015-07-01

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

  6. Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane.

    Science.gov (United States)

    Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

    2015-07-21

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

  7. Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

    OpenAIRE

    Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

    2015-01-01

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

  8. 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.

  9. 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.

  10. Regeneration of ammonia borane from spent fuel materials.

    Science.gov (United States)

    Summerscales, Owen T; Gordon, John C

    2013-07-28

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

  11. Group 4 metallocene catalysed full dehydrogenation of hydrazine borane.

    Science.gov (United States)

    Thomas, Johannes; Klahn, Marcus; Spannenberg, Anke; Beweries, Torsten

    2013-10-01

    A study of the full dehydrogenation of hydrazine borane (H2N-NH2·BH3) to give H2 and N2 as gaseous products catalysed by a variety of group 4 metallocene alkyne complexes of the type CpM(L)(η(2)-Me3SiC2SiMe3) (Cp' = substituted or unsubstituted η(5)-cyclopentadienyl; M = Ti, no L; M = Zr, L = pyridine) and group 4 metallocene hydrides is presented. Volumetric data show that the amount of hydrogen released is strongly dependent on both, the metal and the cyclopentadienyl ligand.

  12. 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 H 2 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

  13. Olefin-borane "van der Waals complexes": intermediates in frustrated Lewis pair addition reactions.

    Science.gov (United States)

    Zhao, Xiaoxi; Stephan, Douglas W

    2011-08-17

    The nature of the borane-olefin interactions that take place prior to frustrated Lewis pair addition reactions has been probed employing a Lewis acidic borane tethered to a vinyl group through an alkyl chain. (1)H{(19)F} HOESY spectral data obtained at -50 °C demonstrated the spatial proximity of the boryl and vinyl groups and computational data support the initial formation of a van der Waals borane-olefin complex. Such species serve as intermediates undergoing facile addition reactions with phosphine bases to afford cyclic zwitterionic products.

  14. Gas desorption properties of ammonia borane and metal hydride composites

    International Nuclear Information System (INIS)

    Matin, M.R.

    2009-01-01

    'Full text': Ammonia borane (NH 3 BH 3 ) has been of great interest owing to its ideal combination of low molecular weight and high H 2 storage capacity of 19.6 mass %, which exceeds the current capacity of gasoline. DOE's year 2015 targets involve gravimetric as well as volumetric energy densities. In this work, we have investigated thermal decomposition of ammonia borane and calcium hydride composites at different molar ratio. The samples were prepared by planetary ball milling under hydrogen gas atmosphere pressure of 1Mpa at room temperature for 2, and 10 hours. The gas desorption properties were examined by thermal desorption mass spectroscopy (TDMS). The identification of phases was carried out by X-ray diffraction. The results obtain were shown in fig (a),(b),and (c). Hydrogen desorption properties were observed at all molar ratios, but the desorption temperature is significantly lower at around 70 o C at molar ratio 1:1 as shown in fig (c), and unwanted gas (ammonia) emissions were remarkably suppressed by mixing with the calcium hydride. (author)

  15. Efficient regeneration of partially spent ammonia borane fuel

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  16. 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...

  17. 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.

  18. Hydrolysis of ammonia borane and metal amidoboranes: A comparative study

    Science.gov (United States)

    Banu, Tahamida; Debnath, Tanay; Ash, Tamalika; Das, Abhijit K.

    2015-11-01

    A gas phase mechanistic investigation has been carried out theoretically to explore the hydrolysis pathway of ammonia borane (NH3BH3) and metal amidoboranes (MNH2BH3, M = Li,Na). The Solvation Model based on Density (SMD) has been employed to show the effect of bulk water on the reaction mechanism. Gibbs free energy of solvation has also been computed to evaluate the stabilization of the participating systems in water medium which directly affects the barrier heights in the potential energy surface of hydrolysis reaction. To validate the experimentally observed kinetics studies, we have carried out transition state theory calculations on these hydrolysis reactions. Our result shows that the hydrolysis of both the metal amidoboranes exhibits greatly improved kinetics over the neat NH3BH3 hydrolysis which corroborates well with the experimental observation. Between the two amidoboranes, hydrolysis of LiNH2BH3 is found to be kinetically favored over that of NaNH2BH3, making it a better candidate for releasing molecular hydrogen.

  19. Redução de amidas por boranos Reduction of amides by boranes

    Directory of Open Access Journals (Sweden)

    Antônio Flávio de Carvalho Alcântara

    2002-05-01

    Full Text Available Despite the fact that boranes are frequently used in amide reductions, the reaction mechanisms of the involved are note well known. This work presents the results of a bibliographic search on probable amide reduction mechanisms and an analysis of the existing literature. Steric and electronic effects were considered in light of reactivity since it could be concluded that the formation of intermediates and products depends mainly on the substitution patterns of both the boron and nitrogen atoms. Otherwise, results described in the literature for the reactions of boranes, sodium borohydride, lithium aluminum hydride, alkylboranes or haloboranes with others functional groups such as carboxylic acids, esters, ketones and alkenes were analysed with the aim to obtain something about the N-substituted amide reactions employing boranes.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    Ammonia borane is a promising hydrogen storage material that liberates hydrogen by thermolysis at moderate temperatures, but it also presents major limitations for practical applications including a long induction time before the initiation of hydrogen release and a difficult regeneration. Previous works have demonstrated that by dissolution of ammonia borane into several ionic liquids, and particularly in 1-butyl-3-methylimidazolium chloride bmimCl, the induction period at the beginning of the thermolysis is eliminated, but some problems persist, including foaming and the formation of a residue after thermolysis that is insoluble in the ionic liquid. In this work, the release of hydrogen from ammonia borane dissolved in different ionic liquids has been analyzed, measuring the kinetics of hydrogen release, visually following the evolution of the sample during the process using pressure glass tube reactors, and analyzing the residue by spectroscopic techniques. While dissolutions of ammonia borane in most ionic liquids analyzed show similar properties as dissolutions in bmimCl, using ionic liquids with bis(trifluoromethylsulfanyl)imide Tf 2 N anion the foaming problem is reduced, and in some cases the residue remains dissolved in the ionic liquid, while with ionic liquids with choline anion higher hydrogen yields are achieved that indicate that the decomposition of ammonia borane proceeds through a different path. - Highlights: • Hydrogen release from ammonia borane dissolved in 13 ionic liquids has been studied. • Induction time is shortened and hydrogen release rate is accelerated in all cases. • The best results are obtained using ionic liquids with Tf 2 N anion. • Ch cation ionic liquids enable higher H 2 yield, but cyclotriborazane is produced.

  1. Synthesis and Application of New Chiral Ligands for the Asymmetric Borane Reduction of Prochiral Ketones

    OpenAIRE

    Hulst, Ron; Heres, Hero; Peper, Nathalie C.M.W.; Kellogg, Richard M.

    1996-01-01

    Two chiral nonracemic γ-amino alcohols, ephedrine thiol and the corresponding (thio)-phosphoramidates and (thio)-phosphinamides have been examined as catalysts for the reduction of propiophenone by various boranes. Up to 95% e.e. can be obtained with the phosphorus derivatives.

  2. Synthesis and Application of New Chiral Ligands for the Asymmetric Borane Reduction of Prochiral Ketones

    NARCIS (Netherlands)

    Hulst, Ron; Heres, Hero; Peper, Nathalie C.M.W.; Kellogg, Richard M.

    Two chiral nonracemic γ-amino alcohols, ephedrine thiol and the corresponding (thio)-phosphoramidates and (thio)-phosphinamides have been examined as catalysts for the reduction of propiophenone by various boranes. Up to 95% e.e. can be obtained with the phosphorus derivatives.

  3. Transition-metal derivatives of nido-boranes and some related species

    International Nuclear Information System (INIS)

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

    1982-01-01

    This paper reviews the wide variety of metalloboranes that have been made by the reactions of transitional-metal compounds with nido-boranes or their anions. The authors concentrate on preparative and structural aspects and discuss presumed reaction mechanisms or postulated modes of bonding. Monoboron, diboron, triboron, tetraboron, pentaboron, hexaboron, nonaboron, decaboron, octadecaboron, and icosaboron compounds are discussed

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

    Science.gov (United States)

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

    2018-01-24

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

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

    Science.gov (United States)

    1980-06-15

    CH) Nil L CH)-C]1, Cllj. 0«IIi. The product is boiled with acidified water (acidified with H2S04 ) to remove any amine-borane adduct which... leaching said pyrolysis product with methylenc chloride, and extracting the re- sultant solid residue with water to recover an aqueous solution

  6. 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.

  7. An experimental study of ammonia borane based hydrogen storage systems

    Science.gov (United States)

    Deshpande, Kedaresh A.

    2011-12-01

    Hydrogen is a promising fuel for the future, capable of meeting the demands of energy storage and low pollutant emission. Chemical hydrides are potential candidates for chemical hydrogen storage, especially for automobile applications. Ammonia borane (AB) is a chemical hydride being investigated widely for its potential to realize the hydrogen economy. In this work, the yield of hydrogen obtained during neat AB thermolysis was quantified using two reactor systems. First, an oil bath heated glass reactor system was used with AB batches of 0.13 gram (+/- 0.001 gram). The rates of hydrogen generation were measured. Based on these experimental data, an electrically heated steel reactor system was designed and constructed to handle up to 2 grams of AB per batch. A majority of components were made of stainless-steel. The system consisted of an AB reservoir and feeder, a heated reactor, a gas processing unit and a system control and monitoring unit. An electronic data acquisition system was used to record experimental data. The performance of the steel reactor system was evaluated experimentally through batch reactions of 30 minutes each, for reaction temperatures in the range from 373 K to 430 K. The experimental data showed exothermic decomposition of AB accompanied by rapid generation of hydrogen during the initial period of the reaction. 90% of the hydrogen was generated during the initial 120 seconds after addition of AB to the reactor. At 430 K, the reaction produced 12 wt.% of hydrogen. The heat diffusion in the reactor system and the process of exothermic decomposition of AB were coupled in a two-dimensional model. Neat AB thermolysis was modeled as a global first order reactions based on Arrhenius theory. The values of equation constants were derived from curve fit of experimental data. The pre-exponential constant and the activation energy were estimated to be 4 s-1 (+/- 0.4 s-1) and 13000 J mol -1 s-1 (+/- 1050 J mol-1 s -1) respectively. The model was solved

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

    Science.gov (United States)

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

    2017-12-01

    Breed, age, coat colour, month and temperature humidity index (THI) influence on body weight (W), body condition score (BCS), thermophysiological variables (rectal temperature (Tr), skin temperature (Tsk)) and hair length was studied in Nguni ( n = 19) and Boran ( n = 16). As a result of this study, breed influenced W, BCS and Tsk on the neck and belly ( P < 0.05). The BCS and W of Nguni cows were higher than the Boran cows. Hair length of both breeds increased from February to August. The THI influenced thermophysiological variables ( P < 0.05). Increased Tr for both breeds was recorded in February and April, respectively ( P < 0.05). Month influenced Tsk and June recorded lower values ( P < 0.05). Younger cows (3-8 years) had lower weight and high Tr and Tsk ( P < 0.05). Nguni cows had high neck and thurl temperatures in June while Boran cows had the highest in August ( P < 0.05). Red, dun and white-black Boran cows had increased BCS. Nguni cows with red, fawn and white cows had high BCS. Fawn-coloured Nguni cows and white-brown Boran cows had the more weight than cows with other colours compared in the study. White-red Nguni and Boran cows recorded the highest Tr. For Nguni cows, neck and belly temperatures were significantly ( P < 0.001) correlated to thurl temperature. Boran cows had significant ( P < 0.001) correlations for THI and neck, belly and thurl temperatures. The current study found that Nguni cows were more adapted to the prevailing bioclimatic changes. However, Boran cows have the potential of performing well under heat stress conditions over time.

  9. Exchange of deuterium for hydrogen during the reaction of dimethylamine-N-d-borane with halogenating agents

    International Nuclear Information System (INIS)

    Myers, W.H.; Ryschkewitsch, G.E.

    1978-01-01

    During the reaction of dimethylamine-N-d-borane with chlorine considerable exchange of hydrogen for deuterium on nitrogen occurred. An extensive investigation of the halogenation reactions of dimethylamine-N-d-borane indicated that the exchange process occurred via the loss of deuterium chloride from a molecule activated as a result of halogenation. The extent of substitution of hydrogen for deuterium in the products of these reactions was estimated by comparing NMR and IR spectra

  10. 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.

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

    Science.gov (United States)

    Hudnall, Todd W; Gabbaï, François P

    2007-10-03

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

  12. 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.

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

    KAUST Repository

    Berke, Heinz

    2017-05-11

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

  14. Hydrogen bonding-mediated dehydrogenation in the ammonia borane combined graphene oxide systems

    Science.gov (United States)

    Kuang, Anlong; Liu, Taijuan; Kuang, Minquan; Yang, Ruifeng; Huang, Rui; Wang, Guangzhao; Yuan, Hongkuan; Chen, Hong; Yang, Xiaolan

    2018-03-01

    The dehydrogenation of ammonia borane (AB) adsorbed on three different graphene oxide (GO) sheets is investigated within the ab initio density functional theory. The energy barriers to direct combination the hydrogens of hydroxyl groups and the hydridic hydrogens of AB to release H2 are relatively high, indicating that the process is energetically unfavorable. Our theoretical study demonstrates that the dehydrogenation mechanism of the AB-GO systems has undergone two critical steps, first, there is the formation of the hydrogen bond (O-H-O) between two hydroxyl groups, and then, the hydrogen bond further react with the hydridic hydrogens of AB to release H2 with low reaction barriers.

  15. 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.

  16. 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.

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

    Science.gov (United States)

    Lawson, James R; Melen, Rebecca L

    2017-08-07

    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(C 6 F 5 ) 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(C 6 F 5 ) 3 is derived from the electronic effects of its three C 6 F 5 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(C 6 F 5 ) 3 in borylation reactions while also focusing on current advances in novel borane and borocation usage that eclipses that of the stalwart B(C 6 F 5 ) 3 .

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

    Science.gov (United States)

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

    2012-05-01

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

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

    Directory of Open Access Journals (Sweden)

    Qi Wang

    2018-04-01

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

  20. Can an amine be a stronger acid than a carboxylic acid? The surprisingly high acidity of amine-borane complexes.

    Science.gov (United States)

    Martín-Sómer, Ana; Lamsabhi, Al Mokhtar; Yáñez, Manuel; Dávalos, Juan Z; González, Javier; Ramos, Rocío; Guillemin, Jean-Claude

    2012-12-03

    The gas-phase acidity of a series of amine-borane complexes has been investigated through the use of electrospray mass spectrometry (ESI-MS), with the application of the extended Cooks kinetic method, and high-level G4 ab initio calculations. The most significant finding is that typical nitrogen bases, such as aniline, react with BH(3) to give amine-borane complexes, which, in the gas phase, have acidities as high as those of either phosphoric, oxalic, or salicylic acid; their acidity is higher than many carboxylic acids, such as formic, acetic, and propanoic acid. Indeed the complexation of different amines with BH(3) leads to a substantial increase (from 167 to 195 kJ mol(-1)) in the intrinsic acidity of the system; in terms of ionization constants, this increase implies an increase as large as fifteen orders of magnitude. Interestingly, this increase in acidity is almost twice as large as that observed for the corresponding phosphine-borane analogues. The agreement between the experimental and the G4-based calculated values is excellent. The analysis of the electron-density rearrangements of the amine and the borane moieties indicates that the dative bond is significantly stronger in the N-deprotonated anion than in the corresponding neutral amine-borane complex, because the deprotonated amine is a much better electron donor than the neutral amine. On the top of that, the newly created lone pair on the nitrogen atom in the deprotonated species, conjugates with the BN bonding pair. The dispersion of the extra electron density into the BH(3) group also contributes to the increased stability of the deprotonated species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Czech Academy of Sciences Publication Activity Database

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

    2013-01-01

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

  2. 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.

  3. Highly Sensitive NH3 Detection Based on Organic Field Effect Transistors with Tris(pentafluorophenyl)Borane as Receptor

    OpenAIRE

    Huang, Weiguo; Besar, Kalpana; LeCover, Rachel; Rule, Ana María; Breysse, Patrick N.; Katz, Howard E.

    2012-01-01

    We have increased organic field-effect transistor (OFET) NH3 response using tris-(pentafluorophenyl)borane (TPFB) as receptor. OFETs with this additive detect concentrations of 450 ppb v/v, with a limit of detection of 350 ppb, the highest sensitivity yet from semiconductor films; in comparison, when triphenylmethane (TPM) and triphenylborane (TFB) were used as an additive, no obvious improvement of sensitivity was observed. These OFETs also show considerable selectivity with respect to commo...

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  5. Solid-state NMR as a spectroscopic tool for characterizing phosphane-borane frustrated lewis pairs.

    Science.gov (United States)

    Wiegand, Thomas; Eckert, Hellmut; Grimme, Stefan

    2013-01-01

    Frustrated Lewis pair (FLP) chemistry has provided a new strategy for small molecule binding and/or catalytic activation. It is based on the cooperative reaction behavior of Lewis acid and Lewis base centers that are in close proximity to each other (e.g., within the same molecule) but cannot form a direct bond because of geometrical constraints. The most prominent FLPs are based on intramolecular phosphane-borane adducts, whose catalytic properties can be tailored over wide ranges of reactivity and selectivity. For the structural and chemical design of such systems, a fundamental understanding needs to be developed on how structure, dynamics and covalent interactions between the Lewis centers influence the reactivity profile. Advanced solid-state nuclear magnetic resonance (NMR) spectroscopic techniques afford new opportunities for addressing this challenge. Following a general introduction into the fundamentals of NMR spectroscopy, this review discusses the different types of internal interactions - magnetic shielding, nuclear electric quadrupolar coupling, indirect spin-spin interactions, and "through-space" dipole-dipole couplings - influencing NMR spectra in the solid state. As discussed in detail, each type of interaction bears specific informational content with regard to structural issues in FLP chemistry. One of the most attractive features of solid-state NMR is the possibility of tailoring the effective Hamiltonian by manipulations in either physical space or spin space. Using such "decoupling" or "recoupling" techniques certain types of interactions can be selectively turned off for spectral simplification or turned on for selective evaluation. The present review summarizes the most important selective averaging techniques that have found applications in the characterization of FLPs. In a second step the interaction parameters need to be connected with structure and bonding information. As illustrated in this chapter, ab initio calculations using density

  6. 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.

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

    International Nuclear Information System (INIS)

    Mutz, M.; Eastwood, Eric; Lee, Mark E.; Bowen, Daniel E.; Dadmun, M. D.

    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 A 2 . A 2 obtained from these measurements was then used to calculate χ, the solute–solvent interaction parameter, and the Hildebrand solubility parameter, δ, 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 χ 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, χ, and δ. For instance, lower values of χ correspond to a smaller radius of gyration (R g ). A list of suitable solvents based on δ is also presented.

  8. 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.

  9. 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.

  10. Interleaved mesoporous copper for the anode catalysis in direct ammonium borane fuel cells.

    Science.gov (United States)

    Auxilia, Francis M; Tanabe, Toyokazu; Ishihara, Shinsuke; Saravanan, Govindachetty; Ramesh, Gubbala V; Matsumoto, Futoshi; Ya, Xu; Ariga, Katsuhiko; Dakshanamoorthy, Arivuoli; Abe, Hideki

    2014-06-01

    Mesoporous materials with tailored microstructures are of increasing importance in practical applications particularly for energy generation and/or storage. Here we report a mesoporous copper material (MS-Cu) can be prepared in a hierarchical microstructure and exhibit high catalytic performance for the half-cell reaction of direct ammonium borane (NH3BH3) fuel cells (DABFs). Hierarchical copper oxide (CuO) nanoplates (CuO Npls) were first synthesized in a hydrothermal condition. CuO Npls were then reduced at room temperature using water solution of sodium borohydride (NaBH4) to yield the desired mesoporous copper material, MS-Cu, consisting of interleaved nanoplates with a high density of mesopores. The surface of MS-Cu comprised high-index facets, whereas a macroporous copper material (MC-Cu), which was prepared from CuO Npls at elevated temperatures in a hydrogen stream, was surrounded by low-index facets with a low density of active sites. MS-Cu exhibited a lower onset potential and improved durability for the electro-oxidation of NH3BH3 than MC-Cu or copper particles because of the catalytically active mesopores on the interleaved nanoplates.

  11. Paramagnetic titanium(III) and zirconium(III) metallocene complexes as precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes.

    Science.gov (United States)

    Helten, Holger; Dutta, Barnali; Vance, James R; Sloan, Matthew E; Haddow, Mairi F; Sproules, Stephen; Collison, David; Whittell, George R; Lloyd-Jones, Guy C; Manners, Ian

    2013-01-02

    Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes, such as Me(2) NH⋅BH(3). Such Ti(III) -amidoborane complexes are generated in [Cp(2)Ti]-catalyzed amine-borane dehydrocoupling reactions, for which diamagnetic M(II) and M(IV) species have been previously postulated as precatalysts and intermediates. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Catalytic Hydrogenation of Carbon Dioxide with Ammonia-Borane by Pincer-type Phosphorus Compound: A Theoretical Prediction.

    Science.gov (United States)

    Zeng, Guixiang; Maeda, Satoshi; Taketsugu, Tetsuya; Sakaki, Shigeyoshi

    2016-10-01

    Theoretically designed pincer-type phosphorus compound is found to be active for the hydrogenation of carbon dioxide (CO 2 ) with ammonia-borane. DFT, ONIOM(CCSD(T):MP2), and CCSD(T) computational results demonstrated that the reaction occurs through the phosphorus-ligand cooperative catalysis function, which provides an unprecedented protocol for metal-free CO 2 conversion. The phosphorus compounds with the NNN ligand are more active than those with the ONO ligand. The conjugate and planar ligand considerably improves the efficiency of the catalyst.

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

    Science.gov (United States)

    Nosheen, Shaneela

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

  14. 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.

  15. 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.

  16. Selective C-O Bond Cleavage of Sugars with Hydrosilanes Catalyzed by Piers' Borane Generated In Situ.

    Science.gov (United States)

    Zhang, Jianbo; Park, Sehoon; Chang, Sukbok

    2017-10-23

    Described herein is the selective reduction of sugars with hydrosilanes catalyzed by using Piers' borane [(C 6 F 5 ) 2 BH] generated in situ. The hydrosilylative C-O bond cleavage of silyl-protected mono- and disaccharides in the presence of a (C 6 F 5 ) 2 BH catalyst, generated in situ from (C 6 F 5 ) 2 BOH, takes place with excellent chemo- and regioselectivities to provide a range of polyols. A study of the substituent effects of sugars on the catalytic activity and selectivity revealed that the steric environment around the anomeric carbon (C1) is crucial. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Management options to accelerate growth rate and reduce age at first calving in Friesian-Boran crossbred heifers.

    Science.gov (United States)

    Gojjam, Yohannes; Tolera, Adugna; Mesfin, Rehrahie

    2011-02-01

    Two experiments were conducted simultaneously to evaluate the effects of different concentrates to roughage ratios on growth performance and attainment of puberty in Friesian-Boran crossbred heifers. Weaned 50% Friesian-Boran crossbred female calves were used in both experiments with 25 and 20 calves in experiments I and II, respectively. In experiment I, the calves were offered diets with concentrate to roughage ratios of 50:50 (treatment 1) or 30:70 (treatment 2). In experiment II, the calves grazed for 8 h a day and supplemented with 2 kg hay and 1 kg concentrate per head per day (treatment 1) or only 2 kg hay per head per day (treatment 2). The concentrate mixture was composed of 34% wheat bran, 31% wheat middling, 31% noug cake, 3% limestone, and 1% salt. In experiment I, heifers fed a ration with 50% concentrate and 50% roughage had higher (P daily body weight gain (0.532 kg) and attained puberty at 221 kg (65% of the mature body weight) in 15 months, while heifers fed a diet with 30% concentrate and 70% roughage gained 0.434 kg/day and reached puberty at 247 kg (70% of the mature body weight), about 3 months later. Heifers in treatments 1 and 2 of experiment II reached puberty 5 and 12 months later, respectively, than those in experiment I. In experiment II, heifers given 1 kg of concentrate supplement had higher (P daily body weight gain (0.346 kg) than those given only 2 kg hay in addition to grazing (0.278 kg). Growth rate of crossbred heifers was enhanced and age at puberty was reduced by changing the rearing management from outdoor to indoor and with increasing level of concentrate in the ration. This helps to bring the dairy heifer into production earlier and enhance to the overall productivity of the dairy industry.

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

    Czech Academy of Sciences Publication Activity Database

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

    2016-01-01

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

  19. Borane Polyhedra as Building Blocks for Unknown but Potentially Isolatable New Molecules – Extensions based on Computations of the Known B18H22 Isomers

    Czech Academy of Sciences Publication Activity Database

    Oliva, J. M.; Rué, J.; Hnyk, Drahomír; Kennedy, John David; Rosenfeld, V.R.

    2013-01-01

    Roč. 86, č. 4 (2013), s. 485-494 ISSN 0011-1643 R&D Projects: GA ČR GAP208/10/2269; GA ČR(CZ) GAP207/11/0705 Institutional support: RVO:61388980 Keywords : boranes * bond * B18H22 * quantum chemistry * mathematical chemistry Subject RIV: CA - Inorganic Chemistry Impact factor: 0.556, year: 2013

  20. Pairing Heterocyclic Cations with closo-Icosahedral Borane and Carborane Anions. I. Benchtop Aqueous Synthesis of Binary Triazolium and Imidazolium Salts with Limited (Preprint)

    Science.gov (United States)

    2009-03-03

    Spectometry Analyses. High resolution mass specta (HRMS) analyses were conducted at UCR Mass Spectrometry Facility, Department of Chemistry, University of...currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1. REPORT DATE (DD-MM-YYYY) 03-03-2009 2. REPORT TYPE...Journal Article 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Pairing Heterocyclic Cations with closo-Icosahedral Borane

  1. P-Tether-Mediated, Iterative SN2'-Cuprate Alkylation Strategy to Skipped Polyol Stereotetrads: Utility of an Oxidative "Function Switch" with Phosphite-Borane Tethers.

    Science.gov (United States)

    Markley, Jana L; Hanson, Paul R

    2017-05-19

    The development of a P-tether-mediated, iterative S N 2'-cuprate alkylation protocol for the formation of 1,3-skipped polyol stereotetrads is reported. This two-directional synthetic strategy builds molecular complexity from simple, readily prepared C 2 -symmetric dienediols and unites the chemistry of both temporary phosphite-borane tethers and temporary phosphate tethers-through an oxidative "function switch" of the P-tether itself-to generate intermediates that were previously inaccessible via either method alone.

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

    International Nuclear Information System (INIS)

    Zahmakiran, Mehmet

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-30

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

  4. Lewis Acid Promoted Hydrogenation of CO2and HCOO-by Amine Boranes: Mechanistic Insight from a Computational Approach.

    Science.gov (United States)

    Roy, Lisa; Ghosh, Boyli; Paul, Ankan

    2017-07-13

    We employ quantum chemical calculations to study the hydrogenation of carbon dioxide by amine boranes, NMe 3 BH 3 ( Me3 AB) and NH 3 BH 3 (AB) weakly bonded to a bulkier Lewis acid, Al(C 6 F 5 ) 3 (LA). Additionally, computations have also been conducted to elucidate the mechanism of hydrogenation of carbon dioxide by Me3 AB while captured between one Lewis base (P(o-tol 3 ), LB) and two Lewis acids, Al(C 6 F 5 ) 3 . In agreement with the experiments, our computational study predicts that hydride transfer to conjugated HCO 2 - , generated in the reaction of Me3 AB-LA with CO 2 , is not feasible. This is in contrast to the potential hydrogenation of bound HCO 2 H, developed in the reduction of CO 2 with AB-LA, to further reduced species like H 2 C(OH) 2 . However, the FLP-trapped CO 2 effortlessly undergoes three hydride (H - ) transfers from Me3 AB to produce a CH 3 O - derivative. DFT calculations reveal that the preference for a H - abstraction by an intrinsically anionic formate moiety is specifically dependent on the electrophilicity of the 2 e - reduced carbon center, which in particular is controlled by the electron-withdrawing capability of the associated substituents on the oxygen. These theoretical predictions are justified by frontier molecular orbitals and molecular electrostatic potential plots. The global electrophicility index, which is a balance of electron affinity and hardness, reveals that the electrophilicity of the formate species undergoing hydrogenation is twice the electrophilicity of the ones where hydrogenation is not feasible. The computed activation energies at M06-2X/6-31++G(d,p) closely predict the observed reactivity. In addition, the possibility of a dissociative channel of the frustrated Lewis pair trapped CO 2 system has been ruled out on the basis of predominantly high endergonicity. Knowledge of the underlying principle of these reactions would be helpful in recruiting appropriate Lewis acids/amine boranes for effective reduction

  5. Synthesis and characterization of branched fcc/hcp ruthenium nanostructures and their catalytic activity in ammonia borane hydrolysis

    KAUST Repository

    AlYami, Noktan

    2018-01-30

    Several systems have shown the ability to stabilize uncommon crystal structures during the synthesis of metallic nanoparticles. By tailoring the nanoparticle crystal structure, the physical and chemical properties of the particles can also be controlled. Herein, we first synthesized branched nanoparticles of mixed hcp/fcc ruthenium, which were formed using tungsten carbonyl [W(CO)6] as both a reducing agent and a source of carbon monoxide. The branched particles were formed from multiple particulates off a central core. High-resolution transmission electron microscopy (HRTEM) clearly showed that the branched structures consisted of aligned hcp crystal domains, a mixture of fcc and hcp crystal domains with several defects and misalignments, and particles that contained multiple cores and branches. Branched particles were also formed with molybdenum carbonyl [Mo(CO)6], and faceted particles of hcp and fcc particles were formed with Re2(CO)10 as a carbon monoxide source. Without metal carbonyls, small particles of spherical hcp ruthenium were produced, and their size could be controlled by the selection of the precursor. The ruthenium nanoparticles were tested for ammonia borane hydrolysis; the branched nanoparticles were more reactive for catalytic hydrogen evolution than the faceted hcp/fcc nanoparticles or the spherical hcp nanoparticles. This work showcases the potential of crystal phase engineering of transition metal nanoparticles by different carbon monoxide precursors for tailoring their catalytic reactivity.

  6. Kinetics study of solid ammonia borane hydrogen release--modeling and experimental validation for chemical hydrogen storage.

    Science.gov (United States)

    Choi, Young Joon; Rönnebro, Ewa C E; Rassat, Scot; Karkamkar, Abhi; Maupin, Gary; Holladay, Jamie; Simmons, Kevin; Brooks, Kriston

    2014-05-07

    Ammonia borane (AB), NH3BH3, is a promising material for chemical hydrogen storage with 19.6 wt% gravimetric hydrogen capacity of which maximum 16.2 wt% hydrogen can be released via an exothermic thermal decomposition below 200 °C. We have investigated the kinetics of hydrogen release from AB and from an AB-methyl cellulose (AB/MC) composite at temperatures of 160-300 °C using both experiments and modeling. The hydrogen release rate at 300 °C is twice as fast as at 160 °C. The purpose of our study was to show safe hydrogen release without thermal runaway effects and to validate system model kinetics. AB/MC released hydrogen at ∼20 °C lower than neat AB and at a faster release rate in that temperature range. Based on the experimental results, the kinetics equations were revised to better represent the growth and nucleation process during decomposition of AB. We explored two different reactor concepts; auger and fixed bed. The current auger reactor concept turned out to not be appropriate, however, we demonstrated safe self-propagation of the hydrogen release reaction of solid AB/MC in a fixed bed reactor.

  7. Preparation of bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes for hydrolytic dehydrogenation of ammonia borane

    Science.gov (United States)

    Liu, Yang; Zhang, Jun; Guan, Huijuan; Zhao, Yafei; Yang, Jing-He; Zhang, Bing

    2018-01-01

    In present work, we prepared the bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes (Cu-Co/PDDA-HNTs) by a deposition-reduction technique at room temperature. The analysis of XRD, SEM, TEM, HAADF-STEM and XPS were employed to systematically investigate the morphology, particle size, structure and surface properties of the nanocomposite. The results reveal that the PDDA coating with thickness of ∼15 nm could be formed on the surface of HNTs, and the existence of PDDA is beneficial to deposit Cu and Co nanoparticles (NPs) with high dispersibility on the surface. While the cost-effective nanocomposite was used for the hydrolytic dehydrogenation of ammonia-borane (NH3BH3), the nanocatalyst showed extraordinary catalytic properties with high total turnover frequency of 30.8 molH2/(molmetal min), low activation energy of 35.15 kJ mol-1 and high recycling stability (>90% conversion at 10th reuse). These results indicate that the bimetallic Cu-Co nanocatalysts on PDDA functionalized HNTs have particular potential for application in release hydrogen process.

  8. Metal-free hydrogenation catalyzed by an air-stable borane: use of solvent as a frustrated Lewis base.

    Science.gov (United States)

    Scott, Daniel J; Fuchter, Matthew J; Ashley, Andrew E

    2014-09-15

    In recent years 'frustrated Lewis pairs' (FLPs) have been shown to be effective metal-free catalysts for the hydrogenation of many unsaturated substrates. Even so, limited functional-group tolerance restricts the range of solvents in which FLP-mediated reactions can be performed, with all FLP-mediated hydrogenations reported to date carried out in non-donor hydrocarbon or chlorinated solvents. Herein we report that the bulky Lewis acids B(C6Cl5)x(C6F5)(3-x) (x=0-3) are capable of heterolytic H2 activation in the strong-donor solvent THF, in the absence of any additional Lewis base. This allows metal-free catalytic hydrogenations to be performed in donor solvent media under mild conditions; these systems are particularly effective for the hydrogenation of weakly basic substrates, including the first examples of metal-free catalytic hydrogenation of furan heterocycles. The air-stability of the most effective borane, B(C6Cl5)(C6F5)2, makes this a practically simple reaction method. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Kinetics Study of Solid Ammonia Borane Hydrogen Release – Modeling and Experimental Validation for Chemical Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Yong-Joon; Ronnebro, Ewa; Rassat, Scot D.; Karkamkar, Abhijeet J.; Maupin, Gary D.; Holladay, Jamelyn D.; Simmons, Kevin L.; Brooks, Kriston P.

    2014-02-24

    Ammonia borane (AB), NH3BH3, is a promising material for chemical hydrogen storage with 19.6 wt% gravimetric hydrogen capacity of which 16.2 wt% hydrogen can be utilized below 200°C. We have investigated the kinetics of hydrogen release from AB and from an AB-methyl cellulose (AB/MC) composite at temperatures of 160-300°C using both experiments and modeling. The purpose of our study was to show safe hydrogen release without thermal runaway effects and to validate system model kinetics. AB/MC released hydrogen at ~20°C lower than neat AB and at a rate that is two times faster. Based on the experimental results, the kinetics equations were revised to better represent the growth and nucleation process during decomposition of AB. We explored two different reactor concepts; Auger and fixed bed. The current Auger reactor concept turned out to not be appropriate, however, we demonstrated safe self-propagation of the hydrogen release reaction of solid AB/MC in a fixed bed reactor.

  10. Organo-Lewis acids as cocatalysts in cationic metallocene polymerization catalysis. Unusual characteristics of sterically encumbered tris(perfluorobiphenyl)borane

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Y.X.; Stern, C.L.; Yang, S.; Marks, T.J. [Northwestern Univ., Evanston, IL (United States)

    1996-12-11

    Organo-Lewis acids such as methylalumoxane (MAO) and B(C{sub 6}F{sub 5} ){sub 3} (I) play pivotal roles as alkide/hydride abstractors/ cocatalysts in generating highly active, cationic olefin polymerization catalysts (II; L,L` = anionic ancillary ligands; X{sup -} = weakly coordinating anion). We communicate here the unusual cocatalytic characteristics of the new, sterically encumbered fluoroarylborane, tris(2,2`,2``-perfluorobiphenyl)-borane (PBB, III). Characteristics include substantially different abstractive and ion pair structure/reactivity relationships vis-a-vis I. PPB was synthesized as colorless microcrystals in 76% yield from C{sub 6}F{sub 5}Br. Reaction with group 4 and Th methyls proceeds cleanly to yield cationic complexes, which were characterized by standard {sup 1}H/{sup 13}C/{sup 19}F NMR spectroscopic and analytical techniques. The results illustrate the substantial and surprising differences in cationic complex ion pair structure and reactivity that can be brought about by modifications in fluoroarylborane catalyst architecture. 10 refs., 1 fig., 1 tab.

  11. 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.

  12. Highly Ordered Boron Nitride Nanotube Arrays with Controllable Texture from Ammonia Borane by Template-Aided Vapor-Phase Pyrolysis

    Directory of Open Access Journals (Sweden)

    Yuting Wang

    2008-01-01

    Full Text Available An efficient approach for the preparation of good-quality boron nitride nanotubes (BNNTs is developed. BNNTs with specific texture were prepared from ammonia borane (BH3NH3 by vapor-phase pyrolysis with the aid of a template in two independent temperature-controlled furnaces. Two kinds of BNNTs, 200–300 nm wide ×60 μm long and 70–80 nm wide ×40 μm long, were produced after removal of the templates. The as-produced BNNTs were heated at different temperatures in the range of 1300–1700°C in NH3. FT-IR and XPS results confirmed the formation of BN from BH3NH3. Ordered arrays of BNNTs without cracks on the surface were seen using microstructural observations. The diameter and length of the BNNTs are controlled using templates with different pore sizes and thickness. The wall thickness of the nanotubes was increased by increasing the number of deposition cycles. The crystallinity of the BNNTs was improved by heating at a high temperature (1700°C in NH3.

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

    Science.gov (United States)

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

    2017-07-01

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

  14. Fabrication of hollow silica–zirconia composite spheres and their activity for hydrolytic dehydrogenation of ammonia borane

    International Nuclear Information System (INIS)

    Umegaki, Tetsuo; Hosoya, Tatsuya; Toyama, Naoki; Xu, Qiang; Kojima, Yoshiyuki

    2014-01-01

    Highlights: • Hollow silica–zirconia composite spheres were fabricated on polystyrene templates by the sol–gel method. • We study the effect of preparation conditions on the activity for hydrolytic dehydrogenation of ammonia borane. • The activity of hollow silica–zirconia composite spheres depends on wall thickness. - Abstract: In this paper, we report fabrication of hollow silica–zirconia composite spheres by polystyrene (PS) template method and control of wall thickness of the hollow spheres in nanoscale. Both the hollow spheres before and after calcination were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and powder X-ray diffraction analysis (XRD). Morphology of the hollow spheres does not significantly change after calcination from the results of SEM and TEM images, while the amount of residual PS templates drastically decreases via the calcination procedure from the results of FTIR and elemental analysis. The sample after calcination mainly includes amorphous silica from the results of XRD, indicating that the hollow silica–zirconia composite spheres consist of amorphous phases and/or fine particles. Wall thicknesses of the samples after calcination are controlled by adjusting the amount of PS template suspension, and hollow silica–zirconia composite spheres with the wall thicknesses of 17.5, 15.0, 10.0, and 2.0 nm are obtained using the PS template suspension of 25.0, 33.5, 100.0, and 400.0 g, respectively. The activities of the hollow spheres for hydrolytic dehydrogenation of ammonia borane (NH 3 BH 3 ) were compared. The evolutions of 2.0, 3.1, 5.0, and 8.0 mL hydrogen from aqueous NH 3 BH 3 solution were finished in about 4, 5, 3, and 7 min in the presence of the hollow spheres with wall thicknesses of 17.5, 15.0, 10.0, and 2.0 nm, respectively. The molar ratios of the hydrolytically generated hydrogen to the initial NH 3

  15. CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

    Science.gov (United States)

    Gao, Doudou; Zhang, Yuhong; Zhou, Liqun; Yang, Kunzhou

    2018-01-01

    The catalysts containing Cu, Ni bi-metallic nanoparticles were successfully synthesized by in-situ reduction of Cu2+ and Ni2+ salts into the highly porous and hydrothermally stable metal-organic framework MIL-101 via a simple liquid impregnation method. When the total amount of loading metal is 3 × 10-4 mol, Cu2Ni1@MIL-101 catalyst shows higher catalytic activity comparing to CuxNiy@MIL-101 with different molar ratio of Cu and Ni (x, y = 0, 0.5, 1.5, 2, 2.5, 3). Cu2Ni1@MIL-101 catalyst has the highest catalytic activity comparing to mono-metallic Cu and Ni counterparts and pure bi-metallic CuNi nanoparticles in hydrolytic dehydrogeneration of ammonia borane (AB) at room temperature. Additionally, in the hydrolysis reaction, the Cu2Ni1@MIL- 101 catalyst possesses excellent catalytic performances, which exhibit highly catalytic activity with turn over frequency (TOF) value of 20.9 mol H2 min-1 Cu mol-1 and a very low activation energy value of 32.2 kJ mol-1. The excellent catalytic activity has been successfully achieved thanks to the strong bi-metallic synergistic effects, uniform distribution of nanoparticles and the bi-functional effects between CuNi nanoparticles and the host of MIL-101. Moreover, the catalyst also displays satisfied durable stability after five cycles for the hydrolytically releasing H2 from AB. The non-noble metal catalysts have broad prospects for commercial applications in the field of hydrogen-stored materials due to the low prices and excellent catalytic activity.

  16. Homogeneous catalytic dehydrocoupling/dehydrogenation of amine-borane adducts by early transition metal, group 4 metallocene complexes.

    Science.gov (United States)

    Sloan, Matthew E; Staubitz, Anne; Clark, Timothy J; Russell, Christopher A; Lloyd-Jones, Guy C; Manners, Ian

    2010-03-24

    The efficient catalytic dehydrocoupling of a range of amine-borane adducts, R'RNH x BH(3) (R' = R = Me 1a; R' = R = (i)Pr 1b; R' = Me, R = CH(2)Ph 1c) by a series of group 4 metallocene type precatalysts has been demonstrated. A reduction in catalytic activity was detected upon descending the group and also on substitution of the cyclopentadienyl (Cp) ligands with sterically bulky or electron-donating substituents. Precatalysts Cp(2)TiCl(2)/2(n)BuLi and Cp(2)Ti(PMe(3))(2), which are believed to act as precursors to [Cp(2)Ti], were found to promote the transformation of 1a to [Me(2)N-BH(2)](2) (3a) in a homogeneous catalytic process. Mechanistic studies identified the linear dimer Me(2)NH-BH(2)-NMe(2)-BH(3) (2a) as a reaction intermediate, which subsequently undergoes further catalytic dehydrogenation to form cyclic dimer 3a. Synthesis of the (2)H-isotopologues of 1a allowed the extraction of phenomenological kinetic isotope effects for 1a --> 2a and 2a --> 3a from initial rate data, which permitted the proposal of a catalytic cycle with plausible intermediates. Support for the presence of an active Ti(II) catalyst was provided by the lack of reactivity of Ti(III) complexes TiCl(3) and Cp(2)TiCl or Ti(0) in the form of THF soluble colloids or bulk Ti powder toward 1a or 1b. Modeling of the rates of consumption of 1a and formation of 3a during catalysis by Cp(2)Ti(PMe(3))(2) supported this conclusion and allowed the proposal of a two cycle, four step reaction mechanism. The proposed first cycle generates 2a in a two step process. In the second cycle, interaction of 2a with the same catalyst then results in a catalytic dehydrogenative ring closing reaction to form 3a, also in a two step process.

  17. A thermodynamic and kinetic study of the heterolytic activation of hydrogen by frustrated borane-amine Lewis pairs.

    Science.gov (United States)

    Karkamkar, Abhi; Parab, Kshitij; Camaioni, Donald M; Neiner, Doinita; Cho, Herman; Nielsen, Thomas K; Autrey, Tom

    2013-01-21

    Calorimetry is used to measure the reaction enthalpies of hydrogen (H(2)) activation by 2,6-lutidine (Lut), 2,2,6,6-tetramethylpiperidine (TMP), N-methyl-2,2,6,6-tetramethylpiperidine (MeTMP), and tri-tert-butylphosphine (TBP) with tris(pentafluorophenyl)borane (BCF). At 6.6 bar H(2) the conversion of the Lewis acid Lewis base pair to the corresponding ionic pair in bromobenzene at 294 K was quantitative in under 60 min. Integration of the heat release from the reaction of the Frustrated Lewis Pair (FLP) with H(2) as a function of time yields a relative rate of hydrogenation in addition to the enthalpy of hydrogenation. The half-lives of hydrogenation range from 230 s with TMP, ΔH(H2) = -31.5(0.2) kcal mol(-1), to 1400 s with Lut, ΔH(H2) = -23.4(0.4) kcal mol(-1). The (11)B nuclear magnetic resonance (NMR) spectrum of B(C(6)F(5))(3) in bromobenzene exhibits three distinct traits depending on the sterics of the Lewis base; (1) in the presence of pyridine, only the dative bond adduct pyridine-B(C(6)F(5))(3) is observed; (2) in the presence of TMP and MeTMP, only the free B(C(6)F(5))(3) is observed; and (3) in the presence of Lut, both the free B(C(6)F(5))(3) and the Lut-B(C(6)F(5))(3) adduct appear in equilibrium. A measure of the change in K(eq) of Lut + B(C(6)F(5))(3) ⇔ Lut-B(C(6)F(5))(3) as a function of temperature provides thermodynamic properties of the Lewis acid Lewis base adduct, ΔH = -17.9(1.0) kcal mol(-1) and a ΔS = -49.2(2.5) cal mol(-1) K, suggesting the Lut-B(C(6)F(5))(3) adduct is more stable in bromobenzene than in toluene.

  18. Cuboid Ni2 P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei

    2017-11-16

    The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Studies on the influence of tris(pentafluorophenyl)borane on the properties of ethylene carbonate, dimethyl carbonate and poly(ethylene oxide) dimethyl ether lithium trifluoromethanesulfonate electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Zukowska, Grazyna Z.; Marcinek, Marek; Drzewiecki, Stanislaw; Kryczka, Jolanta; Syzdek, Jaroslaw; Adamczyk-Wozniak, Agnieszka; Wieczorek, Wladyslaw; Sporzynski, Andrzej [Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland)

    2010-11-15

    In this paper we present our studies on the properties of battery electrolyte based on EC/DMC (ethylene carbonate/dimethyl carbonate, w/w ratio 2:5) and PEODME (poly(ethylene oxide) dimethyl ether) (M{sub w} = 500) doped with LiCF{sub 3}SO{sub 3}-lithium trifluoromethanesulfonate (LiTf) and modified with TPFPB (tris(pentafluorophenyl)borane) as a potential anion trapping agent. We were particularly interested how this compound behaves in different solvents, e.g. battery mixture EC/DMC and model polymeric matrix PEODME. We also verified stability of the proposed solutions by means of DSC and FTIR, determined influence on conductivity and lithium transference numbers by impedance spectroscopy, and finally attempted to define mechanism of influence of boron addition on different systems. (author)

  20. A borane laser

    Czech Academy of Sciences Publication Activity Database

    Cerdán, L.; Braborec, Jakub; Gracia-Moreno, I.; Costela, A.; Londesborough, Michael Geoffrey Stephen

    2015-01-01

    Roč. 6, JAN (2015), s. 2-7 ISSN 2041-1723 R&D Projects: GA ČR(CZ) GAP207/11/1577 Institutional support: RVO:61388980 Keywords : Physical sciences * Optical physics * Physical chemistry * 18H22 * Cluster Subject RIV: CA - Inorganic Chemistry Impact factor: 11.329, year: 2015

  1. Tris(trifluoromethyl)borane carbonyl, (CF3)3BCO-synthesis, physical, chemical and spectroscopic properties, gas phase, and solid state structure.

    Science.gov (United States)

    Finze, Maik; Bernhardt, Eduard; Terheiden, Annegret; Berkei, Michael; Willner, Helge; Christen, Dines; Oberhammer, Heinz; Aubke, Friedhelm

    2002-12-25

    Tris(trifluoromethyl)borane carbonyl, (CF(3))(3)BCO, is obtained in high yield by the solvolysis of K[B(CF(3))(4)] in concentrated sulfuric acid. The in situ hydrolysis of a single bonded CF(3) group is found to be a simple, unprecedented route to a new borane carbonyl. The related, thermally unstable borane carbonyl, (C(6)F(5))(3)BCO, is synthesized for comparison purposes by the isolation of (C(6)F(5))(3)B in a matrix of solid CO at 16 K and subsequent evaporation of excess CO at 40 K. The colorless liquid and vapor of (CF(3))(3)BCO decomposes slowly at room temperature. In the gas phase t(1/2) is found to be 45 min. In the presence of a large excess of (13)CO, the carbonyl substituent at boron undergoes exchange, which follows a first-order rate law. Its temperature dependence yields an activation energy (E(A)) of 112 kJ mol(-)(1). Low-pressure flash thermolysis of (CF(3))(3)BCO with subsequent isolation of the products in low-temperature matrixes, indicates a lower thermal stability of the (CF(3))(3)B fragment, than is found for (CF(3))(3)BCO. Toward nucleophiles (CF(3))(3)BCO reacts in two different ways: Depending on the nucleophilicity of the reagent and the stability of the adducts formed, nucleophilic substitution of CO or nucleophilic addition to the C atom of the carbonyl group are observed. A number of examples for both reaction types are presented in an overview. The molecular structure of (CF(3))(3)BCO in the gas phase is obtained by a combined microwave-electron diffraction analysis and in the solid state by single-crystal X-ray diffraction. The molecule possesses C(3) symmetry, since the three CF(3) groups are rotated off the two possible positions required for C(3)(v)() symmetry. All bond parameters, determined in the gas phase or in the solid state, are within their standard deviations in fair agreement, except for internuclear distances most noticeably the B-CO bond lengths, which is 1.69(2) A in the solid state and 1.617(12) A in the gas phase

  2. Influence of preparation conditions of hollow silica–nickel composite spheres on their catalytic activity for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Umegaki, Tetsuo, E-mail: umegaki.tetsuo@nihon-u.ac.jp [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Seki, Ayano [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Xu, Qiang [National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Kojima, Yoshiyuki [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

    2014-03-05

    Highlights: • We study influence of preparation conditions on activity of hollow silica–nickel composite spheres. • The activity for hydrolytic dehydrogenation of NH{sub 3}BH{sub 3} increases with increase of Si+Ni content. • The particle size distribution affects the activity and reducibility of active nickel species. • The amount of PS residue in the hollow spheres decreases by treatment of as-prepared sample in toluene. -- Abstract: In this paper, we investigated influence of preparation conditions of hollow silica–nickel composite spheres on their morphology and catalytic activity for hydrolytic dehydrogenation of ammonia borane. In the preparation method of this study, when silica–nickel composite shells were coated on polystyrene templates by the sol–gel method using L(+)-arginine as the promoter for the reaction to form silica–nickel composite shell, the polystyrene templates were dissolved subsequently, even synchronously, in the same medium to form hollow spheres. The as-prepared silica–nickel composite spheres were characterized by transmission electron microscopy and scanning electron microscopy. The effects of Si+Ni content on the morphology were systematically evaluated. All the as-prepared hollow silica–nickel composite spheres have the similar morphology as identified by SEM and TEM measurement. Homogeneity of the hollow silica–nickel composite spheres increases with the increase in the Si+Ni content as shown by the laser diffraction particle size analysis. The catalytic activities of the hollow silica–nickel composite spheres for hydrolytic dehydrogenation of ammonia borane prepared with different Si+Ni contents were compared. The catalytic activity for the hydrogen evolution in the presence of the hollow spheres increases with the increase of Si+Ni content. The results of FTIR spectra of the hollow silica–nickel composite spheres indicate that a certain amount of residual PS templates exists in hollow silica

  3. Non-Noble Metal Nanoparticles Supported by Postmodified Porous Organic Semiconductors: Highly Efficient Catalysts for Visible-Light-Driven On-Demand H2Evolution from Ammonia Borane.

    Science.gov (United States)

    Zhang, Hao; Gu, Xiaojun; Song, Jin; Fan, Na; Su, Haiquan

    2017-09-27

    From the viewpoint of controlling the visible-light-driven activities of catalysts containing metal nanoparticles (NPs) by tuning the microstructures of semiconducting supports, we employed a postsynthetic thermal modification approach to prepare carbon nitride (C 3 N 4 ) species featuring different microstructures and then we synthesized Co and Ni NPs supported by these C 3 N 4 species, which were used to catalyze the room-temperature H 2 evolution from ammonia borane (NH 3 BH 3 ). The systematic investigation showed that the catalysts had different activities under light irradiation. Compared with the pristine C 3 N 4 -based catalyst, all the modified C 3 N 4 -based catalysts had enhanced activities. The highest active Co catalyst with a total turnover frequency of 93.8 min -1 was successfully obtained, which exceeded the values of all the reported heterogeneous noble metal-free catalysts. The structure characterizations indicated that the postmodified porous C 3 N 4 species had the different band structures, photoluminescence lifetime, and photocurrent density under visible light irradiation, leading to the different separation efficiency of photogenerated charge carriers. These characteristics helped us regulate the electronic characteristics of Co and Ni NPs in the supported catalysts and then led to the significantly different and enhanced activity in the visible-light-driven H 2 evolution.

  4. Supported rhodium catalysts for ammonia-borane hydrolysis. Dependence of the catalytic activity on the highest occupied state of the single rhodium atoms

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Liangbing; Li, Hongliang; Zhang, Wenbo; Zhao, Xiao; Qiu, Jianxiang; Li, Aowen; Zheng, Xusheng; Zeng, Jie [Hefei National Lab. for Physical Sciences at the Microscale, Key Lab. of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, Hefei, Anhui(China); Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui (China); Hu, Zhenpeng [School of Physics, Nankai University, Tianjin (China); Si, Rui [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences (China)

    2017-04-18

    Supported metal nanocrystals have exhibited remarkable catalytic performance in hydrogen generation reactions, which is influenced and even determined by their supports. Accordingly, it is of fundamental importance to determine the direct relationship between catalytic performance and metal-support interactions. Herein, we provide a quantitative profile for exploring metal-support interactions by considering the highest occupied state in single-atom catalysts. The catalyst studied consisted of isolated Rh atoms dispersed on the surface of VO{sub 2} nanorods. It was observed that the activation energy of ammonia-borane hydrolysis changed when the substrate underwent a phase transition. Mechanistic studies indicate that the catalytic performance depended directly on the highest occupied state of the single Rh atoms, which was determined by the band structure of the substrates. Other metal catalysts, even with non-noble metals, that exhibited significant catalytic activity towards NH{sub 3}BH{sub 3} hydrolysis were rationally designed by adjusting their highest occupied states. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

    Science.gov (United States)

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

    2015-01-21

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

  6. Macropolyhedral borane reaction chemistry: Reductive oligomerisation of (BuNC)-Bu-ter by anti-B18H22 to give the boron-coordinated {((BuNHCH)-Bu-ter) {(BuNHC)-Bu-ter)CN)}CH2:} carbene residue

    Czech Academy of Sciences Publication Activity Database

    Jelínek, Tomáš; Kilner, C. A.; Barrett, S. A.; Štíbr, Bohumil; Thornton-Pett, M.; Kennedy, J.D.

    2005-01-01

    Roč. 8, č. 5 (2005), s. 491-494 ISSN 1387-7003 R&D Projects: GA ČR GA203/05/2646; GA ČR GA203/00/1042; GA MŠk LC523; GA AV ČR IAA4032701 Grant - others:EPSRC(GB) J/56929; EPSRC(GB) K/05818; EPSRC(GB) M/83360 Institutional research plan: CEZ:AV0Z40320502 Keywords : borane cluster * X-ray structure * NMR spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 1.826, year: 2005

  7. In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

    Science.gov (United States)

    Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

    2012-03-20

    The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

  8. New organo-Lewis acids. Tris({beta}-perfluoronaphthyl)borane (PNB) as a highly active cocatalyst for metallocene-mediated Ziegler-Natta {alpha}-olefin polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Li, L.; Marks, T.J. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry

    1998-08-31

    Tris({beta}-perfluoronaphthyl)borane (B(C{sub 10}F{sub 7}){sub 3}, PNB) is synthesized from {beta}-perfluoronaphthyllithium and BCl{sub 3} to serve as a new strong organo-Lewis acid cocatalyst. PNB efficiently activates a variety of group 4 dimethyl complexes to form highly active homogeneous Ziegler-Natta olefin polymerization catalysts. Reaction of PNB with rac-Me{sub 2}Si(Ind){sub 2}ZrMe{sub 2} and CGCMMe{sub 2} (M = Zr, Ti; CGC = Me{sub 2}Si({eta}{sup 5}-Me{sub 4}C{sub 5})({sup t}BuN)) (1:1 molar ratio) rapidly produces the base-free cationic complexes rac-Me{sub 2}Si(Ind){sub 2}ZrMe{sup +}MePNB{sup {minus}} (1) and CGCMMe{sup +}MePNB{sup {minus}} (M = Zr, 2; Ti, 3), respectively. The {mu}-methyl dinuclear cationic complex [(CGCTiMe){sub 2}({mu}-Me)]{sup +}MePNB{sup {minus}} (4) is formed when 2:1 CGCTiMe{sub 2}:PNB stoichiometry is employed. In the case of group 4 dimethyl zirconocenes, L{sub 2}ZrMe{sub 2} (L = {eta}{sup 5}-C{sub 5}H{sub 5}, Cp; {eta}{sup 5}-1,2-Me{sub 2}C{sub 5}H{sub 3}, Cp{double_prime}), reaction in a 1:1 metallocene:PNB ratio affords cationic complexes L{sub 2}ZrMe{sup +}MePNB{sup {minus}} (L = Cp, 5; Cp{double_prime}, 6), while the reaction with a 1:2 molar ratio affords dinuclear {mu}-methyl cationic complexes [(L{sub 2}ZrMe){sub 2}({mu}-Me)]{sup +}MePNB{sup {minus}} (L = Cp, 7; Cp{double_prime}, 8). In both reactions, {mu}-F dinuclear cationic complexes [(L{sub 2}ZrMe){sub 2}({mu}F)]{sup +}MePNB{sup {minus}} (L = Cp, 9; Cp{double_prime}, 10) are formed as byproducts. (C{sub 6}F{sub 5}){sub 3}BNCCH{sub 3} and PNBNCCH{sub 3} were synthesized and characterized.

  9. Microwave-assisted decomplexation and in-situ headspace in-syringe dynamic derivatization of dimethylamine borane with high performance liquid chromatography-fluorescence detection.

    Science.gov (United States)

    Muniraj, Sarangapani; Lee, Hua-Kwang; Hsiech, Chunming; Jen, Jen-Fon

    2018-02-16

    A rapid, sensitive, selective, and simple method for monitoring dimethylamine borane (DMAB) in aqueous sample is proposed by combining microwave-assisted de-complexation, headspace liquid phase in-situ derivatization extraction, and high-performance liquid chromatography-fluorescence detection for the determination of DMAB in samples. The present procedure involves de-complexation of DMAB using microwave irradiation, evolution of dimethylamine (DMA) to the headspace from an alkalized sample solution, and dynamic headspace liquid-phase derivatization extraction (Dy-HS-LPDE) of DMA with 9-fluorenylmethyl chloroformate in a syringe barrel. In addition to the optimal Dy-HS-LPDE and chromatographic parameters described in our previous study, the de-complexation of DMAB by thermal and microwave-assisted procedures and evolution of DMA into the headspace from an alkalized solution and modification of the Dy-HS-LPDE method are thoroughly investigated. The results indicate that complete de-complexation was obtained at 70 °C for 5 min, 30 °C for 10 min, or using microwave irradiation for 30 s at any applied power. It indicates that the DMAB complex easily undergoes de-complexation under microwave irradiation. The linearity range was 0.01-0.5 mg L -1 for DMAB and 0.0077-0.38 mg L -1 for DMA, with a coefficient of determination of 0.9995, and limit of detection of 3 μg L -1 (limit of quantitation of 10 μg L -1 ) for DMAB. The recoveries of DMAB are 95.3% (3.0% RSD) for waste water when spiked 0.05 mg L -1 and 93.5% (5.4% RSD) for the samples spiked with copper and nickel salts (5 mM each in the spiked waste sample). The whole analytical procedure can be completed within 25 min. The results confirm that the present method is a rapid, sensitive, selective, automated, low-cost and eco-friendly procedure to identify DMAB in samples. Copyright © 2018 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    Bhat, Haamid R; Jha, Prakash C

    2017-05-18

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

  11. In situ solid state 11B MAS-NMR studies of the thermal decomposition of ammonia borane: mechanistic studies of the hydrogen release pathways from a solid state hydrogen storage material.

    Science.gov (United States)

    Stowe, Ashley C; Shaw, Wendy J; Linehan, John C; Schmid, Benjamin; Autrey, Tom

    2007-04-21

    The mechanism of hydrogen release from solid state ammonia borane (AB) has been investigated via in situ solid state (11)B and (11)B{(1)H} MAS-NMR techniques in external fields of 7.1 T and 18.8 T at a decomposition temperature of 88 degrees C, well below the reported melting point. The decomposition of AB is well described by an induction, nucleation and growth mechanistic pathway. During the induction period, little hydrogen is released from AB; however, a new species identified as a mobile phase of AB is observed in the (11)B NMR spectra. Subsequent to induction, at reaction times when hydrogen is initially being released, three additional species are observed: the diammoniate of diborane (DADB), [(NH(3))(2)BH(2)](+)[BH(4)](-), and two BH(2)N(2) species believed to be the linear (NH(3)BH(2)NH(2)BH(3)) and cyclic dimer (NH(2)BH(2))(2) of aminoborane. At longer reaction times the sharper features are replaced by broad, structureless peaks of a complex polymeric aminoborane (PAB) containing both BH(2)N(2) and BHN(3) species. The following mechanistic model for the induction, nucleation and growth for AB decomposition leading to formation of hydrogen is proposed: (i) an induction period that yields a mobile phase of AB caused by disruption of the dihydrogen bonds; (ii) nucleation that yields reactive DADB from the mobile AB; and (iii) growth that includes a bimolecular reaction between DADB and AB to release the stored hydrogen.

  12. 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.

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

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

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

  14. 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].

  15. Dynamics of Production and Oxidation of Boranes.

    Science.gov (United States)

    1987-12-01

    crow o oPMv ss s RmoLs .Te UNCLASSIFIED SIECUORY CLASIFICATION OF rMIS PAEC (h Data mInted) uCum’Y CL. iSUFICAI@M OF TIS PAGMNM DWeAA.4etu reaction...molecular densities measured are the concentrations developed along the central streamline. The stainless steel detection chamber is evacuated by a 10

  16. Carbon insertion into borane clusters via nucleophilic addition reactions of borane and carborane anions

    Czech Academy of Sciences Publication Activity Database

    Štíbr, Bohumil

    2013-01-01

    Roč. 747, december (2013), s. 16-24 ISSN 0022-328X R&D Projects: GA ČR(CZ) GAP207/11/0705 Institutional support: RVO:61388980 Keywords : Boron hydrides * Carboranes * Dicarbaboranes * Heterocarboranes * Tricarbaboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 2.302, year: 2013

  17. Distribution of sulfhydryl boranes in mice and rats

    International Nuclear Information System (INIS)

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

    1986-01-01

    The distribution of boron in mice bearing transplanted Harding-Passey melanomas after rapid and slow administration of monomer were studied. Thin layer chromatographic analysis of the corresponding infusion solution revealed a slow-moving principal band that was later shown to correspond to Na 4 B 24 H 22 S 2 , the dimer of Na 2 B 12 H 11 SH. It was found that while monomer and chemically synthesized dimer yielded similar boron concentrations when they were given rapidly intraperitoneally to mice, the dimer yielded higher boron concentrations in mouse melanoma and higher melanoma-blood boron concentration when each was infused slowly intraperitoneally for 8 to 9 days. Studies have been started on the uptake of dimer into an intracerebrally implanted rat glioma. Boron levels in the rat glioma and in the mouse melanoma from slow intraperitoneal infusion of proportionately comparable amounts of dimer, are similar. However, after these slow infusions boron levels in rat blood are about as high as boron levels in rat brain tumor. 6 refs., 1 fig., 4 tabs

  18. Towards chiral diamines as chiral catalytic precursors for the borane ...

    Indian Academy of Sciences (India)

    Administrator

    were carried out at 298 K on a Bruker SMART. APEX CCD area detector system equipped with a graphite monochromator and a Mo-Kα fine-focus sealed tube (λ ..... some light in understanding the structural aspects of the catalyst to provide more enantioselectivities. We have next turned our attention towards the applica-.

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

    African Journals Online (AJOL)

    Unknown

    1Department of Animal Science, University of the Orange Free State, P.O. Box 339, Bloemfontein, 9300, Republic of South. Africa; 2Department of Animal Sciences, ... analyzed by fitting a fixed effect model using the least-squares procedure of the generalized linear model (GLM), of Statistical Analysis Systems (1994).

  20. Genetic parameter estimates for weaning weight of Boran cattle ...

    African Journals Online (AJOL)

    Chrislukovian Wasike

    models that assumed non-zero direct-maternal genetic covariance. In addition to the direct and maternal genetic effects, maternal permanent environmental and sire by herd-year interaction effects were tested. Two datasets were used. Dataset 1 (DS1) included all animals while dataset 2 (DS2) constituted only records of.

  1. Performance of Boran and Crossbred Cattle for Beef Production ...

    African Journals Online (AJOL)

    Residual Standard Deviation after accounting for the effects of breed, sex, age at weighing, age of ... Table 3: Least squares means and standard errors (S.E.) of gestation length, birth weight, and weaning weight for various classes ..... In a crossbreeding experiment in Queensland, Australia, heterosis in weight at 18 months ...

  2. Synthesis of alkylamine boranes | Amupitan | Nigerian Journal of ...

    African Journals Online (AJOL)

    Nigerian Journal of Chemical Research. Journal Home · ABOUT THIS JOURNAL · Advanced Search · Current Issue · Archives · Journal Home > Vol 2 (1997) >. Log in or Register to get access to full text downloads.

  3. Performance of Boran and Crossbred Cattle for Beef Production ...

    African Journals Online (AJOL)

    area, weights of bone, fat and lean (v) On the heart: weight of lean, coronary fat and pericardial fat (vi) Kidney weight and (vii) Weight of perirenal fat. Data handling and analysis. Raw data was in a number of sources. All sources were used in order to complement each other. However, many problems were encountered in.

  4. Polymer Electrolytes Based on Borane/Poly(ethylene glycol Methyl Ether for Lithium Batteries

    Directory of Open Access Journals (Sweden)

    Ali Murat Soydan

    2017-01-01

    Full Text Available This work presents a different approach to preparing polymer electrolytes having borate ester groups for lithium ion batteries. The polymers were synthesized by reaction between poly(ethylene glycol methyl ether (PEGME and BH3-THF complex. Molecular weight of PEGMEs was changed with different chain lengths. Then the polymer electrolytes comprising boron were prepared by doping of the matrices with CF3SO3Li at various molar ratios with respect to EO to Li and they are abbreviated as PEGMEX-B-Y. The identification of the PEGME-borate esters was carried out by FTIR and 1H NMR spectroscopy. Thermal properties of these electrolytes were investigated via thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. The ionic conductivity of these novel polymer electrolytes was studied by dielectric-impedance spectroscopy. Lithium ion conductivity of these electrolytes was changed by the length of PEGME as well as the doping ratios. They exhibit approximate conductivities of 10−4 S·cm−1 at 30°C and 10−3 S·cm−1 at 100°C.

  5. Calorimetric Study of the Activation of Hydrogen by Tris(pentafluorophenyl)borane and Trimesitylphosphine

    Energy Technology Data Exchange (ETDEWEB)

    Houghton, Adrian Y. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, Richland, Washington 99352 United States; Autrey, Tom [Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, Richland, Washington 99352 United States

    2017-11-08

    The mechanism of H2 activation by B(C6F5)3 and P(mes)3 was investigated by isothermal reaction calorimetry, and the heat curves generated were modelled in Berkeley Madonna. The reaction is treated as a single, termolecular step, and an Eyring analysis gave activation parameters of ∆H‡ = 13.6(9) kJ mol-1 and ∆S‡ = -204(85) J K-1 mol-1. The enthalpy of the reaction was found to be -141 kJ mol-1. The kinetic isotope effect was measured as 1.1, consistent with a four-center transition state containing two isotopically exchangeable atoms.

  6. Two-Dimensional Borane with ‘Banana’ Bonds and Dirac-Like Ring

    Science.gov (United States)

    Wu, Hong; Wang, Yun-Hui; Yang, Zhi-Hong; Li, Feng

    2018-03-01

    Not Available Supported by the National Natural Science Foundation of China under Grant Nos 61605087 and 61704083, the International Postdoctoral Exchange Fellowship Program between JUELICH and OCPC under Grant No 20161001, the Natural Science Foundation of Jiangsu Province under Grant No BK20160881, the Jiangsu Provincial Natural Science Research Project under Grant No 16KJB140010, and the Science Foundation of Nanjing University of Posts and Telecommunications under Grant No NY215064.

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

    Science.gov (United States)

    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.

  8. Catalytic dehydrogenation of dimethylamine borane by group 4 metallocene alkyne complexes and homoleptic amido compounds.

    Science.gov (United States)

    Beweries, Torsten; Hansen, Sven; Kessler, Monty; Klahn, Marcus; Rosenthal, Uwe

    2011-08-14

    Dehydrogenation of Me(2)NH·BH(3) (1) by group 4 metallocene alkyne complexes of the type Cp(2)M(L)(η(2)-Me(3)SiC(2)SiMe(3)) [Cp = η(5)-cyclopentadienyl; M = Ti, no L (2Ti); M = Zr, L = pyridine (2Zr)] and group 4 metal amido complexes of the type M(NMe(2))(4) [M = Ti (8Ti), Zr (8Zr)] is presented. This journal is © The Royal Society of Chemistry 2011

  9. Remarkably Intense Emission from Ruthenium(II) Complexes with Multiple Borane Centers.

    Science.gov (United States)

    Nakagawa, Atsushi; Sakuda, Eri; Ito, Akitaka; Kitamura, Noboru

    2015-11-02

    The electrochemical, spectroscopic, and phophysical properties of a series of Ru(II) complexes having a triarylborane-appended 2,2'-bipyridine (bpy) ligand(s) (RuBbpys: [Ru(Bbpy)n(bpy)(3-n)](2+) (B1n) and [Ru(B2bpy)n(bpy)(3-n)](2+) (B2n), B = (dimesityl)boryldurylethynyl group(s) at the 4- or 4,4'-position(s) in bpy, n = 1-3) are described. In the excited states of the complexes, the intramolecular charge transfer transitions between the π-orbital of the aryl group and the vacant p-orbital on the boron atom (π(aryl)-p(B) CT) synergistically interact with the metal-to-ligand charge transfer (MLCT) transitions. The molar absorption coefficient of the MLCT band (ε(MLCT)) of the complex increased with increasing n, and B23 showed extremely intense absorption with ε(MLCT) = 5.6 × 10(4) M(-1) cm(-1) at 488 nm. Furthermore, B23 showed the highest emission quantum yield (0.43) among those of the polypyridine Ru(II) complexes hitherto reported. As one of the interesting results, we report that the radiative rate constant of B2n shows the correlation with ε(MLCT). The effects of the synergistic MLCT/π(aryl)-p(B) CT interactions on the spectroscopic and photophysical characteristics of RuBbpys are discussed in detail.

  10. Pentamethylcyclopentadienylmethyltitanium Silsesquioxanes and Their Zwitterionic Complexes with Tris(pentafluorophenyl)borane

    Czech Academy of Sciences Publication Activity Database

    Varga, V.; Pinkas, Jiří; Císařová, I.; Horáček, Michal; Mach, Karel

    2009-01-01

    Roč. 28, č. 24 (2009), s. 6944-6956 ISSN 0276-7333 R&D Projects: GA AV ČR KAN100400701; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : Pentamethylcyclopentadienylmethyltitanium Silsesquioxanes * zwitteronic complexes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.204, year: 2009

  11. B-11-NMR shielding effects in the closo borane series: sensitivity of shifts and their additivity

    Czech Academy of Sciences Publication Activity Database

    Štíbr, Bohumil

    2017-01-01

    Roč. 41, č. 23 (2017), s. 14452-14456 ISSN 1144-0546 R&D Projects: GA ČR(CZ) GA16-01618S Institutional support: RVO:61388980 Keywords : nmr-spectra * vibrational-spectra * carborane derivatives * decaborate anion * heteroboranes Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 3.269, year: 2016

  12. 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...

  13. Population parameters for traits defining trypanotolerance in an F2 cross of N'Dama and Boran cattle

    NARCIS (Netherlands)

    Waaij, van der E.H.; Hanotte, O.; Arendonk, van J.A.M.; Kemp, S.J.; Kennedy, D.; Gibson, J.P.; Teale, A.J.

    2003-01-01

    Some West African Bos taurus cattle breeds such as the N'Dama and a number of West African Shorthorns are resistant to tsetse fly-transmitted trypanosomosis. The trait is termed trypanotolerance, for which changes in packed red cell volume percent (PCV) and growth rate following infection are

  14. Chalcogens act as inner and outer heteroatoms in borane cages with possible consequences for sigma-hole interactions

    Czech Academy of Sciences Publication Activity Database

    Fanfrlík, Jindřich; Hnyk, Drahomír

    2016-01-01

    Roč. 18, č. 47 (2016), s. 8982-8987 ISSN 1466-8033 R&D Projects: GA ČR(CZ) GBP208/12/G016; GA ČR(CZ) GA15-05677S Institutional support: RVO:61388963 ; RVO:61388980 Keywords : electron diffraction * halogen bond * ab-initio Subject RIV: CF - Physical ; Theoretical Chemistry ; CA - Inorganic Chemistry (UACH-T) Impact factor: 3.474, year: 2016 http://pubs.rsc.org/en/content/articlehtml/2016/ce/c6ce01861k

  15. Novel photocatalyst gold nanoparticles with dumbbell-like structure and their superiorly photocatalytic performance for ammonia borane hydrolysis

    Science.gov (United States)

    Zhu, Mingyun; Dai, Yunqian; Fu, Wanlin; Wu, Yanan; Zou, Xixi; You, Tengye; Sun, Yueming

    2018-04-01

    Gold nanoparticles (Au NPs) have attracted remarkable research interest in heterogeneous catalysis due to their unique physical and chemical properties. However, only small-sized Au NPs (the strengthened localized surface plasmon resonance (LSPR) compensation effect could effectively remedy the loss of catalytic activity resulting from the size enlarging of D-Au NPs, proved by the observation that the heating power of a single Au nanoparticle (Ps) and turnover frequency of AB molecules within 10 min of D-Au NPs are 52.5 and 3.89 times higher, respectively, than those of spherical Au NPs; (ii) the extinction coefficient and Ps of D-Au NPs are almost 2.72 and 2.42 times as high, respectively, as those of rod-like Au NPs, demonstrating the promoting structure-property relationship of the dumbbell-like structure; (iii) when the pH value of the AB solution was lower than 6.0, the hydrolysis rate was highly promoted, indicating that H+ ions play an active role in the hydrolysis process. This work greatly extends the application of noble metals and provides a new insight into AB hydrolysis.

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

    Science.gov (United States)

    2014-08-11

    mechanisms during combustion of these mixtures. For this purpose, isotopic tests, involving use of heavy water and mass-spectroscopy of gaseous combustion...Comparison of hydrogen release from various boron -based chemical hydrides (8)....................7 Figure 2. Comparison of hydrogen release from...acquired from the pressure increase. Isotopic tests (deuterium) were used for revealing the reaction mechanisms. CHAPTER 2: LITERATURE REVIEW 2.1

  17. Effect of L-arginine on the catalytic activity and stability of nickel nanoparticles for hydrolytic dehydrogenation of ammonia borane

    Science.gov (United States)

    Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

    2012-10-01

    Amorphous nickel catalysts were synthesized by reducing the nickel(II) species in an aqueous NaBH4/NH3BH3 solution with and without L-arginine. The nickel catalyst with L-arginine maintains relatively high activity for hydrolysis of NH3BH3 to generate a stoichiometric amount of hydrogen with the cycle number up to 11 (827 mL s-1 (mol-Ni)-1 at the 11th cycle with L-arginine = 35 mg), while the reaction rate in the presence of the bare nickel catalyst was relatively low through the cycle number up to 11 (232 mL s-1 (mol-Ni)-1 at the 11th cycle). After catalytic reaction, the nickel catalyst with L-arginine possesses the high dispersion (diameters of nickel nanoparticles L-arginine maintains the dispersion of nickel nanoparticles (diameters of nickel nanoparticles <10 nm), leading to higher activity against cycle tests than the bare nickel catalyst.

  18. Development and Optimization of a Positron Annihilation Lifetime Spectrometer to Measure Nanoscale Defects in Solids and Borane Cage Molecules in Aqueous Nitrate Solutions

    National Research Council Canada - National Science Library

    Ross, Matthew A

    2008-01-01

    ... +or- 2 ps (as compared to 105 +or- 5 ps in the literature (16)). The PALS system was then used to compare the differences between as grown and neutron-irradiated single crystal silicon carbide (SiC...

  19. Pressure induced structural changes in the potential hydrogen storage compound ammonia borane: A combined X-ray, neutron and theoretical investigation

    International Nuclear Information System (INIS)

    Kumar, Ravhi S.; Ke, Xuezhi; Zhang, Jianzhong; Lin, Zhijun; Vogel, Sven C.; Hartl, Monika; Sinogeikin, Stanislav; Daemen, Luke; Cornelius, Andrew L.; Chen, Changfeng; Zhao, Yusheng

    2010-01-01

    The crystal structure of NH 3 BH 3 was investigated using synchrotron high pressure X-ray diffraction (HPXRD) up to 27 GPa and neutron diffraction up to 5 GPa. Density functional theoretical (DFT) calculations were carried out simultaneously for comparison. The results confirm a pressure induced phase transition from the tetragonal I4mm phase to a high pressure orthorhombic Cmc21 phase around 1.22 GPa. Further increase of pressure above 8 GPa, we observed a second structural transition from Cmc21 to a triclinic P1 phase which are reversible with small hysteresis. The transition pressures and the bulk modulus obtained experimentally are in good agreement with theory.

  20. Interactions of Boranes and Carboranes with Aromatic Systems: CCSD(T) Complete Basis Set Calculations and DFT-SAPT Analysis of Energy Components

    Czech Academy of Sciences Publication Activity Database

    Sedlák, Robert; Fanfrlík, Jindřich; Hnyk, Drahomír; Hobza, Pavel; Lepšík, Martin

    2010-01-01

    Roč. 114, č. 42 (2010), s. 11304-11311 ISSN 1089-5639 R&D Projects: GA MŠk LC512; GA MŠk 1M0508; GA AV ČR IAAX00320901 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40320502 Keywords : noncovalent complex * carborane cage * dispersion Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.732, year: 2010

  1. Development and Optimization of a Positron Annihilation Lifetime Spectrometer to Measure Nanoscale Defects in Solids and Borane Cage Molecules in Aqueous Nitrate Solutions

    National Research Council Canada - National Science Library

    Ross, Matthew A

    2008-01-01

    .... The timing resolution of the optimized system is 197 +or- 14 ps as measured with a known (60)Co source. A single-crystal tungsten sample was used to confirm the system calibration resulting in a lifetime of 101...

  2. Substitution of the laser borane anti-B18H22with pyridine: a structural and photophysical study of some unusually structured macropolyhedral boron hydrides.

    Science.gov (United States)

    Londesborough, Michael G S; Dolanský, Jiří; Jelínek, Tomáš; Kennedy, John D; Císařová, Ivana; Kennedy, Robert D; Roca-Sanjuán, Daniel; Francés-Monerris, Antonio; Lang, Kamil; Clegg, William

    2018-01-30

    Reaction of anti-B 18 H 22 1 with pyridine in neutral solvents gives sparingly soluble B 16 H 18 -3',8'-Py 2 3a as the major product (ca. 53%) and B 18 H 20 -6',9'-Py 2 2 (ca. 15%) as the minor product, with small quantities of B 18 H 20 -8'-Py 4 (ca. 1%) also being formed. The three new compounds 2, 3a and 4 are characterized by single-crystal X-ray diffraction analyses and by multinuclear multiple-resonance NMR spectroscopy. Compound 2 is of ten-vertex nido:ten-vertex arachno two-atoms-in-common architecture, long postulated for a species with borons-only cluster constitution, but previously elusive. Compound 3a is of unprecedented ten-vertex nido:eight-vertex arachno two-atoms-in-common architecture. The single-crystal X-ray diffraction analysis for the picoline derivative B 16 H 18 (NC 5 H 4 Me) 2 3b, similarly obtained, is also presented. B 18 H 20 Py 4 is also previously unreported but is of known ten-vertex nido:ten-vertex nido two-atoms-in-common architecture of anti configuration, but now with the pyridine ligand positioned differently to other reported examples of B 18 H 20 L compounds. Factors behind the remarkably low solubility of 3a and 3b are elucidated in terms of electrostatic potential (ESP) calculations, polarity, and van der Waals complementarities. In view of contemporary developing high interest in the fluorescent properties of macropolyhedral boron-containing species, a detailed assessment of the photophysical characteristics of 3a and 4 is also presented. In contrast to the thermochromic fluorescence of 2 (from 620 nm brick-red at room temperature to 585 nm yellow at 8 K, quantum yield 0.15), compound 3a is only weakly phosphorescent in the yellow region (590 nm, quantum yield 0.01), whereas compound 4 exhibits no luminescence. The far more photoactive nature of compound 2 is associated with S 1 excited-state minima structures that differ from each other only by the relative rotational positions of the pyridine substituents on its disubstituted ten-vertex {arachno-B 10 Py 2 }-subcluster. The wavelength and relative intensity of fluorescence from these structures depends on the rotational positions of the pyridine ligands, which in turn are influenced by temperature and/or rotational inhibition in the solid-state.

  3. Bridged Heterocyclium Di-Cationic closo-Icosahedral Perfluoroborane, Borane, and Carborane Salts via Aqueous, Open-Air Benchtop Synthesis (Preprint)

    Science.gov (United States)

    2010-03-11

    DISTRIBUTION A. Approved for public release; distribution unlimited. 4 High Resolution Mass Spectometry ...currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1. REPORT DATE (DD-MM-YYYY) 11-03-2010 2. REPORT TYPE...Journal Article 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Bridged Heterocyclium Di-Cationic closo-Icosahedral

  4. Substitution of the laser borane anti-B18H22 with pyridine: a structural and photophysical study of some unusually structured acropolyhedral boron hydrides

    Czech Academy of Sciences Publication Activity Database

    Londesborough, Michael Geoffrey Stephen; Dolanský, Jiří; Jelínek, Tomáš; Kennedy, John David; Císařová, I.; Kennedy, R. G.; Roca-Sanjuan, D.; Frances-Monerris, A.; Lang, Kamil; Clegg, W.

    2018-01-01

    Roč. 47, č. 5 (2018), s. 1709-1725 ISSN 1477-9226 R&D Projects: GA ČR(CZ) GA18-20286S Institutional support: RVO:61388980 Keywords : containing cluster chemistry * nuclear-magnetic-resonance * 2nd-order perturbation-theory * self-consistent-field * o-carborane Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 4.029, year: 2016

  5. Mass spectroscopic evidence for icosaborane(26)

    International Nuclear Information System (INIS)

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

    1978-01-01

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

  6. Syntheses and structures of dimeric sodium and potassium ...

    Indian Academy of Sciences (India)

    diisopropyl-anilidophosphine borane ligand. KISHOR NAKTODE, JAYEETA BHATTACHARJEE, ANIRBAN CHAKRABARTI and. TARUN K PANDA∗. Department of Chemistry, Indian Institute of Technology Hyderabad, Ordnance Factory Estate,.

  7. supp9.doc

    Indian Academy of Sciences (India)

    anilidophosphine Borane Ligand. KISHOR NAKTODE, JAYEETA BHATTACHARJEE, ANIRBAN CHAKRABARTI AND TARUN K. PANDA*. Department of Chemistry, Indian Institute of Technology Hyderabad, Ordnance Factory Estate, Yeddumailaram 502205, ...

  8. Beyond alkyl transfer: Synthesis of main group metal (Mg, Ca, Zn) silyl and tris(oxazolinyl)borato complexes and their stoichiometric and catalytic reactions with borane Lewis acids and carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Lampland, Nicole Lynn [Iowa State Univ., Ames, IA (United States)

    2015-05-09

    Recently, the fundamental knowledge of main group metal chemistry has grown. This progress is crucial for the further development of main group metal compounds in silicon chemistry and catalysis and for advancing their applications as green alternatives to many rare earth and transition metal compounds. This thesis focuses on reactivity beyond the welldocumented alkyl-transfer applications for main group metals, and it highlights examples of reactions with Lewis acids and the reduction of carbonyls.

  9. Superovulation response and in vivo embryo production potential of ...

    African Journals Online (AJOL)

    Boran (n=25) and Boran*Holstein (n=11) cows were superovullatedFSH with three doses level (300, 250 and 200IU) divided in to morning and afternoon decreasing doses over 4 daysto study the superovulatory response and embryo production potential. Time to estrus, duration of estrus, and CL count were used to ...

  10. Defence Technology Strategy for the Demands of the 21st Century

    Science.gov (United States)

    2006-10-01

    hydrogen generator system utilising a chemical hydride (Ammonia borane). Ammonia borane pellets are sequentially decomposed to provide an electrical load...problems in the procurement of high quality steels, high hardness aluminium , copper, non-oxide ceramics and the more exotic materials such as titanium

  11. Enantioselective Reduction of Prochiral Ketones using Spiroborate Esters as Catalysts

    Science.gov (United States)

    Stepanenko, Viatcheslav; De Jesus, Melvin; Correa, Wildeliz; Guzman, Irisbel; Vazquez, Cindybeth; de la Cruz, Wilanet; Ortiz-Marciales, Margarita; Barnes, Charles L.

    2009-01-01

    Novel spiroborate esters derived nonracemic 1,2-aminoalcohols and ethylene glycol are reported as highly effective catalysts for the asymmetric borane reduction of a variety of prochiral ketones with borane-dimethyl sulfide complex at room temperature. Optically active alcohols were obtained in excellent chemical yields using 0.1 to 10 mol % of catalysts with up to 99% ee. PMID:19554205

  12. Nanoenergetics and High Hydrogen Content Materials for Space Propulsion

    Science.gov (United States)

    2014-01-28

    ammonia borane, and 3) the integration of nanomaterials into propellants and the combustion analysis of these materials. During the third and final...ammonia borane, and 3) the integration of nanomaterials into propellants and the combustion analysis of these materials. During the third and final...24 Figure 11: FTIR transmission spectra of the residue from AB pyrolysis at 160°C

  13. 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).

  14. 15th International Conference on Boron Chemistry (IMEBORON XV)

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Štíbr, Bohumil

    2015-01-01

    Roč. 87, č. 2 (2015), s. 121 ISSN 0033-4545 Institutional support: RVO:61388980 Keywords : boranes * boron * boron materials * carboranes * IMEBORON XV * medicinal chemistry Subject RIV: CA - Inorganic Chemistry

  15. Regeneration of polyborazylene

    Science.gov (United States)

    Davis, Benjamin L.; Gordon, John C.

    2010-12-07

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

  16. 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.

  17. Fuelling the future

    International Nuclear Information System (INIS)

    Anon.

    2008-01-01

    New routes to hydrogen storage materials, which could offer alternative fuel for cars, have been developed by two teams of the scientists in the US and in Singapore. Ammonia borane (NH 3 BH 3 ) has a high hydrogen content and is stable at room temperature, but has, in the past, proven difficult to prepare in high yield. Now, Tom Autrey and co-workers at the Pacific Northwest National Laboratory, Richland, US, have developed a new one-pot synthetic method to this solid material. Autrey's method requires in situ production of ammonium borohydride (NH 4 BH 4 ) by the addition of NH 4 X and MBH 4 salts (X= Cl, F, M=Na, Li) in liquid ammonia, followed by removal of the majority of the ammonia, then addition of tetrahydrofuran (THF) which causes the NH 4 BH 4 to decompose to ammonia borane in high yield. But at the moment hydrogen release from ammonia borane is not reversible, therefore Autrey says the 'long-term challenge is to regenerate ammonia borane from the spent storage material'. Another problem with ammonia borane is that its decomposition leads to the production of the volatile compound borazine as a by-product. Borazine can poison proton exchange membrane fuel cells. This issue has been addressed by another team, led by Ping Chen at the National University of Singapore. Chen proposes the use of sodium amino-borane (NaNH 2 BH 3 ) as an alternative to ammonia borane as it does not release borazine on decomposition. Chen's wet chemical method allows pure sodium amino-borane to be made. He proposes two routes, the faster of which involves adding sodium hydride (NaH) to a solution of ammonia borane in THF. The reaction occurs within 10 minutes at -3C, giving solid sodium amino-borane which can be filtered off. Xiong Zhitao, a member of Chen's team, says the most important aspect of this work is that 'it opened the road to a new class of materials comprising alkali or alkaline earth metal cation and (NH 2 BH 3 ) - anion for storing hydrogen. (O.M.)

  18. The Parent Hexacarbaborane .I.arachno./I.-C.sub.6./sub.B.sub.6./sub.H.sub.12./sub. and a Methylated Pentacarbaborane .I.arachno./I.-CH.sub.3./sub.C.sub.5./sub.B.sub.7./sub.H.sub.12./sub.: Domains of Incipient Hydrocarbon Behavior within Borane Clusters

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Jelínek, Tomáš; Plzák, Zbyněk; Kennedy, J. D.; Ormsby, D. L.; Greatrex, R.; Štíbr, Bohumil

    1999-01-01

    Roč. 38, č. 12 (1999), s. 1806-1808 ISSN 0044-8249 R&D Projects: GA ČR GA203/97/0060; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4032918 Keywords : NMR spectroscopy * carboranes * boron Subject RIV: CA - Inorganic Chemistry

  19. The boron connection: Roots (routes), grounds, horizons

    Science.gov (United States)

    Zdetsis, Aristides D.

    2012-12-01

    Isoelectronic and isolobal silicon-based analogues to boranes and borane complexes are considered and studied. The framework and the implementation of such isoelectronic and isolobal analogies initially between silicon clusters (cluster dianions) and isovalent boranes, known under the scoptical and synoptical name "boron connection" is critically analyzed and reviewed in considerable depth and breadth, paying special attention to its conceptual simplicity, origin, and originality. It is illustrated that such a concept can be extended to several borane complexes producing analogous silicon based (nano)structures. This is achieved by considering and evaluating several vertical, horizontal and diagonal relationships on the periodical table rooted on Si. It is shown that this type of simple and transparent relationships can lead to far reaching extensions and generalizations of the "boron connection" to encompass structural and electronic relationships between additional simple and mixed clusters based in addition to Si on other group 14 elements. Such clusters include, among others, simple Gen2- and Snn2- dianions and mixed Si-Bi, Ge-Bi and Sn-Bi clusters. Special emphasis is placed on molecular and material engineering and functionalization, in analogy to similar functionalization of borane based molecules and materials. It is illustrated that this enlarged and expanded project is very promising and could be very successful for the design of a practically unlimited number of new group-14-based complexes as well as the rationalization and fictionalization of newly synthesized materials.

  20. 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.

  1. Closo-alanes (Al4H4, AlnHn+2, 4 aluminum hydride chemistry.

    Science.gov (United States)

    Grubisic, A; Li, X; Stokes, S T; Cordes, J; Ganteför, G F; Bowen, K H; Kiran, B; Jena, P; Burgert, R; Schnöckel, H

    2007-05-09

    Anion photoelectron spectroscopy and density functional theory were employed to study aluminum hydride clusters, AlnHm- (4 aluminum versions of hypothetical diprotonated closo-borane dianions (BnHn2- + 2H+). In addition, Al4H4 assumes a closo-tetrahedral geometry, while Al4H6 takes on a distorted tetrahedral (D2d) structure with two counter-positioned bridging hydrogen atoms and has the largest HOMO-LUMO gap (1.9 eV) of all the alanes we studied. All of these species can be understood in terms of underlying polyhedral skeletal electron pair theory (PSEPT) concepts. Although, the herein studied alanes do not have direct borane analogues, the ability to understand their structures in terms of the Wade-Mingos rules and the underlying PSEPT concepts suggests that they can be considered as borane analogues, thereby opening a new chapter in aluminum hydride chemistry.

  2. Synthesis of boron nitride nanotubes with SiC nanowire as template

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  3. Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

    KAUST Repository

    Brzozowska, Aleksandra

    2018-03-30

    The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

  4. SUPPLEMENTARY VALUE OF VETCH (VICIA DASYCARPA) HAY ...

    African Journals Online (AJOL)

    Personal

    on feed intake and digestibility as well as milk production and composition in lactating F1 crossbred. (Boran x Friesian) cows fed .... the start of the experiment. The calves were separated from their dams five days after parturition. Experimental feeds. Vetch was harvested at 50% flowering, field cured, baled and stored in a ...

  5. Synthesis of telechelic vinyl/allyl functional siloxane copolymers with structural control

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt; Javakhishvili, Irakli; Jensen, Rasmus Egekjær

    2014-01-01

    Multifunctional siloxane copolymers with terminal vinyl or allyl functional groups are synthesised through the borane-catalysed polycondensation of hydrosilanes and alkoxysilanes. Copolymers of varying mole- cular weights ( M ̄ w =13200 – 70 300 g mol − 1 ), spatially well-distributed functional ...

  6. C-halogenation of the closo-[CB11H12](-) anion

    Czech Academy of Sciences Publication Activity Database

    Janoušek, Zbyněk; Hilton, C. L.; Schreiber, P. J.; Michl, J.

    2002-01-01

    Roč. 67, č. 7 (2002), s. 1025-1034 ISSN 0010-0765 R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * boron clusters * carboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 0.848, year: 2002

  7. The first metallacarborane triple-decker complexes with a bridging pentaphospholyl ligand

    Czech Academy of Sciences Publication Activity Database

    Loginov, D.A.; Vinogradov, M.M.; Starikova, ZA.; Petrovskii, PV.; Holub, Josef; Kudinov, AR.

    2010-01-01

    Roč. 75, č. 9 (2010), s. 981-993 ISSN 0010-0765 R&D Projects: GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : boranes * metallacarboranes * iron * sandwich compounds Subject RIV: CA - Inorganic Chemistry Impact factor: 0.853, year: 2010

  8. Author Details

    African Journals Online (AJOL)

    Changa, A. Vol 25, No 2 (2008) - Articles Relative performance of buffered Rose Bengal plate test (RBPT) and slow (tube) agglutination test (SAT) for detection of Brucella abortus antibodies in indigenous boran cattle in Tanzania Abstract. ISSN: 0856-1451. AJOL African Journals Online. HOW TO USE AJOL.

  9. Derivatization chemistry of the double-decker dicobalt sandwich ion targeted to design biologically active substances

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Švec, Petr; Hájková, Zuzana; Císařová, I.; Pokorná, Jana; Konvalinka, Jan

    2012-01-01

    Roč. 84, č. 11 (2012), s. 2243-2262 ISSN 0033-4545 R&D Projects: GA AV ČR IAAX00320901 Institutional support: RVO:61388980 ; RVO:61388963 Keywords : AIDS treatment * boranes * canastide ion * carboranes * dicarbollides * HIV -protease Subject RIV: CA - Inorganic Chemistry Impact factor: 3.386, year: 2012

  10. Macropolyhedral boron-containing cluster chemistry [S2B16H17](-). A new eighteen-vertex thiaborane anion

    Czech Academy of Sciences Publication Activity Database

    Carr, MJ.; Clegg, W.; Kennedy, J.D.; Londesborough, Michael Geoffrey Stephen; Kilner, C. A.

    2010-01-01

    Roč. 75, č. 8 (2010), s. 807-812 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40320502 Keywords : borane cluster * thiaborane * macropolyhedral Subject RIV: CA - Inorganic Chemistry Impact factor: 0.853, year: 2010

  11. Macropolyhedral boron-containing cluster chemistry. Ligand-induced two-electron variations of intercluster bonding intimacy. Structures of nineteen-vertex[(eta(5)-C5Me5) HIrB18H19(PMe2Ph)] and the related carbene complex [(eta(5)-C5Me5)HIrB18H19{C(NHMe)(2)}

    Czech Academy of Sciences Publication Activity Database

    Shea, SL.; Jelínek, Tomáš; Perera, SD.; Štíbr, Bohumil; Thornton-Pett, M.; Kennedy, JD.

    -, č. 10 (2004), s. 1521-1523 ISSN 1477-9226 R&D Projects: GA AV ČR IAA4032701 Institutional research plan: CEZ:AV0Z4032918 Keywords : carboranes * 19-vertex * boranes Subject RIV: CA - Inorganic Chemistry Impact factor: 2.926, year: 2004

  12. Monocarbaborane anion chemistry. Syntheses and structures within the closo nine-vertex system

    Czech Academy of Sciences Publication Activity Database

    Jelínek, Tomáš; Thornton-Pett, M.; Kennedy, J. D.

    2002-01-01

    Roč. 67, č. 7 (2002), s. 1035-1050 ISSN 0010-0765 R&D Projects: GA AV ČR IBS4032007 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * monocarbaboranes * thermolyses Subject RIV: CA - Inorganic Chemistry Impact factor: 0.848, year: 2002

  13. NMR ASSIGNMENTS OF [6-r-.I.nido./I.5,6-C.sub.2./sub.B.sub.8./sub.H.sub.10./sub.].sup.-./sup. ANIONS (WHERE R=H, Me, AND n-C.sub.6./sub.H.sub.13./sub.). AN IRREVERSIBLE 5 -> 6 ALKYL MIGRATION .I.via./I. A B9 VERTEX-SWING MECHANISM

    Czech Academy of Sciences Publication Activity Database

    Janoušek, Zbyněk; Kaszynski, P.; Kennedy, J. D.; Štíbr, Bohumil

    1999-01-01

    Roč. 64, č. 6 (1999), s. 986-992 ISSN 0010-0765 R&D Projects: GA ČR GA203/97/0060 Grant - others:NSF CAREER(US) DMR-9703002 Institutional research plan: CEZ:AV0Z4032918 Keywords : carboranes * boron clusters * boranes Subject RIV: CA - Inorganic Chemistry Impact factor: 0.717, year: 1999

  14. Ten-vertex rhodadithiaborane chemistry:[8-{I(CH2)5}-3-(.eta.5-C5Me5)-arachno-3,7,8,-RhS2B8H9

    Czech Academy of Sciences Publication Activity Database

    Marcías, R.; Barrett, S. A.; Bould, J.; Dörfler, U.; Holub, Josef; Kennedy, J. D.; Thornton-Pett, M.; Štíbr, Bohumil

    2001-01-01

    Roč. 57, č. 5 (2001), s. 520-522 ISSN 0108-2701 R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * heteroboranes * metalladithiaboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 0.570, year: 2001

  15. Macropolyhedral boron-containing cluster chemistry: two-electron variations in intercluster bonding intimacy. Contrasting structures of 19-vertex [(eta(5)-C5Me5)HIrB18H19(PHPh2)] and [(eta(5) -C5Me5)IrB18H18(PH2Ph)

    Czech Academy of Sciences Publication Activity Database

    Shea, S. L.; Jelínek, Tomáš; Perera, S. D.; Štíbr, Bohumil; Thorton-Pett, M.; Kennedy, J.D.

    2004-01-01

    Roč. 357, č. 10 (2004), s. 3119-3123 ISSN 0020-1693 Institutional research plan: CEZ:AV0Z4032918 Keywords : borane cluster * macropolyhedral opening and closure * X-ray structure Subject RIV: CA - Inorganic Chemistry Impact factor: 1.554, year: 2004

  16. Tanzania Veterinary Journal - Vol 25, No 2 (2008)

    African Journals Online (AJOL)

    Strategic control of ticks with synthetic pyrethroids in Theileria parva endemic areas in Tanzania increases calf growth and survival rates. GK Mbassa, FOK Mgongo, ... Factors affecting calving intervals, extracted milk yield and lactation length of Teso cattle and their crosses with Sahiwal and Boran. HE Mulindwa, GC Kifaro, ...

  17. Electrochemistry of parent and exo-skeletally substituted icosahedral monocarba and dicarbaboranes and their derivatives at the graphite carbon electrode in aqueous phosphate buffers

    Czech Academy of Sciences Publication Activity Database

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

    Roč. 730, SEP15 ( 2014 ), s. 16-19 ISSN 1572-6657 R&D Projects: GA ČR(CZ) GBP206/12/G151 Institutional support: RVO:68081707 ; RVO:61388980 Keywords : Boranes * Carboranes * Glassy carbon electrode Subject RIV: BO - Biophysics; CA - Inorganic Chemistry (UACH-T) Impact factor: 2.729, year: 2014

  18. The Zwitterion [8,8′-μ-CH2O(CH3)-(1,2-C2B9H10)2-3,3′-Co]0 as a Versatile Building Block To Introduce Cobalt Bis(Dicarbollide) Ion into Organic Molecules

    Czech Academy of Sciences Publication Activity Database

    Plešek, Jaromír; Grüner, Bohumír; Šícha, Václav; Böhmer, V.; Císařová, I.

    2012-01-01

    Roč. 31, č. 5 (2012), s. 1703-1715 ISSN 0276-7333 R&D Projects: GA MŠk LC523; GA AV ČR IAAX00320901 Institutional research plan: CEZ:AV0Z40320502 Keywords : boranes * carboranes * dicarbollides * X-ray diffraction * NMR Subject RIV: CA - Inorganic Chemistry Impact factor: 4.145, year: 2012

  19. Milk Yield and Quality of Crossbred Dairy Cows Fed with Different ...

    African Journals Online (AJOL)

    composition of 50:50 Boran-Freisian crossbred dairy cows fed a basal diet of napier grass (Penissetium ... appropriate options to produce quality feed supplements in the tropics. Many cultivated forage .... Chemical composition and in-vitro dry matter digestibility of napier grass, natural pasture hay, vetch (Vicia dasycarpa) ...

  20. Organic Monolayers by B(C

    NARCIS (Netherlands)

    Escorihuela Fuentes, Jorge; Pujari, Sidharam P.; Zuilhof, Han

    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

  1. Genetic and phenotypic parameters of reproduction and lactation ...

    African Journals Online (AJOL)

    This study was done to estimate genetic and phenotypic parameters for Friesian x Boran crossbred dairy cattle of Kagera region. Parameters estimated were heritability, repeatability and phenotypic correlations of various lactation and reproductive traits. Variance component (VARCOMP) procedure and general linear ...

  2. Author Details

    African Journals Online (AJOL)

    Kitilit, JK. Vol 68 (2002) - Articles Feeding sorghum silage and pyrethrum marc for sustained growth of Boran steers. Abstract. ISSN: 0012-8325. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's · More about AJOL · AJOL's Partners · Terms and Conditions of Use ...

  3. Kenya Veterinarian - Vol 28 (2005)

    African Journals Online (AJOL)

    Coat Colour: Its Relevance and Influence on Reproductive and Production Performance in Boran Cows · EMAIL FULL TEXT EMAIL FULL TEXT DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT. A M Okeyo, R O Mosi, J E Rege, 37-45. http://dx.doi.org/10.4314/kenvet.v28i1.39584 ...

  4. Untitled

    African Journals Online (AJOL)

    The reaction of mercaptomethyleiminium salts with sodium borohydride is used to synthesize alkylamine boranes in moderate to good yields. ... instrument was used for ir, spectra run as nujol mulls. All melting points (uncorrected) were ... cooled in ice-salt-water mixture. Thiobenzdimethylamide methiodide (X=H. Equation 2 ...

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

    Czech Academy of Sciences Publication Activity Database

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

    2004-01-01

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

  6. New ways to a series of parent representatives of the eight-, nine-, and ten-vertex monocarbaborane family

    Czech Academy of Sciences Publication Activity Database

    Brellochs, B.; Bačkovský, Jaroslav; Štíbr, Bohumil; Jelínek, Tomáš; Holub, Josef; Bakardjiev, Mario; Hnyk, Drahomír; Hofmann, M.; Cásařová, I.; Wrackmeyer, B.

    -, č. 18 (2004), s. 3605-3611 ISSN 1434-1948 R&D Projects: GA AV ČR IBS4032007; GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes * geometry optimization Subject RIV: CA - Inorganic Chemistry Impact factor: 2.336, year: 2004

  7. Metal-promoted cage rearrangements in the tricarbollide series: Conversion of ligand derivatives 7-L-nido-7,8,9-C3B8H10 (L=H3N, tBuH(2)N, Me2HN) into neutral 8-R-nido-7,8,9-C3B8H11 (R=H2N, tBuHN, Me2N) compounds

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Štíbr, Bohumil; Holub, Josef; Císařová, I.

    č. 8 (2003), s. 1533-1539 ISSN 1434-1948 R&D Projects: GA MŠk LN00A028; GA ČR GA203/00/1042 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes * NMR spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 2.482, year: 2003

  8. Metallacarborane chemistry of the hypho-[6,7-C2B6H13](-) anion: Reaction with nickelocene and the formation of three multimetallic nickel-boron clusters

    Czech Academy of Sciences Publication Activity Database

    Londesborough, Michael Geoffrey Stephen; Jelínek, Tomáš; Grüner, Bohumír; Štíbr, Bohumil; Císařová, I.; Carr, MJ.

    2005-01-01

    Roč. 690, č. 11 (2005), s. 2835-2839 ISSN 0022-328X R&D Projects: GA ČR(CZ) GA203/05/2646 Institutional research plan: CEZ:AV0Z40320502 Keywords : boranes * carboranes * metallacarboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 2.025, year: 2005

  9. Productivity of Indigenous and Exotic Cattle on Kenya Ranches ...

    African Journals Online (AJOL)

    A comparison of productivity and adaptability of indigenous (Boran and Small East African Zebu) and the exotic (Sahiwal and Ayrshire) cattle on Kenyan ranches located in semi-arid areas of the Rift Valley Provinces was done. Data sets of the cattle breeds over the 1979-1993 period on Deloraine, Elkarama, Ilkerin, ...

  10. Mechanisms of chemical generation of volatile hydrides for trace element determination (IUPAC Technical Report)

    Czech Academy of Sciences Publication Activity Database

    D'Ulivo, A.; Dědina, Jiří; Mester, Z.; Sturgeon, R. E.; Wang, Q.; Welz, B.

    2011-01-01

    Roč. 83, č. 6 (2011), s. 1283-1340 ISSN 0033-4545 Institutional research plan: CEZ:AV0Z40310501 Keywords : borane complexes * chemical generation of volatile hydrides (CHG) * volatile hydrides Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.789, year: 2011

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

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

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

  12. 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 polyamine...

  13. South African Journal of Animal Science - Vol 30 (2000)

    African Journals Online (AJOL)

    The reproductive performance of South African indigenous goats grazing Leucaena leucocephala pasture and natural veld during gestation · EMAIL FREE FULL ... Crossbreeding Holstein-Friesian with Ethiopian Boran cattle in a tropical highland environment: preliminary estimates of additive and heterotic effects on milk ...

  14. The synthesis of 10-halo-substituted derivatives of nido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]- and new linear correlations between NMR parameters

    Czech Academy of Sciences Publication Activity Database

    Holub, Josef; Bakardjiev, Mario; Štíbr, Bohumil

    2005-01-01

    Roč. 70, č. 11 (2005), s. 1861-1872 ISSN 0010-0765 R&D Projects: GA MŠk(CZ) LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : boron * carboranes * borane cluster Subject RIV: CA - Inorganic Chemistry Impact factor: 0.949, year: 2005

  15. Replacement of Concentrate Mix With Vetch ( Vicia dasycarpa ) Hay ...

    African Journals Online (AJOL)

    The experiment was conducted with the objective to assess the effect of replacing vetch for concentrate mix on feed intake and digestibility as well as milk production and composition in lactating crossbred (Boran x Friesian) cows kept on a basal feed of urea- molasses treated wheat straw (UMTWS). Eight crossbred cows of ...

  16. String theory and particle physics

    International Nuclear Information System (INIS)

    Uranga, Angel

    2006-01-01

    I will provide a basic introduction to string theory as a unified theory of gravitational and gauge interactions. I will review recent constructions of string theory models leading at low energies to the Standard Model of particle interactions, and which include interesting new phenomenology beyond the standard model, like supersymmetry, boranes, and (possible large) extra dimensions

  17. Two forgotten ten-vertex arachno triheteroboranes: arachno-5,6,9-C2SB7H11 and arachno-5,6,9-C3B7H13, their molecular structure determination by ab initio/nmr approach and synthesis of the thiacarbaborane

    Czech Academy of Sciences Publication Activity Database

    Hnyk, Drahomír; Holub, Josef

    2002-01-01

    Roč. 67, č. 6 (2002), s. 813-821 ISSN 0010-0765 R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes * thiaboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 0.848, year: 2002

  18. The first (tricarbollide)rhodium halide complexes

    Czech Academy of Sciences Publication Activity Database

    Loginov, D.A.; Starikova, ZA.; Petrovskii, PV.; Holub, Josef; Kudinov, AR.

    2011-01-01

    Roč. 14, č. 1 (2011), s. 313-315 ISSN 1387-7003 R&D Projects: GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : boranes * metallacarboranes * rhodium * tricarbollide Subject RIV: CA - Inorganic Chemistry Impact factor: 1.972, year: 2011

  19. Population structure and genetic trends for indigenous African beef ...

    African Journals Online (AJOL)

    The aim of this study was to investigate population structure and genetic trends based on pedigree and performance records of five indigenous African beef cattle breeds (Afrikaner, Boran, Drakensberger, Nguni and Tuli) in South Africa. Pedigree completeness over six generations was higher than 88.5% in the first ...

  20. Hydroboration of Graphene Oxide: Towards Stoichiometric Graphol and Hydroxygraphane

    Czech Academy of Sciences Publication Activity Database

    Poh, H. L.; Sofer, Z.; Šimek, P.; Tomandl, Ivo; Pumera, M.

    2015-01-01

    Roč. 21, č. 22 (2015), s. 8130-8136 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GA15-09001S; GA MŠk LM2011019 Institutional support: RVO:61389005 Keywords : boranes * electrochemistry * graphene * hydroboration * synthetic methods Subject RIV: CA - Inorganic Chemistry Impact factor: 5.771, year: 2015

  1. UJAS 35.pmd

    African Journals Online (AJOL)

    Prof. Adipala Ekwamu

    A study was carried out to evaluate growth performance of Zebu cattle and their crosses with. Sahiwal and Boran at the National Semi-Arid Resources Research Institute (NASARRI), Serere,. Uganda. Analysis of variance based on General Linear Model of SAS 2002 was used to analyse the data. The overall means for ...

  2. Author Details

    African Journals Online (AJOL)

    Relative performance of buffered Rose Bengal plate test (RBPT) and slow (tube) agglutination test (SAT) for detection of Brucella abortus antibodies in indigenous boran cattle in Tanzania Abstract · Vol 28 (2013): Special Issue - Articles Spatial distribution of non-clinical Rift Valley fever viral activity in domestic and wild ...

  3. Alpha shift correlation (ASC) method. Sensitivity of B-11 NMR shifts to halogen substitution in the ten-vertex nido and arachno series of boron clusters. Linear behavior of NMR effects

    Czech Academy of Sciences Publication Activity Database

    Štíbr, Bohumil

    2018-01-01

    Roč. 471, FEB (2018), s. 615-619 ISSN 0020-1693 R&D Projects: GA ČR(CZ) GA16-01618S Institutional support: RVO:61388980 Keywords : Boranes * Dicarbaboranes * NMR shifts- B NMR correlation 11 * Sensitivity factors * Substitution effects Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 2.002, year: 2016

  4. Amino-substituted ferra-bis(tricarbollides) - Metallatricarbaboranes designed for linear molecular constructions

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Bačkovský, Jaroslav; Sillanpää, R.; Kivekäs, R.; Císařová, I.; Teixidor, F.; Viñas, C.; Štíbr, Bohumil

    -, č. 7 (2004), s. 1402-1410 ISSN 1434-1948 R&D Projects: GA ČR GA203/00/1042; GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes * metallacarboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 2.336, year: 2004

  5. Monocarbaborane chemistry: Cage opening of nido-1-CB8H12 by tertiary bases - an example of a straightforward nido -> arachno transformation; Isolation of a new series of 4-L-arachno-5-CB8H12 compounds (L = NMe3, NEt3, and quinoline)

    Czech Academy of Sciences Publication Activity Database

    Štíbr, Bohumil; Holub, Josef; Bakardjiev, Mario; Milius, W.; Wrackmeyer, B.

    -, č. 18 (2004), s. 3601-3604 ISSN 1434-1948 R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes * monocarbaboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 2.336, year: 2004

  6. Investigation on reactivity of non-classical carbenes with sterically ...

    Indian Academy of Sciences (India)

    (OH2). ] (1). As a part of our ongoing research interest in aNHC chemistry,24 the present study reports the reactivity of the strongly acidic, sterically encumbered borane. B(C6F5)3 towards non-classical carbenes as Lewis bases. Herein we report the isolation and characteri- zation of four new boron compounds resulted by ...

  7. Formation of BH3 Adducts with Pyridine-2-Methylaminophosphine ...

    Indian Academy of Sciences (India)

    tional theoretical (DFT) calculations were performed on the BH3 adducts 1a and 2a. The results are consistent with the experimental results. Keywords. Pyridine; Borane; DFT calculation; X-ray analysis; HOMO; LUMO. 1. Introduction. Various P-N ligands are often used in organometallic chemistry to achieve well-defined ...

  8. Difluoroborane, a hydrogen-deuterium exchange catalyst. Application to pentaborane (9) and methylpentaborane (9)

    International Nuclear Information System (INIS)

    Kline, G.A.; Porter, R.F.

    1981-01-01

    The hydrogen exchange reaction of pentaborane with difluoroborane suggests the existence of a multicentered intermediate similar to that proposed by DeStefano and Porter for the difluoroborane-borazine exchange reaction. A similar intermediate may apply to the borane-pentaborane exchange reaction

  9. Facile two-electron reduction of a closo-rhodathiadecaborane

    Czech Academy of Sciences Publication Activity Database

    Luaces, S.; Bould, Jonathan; Macias, R.; Sancho, R.; Lahoz, F.J.; Oro, L.A.

    2012-01-01

    Roč. 41, č. 38 (2012), s. 11627-11634 ISSN 1477-9226 R&D Projects: GA ČR(CZ) GAP207/11/1577 Institutional research plan: CEZ:AV0Z40320502 Keywords : METALLATHIABORANE CLUSTER * BORANES * METALLACARBORANES * 11-VERTEX Subject RIV: CA - Inorganic Chemistry Impact factor: 3.806, year: 2012

  10. O tautomerii. Příběh objevu absolutní tautomerie, ojedinělého jevu v chemii

    Czech Academy of Sciences Publication Activity Database

    Štíbr, Bohumil

    2008-01-01

    Roč. 102, č. 10 (2008), s. 902-905 ISSN 0009-2770 R&D Projects: GA ČR GA203/05/2646 Institutional research plan: CEZ:AV0Z40320502 Keywords : borane * tautomerism * structural dualism Subject RIV: CA - Inorganic Chemistry Impact factor: 0.593, year: 2008

  11. Chemistry of cobalt bis(1,2-dicarbollide) ion; the synthesis of carbon substituted alkylamino derivatives from hydroxyalkyl derivatives via methylsulfonyl or p-toluenesulfonyl esters

    Czech Academy of Sciences Publication Activity Database

    Nekvinda, Jan; Švehla, Jaroslav; Císařová, I.; Grüner, Bohumír

    2015-01-01

    Roč. 798, č. 1 (2015), s. 112-120 ISSN 0022-328X R&D Projects: GA ČR GA15-05677S Institutional support: RVO:61388980 Keywords : Boranes * Carboranes * Metallacarboranes * Dicarbollide * Building blocks Subject RIV: CA - Inorganic Chemistry Impact factor: 2.336, year: 2015

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

    Czech Academy of Sciences Publication Activity Database

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

    2016-01-01

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

  13. Bovine Mastitis in Selected Districts of Borena Zone, Southern Ethiopia

    African Journals Online (AJOL)

    A cross-sectional study was conducted on 397 lactating Boran cows in pastoral areas of Borana Zone, Ethiopia to determine the prevalence of mastitis, major causes and associated risk factors of mastitis using California mastitis test and bacteriology. The study showed an overall prevalence of 70.8%; out of which 12.4% ...

  14. Short communication Population structure and genetic trends for ...

    African Journals Online (AJOL)

    user

    2016-05-23

    May 23, 2016 ... Abstract. The aim of this study was to investigate population structure and genetic trends based on pedigree and performance records of five indigenous African beef cattle breeds (Afrikaner, Boran, Drakensberger,. Nguni and Tuli) in South Africa. Pedigree completeness over six generations was higher ...

  15. The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides - A Simple and Versatile Approach to ortho-Functionalized Arylphosphine Oxides

    Czech Academy of Sciences Publication Activity Database

    Mahamulkar, Shraddha G.; Císařová, I.; Jahn, Ullrich

    2015-01-01

    Roč. 357, č. 4 (2015), s. 793-799 ISSN 1615-4150 R&D Projects: GA ČR GAP207/11/1598 Institutional support: RVO:61388963 Keywords : lithiation * nucleophilic substitution * organolithium reagents * phosphine oxides * phosphine-borane complexes Subject RIV: CC - Organic Chemistry Impact factor: 6.453, year: 2015

  16. 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.

  17. Thermal and epithermal neutrons in the treatment of neoplasms

    International Nuclear Information System (INIS)

    Sweet, W.H.; Wellum, G.; Tolpin, E.; Messer, J.R.

    1975-01-01

    Progress is reported in the preparation and testing of boron compounds for use as targets in the neutron capture therapy of neoplasms. The synthesis and structural confirmation of the disulfide, B 1 H 11 SSB 12 H 11 -4 is reported as well as a new structural model for its mono-oxidized derivative, B 12 H 11 SOSB 12 H 11 -4 , which showed useful tumor:blood concentration ratios in rats after three I. V. injections. The material, B 12 H 11 (SH) 2 -2 , was isolated and identified from impure Cs 2 B 12 H 11 SH. The former anion was shown to be responsible, in its oxidized form, for the excellent tumor uptake results shown by impure B 12 H 11 SH -2 in the past. As a consequence of this work, a borane polymer was synthesized which has shown extremely encouraging tumor uptake properties. The synthesis of this polymer depended on our production and characterization of the first stable thiyl radical at room temperature, B 12 H 11 -S: -2 . The retesting of certain phosphate boranes is reported. And a reagent, namely acetyl sulfenyl chloride, lSCOCH 3 , has been found which will produce B 12 H 11 SH -2 in a laboratory synthesis. The ability of sulfur derivatives of B 12 H 11 SH -2 to bind to proteins was examined, as was the blood distribution of two of these interesting boranes. The amount of non-protein bound borane was related to the rate of blood clearance of the borane in rats. Progress is also reported on dog irradiation experiments. (U.S.)

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

    International Nuclear Information System (INIS)

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

    1993-01-01

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

  19. 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.

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

    Science.gov (United States)

    Ley, Morten B.; Meggouh, Mariem; Moury, Romain; Peinecke, Kateryna; Felderhoff, Michael

    2015-01-01

    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. PMID:28793541

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

    KAUST Repository

    Wang, De

    2017-05-09

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

  2. Tuning the Phosphorescence and Solid State Luminescence of Triarylborane-Functionalized Acetylacetonato Platinum Complexes.

    Science.gov (United States)

    Rajendra Kumar, George; Thilagar, Pakkirisamy

    2016-12-05

    A new series of luminescent cyclometalated platinum complexes with triarylborane-functionalized acetylacetonate ligands is reported. The complexes exhibit solid state luminescence and phosphorescence under ambient conditions. The luminescence color can be tuned from green to red by varying the cyclometalating ligand [2-phenylpyridine (for 1 and 2), 2-thiophenylpyridine (for 3 and 4), 2-thianapthenylpyridine (for 5 and 6)]. The luminescence originates from mixed 3 MLCT/ 3 IL [MLCT, metal to ligand charge transfer; IL, intraligand] states of square planar platinum and borane moieties. The π spacer (phenyl or duryl) which connects the boryl and platinum entities has a significant role in determining the photoluminescence efficiency. The bulky duryl spacer in 2, 4, and 6 significantly reduces π-π stacking of the square planar platinum moiety in the solid state and provides a rigid backbone, thereby increasing their quantum yield significantly. The role of Lewis-acidic borane on the photoluminescence features is evaluated by fluoride binding experiments.

  3. Synthesis of phosphinic polyamine analogues and phosphorus labelled compounds towards new anticancer therapeutics; Synthese d'analogues phosphores de polyamines naturelles molecules marquees au phosphore-32 en vue d'une utilisation therapeutique anti-cancereuse

    Energy Technology Data Exchange (ETDEWEB)

    Fortineau, A.D

    1998-07-01

    This thesis deals with the synthesis of phosphorus molecules towards anticancer therapeutics. A simple method which allows the tri-alkyl-phosphines oxides synthesis radiolabelled by phosphorus 32 has been established, with a satisfactory specific activity for biological studies on animal model. A increase of the specific activity seems to be possible from the point of view of a human therapy utilization. Results on healthy mice are very hopeful. An original method to obtain N substituted amino-phosphonic acid esters, by reaction of an organo-borane with an azido-alkyl-phosphonate, has been tested. A simple method for the hydrolyze of esters phosphonic functions by the dichloro-boranes, has also been developed. (A.L.B.)

  4. 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.

  5. Metal interactions with boron clusters

    International Nuclear Information System (INIS)

    Grimes, R.N.

    1982-01-01

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

  6. The behavior of a paramagnetic system in electric and magnetic fields as exemplified by revisiting Li@B10H14

    Czech Academy of Sciences Publication Activity Database

    Medved, M.; Demissie, T.B.; McKee, M.L.; Hnyk, Drahomír

    2017-01-01

    Roč. 19, č. 19 (2017), s. 12229-12236 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GA16-01618S Institutional support: RVO:61388980 Keywords : nonlinear-optical properties * coupled-cluster theory * open -shell systems * 3-dimensional aromaticity * polyhedral boranes Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 4.123, year: 2016

  7. Development of Hazards Classification Data on Propellants and Explosives

    Science.gov (United States)

    1978-11-01

    fire if fuel is present - fluorine, halogen fluorides, LOX. Ill Container rupture or explosion -boranes, methane, ethylene oxide , LH_. IV...both fuel and oxidizer may be accom- plished using the procedures of TB700-2. This is impossible as either the tests in TB700-2 are not capable of...heat flux, firebrands, or fireball diameter. Fragment recovery and mapping is required; however, test procedures are nut specified. • No criteria

  8. Macropolyhedral boron-containing cluster chemistry: The reaction of syn-B18H22 with SMe2 and I2 in monoglyme: Structure of [7-(SMe2)-syn-B18H20

    Czech Academy of Sciences Publication Activity Database

    Jelínek, Tomáš; Grüner, Bohumír; Císařová, I.; Štíbr, Bohumil; Kennedy, D. J.

    2007-01-01

    Roč. 10, č. 2 (2007), s. 125-128 ISSN 1387-7003 R&D Projects: GA ČR GA203/05/2646; GA AV ČR(CZ) IAA400320601; GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : borane cluster * macropolyhedral * ligand addition Subject RIV: CA - Inorganic Chemistry Impact factor: 1.850, year: 2007

  9. Future boronated molecules for neutron capture therapy

    International Nuclear Information System (INIS)

    Soloway, A.H.; Alam, F.; Barth, R.F.

    1986-01-01

    The ability of several boron compounds to localize in tumor cells is examined. A number of first and second generation compounds which were not synthesized specifically for localization are described. Among these are the boron hydrides and boranes. A third generation of boron compounds are designed for selective localization. These fall into two groups: relatively small organic compounds and boronated antibodies, both of which are discussed here

  10. 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.

  11. Immigration and Unemployment Application of Game Theory on Diyarbakir: Istanbul Samples

    Science.gov (United States)

    Özgönül, Müge; Kaplan, Aslı

    The aim of this poster is to make a research about the relationship between unemployment and immigration. A mathematical model for the relationship between unemployment and immigration to İstanbul and Diyarbakır will be suggested by grade 11 International Baccalaureate Diploma Programme students, Boran Çıplak, Teoman Kenn Küçük, Emre Orhan, Meriç Tansi, Aysu Bulak, Özgün Karataş, Mavi Deniz Koçak.

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

    Science.gov (United States)

    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.

  13. Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions.

    Science.gov (United States)

    Metin, Önder; Sun, Xiaolian; Sun, Shouheng

    2013-02-07

    Monodisperse 4 nm AuPd alloy nanoparticles with controlled composition were synthesized by co-reduction of hydrogen tetrachloroaurate(III) hydrate and palladium(II) acetylacetonate with a borane-morpholine complex in oleylamine. These NPs showed high activity (TOF = 230 h(-1)) and stability in catalyzing formic acid dehydrogenation and hydrogen production in water at 50 °C without any additives.

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

    International Nuclear Information System (INIS)

    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

  15. An efficient synthesis of S-γ-[(4-trifluoromethyl)phenoxy] benzenepropanamine-[1-14C]maleate, an important metabolite of fluoxetine hydrochloride

    International Nuclear Information System (INIS)

    Wheeler, W.J.

    1992-01-01

    S-γ-[(4-Trifluoromethyl)phenoxy]benzenepropanamine-[1- 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-[ 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-γ-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[1- 14 C] maleate. (Author)

  16. 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).

  17. Thermochromic Fluorescence from B18H20(NC5H5)(2): An Inorganic-Organic Composite Luminescent Compound with an Unusual Molecular Geometry

    Czech Academy of Sciences Publication Activity Database

    Londesborough, Michael Geoffrey Stephen; Dolanský, Jiří; Cerdán, L.; Lang, Kamil; Jelínek, Tomáš; Oliva, J. M.; Hnyk, Drahomír; Roca-Sanjuan, D.; Frances-Monerris, A.; Martinčík, Jiří; Nikl, Martin; Kennedy, John David

    2017-01-01

    Roč. 5, č. 6 (2017), č. článku UNSP 1600694. ISSN 2195-1071 R&D Projects: GA ČR(CZ) GA13-09876S Institutional support: RVO:61388980 ; RVO:68378271 Keywords : boranes * energy transfer * fluorescence * solar concentrators * thermochromicity Subject RIV: CA - Inorganic Chemistry; BH - Optics, Masers, Lasers (FZU-D) OBOR OECD: Inorganic and nuclear chemistry; Optics (including laser optics and quantum optics) (FZU-D) Impact factor: 6.875, year: 2016

  18. Polyhalogenated Decaborate and 1-Ammoniododecaborate Ions: An Improved Synthesis with Elemental Halogens, and Physicochemical and Chemical Properties

    Czech Academy of Sciences Publication Activity Database

    Holub, Josef; El Anwar, Suzan; Jelínek, T.; Fojt, Lukáš; Růžičková, Z.; Šolínová, Veronika; Kašička, Václav; Gabel, D.; Grüner, Bohumír

    2017-01-01

    Roč. 2017, 38/39 (2017), s. 4499-4509 ISSN 1434-1948 R&D Projects: GA TA ČR(CZ) TH01020844 Institutional support: RVO:61388980 ; RVO:68081707 ; RVO:61388963 Keywords : Boranes * Borates * Capillary electrophoresis * Electrochemistry * Halogenation Subject RIV: CA - Inorganic Chemistry; BO - Biophysics (BFU-R) OBOR OECD: Inorganic and nuclear chemistry; Biophysics (BFU-R) Impact factor: 2.444, year: 2016

  19. Synthesis of 12-hydroxy and 12-dioxane derivatives of the closo-1-carbadodecaborate(1-) ion. Variations on the Plesek's cobalt bis(dicarbollide) pattern

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Císařová, I.; Čáslavský, Josef; Bronnetot, B.; Cornu, D.

    2002-01-01

    Roč. 67, č. 7 (2002), s. 953-964 ISSN 0010-0765 R&D Projects: GA MŠk LN00A028; GA ČR GA203/00/1042; GA ČR GA203/02/0436; GA ČR GA203/99/M037 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes * monocarbaboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 0.848, year: 2002

  20. An Experimental Solution to the "Missing Hydrogens" Question Surrounding the Macropolyhedral 19-Vertex Boron Hydride Monoanion [B19H22](-), a Simplification of Its Synthesis, and Its Use As an Intermediate in the First Example of syn-B18H22 to anti-B18H22 Isomer Conversion

    Czech Academy of Sciences Publication Activity Database

    Londesborough, Michael Geoffrey Stephen; Bould, Jonathan; Baše, Tomáš; Hnyk, Drahomír; Bakardjiev, Mario; Holub, Josef; Císařová, I.; Kennedy, D. J.

    2010-01-01

    Roč. 49, č. 9 (2010), s. 4092-4098 ISSN 0020-1669 R&D Projects: GA MŠk LC523; GA AV ČR IAA400320901; GA AV ČR(CZ) KAN400480701 Institutional research plan: CEZ:AV0Z40320502 Keywords : neutron-capture therapy * crystal-structure * boranes Subject RIV: CA - Inorganic Chemistry Impact factor: 4.326, year: 2010

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

    Czech Academy of Sciences Publication Activity Database

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

    2018-01-01

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

  2. Solid-state-reaction synthesis of cotton-like CoB alloy at room temperature as a catalyst for hydrogen generation.

    Science.gov (United States)

    Wang, Xingpu; Liao, Jinyun; Li, Hao; Wang, Hui; Wang, Rongfang

    2016-08-01

    A novel room-temperature solid-state reaction is developed to synthesize cotton-like CoB alloy (CoBSSR) catalysts with a large specific surface area of 222.4m(2)g(-1). In the hydrolysis of ammonia borane catalyzed by the CoBSSR, the rate of hydrogen generation can reach 68.7mLmin(-1) with a turnover frequency (TOF) value of ca. 6.9Lhydrogenmin(-1)gcatalyst(-1) at 25°C. The TOF value is about 2 times as large as that of CoB alloy prepared by a regular solid-state reaction, which is also much higher than those of the CoB catalysts recently reported in the literature. The activation energy of the hydrolysis of ammonia borane catalyzed by the CoBSSR is as low as 22.78kJmol(-1), hinting that the CoBSSR possesses high catalytic activity, which may be attributed to the large specific surface area and the abundant porous structure. The high catalytic performance, good recoverability and low cost of the CoBSSR enable it to be a promissing catalyst condidate in the hydrolysis of ammonia borane for hydrogen production in commercial application. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Communication: A novel method for generating molecular mixtures at extreme conditions: The case of hydrogen and oxygen

    International Nuclear Information System (INIS)

    Pravica, Michael; Sneed, Daniel; White, Melanie; Wang, Yonggang

    2014-01-01

    We have successfully created a segregated mixture of hydrogen and oxygen at high pressure in a diamond anvil cell using hard x-ray photochemistry. A keyhole (two holes connected by an opening) sample chamber was created in a metallic gasket to support two segregated powders of ammonia borane and potassium perchlorate, respectively, in each hole at a pressure of ∼5.0 GPa. Both holes were separately irradiated with synchrotron hard x-rays to release molecular oxygen and molecular hydrogen, respectively. Upon irradiation of the first KClO 4 -containing hole, solid reddish-orange O 2 appeared in the region of irradiation and molecular oxygen was found to diffuse throughout the entire sample region. The second ammonia borane-containing hole was then irradiated and H 2 was observed to form via Raman spectroscopy. Water also was observed in the ammonia borane-containing hole and possibly (in the form of ice VII) in the second hole. This unique experiment demonstrates the ability to easily create solid mixtures of simple molecular systems via x-ray irradiation and then react them via further irradiation which will aid the study of chemistry under extreme conditions

  4. New approaches to the design of polymer and liquid electrolytes for lithium batteries

    Science.gov (United States)

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

    All non-aqueous lithium battery electrolytes are Lewis bases that interact with cations. Unlike water, they do not interact with anions. The result is a high degree of ion pairing and the formation of triplets and higher aggregates. This decreases the conductivity and the lithium ion transference, and results in polarization losses in batteries. Approaches that have been used to increase ion dissociation in poly(ethylene oxide) (PEO)-based electrolytes are the use of salts with low lattice energy, the addition of polar plasticizers to the polymer, and the addition of cation complexing agents such as crown ethers or cryptands. Complexing of the anions is a more promising approach, since it should increase both ion dissociation and the lithium transference. At Brookhaven National Laboratory (BNL) we have synthesized two new families of neutral anion complexing agents, each based on Lewis acid centers. One is based on electron deficient nitrogen sites on substituted aza-ethers, wherein the hydrogen on the nitrogen is replaced by electron withdrawing groups such as CF 3SO 3-. The other is based on electron deficient boron sites on borane or borate compounds with various fluorinated aryl or alkyl groups. Some of the borane-based anion receptors can promote the dissolution of LiF in several solvents. Several of these compounds, when added in equivalent amounts, produce 1.2 M LiF solutions in DME, an increase in solubility of LiF by six orders of magnitude. Some of these LiF electrolytes have conductivities as high as 6×10 -3 S cm -1. The LiF electrolytes with borane anion acceptors in PC:EC:DEC solvents have excellent electrochemical stability. This has been demonstrated in small Li/LiMn 2O 4 cells.

  5. New Polymer and Liquid Electrolytes for Lithium Batteries

    International Nuclear Information System (INIS)

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

    1999-01-01

    All non-aqueous lithium battery electrolytes are Lewis bases that interact with cations. Unlike water, they don't interact with anions. The result is a high degree of ion pairing and the formation of triplets and higher aggregates. This decreases the conductivity and the lithium ion transference and results in polarization losses in batteries. Approaches that have been used to increase ion dissociation in PEO based electrolytes are the use of salts with low lattice energy, the addition of polar plasticizers to the polymer, and the addition of cation completing agents such as crown ethers or cryptands. Complexing of the anions is a more promising approach since it should increase both ion dissociation and the lithium transference. At Brookhaven National Laboratory (BNL) we have synthesized two new families of neutral anion completing agents, each based on Lewis acid centers. One is based on electron deficient nitrogen sites on substituted aza-ethers, wherein the hydrogen on the nitrogen is replaced by electron withdrawing groups such as CF 3 SO 3- . The other is based on electron deficient boron sites on borane or borate compounds with various fluorinated aryl or alkyl groups. Some of the borane based anion receptors can promote the dissolution of LiF in several solvents. Several of these compounds, when added in equivalent amounts, produce 1.2M LiF solutions in DME, an increase in volubility of LiF by six orders of magnitude. Some of these LiF electrolytes have conductivities as high as 6 x 10 -3 Scm -1 . The LiF electrolytes with borane anion acceptors in PC:EC:DEC solvents have excellent electrochemical stability. This has been demonstrated in small Li/LiMn 2 O 4 cells

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

    Science.gov (United States)

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

    2017-08-07

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

  7. The Synthesis, Characterization and Dehydrogenation of Sigma‐Complexes of BN‐Cyclohexanes

    Science.gov (United States)

    Kumar, Amit; Ishibashi, Jacob S. A.; Hooper, Thomas N.; Mikulas, Tanya C.; Dixon, David A.

    2015-01-01

    Abstract The coordination chemistry of the 1,2‐BN‐cyclohexanes 2,2‐R2‐1,2‐B,N‐C4H10 (R2=HH, MeH, Me2) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid‐state (X‐ray diffraction) characterization of [Ir(PCy3)2(H)2(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH) and [Rh(iPr2PCH2CH2CH2PiPr2)(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH, NMe2). For NR2=NH2 subsequent metal‐promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC4H8]3, via amino‐borane and, tentatively characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR2=NMeH the final product is the cyclic amino‐borane HBNMeC4H8. The mechanism of dehydrogenation of 2,2‐H,Me‐1,2‐B,N‐C4H10 using the {Rh(iPr2PCH2CH2CH2PiPr2)}+ catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh2(iPr2PCH2CH2CH2PiPr2)2H5][BArF 4]. Using the initial rate method starting from this dimer, a first‐order relationship to [amine‐borane], but half‐order to [Rh] is established, which is suggested to be due to a rapid dimer–monomer equilibrium operating. PMID:26602704

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

    Czech Academy of Sciences Publication Activity Database

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

    2014-01-01

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

  9. 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

    Beef production in Uganda is progressing from the traditional pastoral practices to sedentary semi-intensive systems. Consequently, farmers are continuously crossbreeding the indigenous cattle with exotic genotypes to improve meat yield. This study was conducted on-farm to evaluate the effects...... of feeding systems and feeding durations on performance of three locally available genotypes. A 2×3×3 factorial experiment was used to randomly allot 108 young bulls (9–15 months old), 36 for each of the three genotypes; Ankole x Holstein Friesian (AXF) (175±22 kg), pure Boran (208±34 kg) and a composite...

  10. Use of organoboranes in modern medical imaging

    International Nuclear Information System (INIS)

    Kabalka, G.W.

    1991-01-01

    Isotopically labeled materials have proven to be invaluable in chemical, medical, and biological research. Organoboranes are beginning to play a significant role in the synthesis of medically important materials which contain both stable and short-lived isotopes. The organic compounds of boron possess characteristics which make them ideal intermediates in radiopharmaceutical pathways; these include the facts that boron reactions tolerate a wide variety of physiologically active functionality and that the reactions proceed rapidly and in high yields. Boranes have found important applications in modern medical imaging techniques such as positron emission tomography (PET) and magnetic resonance imaging (MRI). (author)

  11. Macropolyhedral boron-containing cluster chemistry. Isolation and structure of the twenty-one-vertex globular cluster compound [(.eta..sup.5./sup.-C.sub.5./sub.Me.sub.5./sub.).sub.3./sub.Ir.sub.3./sub.B.sub.18./sub.H.sub.15./sub.(OH)].sup.1./sup..

    Czech Academy of Sciences Publication Activity Database

    Shea, S. L.; Jelínek, Tomáš; Štíbr, Bohumil; Thornton-Pett, M.; Kennedy, J. D.

    2000-01-01

    Roč. 3, č. 4 (2000), s. 169-172 ISSN 1387-7003 R&D Projects: GA AV ČR IAA4032701; GA ČR GA203/00/1042; GA AV ČR KSK2050602 Grant - others:EPSRC(GB) F/78323; EPSRC(GB) J/56929; EPSRC(GB) K/05818; EPSRC(GB) L/49505; EPSRC(GB) M/83360 Institutional research plan: CEZ:AV0Z4032918 Keywords : globular * cluster * borane Subject RIV: CA - Inorganic Chemistry Impact factor: 1.090, year: 2000

  12. 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.

  13. Pd-Boron-Catalyzed One Carbon Isomerization of Olefins: Water Assisted Process at Room Temperature.

    Science.gov (United States)

    Ojha, Devi Prasan; Gadde, Karthik; Prabhu, Kandikere Ramaiah

    2017-05-05

    A palladium-boronate/borane-system -catalyzed isomerization of olefins has been uncovered. An efficient catalytic combination of [Pd(OAc) 2 ] 3 -boronate-PCy 3 -enabled olefin isomerization at 80 °C has been investigated. Addition of water to the reaction showed a remarkable improvement and the isomerization occurred at ambient temperature. These catalytic systems function efficiently for the isomerization of functionalized as well as unfunctionalized olefins. The catalytic conditions demonstrate the involvement of both nonhydride and metal-hydride medium and can be switchable with water as an additive.

  14. 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.

  15. Untangling the Energetics and Dynamics of Boron Monoxide Radical Reactions (11BO; X2Sigma+)

    Science.gov (United States)

    2015-04-15

    Crossed Beam Reaction of Boron Monoxide with Benzene (P6) Organyl oxoboranes (RBO) are valuable reagents in organic synthesis due to their role in...technique, phenyl oxoborane (C6H5BO) is formed through the reaction of boronyl radicals (BO) with benzene (C6H6). The reaction is indirect...Phenyloxo-borane (C6H5BO) via the Reaction of Boron Monoxide with Benzene . JOC 78, 11896- 11900 (2013). P7. R.I. Kaiser, S. Maity, B. Dangi, A,H.H

  16. PowerPoint Presentation

    Indian Academy of Sciences (India)

    Slide 41 · Slide 42 · Slide 43 · Slide 44 · Slide 45 · Slide 46 · Slide 47 · Slide 48 · Slide 49 · Slide 50 · The mno Rule for Polycondensed Boranes, Metallaboranes, and Metallocenes · m+n+o = 2+21+0 = 23 ep 18BH + 3B 18+4.5 = 22.5 ep -1 charge · B30H24 m+n+o = 3+30+0 = 33 ep 24BH + 6B 24 + 9 =33 ep. neutral.

  17. 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).

  18. Selective hydroboration of catalyzed olephynes by new cationic complex of Rh(I) heterogeniated over zeolites; Hidroboracion selective de olefinas catalizada por nuevos complejos cationicos de Rh(I) heterogeneizador sobre zeolitas

    Energy Technology Data Exchange (ETDEWEB)

    Corma, A.; Dios, M.I.; Iglesias, M.; Sanchez, F. [Instituto de Quimica Organica, CSIC, Madrid (Spain)

    1995-12-01

    The synthesis and characterization of new cationic Rh(I) complexes with NN-ligands (1a,1b) and NP-ligands (2a-2b) are reported. The complexes bearing the triethoxysilil group were covalently bonded to a modified USY zeolite to give heterogeniated catalysts. The reaction of 1-decene, cyclohexene and styrene with catechol borane in presence of 1% mol of new prepared homogeneous and heterogenized Rh catalysts proceed regiselectively to give, after oxidation, 1-decanol, cyclohexanol and 1-phenylethanol respectively in excellent yields, whilts the more bulky 1-methylstyrene did not react at the same operations conditions. 11 refs.

  19. Functional silicone elastomers via novel siloxane copolymers and chain extenders

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt; Daugaard, Anders Egede; Hvilsted, Søren

    of siloxane copolymers[1] (via the tris(pentafluorophenyl)borane catalysed Piers-Rubinsztajn reaction[2]), which allows for the attachment of functional molecules through copper-catalysed azide-alkyne 1,3-dipolar cycloaddition (CuAAC)[3]. The synthesised copolymers allow for a high degree of chemical freedom...... by changing the feed of functional molecules. As a result, a completely tuneable elastomer system, with respect to functionalisation, is achieved. The second method of functionalising silicone elastomers involves the synthesis of a so-called ‘chain extender’ that allows for chemical modifications such as CuAAC...

  20. 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.

  1. 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.

  2. Soluble and meltable hyperbranched polyborosilazanes toward high-temperature stable SiBCN ceramics.

    Science.gov (United States)

    Kong, Jie; Wang, Minjun; Zou, Jianhua; An, Linan

    2015-04-01

    High-temperature stable siliconborocarbonitride (SiBCN) ceramics produced from single-source preceramic polymers have received increased attention in the last two decades. In this contribution, soluble and meltable polyborosilazanes with hyperbranched topology (hb-PBSZ) were synthesized via a convenient solvent-free, catalyst-free and one-pot A2 + B6 strategy, an aminolysis reaction of the A2 monomer of dichloromethylsilane and the B6 monomer of tris(dichloromethylsilylethyl)borane in the presence of hexamethyldisilazane. The amine transition reaction between the intermediates of dichlorotetramethyldisilazane and tri(trimethylsilylmethylchlorosilylethyl)borane led to the formation of dendritic units of aminedialkylborons rather than trialkylborons. The cross-linked hb-PBSZ precursors exhibited a ceramic yield higher 80%. The resultant SiBCN ceramics with a boron atomic composition of 6.0-8.5% and a representative formula of Si1B(0.19)C(1.21)N(0.39)O(0.08) showed high-temperature stability and retained their amorphous structure up to 1600 °C. These hyperbranched polyborosilazanes with soluble and meltable characteristics provide a new perspective for the design of preceramic polymers possessing advantages for high-temperature stable polymer-derived ceramics with complex structures/shapes.

  3. Formation of graphitic carbon nitride and boron carbon nitride film on sapphire substrate

    Science.gov (United States)

    Kosaka, Maito; Urakami, Noriyuki; Hashimoto, Yoshio

    2018-02-01

    As a novel production method of boron carbon nitride (BCN) films, in this paper, we present the incorporation of B into graphitic carbon nitride (g-C3N4). First, we investigated the formation of g-C3N4 films via chemical vapor deposition (CVD) using melamine powder as the precursor. The formation of g-C3N4 films on a c-plane sapphire substrate was confirmed by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Raman spectroscopy measurements. The deposition temperature of g-C3N4 films was found to be suitable between 550 and 600 °C since the degradation and desorption of hexagonal C–N bonds should be suppressed. As for BCN films, we prepared BCN films via two-zone extended CVD using ammonia borane as the B precursor. Several XPS signals from B, C, and N core levels were detected from B-incorporated g-C3N4 films. While the N composition was almost constant, the marked tendencies for increasing B composition and decreasing C composition were achieved with the increase in the B incorporation, indicating the incorporation of B atoms by the substitution for C atoms. Optical absorptions were shifted to the high-energy side by B incorporation, which indicates the successful formation of BCN films using melamine and ammonia borane powders as precursors.

  4. Facile Arylation of Four-Coordinate Boron Halides by Borenium Cation Mediated Boro-desilylation and -destannylation.

    Science.gov (United States)

    Crossley, Daniel L; Cid, Jessica; Curless, Liam D; Turner, Michael L; Ingleson, Michael J

    2015-12-28

    The addition of AlCl 3 to four-coordinate boranes of the general formula (C-N-chelate)BCl 2 results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl] + . The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl 3 were sufficient to effect high-yielding arylation of (C-N-chelate)BCl 2 . Boro-destannylation is more rapid than boro-desilylation and leads to double arylation at the boron center, whereas in reactions with arylsilanes either single or double arylation occurs dependent on the nucleophilicity of the arylsilane and on the electrophilicity of the borenium cation. The electrophilicity of the borenium cation derived from 2-phenylpyridine was greater than that of the benzothiadiazole analogues, enabling the boro-desilyation of less nucleophilic silanes and the direct electrophilic borylation of 2-methylthiophene.

  5. Direct synthesis of B-allyl and B-allenyldiisopinocampheylborane reagents using allyl or propargyl halides and indium metal under Barbier-type conditions.

    Science.gov (United States)

    Hirayama, Lacie C; Haddad, Terra D; Oliver, Allen G; Singaram, Bakthan

    2012-05-04

    We report the first one-pot process for the asymmetric addition of allyl, methallyl, and propargyl groups to aldehydes and ketones using B-chlorodiisopinocampheylborane ((d)DIP-Cl) and indium metal. Under Barbier-type conditions, indium metal was used to generate allyl- and allenylindium intermediates, and subsequent reaction with (d)DIP-Cl successfully promoted the transfer of these groups to boron forming the corresponding chiral borane reagents. The newly formed borane reagents were reacted with aldehydes and ketones to produce the corresponding alcohol products in high yields and up to excellent enantioselectivity (98% ee). This method produced excellent enantioenriched secondary homoallylic alcohols from the allylation and methallylation of benzaldehyde. Using this method, the methallylation and cinnamylation of ketones afforded the highest enantioselectivities, while the propargylation of both aldehydes and ketones provided low enantiomeric excesses. In addition, this procedure provided the first synthesis of B-allenyldiisopinocampheylborane, which was characterized by (1)H and (11)B NMR spectroscopy. This is the first example of the direct synthesis of allylboranes that contained substitutions from the corresponding allyl bromide and indium, thereby expanding the utility of the DIP-Cl reagent. Hence, a general and straightforward route to these chiral organoborane reagents in one-pot has been developed along with the asymmetric Barbier-type allylation and propargylation of aldehyde and ketone substrates using these chiral organoborane reagents in subsequent coupling reactions.

  6. Reactivity and catalytic activity of tert-butoxy-aluminium hydride reagents.

    Science.gov (United States)

    Less, Robert J; Simmonds, Hayley R; Wright, Dominic S

    2014-04-21

    The reactivity and catalytic activities of the tert-butoxy aluminium hydride reagents [((t)BuO)xAlH3-x] [x = 1 (1), 2 (2)] and (L)Li[((t)BuO)2AlH2] [L = THF (3), 1,4-dioxane (4)] are investigated. The structural characterisation of the novel compounds 3 and 4 shows that the nature of the hydridic species present is affected dramatically by the donor ligand coordinating the Li(+) cation. Stoichiometric reaction of 1 with pyridine gives [(1,4-H-pyrid-1-yl)4Al](-)[(pyridine)4AlH2](+) (5) while reaction with the amine-borane Me2NHBH3 in the presence of PMDETA [(Me2NCH2CH2)2NMe] affords [(PMDETA)AlH2](+)[(BH3)2NMe2](-) (6). The reagents 1-4 catalyse the dehydrocoupling reaction of the amine-borane Me2NHBH3 into the ring compound [Me2NBH2]2, with the activity decreasing in the order 1≫2∼3 > 4. The greater reactivity of the neutral dihydride 1 provides the potential basis for future catalytic optimisation.

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

    International Nuclear Information System (INIS)

    Haubner, R.; Tang, X.

    2001-01-01

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

  8. 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.

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

    DEFF Research Database (Denmark)

    Godskesen, Michael Anders

    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...... 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...... 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...

  10. Reactions of coordinated hydroxymethylphosphines with NH-functional amines: the phosphorus lone pair is crucial for the phosphorus Mannich reaction.

    Science.gov (United States)

    Swor, Charles D; Hanson, Kyle R; Zakharov, Lev N; Tyler, David R

    2011-09-14

    Non-coordinated hydroxymethylphosphines react readily with primary and secondary amines by the phosphorus Mannich reaction. To determine if this reactivity can be used to synthesize phosphine macrocycles, trans-Fe(DHMPE)(2)Cl(2) (DHMPE = 1,2-bis(dihydroxymethylphosphino)ethane) was prepared and reacted with various amines. However, no phosphorus Mannich reactivity was observed. In order to understand why no reactions occurred, the Mannich reactivity of the borane-coordinated hydroxymethylphosphines DHMPE·2BH(3) and Ph(2)PCH(2)OH·BH(3) was investigated. These borane-coordinated phosphines also did not undergo the phosphorus Mannich reaction. These results suggest that the lone pair of electrons on the phosphorus atom is essential for the phosphorus Mannich reaction to occur, and therefore it is not possible to use this reaction in a templated synthesis of phosphine macrocycles. It is speculated that the mechanism of the phosphorus Mannich reaction may involve a methylenephosphonium intermediate, analogous to an iminium in the standard Mannich reaction. X-ray crystal structures of trans-Fe(DHMPE)(2)Cl(2) and DHMPE·2BH(3) are also presented. Both crystal structures display an extended hydrogen-bonding network in the solid state. This journal is © The Royal Society of Chemistry 2011

  11. Electrochemical hydrogen Storage Systems

    International Nuclear Information System (INIS)

    Macdonald, Digby

    2010-01-01

    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 halides. To enable a

  12. 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

  13. 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 used at 5 wt. % loading throughout testing. The activation

  14. The chemical state of BSH following administration to patients with glioblastoma multiforme

    International Nuclear Information System (INIS)

    Gilbert, B.; Stasio, G. de; Andres, R.; Neumann, M.; Gabel, D.

    2000-01-01

    Laterally resolved x-ray absorption spectroscopy of tissue sections from patients administered with BSH consistently revealed a modified signal at the boron K-edge compared to spectra from BSH reference standards. Unusually for boron compounds, the energy position of this sharp resonance was below 190 eV. Spectroscopy of reference systems indicates that this signal is unlikely either to be a result of ionic bonding of BSH to proteins or phospholipids, or of the formation of disulfide bonds. The lineshape from tissue is most closely matched by the spectrum from a nido borane, suggesting that the BSH cage may be opened in vivo. The signal was not associated with our sample preparation procedures, and was not observed in control tissues. (author)

  15. Reactions of the tert-butylthiyl radical with organometallic compounds and alkenes

    Energy Technology Data Exchange (ETDEWEB)

    McPhee, D.J.; Campredon, M.; Lesage, M.; Griller, D. (National Research Council of Canada, Ottawa, Ontario (Canada))

    1989-09-13

    Absolute rate constants for the reactions of the tert-butylthiyl radical with a variety of substrates were measured by using a combination of laser flash photolysis techniques and product studies. Reactions with organometallic substrates such as boranes, phosphines, and phosphites were extremely rapid with rate constants in the range 10{sup 8}-10{sup 9} M{sup {minus}1} s{sup {minus}1}. By contrast, addition to a simple olefin, oct-1-ene, was ca. 100 times less rapid. However, 1,1-diphenyl- and 1,1-dicyclopropylethylene were remarkably efficient traps for tert-butylthiyl and scavenged the radical with rate constants of 9.9 {times} 10{sup 8} and 2.4 {times} 10{sup 8} M{sup {minus}1} s{sup {minus}1}, respectively.

  16. Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation

    Science.gov (United States)

    Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman

    2014-12-01

    Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.

  17. Technical Report (Final): Development of Solid State Reagents for Preparing Radiolabeled Imaging Agents

    Energy Technology Data Exchange (ETDEWEB)

    Kabalka, George W

    2011-05-20

    The goal of this research was on the development of new, rapid, and efficient synthetic methods for incorporating short-lived radionuclides into agents of use in measuring dynamic processes. The initial project period (Year 1) was focused on the preparation of stable, solid state precursors that could be used to efficiently incorporate short-lived radioisotopes into small molecules of use in biological applications (environmental, plant, and animal). The investigation included development and evaluation of new methods for preparing carbon-carbon and carbon-halogen bonds for use in constructing the substrates to be radiolabeled. The second phase (Year 2) was focused on developing isotope incorporation techniques using the stable, boronated polymeric precursors. The final phase (Year 3), was focused on the preparation of specific radiolabeled agents and evaluation of their biodistribution using micro-PET and micro-SPECT. In addition, we began the development of a new series of polymeric borane reagents based on polyethylene glycol backbones.

  18. 18O isotope shift in 15N NMR spectroscopy. 2. Synthesis of 15N, 18O-labeled hydroxylamine hydrochloride

    International Nuclear Information System (INIS)

    Rajendran, G.; Van Etten, R.L.

    1986-01-01

    Since hydroxylamine can serve as a key intermediate in the synthesis of a variety of compounds, the synthesis of [ 15 N, 18 O]-labelled hydroxylamine hydrochloride was undertaken. Published procedures for the synthesis of hydroxylamine resulted in poor yields in some cases and in lower percentage of 18 O in the product than expected in other cases. The compound was synthesized in dry tetrahydrofuran (THF) by treating NaNO 2 with borane-methyl sulfide. The course of the reaction was examined using 11 B NMR spectroscopy, and the product yield was 74%. The 18 O enrichment was demonstrated by both mass spectrometry and 15 N NMR of the isolated acetoxime. 23 references, 1 figure

  19. Synthesis of Plasmonic Cu2-x Se@ZnS Core@Shell Nanoparticles.

    Science.gov (United States)

    Wolf, Andreas; Härtling, Thomas; Hinrichs, Dominik; Dorfs, Dirk

    2016-03-03

    We report the synthesis of plasmonic Cu2-x Se@ZnS core@shell nanoparticles (NPs). We used a shell growth approach, starting from Cu2-x Se NPs that have been shown before to exhibit a localized surface plasmon resonance (LSPR). By careful synthesis planning we avoided cation exchange reactions and received core@shell nanoparticles that, after oxidation under air, exhibit a strong LSPR in the NIR. Interestingly, the crystalline, closed ZnS shell that we grew with variable thickness still allowed a slow oxidation of the core under ambient conditions, while the core was effectively protected from reduction, even in the presence of reducing agents such as borane tert-butyamine complex and diisobutylaluminum hydride, giving rise to a stable particle LSPR, also under strongly reducing conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Synthetic Strategies for High Dielectric Constant Silicone Elastomers

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt

    synthetic strategies were developed in this Ph.D. thesis, in order to create silicone elastomers with high dielectric constants and thereby higher energy densities. The work focused on maintaining important properties such as dielectric loss, electrical breakdown strength and elastic modulus...... extender’ that allowed for chemical modifications such as Cu- AAC. This route was promising for one-pot elastomer preparation and as a high dielectric constant additive to commercial silicone systems. The second approach used the borane-catalysed Piers-Rubinsztajn reaction to form spatially well...... of functional groups was identified. At a concentration of 5.6 wt% of a nitrobenzene functional group the dielectric permittivity increased 70% while at this loading important properties such as electrical breakdown strength, elastic modulus and dielectric loss were not significantly compromised. The developed...

  1. Ether and ester derivatives of the perborate icosahedron

    Science.gov (United States)

    Hawthorne, M. Frederick; Peymann, Toralf; Maderna, Andreas

    2003-12-16

    New boron icosahedral ethers and esters formed from Cs.sub.2 [closo-B.sub.12 (OH).sub.12 ],; Cs[closo-1-H-1-CB.sub.11 (OH).sub.11 ]; and closo-1,12-H.sub.2 -1,12-C.sub.2 B.sub.10 (OH).sub.10 are disclosed. Also set forth are their preparation by reacting the icosahedral boranes [closo-B.sub.12 H.sub.12 ].sup.2-, [closo-1-CB.sub.11 H.sub.12 ].sup.- and closo-1,12-(CH.sub.2 OH).sub.2 -1,12-C.sub.2 B.sub.10 H.sub.10 with an acid anhdride or acid chloride to form the ester or an alkylating agent to form the ether.

  2. Preparation and hydrogen-deuterium exchange of alkyl and hydride bis(trimethylsilyl)amido derivatives of the actinide elements

    International Nuclear Information System (INIS)

    Simpson, S.J.; Turner, H.W.; Andersen, R.A.

    1981-01-01

    The monomeric, hydrocarbon-soluble monohydrides and monodeuterides of the actinide metals (thorium or uranium) of the type HM[N(SiMe 3 ) 2 ] 3 have been prepared. Their reaction chemistry - n-BuLi followed by MeBr yields MeM[N(SiMe 3 ) 2 ] 3 and borane in tetrahydrofuran yields BH 4 M[N(SiMe 3 ) 2 ] 3 - suggests that the hydrogen atom is hydridic. Pyrolysis of the hydrides yields the novel, four-membered ring metallacycle [(Me 3 Si) 2 N] 2 MCH 2 Si(Me) 2 NSiMe 3 where M is Th or U. These metallacycles are the key intermediates in the hydrogen-deuterium exchange reaction that yields ([CD 3 ) 3 Si] 2 N) 3 MD

  3. A mass spectrometric investigation of the exchange of deuterium with tetraborane(10) in the gas phase

    International Nuclear Information System (INIS)

    Greatrex, R.; Greenwood, N.N.; Potter, C.D.

    1984-01-01

    Mass spectrometry has been used to establish direct exchange between dideuterium (D 2 ) and B 4 H 10 in the gas phase. In a mixture of stoicheiometry B 4 H 10 :3D 2 at 42 deg C, ca. 7% of the hydrogen atoms were replaced by deuterium in 130 min. The possibility that the exchange might be occurring by an indirect or autocatalytic mechanism was eliminated by a series of experiments in which the rate of exchange was shown to be independent of small admixtures of the decomposition products. The present work resolves a troublesome inconsistency in the literature and strengthens the view that the equilibrium B 4 H 10 brace B 4 H 8 brace + H 2 plays a key role in borane interconversion reactions. (author)

  4. 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

    . However, carcass quality grade scores were higher (Plive weight gain (ADG) for all genotypes was approximately twice under feedlot finishing compared to sole grazing while hot carcass...... 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...... DM per kg of body weight gain than the AXF and composite. Feed conversion ratio (kg DM/kg body weight gain) ranged between 6.3±0.6 to 8.2±1.5 at the feedlot and 11.1±4.1 to 17±4.0 for all genotypes and all durations. Growth and slaughter characteristics did not vary (P>0.05) between genotypes...

  5. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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.

  7. Acid-base properties of 1-methyl-1,4-dilhydroborabenzene, CH3BC5H6

    International Nuclear Information System (INIS)

    Sullivan, S.A.; Sandford, H.; Beauchamp, J.L.; Ashe, A.J. III

    1978-01-01

    Ion cyclotron resonance techniques are employed to determine the gas-phase Bronsted and Lewis acidities as well as the Bronsted basicity of 1-methyl-1,4-dihydroborabenzene, CH 3 BC 5 H 6 . The ring proton is found to be highly acidic with PA(CH 3 BC 5 H 5 - ) = 337 +- 3 kcal/mol. This acidity results from the formation of 6π electron aromatic anion CH 3 BC 5 H 5 - , which is isoelectronic with toluene. Both the Lewis acidity toward F - as a reference base and the proton basicity of the parent molecule suggest that there is little interaction between the diene π system and the electron-deficient boron. This is further confirmed by the similarity of both negative and positive ion chemistry of the borabenzene to that of aliphatic boranes

  8. Multicomponent Molecular Puzzles for Photofunction Design: Emission Color Variation in Lewis Acid-Base Pair Crystals Coupled with Guest-to-Host Charge Transfer Excitation.

    Science.gov (United States)

    Ono, Toshikazu; Sugimoto, Manabu; Hisaeda, Yoshio

    2015-08-05

    Simple yet ubiquitous multimolecular assembly systems with color-tunable emissions are realized by cooperative electron donor-acceptor interactions, such as the boron-nitrogen (B-N) dative bond as a Lewis acid-base pair and charge transfer (CT) interactions. These are ternary-component systems consisting of a naphthalenediimide derivative (NDI), tris(pentafluorophenyl)borane (TPFB), and aromatic molecules (guest) with an NDI:TPFB:guest ratio of 1:2:2. The crystal shows guest-dependent color-tunable emissions such as deep blue to orange when a guest molecule of benzene is replaced with other π-conjugated systems. A good correlation between the emission wavelength and ionization potential of the guest and electronic structure calculations indicated that the emission is due to the CT transition from the guest to the NDI. The present study suggests that a rational solution of multcomponent molecular puzzles would be useful for obtaining novel photofunctional solid-state systems.

  9. Boron clusters in luminescent materials.

    Science.gov (United States)

    Mukherjee, Sanjoy; Thilagar, Pakkirisamy

    2016-01-21

    In recent times, luminescent materials with tunable emission properties have found applications in almost all aspects of modern material sciences. Any discussion on the recent developments in luminescent materials would be incomplete if one does not account for the versatile photophysical features of boron containing compounds. Apart from triarylboranes and tetra-coordinate borate dyes, luminescent materials consisting of boron clusters have also found immense interest in recent times. Recent studies have unveiled the opportunities hidden within boranes, carboranes and metalloboranes, etc. as active constituents of luminescent materials. From simple illustrations of luminescence, to advanced applications in LASERs, OLEDs and bioimaging, etc., the unique features of such compounds and their promising versatility have already been established. In this review, recent revelations about the excellent photophysical properties of such materials are discussed.

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

    International Nuclear Information System (INIS)

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

    1992-01-01

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

  11. Occlusion and storage of krypton in solids

    International Nuclear Information System (INIS)

    Vansant, E.F.; Thijs, A.; Peeters, G.; Bievre, P. de; Verhaert, I.

    1984-01-01

    The modification process in order to change in a controlled way the effective pore size of zeolites was optimized by investigating the reaction conditions such as degree of chemisorption, reaction temperature, extent of primary/secondary reactions, type of modifying agent, type of substrate, etc. Different reaction and adsorption conditions have been tested to increase the thermal stability of encapsulated krypton in modified zeolites. The possibilities for zeolite modification have been enlarged by combining boranation and silanation with a thermal treatment of sepiolite, and by the formation of boron-nitrogen compounds in zeolites. Screening experiments, on a semi-industrial scale, of the krypton removal from air were carried out. Two kinds of Kr/air separation have been tested suscessfully on modified mordenite

  12. Chemical bonding in carbonitride nanolayers

    Science.gov (United States)

    Hoffmann, P.; Baake, O.; Beckhoff, B.; Ensinger, W.; Fainer, N.; Klein, A.; Kosinova, M.; Pollakowski, B.; Trunova, V.; Ulm, G.; Weser, J.

    2007-05-01

    First results are presented for the identification of chemical bonds and structures (speciation) in boron and silicon carbonitrides, produced as layers of some hundred nm. The boron carbonitride (BC xN y) films are synthesized by low-pressure chemical vapor deposition (LPCVD) using the precursor substance trimethylamine borane. The samples of silicon carbonitride (SiC xN y) films are synthesized by plasma-enhanced chemical vapor deposition (PECVD) using hexamethyl disilazane. The measurements were performed by total reflection X-ray fluorescence analysis combined with near-edge X-ray absorption fine structure investigations (TXRF-NEXAFS) and by X-ray photo-electron spectroscopy (XPS). The results are compared with those obtained for standard samples boron carbide (B 4C), boron nitride (e.g., h-BN, c-BN), silicon carbide (SiC), and silicon nitride (Si 3N 4).

  13. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis of variable size molecules using poly-homologation of boron compounds

    International Nuclear Information System (INIS)

    Goddard, J.P.

    2002-01-01

    During this work, we developed a method of original synthesis allowing to lead mixtures of molecules of variable size with an aim of discovering new chelating molecules of cesium. This method utilizes a reaction of poly-homologation of borated compounds with the nucleophilic ones comprising a grouping leaving in alpha of the negative charge. We tested various families from nucleophilic like anions of sulfones, sulfonium ylides, anions of hydrazones, tri-methylsilyldiazomethane and arsonium ylides. The first three families did not allow us to carry out reactions of poly-homologation. The tri-methylsilyldiazomethane possesses not either the capacity to carry out reactions successive insertions but this property was exploited to propose a chemical conversion of olefinic hydrocarbon into alkyl-methanol corresponding. The arsonium ylides made it possible to carry out reactions of poly-homologation with boronates and boranes. The alkyl-arsonium ylides were used to form polymers of controlled size having a ramification on each carbon atom of the principal chain. This type of polymer is not accessible by the current methods of polymerization. The allyl-arsonium ylides have a particular reactivity since the allyl boranes formed during the insertion reactions undergo a sigma-tropic [1,3] rearrangement before reacting again with a ylide. It is thus possible to lead with polymers of big size to which the structure is close to that of the natural rubber. By this method it is possible to lead with linear or cyclic polymers. This method is currently under development at the laboratory to form chelating structures of cesium. (author) [fr

  15. 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

  16. 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.

  17. Amineborane Based Chemical Hydrogen Storage - Final Report

    International Nuclear Information System (INIS)

    Sneddon, Larry G.

    2011-01-01

    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, NH 3 BH 3 (AB), 19.6-wt% H 2 , and ammonia triborane NH 3 B 3 H 7 (AT), 17.7-wt% H 2 , 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 H 2 -release and on new strategies for the regeneration the amineborane spent-fuel materials. The Penn approach to improving amineborane H 2 -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 H 2 -release, the tunability of both their H 2 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

  18. 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

  19. Synthesis, structures and thermal decomposition of ammine MxB12H12complexes (M = Li, Na, Ca).

    Science.gov (United States)

    Hansen, Bjarne R S; Tumanov, Nikolay; Santoru, Antonio; Pistidda, Claudio; Bednarcik, Jozef; Klassen, Thomas; Dornheim, Martin; Filinchuk, Yaroslav; Jensen, Torben R

    2017-06-28

    A series of ammine metal-dodecahydro-closo-dodecaboranes, M x B 12 H 12 ·nNH 3 (M = Li, Na, Ca) were synthesized and their structural and thermal properties studied with in situ time-resolved synchrotron radiation powder X-ray diffraction, thermal analysis, Fourier transformed infrared spectroscopy, and temperature-programmed photographic analysis. The synthesized compounds, Li 2 B 12 H 12 ·7NH 3 , Na 2 B 12 H 12 ·4NH 3 and CaB 12 H 12 ·6NH 3 , contain high amounts of NH 3 , 43.3, 26.6 and 35.9 wt% NH 3 , respectively, which can be released and absorbed reversibly at moderate conditions without decomposition, thereby making the closo-boranes favorable 'host' materials for ammonia or indirect hydrogen storage in the solid state. In this work, fifteen new ammine metal dodecahydro-closo-dodecaborane compounds are observed by powder X-ray diffraction, of which six are structurally characterized, Li 2 B 12 H 12 ·4NH 3 , Li 2 B 12 H 12 ·2NH 3 , Na 2 B 12 H 12 ·4NH 3 , Na 2 B 12 H 12 ·2NH 3 , CaB 12 H 12 ·4NH 3 and CaB 12 H 12 ·3NH 3 . Li 2 B 12 H 12 ·4NH 3 and Na 2 B 12 H 12 ·4NH 3 are isostructural and monoclinic (P2 1 /n) whereas Na 2 B 12 H 12 ·2NH 3 and CaB 12 H 12 ·3NH 3 are both trigonal with space groups P3[combining macron]m1 and R3[combining macron]c, respectively. Generally, coordination between the metal and the icosahedral closo-borane anion is diverse and includes point sharing, edge sharing, or face sharing, while coordination of ammonia always occurs via the lone pair on nitrogen to the metal. Furthermore, a liquid intermediate is observed during heating of Li 2 B 12 H 12 ·7NH 3 . This work provides deeper insight into the structural, physical, and chemical properties related to thermal decomposition and possible ammonia and hydrogen storage.

  20. 1,3-Diene Polymerization Mediated by Homoleptic Tetramethylaluminates of the Rare-Earth Metals

    Directory of Open Access Journals (Sweden)

    Christoph O. Hollfelder

    2018-02-01

    Full Text Available During the past two decades homoleptic tetramethylaluminates of the trivalent rare-earth metals, Ln(AlMe43, have emerged as useful components for efficient catalyst design in the field of 1,3-diene polymerization. Previous work had focused on isoprene polymerization applying Ln(AlMe43 precatalysts with Ln = La, Ce, Pr, Nd, Gd and Y, in the presence of Et2AlCl as an activator. Polymerizations employing Ln(AlMe43 with Ln = La, Y and Nd along with borate/borane co-catalysts [Ph3C][B(C6F54], [PhNMe2H][B(C6F54] and [B(C6F53] were mainly investigated for reasons of comparison with ancillary ligand-supported systems (cf. half-sandwich complexes. The present study investigates into a total of eleven rare-earth elements, namely Ln = La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Er and Lu. A full overview on the polymerization behavior of Ln(AlMe43 in the presence of perfluorinated borate/borane cocatalysts and R2AlCl-type activators (R = Me, Et is provided, probing the monomers isoprene and 1,3-butadiene (and preliminary ethylene. Virtually complete cis-1,4-selectivities are obtained for several catalyst/cocatalyst combinations (e.g., Gd(AlMe43/Me2AlCl, >99.9%. Insights into the ‘black box’ of active species are obtained by indirect observations via screening of pre-reaction time and cocatalyst concentration. The microstructure of the polydienes is investigated by combined 1H/13C NMR and ATR-IR spectroscopies. Furthermore, the reaction of [LuMe6(Li(thfx3] with AlMe3 has been applied as a new strategy for the efficient synthesis of Lu(AlMe43. The solid-state structures of Gd(AlMe43 and Tb(AlMe43 are reported.

  1. Reversible Coordination of Boron-, Aluminum-, Zinc-, Magnesium-, and Calcium-Hydrogen Bonds to Bent {CuL2} Fragments: Heavy σ Complexes of the Lightest Coinage Metal.

    Science.gov (United States)

    Hicken, Alexandra; White, Andrew J P; Crimmin, Mark R

    2017-08-07

    A series of copper(I) complexes bearing electron-deficient β-diketiminate ligands have been prepared. The study includes [{{ArNC(CR 3 )} 2 CH}Cu(η 2 -toluene) n ] (Ar = Mes, R = F, n = 0.5, [1 2 ·tol]; Ar = C 6 F 5 , R = Me, n = 1, [2·tol]; Ar = 2,6-Cl 2 C 6 H 3 , R = H, n = 0.5, [3 2 ·tol]). Reactions of [1-3 n ·tol] with boranes, alanes, a zinc hydride, a magnesium hydride, and a calcium hydride generate the corresponding σ complexes ([1-3·B], [3·B'], [3·Al], [3·Al'], [1-3·Zn], [1·Mg], and [1·Ca]). These species all form reversibly, being in equilibrium with the arene solvates in solution. With the exception of the calcium complex, the complexes have all been characterized by single-crystal X-ray diffraction studies. In solution, the σ-hydride of the aluminum, zinc, magnesium, and calcium derivatives resonates between -0.12 and -1.77 ppm (C 6 D 6 or toluene-d 8 , 193-298 K). For the σ-borane complexes, the hydrides are observed as a single resonance between 2 and 3.5 ppm (C 6 D 6 , 298 K) and bridging and terminal hydrides rapidly exchange on the NMR time scale even at 193 K. Quantification of the solution dynamics by van't Hoff analysis yields expectedly small values of ΔH° and negative values of ΔS° consistent with weak binding and a reversible process that does not involve aggregation of the copper species. The donor-acceptor complexes can be rationalized in terms of the Dewar-Chatt-Duncanson model. Density functional theory calculations show that the donation of σ-M-H (or E-H) electrons into the 4s-based orbital (LUMO or LUMO+1) of the copper fragment is accompanied by weak back-donation from a d xz -based orbital (HOMO or HOMO-1) into the σ*-M-H (or E-H) orbital.

  2. 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

  3. Performance of Beef Steers Fed Brewers Grain Ensiled With Hay or Forage

    International Nuclear Information System (INIS)

    Irungu, K.R.G.; Keingatti, R.K.; Abate, A.N.

    1999-01-01

    yearling Boran beef steers were fed on brewers grain ensiled with Rhodes grass hay or sorghum silage to assess steer nutrient intake, growth and fed conversion efficiency. Forage sorghum variety 'E6518' harvested at grain milk growth stage produced young sorghum silage while that harvested beyond had dough stage made old sorghum silage. At ensiling, brewers grain was mixed with hay, young or old sorghum at ratio of 60:40, 50:50 and 50:50 to produce silage A, B and C. Thirty Boran Steers were used in the experiment where 10 steers were fed on each of the three types of silage. The initial steer group weight averaged 187.6, 188.6 and 186.2 kg for those on diet A, B and C. The steers ate silage A,B and C for 68 days, the initial 12 days being the adaptation period. The pH of A, B and C were 4.7, 4.6 and 4.7. The mean composition of A, B and C were dry matter, 27.5, 23.2 and 23.4%, organic matter, 91.4, 90.0 and 90.3%, crude protein, 12.1 11.2 and 9.8%, crude fibre,26.5, 24.2 and 25.3%. Steer dry matter intake was 3.1, 4.3 and 4.5 kg on A, B and C. Diet A caused loss in steer weight while B and C produced steady growth. Steers on A lost 243 g daily while those on B and C gained 357 and 371 g daily. Feed efficiency expressed in gain per 100 kg dry matter was negative on A but 8.28 and 8.30 kg on B and C. The steer growth rates are similar to cattle grazed on improved ley or fodder and fed a limited amount of concentrates. The three types of silage required protein supplementation to increase growth

  4. Synthesis of functional boron or aluminium nitride materials for energy applications (production and storage of hydrogen)

    International Nuclear Information System (INIS)

    Salameh, Chrystelle

    2014-01-01

    Porous inorganic materials are of great interest owing to their potential in energy applications. The general objective of the present thesis concerns the development of functional (carbon)nitrides for hydrogen generation and storage (material design, elaboration, properties and applications). The PDCs route, which offers a large number of opportunities in chemistry and ceramic sciences, has been applied to produce functional (carbon)nitrides materials. Firstly, we prepared porous binary systems such as AlN and BN by replicating the structure of CMK-3 and that of activated carbon. After pyrolysis and removal of the template, we demonstrated the feasibility of producing nitrides with tailored porosity. Moreover, by coupling the PDCs route with the aerogel technology, we succeeded in preparing polymer-derived AlN and BN aerogels. We assessed the potential of these porous AlN and BN materials in nano-confinement of two chemical hydrides, namely sodium alanate and ammonia borane, respectively. In both cases, the nano-confinement destabilized the network of the hydride and favored the release of H 2 at low temperature. Besides, in the case of nano-confined ammonia borane, no evolution of undesired gaseous by-products was observed, which means that pure hydrogen was produced in our conditions. Secondly, we prepared porous quaternary systems through the association of AlN/BN with Si-based ceramics. In particular, we investigated the preparation of SiAlCN with tailored porosity by using two approaches: the 'molecular building block' and 'single-source precursor' approaches. Concerning the former, we investigated the preparation of ordered meso-porous materials to be used as catalytic supports for hydrolysis of alkaline solution of sodium borohydride. We succeeded in generating high amounts of H 2 with attractive kinetics. Concerning the latter approach, the work was focused on the investigation of the chemistry of SiAlCN and SiBCN materials with a

  5. 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)

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

    Science.gov (United States)

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

    2012-07-23

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

  7. Sequence diversity between class I MHC loci of African native and introduced Bos taurus cattle in Theileria parva endemic regions: in silico peptide binding prediction identifies distinct functional clusters.

    Science.gov (United States)

    Obara, Isaiah; Nielsen, Morten; Jeschek, Marie; Nijhof, Ard; Mazzoni, Camila J; Svitek, Nicholas; Steinaa, Lucilla; Awino, Elias; Olds, Cassandra; Jabbar, Ahmed; Clausen, Peter-Henning; Bishop, Richard P

    2016-05-01

    There is strong evidence that the immunity induced by live vaccination for control of the protozoan parasite Theileria parva is mediated by class I MHC-restricted CD8(+) T cells directed against the schizont stage of the parasite that infects bovine lymphocytes. The functional competency of class I MHC genes is dependent on the presence of codons specifying certain critical amino acid residues that line the peptide binding groove. Compared with European Bos taurus in which class I MHC allelic polymorphisms have been examined extensively, published data on class I MHC transcripts in African taurines in T. parva endemic areas is very limited. We utilized the multiplexing capabilities of 454 pyrosequencing to make an initial assessment of class I MHC allelic diversity in a population of Ankole cattle. We also typed a population of exotic Holstein cattle from an African ranch for class I MHC and investigated the extent, if any, that their peptide-binding motifs overlapped with those of Ankole cattle. We report the identification of 18 novel allelic sequences in Ankole cattle and provide evidence of positive selection for sequence diversity, including in residues that predominantly interact with peptides. In silico functional analysis resulted in peptide binding specificities that were largely distinct between the two breeds. We also demonstrate that CD8(+) T cells derived from Ankole cattle that are seropositive for T. parva do not recognize vaccine candidate antigens originally identified in Holstein and Boran (Bos indicus) cattle breeds.

  8. Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds.

    Science.gov (United States)

    Fux, Samuel; Jacob, Christoph R; Neugebauer, Johannes; Visscher, Lucas; Reiher, Markus

    2010-04-28

    The frozen-density embedding (FDE) scheme [Wesolowski and Warshel, J. Phys. Chem. 97, 8050 (1993)] relies on the use of approximations for the kinetic-energy component v(T)[rho(1),rho(2)] of the embedding potential. While with approximations derived from generalized-gradient approximation kinetic-energy density functional weak interactions between subsystems such as hydrogen bonds can be described rather accurately, these approximations break down for bonds with a covalent character. Thus, to be able to directly apply the FDE scheme to subsystems connected by covalent bonds, improved approximations to v(T) are needed. As a first step toward this goal, we have implemented a method for the numerical calculation of accurate references for v(T). We present accurate embedding potentials for a selected set of model systems, in which the subsystems are connected by hydrogen bonds of various strength (water dimer and F-H-F(-)), a coordination bond (ammonia borane), and a prototypical covalent bond (ethane). These accurate potentials are analyzed and compared to those obtained from popular kinetic-energy density functionals.

  9. 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.)

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

    Energy Technology Data Exchange (ETDEWEB)

    Hua, Wang, E-mail: wmsu2008@sinano.ac.cn, E-mail: wanghua001@tyut.edu.cn; Du, Xiaogang [Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology, Ministry of Education, Taiyuan 030024 (China); Research Center of Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Su, Wenming, E-mail: wmsu2008@sinano.ac.cn, E-mail: wanghua001@tyut.edu.cn; Zhang, Dongyu [Printable Electronics Research Centre, Suzhou Institute of Nano-Tech and Nano-Bionics, CAS, suzhou 215123 (China); Lin, Wenjing [Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology, Ministry of Education, Taiyuan 030024 (China); Research Center of Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Printable Electronics Research Centre, Suzhou Institute of Nano-Tech and Nano-Bionics, CAS, suzhou 215123 (China)

    2014-02-15

    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{sup ′}-N,N{sup ′}-dicarbazole)biphenyl (CBP) : tris(2-phenylquinoline-C2,N{sup ′})iridium(III) (Ir(2-phq){sub 3}) was sandwiched by double blue-light emission layers of 1,1-bis-[(di-4-tolylamino)pheny1]cyclohexane (TAPC) : bis[4,6-(di-fluorophenyl)-pyridinato-N,C2{sup ′}]picolinate (FIrpic) and tris[3-(3-pyridyl)mesityl]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/m{sup 2}. 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.

  12. 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.

  13. From ``structural democracy'' to ``boron connection''

    Science.gov (United States)

    Zdetsis, Aristides D.

    2009-03-01

    It is shown here that the Si62--B6H62- analogy [A. D. Zdetsis J. Chem. Phys., 127, 014314 (2007)] originated from the fluxionality of Si6 cluster can be extended and generalized in such a way as to include silicon-carbon clusters of the form Sin-2C2H2, n = 3-7, which are fully homologous and isolobal to the corresponding isovalent carboranes C2Bn_-Hn. This is an extended version of the "boron connection" suggested recently by the author [J. Chem. Phys., 128, 184305 (2008)]. Further extensions and generalizations are possible, but not necessarily as successful as the Si62--B6H62 and Sin-2C2H2-C2Bn-2Hn, n = 3-7, isolobal analogies. It is furthermore demonstrated that these ideas and concepts which are "aesthetically appealing" are also very useful and powerful despite their simplicity. It is anticipated that such strong and successful analogies would facilitate the exploitation of the rich borane/carborane Chemistry for the design and development of novel silicon, carbon, and silicon-carbon composite materials.

  14. IR-Driven Ultrafast Transfer of Plasmonic Hot Electrons in Nonmetallic Branched Heterostructures for Enhanced H2Generation.

    Science.gov (United States)

    Zhang, Zhenyi; Jiang, Xiaoyi; Liu, Benkang; Guo, Lijiao; Lu, Na; Wang, Li; Huang, Jindou; Liu, Kuichao; Dong, Bin

    2018-03-01

    The ultrafast transfer of plasmon-induced hot electrons is considered an effective kinetics process to enhance the photoconversion efficiencies of semiconductors through strong localized surface plasmon resonance (LSPR) of plasmonic nanostructures. Although this classical sensitization approach is widely used in noble-metal-semiconductor systems, it remains unclear in nonmetallic plasmonic heterostructures. Here, by combining ultrafast transient absorption spectroscopy with theoretical simulations, IR-driven transfer of plasmon-induced hot electron in a nonmetallic branched heterostructure is demonstrated, which is fabricated through solvothermal growth of plasmonic W 18 O 49 nanowires (as branches) onto TiO 2 electrospun nanofibers (as backbones). The ultrafast transfer of hot electron from the W 18 O 49 branches to the TiO 2 backbones occurs within a timeframe on the order of 200 fs with very large rate constants ranging from 3.8 × 10 12 to 5.5 × 10 12 s -1 . Upon LSPR excitation by low-energy IR photons, the W 18 O 49 /TiO 2 branched heterostructure exhibits obviously enhanced catalytic H 2 generation from ammonia borane compared with that of W 18 O 49 nanowires. Further investigations by finely controlling experimental conditions unambiguously confirm that this plasmon-enhanced catalytic activity arises from the transfer of hot electron rather than from the photothermal effect. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Hypovalency--a kinetic-energy density description of a 4c-2e bond.

    Science.gov (United States)

    Jacobsen, Heiko

    2009-06-07

    A bond descriptor based on the kinetic energy density, the localized-orbital locator (LOL), is used to characterize the nature of the chemical bond in electron deficient multi-center bonds. The boranes B(2)H(6), B(4)H(4), B(4)H(10), [B(6)H(6)](2-), and [B(6)H(7)](-) serve as prototypical examples of hypovalent 3c-2e and 4c-2e bonding. The kinetic energy density is derived from a set of Kohn-Sham orbitals obtained from pure density functional calculations (PBE/TZVP), and the topology of LOL is analyzed in terms of (3,-3) attractors (Gamma). The B-B-B and B-H-B 3c-2e, and the B-B-H-B 4c-2e bonding situations are defined by their own characteristic LOL profiles. The presence of one attractor in relation to the three or four atoms that are engaged in electron deficient bonding provides sufficient indication of the type of 3c-2e or 4c-2e bond present. For the 4c-2e bond in [B(6)H(7)](-) the LOL analysis is compared to results from an experimental QTAIM study.

  16. Occupational Neurotoxic Diseases in Taiwan

    Directory of Open Access Journals (Sweden)

    Chi-Hung Liu

    2012-12-01

    Full Text Available Occupational neurotoxic diseases have become increasingly common in Taiwan due to industrialization. Over the past 40 years, Taiwan has transformed from an agricultural society to an industrial society. The most common neurotoxic diseases also changed from organophosphate poisoning to heavy metal intoxication, and then to organic solvent and semiconductor agent poisoning. The nervous system is particularly vulnerable to toxic agents because of its high metabolic rate. Neurological manifestations may be transient or permanent, and may range from cognitive dysfunction, cerebellar ataxia, Parkinsonism, sensorimotor neuropathy and autonomic dysfunction to neuromuscular junction disorders. This study attempts to provide a review of the major outbreaks of occupational neurotoxins from 1968 to 2012. A total of 16 occupational neurotoxins, including organophosphates, toxic gases, heavy metals, organic solvents, and other toxic chemicals, were reviewed. Peer-reviewed articles related to the electrophysiology, neuroimaging, treatment and long-term follow up of these neurotoxic diseases were also obtained. The heavy metals involved consisted of lead, manganese, organic tin, mercury, arsenic, and thallium. The organic solvents included n-hexane, toluene, mixed solvents and carbon disulfide. Toxic gases such as carbon monoxide, and hydrogen sulfide were also included, along with toxic chemicals including polychlorinated biphenyls, tetramethylammonium hydroxide, organophosphates, and dimethylamine borane. In addition we attempted to correlate these events to the timeline of industrial development in Taiwan. By researching this topic, the hope is that it may help other developing countries to improve industrial hygiene and promote occupational safety and health care during the process of industrialization.

  17. Defense by-products production and utilization program: noble metal recovery screening experiments

    International Nuclear Information System (INIS)

    Hazelton, R.F.; Jensen, G.A.; Raney, P.J.

    1986-03-01

    Isotopes of the platinum metals (rutheium, rhodium, and palladium) are produced during uranium fuel fission in nuclear reactors. The strategic values of these noble metals warrant considering their recovery from spent fuel should the spent fuel be processed after reactor discharge. A program to evaluate methods for ruthenium, rhodium, and palladium recovery from spent fuel reprocessing liquids was conducted at Pacific Northwest Laboratory (PNL). The purpose of the work reported in this docuent was to evaluate several recovery processes revealed in the patent and technical literature. Beaker-scale screening tests were initiated for three potential recovery processes: precipitation during sugar denitration of nitric acid reprocessing solutions after plutonium-uranium solvent extraction, adsorption using nobe metal selective chelates on active carbon, and reduction forming solid noble metal deposits on an amine-borane reductive resin. Simulated reprocessing plant solutions representing typical nitric acid liquids from defense (PUREX) or commercial fuel reprocessing facilities were formulated and used for evaluation of the three processes. 9 refs., 3 figs., 9 tabs

  18. Abnormalities of the testes and epididymis in bucks and rams slaughtered at Debre Zeit abattoir, Ethiopia.

    Science.gov (United States)

    Regassa, F; Terefe, F; Bekana, M

    2003-12-01

    A study was conducted at Debre Zeit export abattoir on 404 bucks belonging to four breeds and 167 rams of two breeds. The animals were selected from the slaughter flock using stratified sampling based on breed. Ante-mortem and post-mortem examinations were carried out after each animal was carefully identified. Various genital abnormalities were observed, among which testicular atrophy and epididymitis were the predominant genital problems in both bucks and rams. The prevalence of cryptorchidism was higher (p0.05). However, testicular atrophy (p<0.01), epididymitis (p<0.01) and haemorrhagic lesions (p<0.05) were associated with breed, the prevalence being higher in Woito-Guji and Boran bucks than in the Arsi-Bale and Afar breeds. In rams, age affected (p<0.05) the incidence of testicular atrophy, epididymitis and sperm granulomas. Epididymitis, sperm granuloma and epididymal cysts were more frequent (p<0.01) in Adal rams than in Black Head Somalis.

  19. 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.

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

    International Nuclear Information System (INIS)

    Hua, Wang; Du, Xiaogang; Su, Wenming; Zhang, Dongyu; Lin, Wenjing

    2014-01-01

    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 ′ -dicarbazole)biphenyl (CBP) : tris(2-phenylquinoline-C2,N ′ )iridium(III) (Ir(2-phq) 3 ) was sandwiched by double blue-light emission layers of 1,1-bis-[(di-4-tolylamino)pheny1]cyclohexane (TAPC) : bis[4,6-(di-fluorophenyl)-pyridinato-N,C2 ′ ]picolinate (FIrpic) and tris[3-(3-pyridyl)mesityl]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/m 2 . 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

  1. Aminopyridinate-FI hybrids, their hafnium and titanium complexes, and their application in the living polymerization of 1-hexene.

    Science.gov (United States)

    Haas, Isabelle; Dietel, Thomas; Press, Konstantin; Kol, Moshe; Kempe, Rhett

    2013-10-11

    Based on two well-established ligand systems, the aminopyridinato (Ap) and the phenoxyimine (FI) ligand systems, new Ap-FI hybrid ligands were developed. Four different Ap-FI hybrid ligands were synthesized through a simple condensation reaction and fully characterized. The reaction of hafnium tetrabenzyl with all four Ap-FI hybrid ligands exclusively led to mono(Ap-FI) complexes of the type [(Ap-FI)HfBn2 ]. The ligands acted as tetradentate dianionic chelates. Upon activation with tris(pentafluorophenyl)borane, the hafnium-dibenzyl complexes led to highly active catalysts for the polymerization of 1-hexene. Ultrahigh molecular weights and extremely narrow polydispersities support the living nature of this polymerization process. A possible deactivation product of the hafnium catalysts was characterized by single-crystal X-ray analysis and is discussed. The coordination modes of these new ligands were studied with the help of model titanium complexes. The reaction of titanium(IV) isopropoxide with ligand 1 led to a mono(Ap-FI) complex, which showed the desired fac-mer coordination mode. Titanium (IV) isopropoxide reacted with ligand 4 to give a complex of the type [(ApH-FI)2 Ti(OiPr)2 ], which featured the ligand in its monoanionic form. The two titanium complexes were characterized by X-ray crystal-structure analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthetic approach of norbadione A: new preparation of alcohols from sulfones and boron compounds

    International Nuclear Information System (INIS)

    Billaud, C.

    2005-12-01

    The synthetic approach of norbadione A, a pigment from mushrooms related to pulvinic acids, was studied. This compound has the property to complex caesium and has shown an antioxidant activity. The first strategy, based on a double Suzuki-Miyaura coupling between a naphtho-lactone with two boron functions and two pulvinic moieties with a triflate was unsuccessful and has shown a deactivating effect of the lactone. Modifications aimed to inhibit the electro-attracting character of the lactone permitted to obtain a bis(coupled) product with a poor yield. A second approach based on a the cyclization of enol aryl-acetates was studied in order to build the pulvinic moiety in several steps. The important reaction of introduction of an alkyl-acetate from a triflate was realised by a palladium-mediated coupling. The cyclization attempts carried out using a naphthalenic compound allowed us to isolate a monocyclised product. A parallel study was to first build a tetronic moiety and then to construct the exocyclic double bond by a method developed in the laboratory for the preparation of an iodated pulvinic compound. Finally, a new preparation of alcohols from sulfones and boron compounds was developed. Two known reactions in the chemistry of boron were combined. The first one is the reaction between anions of sulfones and tri-alkyl-boranes, the second one is a thermal isomerization which places the boron atom in a terminal position. A new preparation of primary alcohols was thus carried out. (author)

  3. Evaluation of physical and biologic properties of the mixture of mineral trioxide aggregate and 4-META/MMA-TBB resin.

    Science.gov (United States)

    Chung, Hyunsook; Kim, Miri; Ko, Hyunjung; Yang, Wonkyung

    2011-11-01

    This study examined whether 4-methacryloxyethyl trimellitate anhydride/methylmethacrylate-tri-n-butyl borane (4-META/MMA-TBB) resin can be used with mineral trioxide aggregate (MTA) to overcome MTA's shortcomings. The biologic reactions of the mixture of MTA powder and 4-META/MMA-TBB resin (MTA/4-META) and its potential in clinical applications were also investigated. MTA powder was mixed with 4-META/MMA-TBB resin instead of water at the appropriate proportions determined by a series of studies prior to this experiment. MTA powder mixed with sterile water was used as control. The setting time, compressive strength, pH, and dye leakage of MTA/4-META and MTA were assessed by Gilmore apparatus, universal mechanical testing machine, pH meter, and methylene blue penetration method, respectively. Cytotoxicity also was evaluated by MTT assay with MC3T3-E1 cells. The setting time of MTA/4-META was significantly lower than that of MTA: 11.2 ± 0.8 minutes versus 318 ± 56.0 minutes, respectively (P MMA-TBB resin as a mixing vehicle of MTA powder can improve the setting and handling properties of MTA and may maintain or improve its other biophysical properties. Copyright © 2011 Mosby, Inc. All rights reserved.

  4. Ab initio studies on the electronic structure and properties of aluminum hydrides that are analogues of boron hydrides.

    Science.gov (United States)

    Srinivasu, K; Chandrakumar, K R S; Ghosh, Swapan K

    2010-11-25

    Although the boron hydrides are well-known in the literature, the aluminum hydride chemistry is limited to very few systems such as AlH(3), its dimer, and its polymeric form. In view of the recent experimental studies on the possible existence of the aluminum hydrides, herein, we have undertaken a systematic study on the electronic structure and properties of these aluminum hydrides. Under this, we have studied different classes of hydrides, viz., closo (Al(n)H(n+2)), nido (Al(n)H(n+4)), and arachno (Al(n)H(n+6)), similar to the boranes. All the aluminum hydrides are found to have exceptionally large highest-occupied molecular orbital-lowest-unoccupied molecular orbital gaps, low electron affinities, large ionization potentials and also large enthalpy and free energy of atomization. In addition, most of the structures are also found to have high symmetries. These exceptional properties can be indicative of the pronounced stability, and hence, it is expected that other aluminum hydride complexes can indeed be observed experimentally.

  5. 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.

  6. Synthesis and biodistribution of no-carrier-added [1-/sup 11/C]putrescine

    International Nuclear Information System (INIS)

    McPherson, D.W.; Fowler, J.S.; Wolf, A.P.; Arnett, C.D.; Brodie, J.D.; Volkow, N.

    1985-01-01

    Recent studies using [/sup 3/H] and [/sup 14/C]putrescine have demonstrated the feasibility of using [/sup 11/C]putrescine as a selective metabolic tracer both for imaging brain tumors and, with the appropriate tracer kinetic model, for the quantitation tumor growth rate in humans using PET. The development of this new PET method requires, among other things, that the synthesis of the /sup 11/C-putrescine provide the labeled compound in sufficiently high specific activity that the normally low endogeneous levels of the diamine are not perturbed on administration of the tracer. Since a previous method for synthesis of [/sup 11/C]putrescine was not applicable to the NCA synthesis a new synthesis was developed. The synthesis of NCA [1-/sup 11/C]putrescine was based on the Michael addition of [/sup 11/C]cyanide to acrylonitrile followed by reduction of the /sup 11/C-labeled dinitrile with borane-methylsulfide complex. Radiochemical yield was 20%, synthesis time was 50 minutes and specific activity was > 1.4 Ci/μmol (EOB). This represents the first example of the use of the Michael addition reaction in the synthesis of a C-11 labeled compound. Tissue distribution in normal mice at 5, 30 and 60 minutes showed the expected low uptake in normal brain

  7. 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.

  8. 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.

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

    Science.gov (United States)

    Kündig, E Peter; Enriquez-Garcia, Alvaro

    2008-01-01

    The 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. The 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). NaBH(4), LiAlH(4), and BH(3) 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). Diastereoselective 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.

  10. Thermodynamics study of hydrogen storage materials

    International Nuclear Information System (INIS)

    Song Lifang; Wang Shuang; Jiao Chengli; Si Xiaoliang; Li Zhibao; Liu Shuang; Liu Shusheng; Jiang Chunhong; Li Fen; Zhang Jian; Sun Lixian; Xu Fen; Huang Fenglei

    2012-01-01

    Highlights: ► Chemical modification is an effective way to improve the thermodynamics. ► Nanodispersion can improve the thermodynamics of chemical storage system. ► Hybridization is an practicable strategy to improve the thermodynamics. ► Nanoconfinement is feasible to improve thermodynamics of chemical storage system. ► MOFs materials possess suitable interaction with H 2 molecule should be investigated. - Abstract: The growing use of conventional energy such as fossil fuels results in problems degrading our environment. Hydrogen is frequently discussed as a clean energy in the future without pollution. However, efficient and safe storage of hydrogen constitute a key challenge and unresolved problem. One of the main options is solid-state storage technology. A successful solid-state reversible storage material should meet the requirements of high storage capacity, suitable thermodynamic properties, reversibility and fast adsorption and desorption kinetics. This feature article focuses mainly on the development of thermodynamic improvement of hydrogen storage materials in the past few years including the complex hydride, ammonia borane, and metal-organic frameworks.

  11. Interface modifications by anion receptors for high energy lithium ion batteries

    Science.gov (United States)

    Zheng, Jianming; Xiao, Jie; Gu, Meng; Zuo, Pengjian; Wang, Chongmin; Zhang, Ji-Guang

    2014-03-01

    Li-rich, Mn-rich (LMR) layered composite has attracted extensive interests because of its highest energy density among all cathode candidates for lithium ion batteries (LIB). However, capacity degradation and voltage fading remain the major challenges for LMR cathodes prior to their practical applications. Here, we demonstrate that anion receptor, tris(pentafluorophenyl)borane ((C6F5)3B, TPFPB), substantially enhances the stability of electrode/electrolyte interface and thus improves the cycling stability of LMR cathode Li[Li0.2Ni0.2Mn0.6]O2. In the presence of 0.2 M TPFPB, Li[Li0.2Ni0.2Mn0.6]O2 shows an improved capacity retention of 76.8% after 500 cycles. It is proposed that TPFPB effectively confines the highly active oxygen species released from structural lattice through its strong coordination ability and high oxygen solubility. The electrolyte decomposition caused by the oxygen species attack is therefore largely mitigated, forming reduced amount of byproducts on the cathode surface. Additionally, other salts such as insulating LiF derived from electrolyte decomposition are also soluble in the presence of TPFPB. The collective effects of TPFPB mitigate the accumulation of parasitic reaction products and stabilize the interfacial resistances between cathode and electrolyte during extended cycling, thus significantly improving the cycling performance of Li[Li0.2Ni0.2Mn0.6]O2.

  12. Highly Efficient One-Pot Synthesis of COS-Based Block Copolymers by Using Organic Lewis Pairs.

    Science.gov (United States)

    Yang, Jia-Liang; Cao, Xiao-Han; Zhang, Cheng-Jian; Wu, Hai-Lin; Zhang, Xing-Hong

    2018-01-31

    A one-pot synthesis of block copolymer with regioregular poly(monothiocarbonate) block is described via metal-free catalysis. Lewis bases such as guanidine, quaternary onium salts, and Lewis acid triethyl borane (TEB) were equivalently combined and used as the catalysts. By using polyethylene glycol (PEG) as the macromolecular chain transfer agent (CTA), narrow polydispersity block copolymers were obtained from the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO). The block copolymers had a poly(monothiocarbonate) block with perfect alternating degree and regioregularity. Unexpectedly, the addition of CTA to COS/PO copolymerization system could dramatically improve the turnover frequency (TOF) of PO (up to 240 h -1 ), higher than that of the copolymerization without CTA. In addition, the conversion of CTA could be up to 100% in most cases, as revealed by ¹H NMR spectra. Of consequence, the number-average molecular weights ( M n s) of the resultant block copolymers could be regulated by varying the feed ratio of CTA to PO. Oxygen-sulfur exchange reaction (O/S ER), which can generate randomly distributed thiocarbonate and carbonate units, was effectively suppressed in all of the cases in the presence of CTA, even at 80 °C. This work presents a versatile method for synthesizing sulfur-containing block copolymers through a metal-free route, providing an array of new block copolymers.

  13. Nonspherical Deltahedra in Low-Energy Dicarbalane Structures Testing the Wade-Mingos Rules: The Regular Icosahedron Is Not Favored for the 12-Vertex Dicarbalane.

    Science.gov (United States)

    Attia, Amr A A; Lupan, Alexandru; King, R Bruce

    2015-12-07

    Theoretical studies on the dicarbalanes C2Al(n-2)Men (n = 7-14; Me = methyl) predict both carbon atoms to be located at degree 4 vertices of a central C2Al(n-2) deltahedron in the lowest energy structures. As a consequence, deltahedra having two degree 4 vertices, two degree 6 vertices, and eight degree 5 vertices rather than the regular icosahedron having exclusively degree 5 vertices are found for the 12-vertex dicarbalane C2Al10Me12. However, the lowest energy C2Al(n-2)Men (n = 7-11) structures are based on the same most spherical (closo) deltahedra as the corresponding deltahedral boranes. The lowest energy structures for the 13- and 14-vertex systems C2Al(n-2)Men (n = 13 and 14) are also deltahedra having exactly two degree 4 vertices for the carbon atoms. The six-vertex C2Al4Me6 system is exceptional since bicapped tetrahedral and capped square pyramidal structures with degree 3 vertices for the carbon atoms are energetically preferred over the octahedral structure suggested by the Wade-Mingos rules.

  14. 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.

  15. Impact of Surface Functionalization on the Quantum Coherence of Nitrogen-Vacancy Centers in Nanodiamonds.

    Science.gov (United States)

    Ryan, Robert G; Stacey, Alastair; O'Donnell, Kane M; Ohshima, Takeshi; Johnson, Brett C; Hollenberg, Lloyd C L; Mulvaney, Paul; Simpson, David A

    2018-04-18

    Nanoscale quantum probes such as the nitrogen-vacancy (NV) center in diamonds have demonstrated remarkable sensing capabilities over the past decade as control over fabrication and manipulation of these systems has evolved. The biocompatibility and rich surface chemistry of diamonds has added to the utility of these probes but, as the size of these nanoscale systems is reduced, the surface chemistry of diamond begins to impact the quantum properties of the NV center. In this work, we systematically study the effect of the diamond surface chemistry on the quantum coherence of the NV center in nanodiamonds (NDs) 50 nm in size. Our results show that a borane-reduced diamond surface can on average double the spin relaxation time of individual NV centers in nanodiamonds when compared to thermally oxidized surfaces. Using a combination of infrared and X-ray absorption spectroscopy techniques, we correlate the changes in quantum relaxation rates with the conversion of sp 2 carbon to C-O and C-H bonds on the diamond surface. These findings implicate double-bonded carbon species as a dominant source of spin noise for near surface NV centers. The link between the surface chemistry and quantum coherence indicates that through tailored engineering of the surface, the quantum properties and magnetic sensitivity of these nanoscale systems may approach that observed in bulk diamond.

  16. Sodium triacetoxyborotritide: its preparation and use

    International Nuclear Information System (INIS)

    Morimoto, H.; Williams, P.G.; Than, C.; Chehade, K.; Spielman, P.

    1997-01-01

    Full text: Tritide reducing agents provide attractive approaches for the preparation of tritiated molecules of high specific activity. During the last decade we have demonstrated the synthesis and use of fully tritiated highly reactive tritide reagents such as lithium triethylborotritide. Lithium aluminium tritide and borane. Recently, the biological molecules of interest have become more complex and the appropriate labelling reagents have become more selective and sophisticated. Sodium triacetoxyborohydride is a very mild and highly selective reducing agent, capable of reducing aldehydes selectively in the presence of ketones. It also reduces indole double bonds, acid chlorides and lactones. It is the reagent of choice for the reductive amination of aldehydes, and saturated aliphatic ketones with primary and secondary amines. Over the past year, we have developed simple, convenient and efficient methods for the labelling of metal borohydrides by exchange with tritium gas. Direct treatment of NaBT 4 with glacial acetic under mild conditions produces sodium triacetoxyborotritide. This reagent was characterized by proton, tritium, and boron NMR spectroscopy. Its utility was demonstrated by its ability to reduce an aldehyde in the presence of a ketone, and by a reductive amination of farnesal acetate and aniline

  17. Core-shell nanospheres Pt@SiO2 for catalytic hydrogen production

    Science.gov (United States)

    Hu, Yujuan; Wang, Yuqing; Lu, Zhang-Hui; Chen, Xiangshu; Xiong, Lihua

    2015-06-01

    Ultrafine platinum nanoparticles (NPs) embedded in silica nanospheres (Pt@SiO2) have been synthesized in a NP-5/cyclohexane reversed-micelle system followed by NaBH4 reduction. The as-synthesized core-shell nanocatalysts Pt@SiO2 were characterized by scanning electron microscopy, transmission electron microscopes, X-ray powder diffraction analysis, energy dispersive X-ray spectrometer and nitrogen adsorption-desorption investigations. Interestingly, the as-synthesized core-shell nanocatalysts Pt@SiO2 showed an excellent catalytic performance in hydrogen generation from the hydrolysis of ammonia borane (BH3NH3, AB) at room temperature. Especially, the catalytic performance of the Pt@SiO2 remained almost unchanged after the five recycles and even after the heat treatment (673 K), because the silica shells inhibit aggregation or deformation of the metal cores. Besides, the kinetic studies showed that the catalytic hydrolysis of AB was first order with respect to the catalyst concentration and zero order with respect to the substrate concentration, respectively. The excellent catalytic activity and stability of Pt@SiO2 can make it have a bright future in the practical application.

  18. Analysis of boron containing biological samples by ICP

    International Nuclear Information System (INIS)

    Bauer, W.F.; Johnson, D.A.; Messick, K.M.; Miller, D.L.; Propp, W.A.; Steele, S.M.

    1988-01-01

    An important aspect of boron neutron capture therapy (BNCT) is the determination of the biological distribution of the boron within an organism at some point in time after administration of a boron- containing species. Techniques include prompt gamma analysis, colorimetric techniques, and most recently, inductively coupled plasma atomic emission spectroscopy (ICP-AES) techniques. In this paper, an ICP technique was used to determine the boron content in tissue and various biological fluid samples obtained from dogs have spontaneously-occurring brain tumors and to which had been administered the sodium salt of the sulfhydryl borane (B 12 H 11 SH)/sup 2/minus//. The spontaneous error model allowed tissue to be collected that had the same relative kinetics and disruptions of the blood brain barrier as found in human brain cancer. Many of these subjects also had peritumor edematous tissue that did not have a visibly detected alteration in the blood brain barrier. The large size of the dog allowed tissues to be collected for analysis that may be affected during irradiation

  19. 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.

  20. Blue Phosphorescent Organic Light-Emitting Devices with the Emissive Layer of mCP:FCNIr(pic

    Directory of Open Access Journals (Sweden)

    Ji Geun Jang

    2012-01-01

    Full Text Available New high-efficiency blue-light-emitting phosphorescent devices with 300 Å-thick emissive layer of N,N′-dicarbazolyl-3,5-benzene [mCP] doped with 10 vol.% bis[(3,5-difluoro-4-cyanophenylpyridine]iridium picolinate [FCNIr(pic] were fabricated with the different treatments of hole and electron transport layers. In the experiments, a single layer of 1,1-bis-(di-4-polyaminophenylcyclohexane [TAPC] and a double layer of N,N′-di(1-naphthyl-N,N′-diphenylbenzidine [NPB] and mCP were used as hole transport layers (HTLs. In addition, 500 Å-thick double layers of tris-[3-(3-pyridylmesityl]borane [3TPYMB] and 4,7-diphenyl-1,10-phenanthroline [Bphen] were used as electron transport layers (ETLs with various thickness combination of 3TPYMB/Bphen. Among the fabricated devices, the one using TAPC as an HTL and 3TPYMB(100 Å/Bphen(400 Å as an ETL showed best electroluminescent characteristics with a maximum quantum efficiency of 13.3% and a luminance of 950 cd/m2 at 10 V. The color coordinates were (0.14, 0.22 on the Commission Internationale de I'Eclairage (CIE chart, and the electroluminescent spectra showed the double-peak emissions at 458 nm and 483 nm.

  1. The Indian drawings of the poet Cesare Pascarella: non-destructive analyses and conservation treatments.

    Science.gov (United States)

    Bicchieri, Marina; Monti, Michela; Piantanida, Giovanna; Pinzari, Flavia; Iannuccelli, Simonetta; Sotgiu, Silvia; Tireni, Lorena

    2012-02-01

    The Italian dialect poet Cesare Pascarella travelled all around the world, noting down in notebooks his keen and caustic observations, and drawing sketches that are a visual reportage of his journeys. The sketches were mounted as a random collage over acidic cardboards that were exposed to direct sunlight in his studio. Their poor state of conservation is related to the use of modern paper: chemical instability of raw materials caused acidification and strong oxidation of the support, with intense yellowing of the surfaces and brittleness of the paper. To ensure future preservation of the drawings, chemical stabilisation with simultaneous alcoholic treatment by deacidification (calcium propionate) and reduction (borane tert-butylamine complex) appeared necessary. To verify its applicability, it was indispensible to characterise the support and identify the nature of all the graphic media. The use of Raman, Infrared, X-ray fluorescence spectroscopies and scanning electron microscopy coupled with X-ray microanalysis allowed us to clear the problems related to the different penetration depth of each analytical technique and the different responses of pigments/dyes to each spectroscopy. The palette, how it varied along the journeys, the different supports used and preparations were completely identified showing a choice of colours compatible with the reduction treatment.

  2. 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.

  3. Evaluation of larch trees (Larix Mill., Pinaceae

    Directory of Open Access Journals (Sweden)

    Firsov Gennadii

    2016-12-01

    Full Text Available Peter the Great Botanical Garden of the Komarov Boranical Institute has 148 larch samples (Larix Mill., Pinaceae which represent 22 taxa. They are long-lived large trees, up to 200 years of age, representing the base for a forest stand of an arboretum and forming alleys in the oldest regular part of the Garden. The tallest trees reach 31,6 m (L. dahurica and 113 cm in diameter (L. decidua and L. dahurica. Due to the warming in the St. Petersburg area, there is a noticeable drying found on the trees' crowns. Based on the results of an inventory in 2015, 43 trees can be assigned to the first category; the other 105 trees suffer from drying of shoots, twigs and branches. The degree of drying corresponds with the age of trees. One of the possible reasons of the deterioration in the conditions of larch trees at the arboretum of the Komarov Botanical Institute may be the influence of the Phytophthora species. Soil research samples show presence of Phytophthora syringae (Berk. Kleb. in the risosphere of L. decidua. It is the first time, this species of Phytophthora has been discovered at the Peter the Great Botanical Garden.

  4. 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.

  5. In vitro suppression of K65R reverse transcriptase-mediated tenofovir- and adefovir-5'-diphosphate resistance conferred by the boranophosphonate derivatives.

    Science.gov (United States)

    Frangeul, Antoine; Barral, Karine; Alvarez, Karine; Canard, Bruno

    2007-09-01

    9-[2-(Boranophosphonomethoxy)ethyl]adenine diphosphate (BH(3)-PMEApp) and (R)-9-[2-(boranophosphonomethoxy)propyl]adenine diphosphate (BH(3)-PMPApp), described here, represent the first nucleoside phosphonates modified on their alpha-phosphates that act as efficient substrates for the human immunodeficiency virus type 1 (HIV-1) reverse transcriptase (RT). These analogues were synthesized and evaluated for their in vitro activity against wild-type (WT), K65R, and R72A RTs. BH(3)-PMEApp and BH(3)-PMPApp exhibit the same inhibition properties as their nonborane analogues on WT RT. However, K65R RT was found hypersensitive to BH(3)-PMEApp and as sensitive as WT RT to BH(3)-PMPApp. Moreover, the presence of the borane group restores incorporation of the analogue by R72A HIV RT, the latter being nearly inactive with regular nucleotides. The BH(3)-mediated suppression of HIV-1 RT resistance, formerly described with nucleoside 5'-(alpha-p-borano)-triphosphate analogues, is thus also conserved at the phosphonate level. The present results show that an alpha-phosphate modification is also possible and interesting for phosphonate analogues, a result that might find application in the search for a means to control HIV RT-mediated drug resistance.

  6. From boron analogues of amino acids to boronated DNA: potential new pharmaceuticals and neutron capture agents

    International Nuclear Information System (INIS)

    Spielvogel, B.F.; Sood, Anup; Duke Univ., Durham, NC; Shaw, B.R.; Hall, I.H.

    1991-01-01

    Isoelectronic and isostructural boron analogues of the α-amino acids ranging from simple glycine analogues such as H 3 NBH 2 COOH and Me 2 NHBH 2 COOH to alanine analogues have been synthesised. A diverse variety of analogues, including precursors and derivatives (such as peptides) have potent pharmacological activity, including anticancer, antiinflammatory, analgesic, and hypolipidemic activity in animal model studies and in vitro cell cultures. Boronated nucleosides and (oligo)nucleotides, synthetic oligonucleotide analogues of ''antisense'' agents interact with a complementary nucleic acid sequence blocking the biological effect of the target sequence. Nucleosides boronated on the pyrimidine and purine bases have been prepared. It has been established that an entirely new class of nucleic acid derivatives is feasible in which one of the non-bridging oxygens in the internucleotide phosphodiester linkage can be replaced by an isoelectronic analogue, the borane group, (BH 3 ). The boronated oligonucleotides can be viewed as hybrids of the normal oxygen oligonucleotides and the methylphosphonate oligonucleotides. (author)

  7. Introduction of Boron Functionalities into Silsesquioxanes: Novel Independent Methodologies.

    Science.gov (United States)

    Kaźmierczak, Joanna; Kuciński, Krzysztof; Stachowiak, Hanna; Hreczycho, Grzegorz

    2018-02-16

    Owing to their versatile application possibilities, silsesquioxanes (SQs) are of considerable interest for creating hybrid inorganic-organic materials. In this report, two novel and independent strategies for the direct attachment of boron functionalities to silsesquioxanes are presented. Encouraged by our previous work concerning the synthesis of borasiloxanes through the catalyst-free dehydrogenative coupling of silanols and boranes, we decided to apply our method to a synthesis of various boron-functionalized silsesquioxanes. During our tests, we also investigated the activity of scandium(III) triflate, which we have previously used as an excellent catalyst for the obtaining of Si-O-Si and Si-O-Ge moieties. As a result, we also discovered a novel approach for the O-borylation of Si-OH groups in silsesquioxanes with allylborane. Both routes are highly chemoselective and efficiently lead to the obtaining of Si-O-B moiety under air atmosphere and at room temperature. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Dynamic nuclear polarization of irradiated target materials

    International Nuclear Information System (INIS)

    Seely, M.L.

    1982-01-01

    Polarized nucleon targets used in high energy physics experiments usually employ the method of dynamic nuclear polarization (DNP) to polarize the protons or deuterons in an alcohol. DNP requires the presence of paramagnetic centers, which are customarily provided by a chemical dopant. These chemically doped targets have a relatively low polarizable nucleon content and suffer from loss of polarization when subjected to high doses of ionizing radiation. If the paramagnetic centers formed when the target is irradiated can be used in the DNP process, it becomes possible to produce targets using materials which have a relatively high polarizable nucleon content, but which are not easily doped by chemical means. Furthermore, the polarization of such targets may be much more radiation resistant. Dynamic nuclear polarization in ammonia, deuterated ammonia, ammonium hydroxide, methylamine, borane ammonia, butonal, ethane and lithium borohydride has been studied. These studies were conducted at the Stanford Linear Accelerator Center using the Yale-SLAC polarized target system. Results indicate that the use of ammonia and deuterated ammonia as polarized target materials would make significant increases in polarized target performance possible

  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. 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.

  11. Pretreatment with buthionine sulfoximine enhanced uptake and retention of BSH in brain tumor

    International Nuclear Information System (INIS)

    Yoshida, F.; Yamamoto, T.; Nakai, K.; Zaboronok, A.; Matsuda, M.; Akutsu, H.; Ishikawa, E.; Shirakawa, M.; Matsumura, A.

    2014-01-01

    To determine the influence of buthionine sulfoximine (BSO) on boron biodistribution after sulfhydryl borane (BSH) administration for boron neutron capture therapy, the effectiveness of the combination of BSO with sulfhydril- (BSH) and non-sulfhydril (B 12 H 12 and BNH 3 ) boron compounds, and the interval between BSO and BSH administration, the retention of boron in tissues have been evaluated using a 9L rat tumor model. Simultaneous administration of BSH and BSO showed significantly higher boron accumulation compared to that without BSO, however there was no difference in tissue boron level between B 12 H 12 and BNH 3 administration with BSO or without BSO. The longer interval (6 h) between BSH and BSO administration related to the highest boron concentration in the brain and subcutaneous tumors compared to shorter intervals (0.5, 3 h). Boron concentration in subcutaneous and brain tumors was maintained for 6 and 12 h after the administration of BSH following BSO pretreatment. - Highlights: • Coadministration of BSH and BSO showed higher tumor boron uptake than BSH only. • Higher boron uptake was not observed after B 12 H 12 or BNH 3 administration. • The increase in tumor boron accumulation might be related to SH-groups. • BSO injection 6 h before BSH showed further increase in tumor boron uptake. • High boron concentration maintained for 6 and 12 h after BSH with BSO administration

  12. 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

  13. Genetically programmed chiral organoborane synthesis

    Science.gov (United States)

    Kan, S. B. Jennifer; Huang, Xiongyi; Gumulya, Yosephine; Chen, Kai; Arnold, Frances H.

    2017-12-01

    Recent advances in enzyme engineering and design have expanded nature’s catalytic repertoire to functions that are new to biology. However, only a subset of these engineered enzymes can function in living systems. Finding enzymatic pathways that form chemical bonds that are not found in biology is particularly difficult in the cellular environment, as this depends on the discovery not only of new enzyme activities, but also of reagents that are both sufficiently reactive for the desired transformation and stable in vivo. Here we report the discovery, evolution and generalization of a fully genetically encoded platform for producing chiral organoboranes in bacteria. Escherichia coli cells harbouring wild-type cytochrome c from Rhodothermus marinus (Rma cyt c) were found to form carbon-boron bonds in the presence of borane-Lewis base complexes, through carbene insertion into boron-hydrogen bonds. Directed evolution of Rma cyt c in the bacterial catalyst provided access to 16 novel chiral organoboranes. The catalyst is suitable for gram-scale biosynthesis, providing up to 15,300 turnovers, a turnover frequency of 6,100 h-1, a 99:1 enantiomeric ratio and 100% chemoselectivity. The enantiopreference of the biocatalyst could also be tuned to provide either enantiomer of the organoborane products. Evolved in the context of whole-cell catalysts, the proteins were more active in the whole-cell system than in purified forms. This study establishes a DNA-encoded and readily engineered bacterial platform for borylation; engineering can be accomplished at a pace that rivals the development of chemical synthetic methods, with the ability to achieve turnovers that are two orders of magnitude (over 400-fold) greater than those of known chiral catalysts for the same class of transformation. This tunable method for manipulating boron in cells could expand the scope of boron chemistry in living systems.

  14. 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.

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

    Science.gov (United States)

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

    2015-06-01

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

  16. Charge retention by gold clusters on surfaces prepared using soft landing of mass selected ions.

    Science.gov (United States)

    Johnson, Grant E; Priest, Thomas; Laskin, Julia

    2012-01-24

    Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Ligand-stabilized gold clusters were prepared in methanol solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine complex in the presence of 1,3-bis(diphenylphosphino)propane. Electrospray ionization was used to introduce the clusters into the gas phase, and mass selection was employed to isolate a single ionic cluster species (Au(11)L(5)(3+), L = 1,3-bis(diphenylphosphino)propane), which was delivered to surfaces at well-controlled kinetic energies. Using in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS), it is demonstrated that the Au(11)L(5)(3+) cluster retains its 3+ charge state when soft landed onto the surface of a 1H,1H,2H,2H-perfluorodecanethiol self-assembled monolayer (FSAM) on gold. In contrast, when deposited onto 16-mercaptohexadecanoic acid (COOH-SAM) and 1-dodecanethiol (HSAM) surfaces on gold, the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the FSAM and HSAM surfaces are investigated using in situ Fourier transform ion cyclotron resonance (FT-ICR) SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the FSAM surface while an almost instantaneous neutralization takes place on the surface of the HSAM. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto carefully selected substrates. © 2011 American Chemical Society

  17. 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.

  18. Synthesis and radiofluorination of putative NMDA receptor ligands

    International Nuclear Information System (INIS)

    Kronenberg, U.

    2011-01-01

    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-[ 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, but no

  19. 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

  20. A study of the radiosynthesis of fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ and its application in labeling 1,2,3-triazole analogs obtained by click chemistry.

    Science.gov (United States)

    Wang, Cheng; Zhou, Wei; Yu, Junfeng; Zhang, Lan; Wang, Ni

    2012-01-01

    To optimize the conditions for the preparation of the organometallic precursor fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ and to synthesize the radiolabeling compounds of tricarbonyl rhenium. 1,2,3-Triazole analogs were synthesized by click chemistry and labeled with fac-[ReCO₃(H₂O)₃]Br and fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺. The aim was to improve the methods for the synthesis of ¹⁸⁸Re-labeled radiopharmaceuticals for therapy. With potassium boranocarbonate as the CO source and ammonia borane as the reducing agent, fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ was synthesized, and the click chemistry method was used to prepare the tricarbonyl rhenium complex. At the optimal reaction condition (the amounts of K₂[H₃BCO₂] and BH₃·NH₃ are 5 and 5 mg, respectively; reaction temperature is 75°C; and reaction time is 15 min), the radiochemical yields were 90%, and the labeling yield of bis(pyridin-2-ylmethyl) amine with fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ was more than 99% in 1 h at 75°C; the conjugation yields of triazole analog obtained by click chemistry with 'cold' and 'radio' tricarbonyl rhenium were more than 80%. The organometallic precursor fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ was prepared under optimal reaction conditions with a yield of 90%, and the triazole analogs synthesized by click chemistry were suitable ligands for tricarbonyl rhenium.

  1. Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH32BH3 and KN(CH32BH3

    Directory of Open Access Journals (Sweden)

    Filip Sagan

    2016-03-01

    Full Text Available In the present work, an in-depth, qualitative and quantitative description of non-covalent interactions in the hydrogen storage materials LiN(CH32BH3 and KN(CH32BH3 was performed by means of the charge and energy decomposition method (ETS-NOCV as well as the Interacting Quantum Atoms (IQA approach. It was determined that both crystals are stabilized by electrostatically dominated intra- and intermolecular M∙∙∙H–B interactions (M = Li, K. For LiN(CH32BH3 the intramolecular charge transfer appeared (B–H→Li to be more pronounced compared with the corresponding intermolecular contribution. We clarified for the first time, based on the ETS-NOCV and IQA methods, that homopolar BH∙∙∙HB interactions in LiN(CH32BH3 can be considered as destabilizing (due to the dominance of repulsion caused by negatively charged borane units, despite the fact that some charge delocalization within BH∙∙∙HB contacts is enforced (which explains H∙∙∙H bond critical points found from the QTAIM method. Interestingly, quite similar (to BH∙∙∙HB intermolecular homopolar dihydrogen bonds CH∙∙∙HC appared to significantly stabilize both crystals—the ETS-NOCV scheme allowed us to conclude that CH∙∙∙HC interactions are dispersion dominated, however, the electrostatic and σ/σ*(C–H charge transfer contributions are also important. These interactions appeared to be more pronounced in KN(CH32BH3 compared with LiN(CH32BH3.

  2. Theoretical study of the regioselectivity of the interaction of 3-methyl-4-pyrimidone and 1-methyl-2-pyrimidone with Lewis acids.

    Science.gov (United States)

    Kasende, Okuma Emile; Muya, Jules Tshishimbi; Broeckaert, Lies; Maes, Guido; Geerlings, Paul

    2012-08-23

    A density functional theory (DFT) study is performed to determine the stability of the complexes formed between either the N or O site of 3-methyl-4-pyrimidone and 1-methyl-2-pyrimidone molecules and different ligands. The studied ligands are boron and alkali Lewis acids, namely, B(CH(3))(3), HB(CH(3))(2), H(2)B(CH(3)), BH(3), H(2)BF, HBF(2), BF(3), Li(+), Na(+), and K(+). The acids are divided into two groups according to their hardness. The reactivity predictions, according to the molecular electrostatic potential (MEP) map and the natural bond orbital (NBO) analysis, are in agreement with the calculated relative stabilities. Our findings reveal a strong regioselectivity with borane and its derivatives preferring the nitrogen site in both pyrimidone isomers, while a preference for oxygen is observed for the alkali acids in the 3-methyl-4-pyrimidone molecule. The complexation of 1-methyl-2-pyrimidone with these hard alkali acids does not show any discrimination between the two sites due to the presence of a continuous delocalized density region between the nitrogen and the oxygen atoms. The preference of boron Lewis acids toward the N site is due to the stronger B-N bond as compared to the B-O bond. The influence of fluorine or methyl substitution on the boron atom is discussed through natural orbital analysis (NBO) concentrating on the overlap of the boron empty p-orbital with the F lone pairs and methyl hyperconjugation, respectively. The electrophilicity of the boron acids gives a good overall picture of the interaction capabilities with the Lewis base.

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

    Science.gov (United States)

    Kaul, Rudra; Farooq, Riyaz; Kaul, Vibhuti; Malik, Altaf H; Purra, Aamir Rashid; Ahmad, Lateef

    2013-01-01

    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. 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. 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. 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.

  4. Effects of exposure to 4-META/MMA-TBB resin on pulp cell viability.

    Science.gov (United States)

    Imaizumi, Nakako; Kondo, Hisatomo; Ohya, Keiichi; Kasugai, Shohei; Araki, Kouji; Kurosaki, Norimasa

    2006-06-01

    Adhesive restorative systems have expanded the range of possibilities for direct pulp-capping technique, with evidences of clinical success in vital pulp therapy. However, quite few studies have described the direct responses of pulp cells following the application of resinous materials to pulp exposure. To address this issue, effects of exposure to an adhesive resin, 4-methacryloxyethyl trimellitate anhydride/methyl methacrylate-tri-n-butyl borane (4-META/MMA-TBB) resin on cellular activity were investigated in an established rat dental pulp cell line (RPC-C2A). RPC-C2A cells were cultured on normal plastic plates or the disks prepared from 4-META/MMA-TBB resin (Super Bond C&B) in a-MEM containing 10% FBS. After 3, 7 and 14 days, DNA content and alkaline phosphatase (ALP) activity were measured. Total RNA in each group was extracted and RT-PCR analysis was performed. Moreover, the live cell ratio was also evaluated by cytotoxicity assay after treatment with various concentrations of 4-META/MMA-TBB. At day 3, 7 and 14, amount of DNA and ALP activity of the cells on normal plastic plates and the one on the 4-META/MMA-TBB were comparable. Cells of both groups expressed mRNA of type I collagen (Coll), ALP, osteopontin (OPN), osteocalcin (OC), and bone morphogenetic protein (BMP-2). Furthermore, 4-META/MMA-TBB (10(-1)% or less) did not influence dead cell ratio in the confluent state. According to the results of these in vitro studies, exposure to this resinous material would not induce cytotoxic response in the pulp cells.

  5. 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%.

  6. Fe-Mediated Nitrogen Fixation with a Metallocene Mediator: Exploring pKa Effects and Demonstrating Electrocatalysis.

    Science.gov (United States)

    Chalkley, Matthew J; Del Castillo, Trevor J; Matson, Benjamin D; Peters, Jonas C

    2018-04-18

    Substrate selectivity in reductive multi-electron/proton catalysis with small molecules such as N2, CO2, and O2 is a major challenge for catalyst design, especially where the competing hydrogen evolution reaction (HER) is thermo-dynamically and kinetically competent. In this study, we investigate how the selectivity of a tris(phosphine)borane iron(I) catalyst, P3BFe+, for catalyzing the nitrogen reduction reaction (N2RR, N2-to-NH3 conversion) versus HER changes as a function of acid pKa. We find that there is a strong correlation between pKa and N2RR efficiency. Stoi-chiometric studies indicate that the anilinium triflate acids employed are only compatible with the formation of ear-ly stage intermediates of N2 reduction (e.g., Fe(NNH) or Fe(NNH2)) in the presence of the metallocene reductant Cp*2Co. This suggests that the interaction of acid and reductant is playing a critical role in N-H bond forming reac-tions. DFT studies identify a protonated metallocene species as a strong PCET donor and suggest that it should be capable of forming the early stage N-H bonds critical for N2RR. Furthermore, DFT studies also suggest that the observed pKa effect on N2RR efficiency is attributable to the rate and thermodynamics, of Cp*2Co protonation by the different anilinium acids. Inclusion of Cp*2Co+ as a co-catalyst in controlled potential electrolysis experiments leads to improved yields of NH3. The data presented provide what is to our knowledge the first unambiguous demonstration of electrocatalytic nitrogen fixation by a molecular catalyst (up to 6.7 equiv NH3 per Fe at -2.1 V vs Fc+/0).

  7. 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.

  8. 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).

  9. 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.

  10. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-09-20

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

  12. Nanoengineering of Ruthenium and Platinum-based Nanocatalysts by Continuous-Flow Chemistry for Renewable Energy Applications

    KAUST Repository

    AlYami, Noktan Mohammed

    2017-04-15

    This thesis presents an integrated study of nanocatalysts for heterogenous catalytic and electrochemical processes using pure ruthenium (Ru) with mixed-phase and platinum-based nanomaterials synthesized by continuous-flow chemistry. There are three major challenges to the application of nanomaterials in heterogenous catalytic reactions and electrocatalytic processes in acidic solution. These challenges are the following: (i) controlling the size, shape and crystallography of nanoparticles to give the best catalytic properties, (ii) scaling these nanoparticles up to a commercial quantity (kg per day) and (iii) making stable nanoparticles that can be used catalytically without degrading in acidic electrolytes. Some crucial limitations of these nanostructured materials in energy conversion and storage applications were overcome by continuous-flow chemistry. By using a continuous-flow reactor, the creation of scalable nanoparticle systems was achieved and their functionality was modified to control the nanoparticles’ physical and chemical characteristics. The nanoparticles were also tested for long-term stability, to make sure these nanoparticles were feasible under realistic working conditions. These nanoparticles are (1) shape- and crystallography-controlled ruthenium (Ru) nanoparticles, (2) size-controlled platinum-metal (Pt-M= nickel (Ni) & copper (Cu)) nanooctahedra (while maintaining morphology) and (3) core-shell platinum@ruthenium (Pt@Ru) nanoparticles where an ultrathin ruthenium shell was templated onto the platinum core. Thus, a complete experimental validation of the formation of a scalable amount of these nanoparticles and their catalytic activity and stability towards the oxygen evolution reaction (OER) in acid medium, hydrolysis of ammonia borane (AB) along with plausible explanations were provided.

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

    Science.gov (United States)

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

    2009-01-01

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

  14. Application of HVJ envelope system to boron neutron capture therapy (BNCT)

    International Nuclear Information System (INIS)

    Nakai, Kei; Kurooka, Masaaki; Kaneda, Yasufumi; Yamamoto, Tetsuya; Matsumura, Akira; Asano, Tomoyuki

    2006-01-01

    Boron Neutron Capture Therapy (BNCT) has been used clinically for the treatment of malignant tumors. Two drugs, p-boronophenylalanine (BPA) and sulfhydral borane (BSH), have been used as boron delivery agents. These drugs seem to be taken up preferentially in solid tumors, but it is uncertain whether therapeutic quantities of boron atoms are taken up by micro-invasive or distant tumor cells. High accumulation and high selective delivery of boron into tumor tissues are the most important requirements to achieve efficient BNCT for malignant tumor. The HVJ envelope (HVJ-E) vector system is a novel fusion-mediated gene delivery system based on inactivated hemagglutinating virus of Japan (HVJ; Sendai virus). Although we developed this vector system for gene transfer, it can also deliver proteins, synthetic oligonucleotides, and drugs. HVJ-liposome, which is liposome fused with HVJ-E, has higher boron trapping efficiency than HVJ-E alone. We report the boron delivery into cultured cells with HVJ-liposome systems. The cellular 10 B concentration after 60 min incubation with HVJ-E containing BSH was 24.9 μg/g cell pellet for BHK-21 cells (baby hamster kidney cells) and 19.4 μg/g cell pellet for SCC VII cells (murine squamous cell carcinoma). These concentrations are higher than that of 60 min incubated cells with BSH containing (100μg 10 B/ml) medium. These results indicate the HVJ-E fused with tumor cell membrane and rapidly delivered boron agents, and that the HVJ-E-mediated delivery system could be applicable to BNCT. Plans are underway to begin neutron radiation experiments in vivo and in vitro. (author)

  15. 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.

  16. Reaction mechanisms of CO2 activation and catalytic reduction

    International Nuclear Information System (INIS)

    Wolff, Niklas von

    2016-01-01

    The use of CO 2 as a C1 chemical feedstock for the fine chemical industry is interesting both economically and ecologically, as CO 2 is non-toxic, abundant and cheap. Nevertheless, transformations of CO 2 into value-added products is hampered by its high thermodynamic stability and its inertness toward reduction. In order to design new catalysts able to overcome this kinetic challenge, a profound understanding of the reaction mechanisms at play in CO 2 reduction is needed. Using novel N/Si+ frustrated Lewis pairs (FLPs), the influence of CO 2 adducts and different hydro-borane reducing agents on the reaction mechanism in the catalytic hydroboration of CO 2 were investigated, both by DFT calculations and experiments. In a second step, the reaction mechanism of a novel reaction for the creation of C-C bonds from CO 2 and pyridyl-silanes (C 5 H 4 N-SiMe 3 ) was analyzed by DFT calculations. It was shown that CO 2 plays a double role in this transformation, acting both as a catalyst and a C1-building block. The fine understanding of this transformation then led to the development of a novel approach for the synthesis of sulfones and sulfonamides. Starting from SO 2 and aromatic silanes/amine silanes, these products were obtained in a single step under metal-free conditions. Noteworthy, sulfones and sulfonamides are common motifs in organic chemistry and found in a variety of highly important drugs. Finally, this concept was extended to aromatic halides as coupling partners, and it was thus shown for the first time that a sulfonylative Hiyama reaction is a possible approach to the synthesis of sulfones. (author) [fr

  17. 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

  18. Melissa officinalis L. extract – an effective remedy

    Directory of Open Access Journals (Sweden)

    Karol Terlecki

    2014-04-01

    Full Text Available Lemon balm is the popular name of Melissa officinalis L. Melissa comes from the Greek word Mélissa meaning honeybee. Within the species were distinguished three subspecies: M. officinalis ssp. altissima Arcangeli, M. officinalis ssp. officinalis, and M. officinalis ssp. indora Boran. These are the plants from Lamiaceae group, native to the Mediterranean, but also widespread distributed in moderate and subtropical climate regions. M. officinalis is commonly used for nervous complaints, lower abdominal disorders and more recently in the treatment of Herpes simplex lesions. Leaves are pharmacopeia material. In the fresh herb a content of balm oil is 0.01-0.10% and in the dried leaves from 0.1% up to 0.3%. The main components of M. officinalis usually are: citronellal (approximately 40% of content of balm oil, citral, neral, linalool, flavonoids, chlorogenic, ferulic, rosmarinic (4% of content of balm oil and caffeic acid. The aim of the study was to analyze the literature date about the application of balm extract and oil in the contemporary medicine. The latest studies showed the evidence that the alcoholic lemon balm leaves extract has antihyperlipidemic and antihyperglycemic effects. Thus could be used for the treatment of diabetes mellitus type 2 or dyslipidemia by the activation of receptors PPAR playing the major role in glucose and lipids metabolism. Another importance of the lemon balm leaves extract is its antiviral activity, owes to rosmarinic acid. Melissa extract demonstrates high virucidal activity even at very low concentrations; it demonstrates low toxicity and inhibits HSV-1 attachment to host cells in vitro. The volatile oils included in lemon balm inhibit the replication of HSV-2. Moreover, the rosmarinic acid found out to be cytotoxic against Human Colon Cancer Cell Line. The substance contained in an alcoholic extract from M. officinalis turned out to be anti-proliferative and decrease in cell number neoplasmatic cell

  19. Numerical simulation of the submarine landslides and tsunami occurred at Port Valdez, AK during 1964 Alaska Earthquake with Landslide-HySEA model

    Science.gov (United States)

    González-Vida, Jose M.; Ortega, Sergio; Macías, Jorge; Castro, Manuel J.; Escalante, Cipriano

    2017-04-01

    .J., Parés, C. (2011). On an Intermediate Field Capturing Riemann Solver Based on a Parabolic Viscosity Matrix for the Two-Layer Shallow Water System. J. Sci. Comp. 48:117-140. Macías, J., Vázquez, J.T., Fernández-Salas, L.M., González-Vida, J.M., Bárcenas, P., Castro, M.J., Díaz-del-Río, and V., Alonso, B. (2015). The Al-Boraní submarine landslide and associated tsunami. A modelling approach. Marine Geology, 361:79-95.

  20. Comparison of the Coordination of B12F122-, B12Cl122-, and B12H122- to Na+ in the Solid State: Crystal Structures and Thermal Behavior of Na2(B12F12), Na2(H2O)4(B12F12), Na2(B12Cl12), and Na2(H2O)6(B12Cl12).

    Science.gov (United States)

    Bukovsky, Eric V; Peryshkov, Dmitry V; Wu, Hui; Zhou, Wei; Tang, Wan Si; Jones, W Matthew; Stavila, Vitalie; Udovic, Terrence J; Strauss, Steven H

    2017-04-17

    The synthesis of high-purity Na 2 B 12 F 12 and the crystal structures of Na 2 (B 12 F 12 ) (5 K neutron powder diffraction (NPD)), Na 2 (H 2 O) 4 (B 12 F 12 ) (120 K single-crystal X-ray diffraction (SC-XRD)), Na 2 (B 12 Cl 12 ) (5 and 295 K NPD), and Na 2 (H 2 O) 6 (B 12 Cl 12 ) (100 K SC-XRD) are reported. The compound Na 2 (H 2 O) 4 (B 12 F 12 ) contains {[(Na(μ-H 2 O) 2 Na(μ-H 2 O) 2 )] 2+ } ∞ infinite chains; the compound Na 2 (H 2 O) 6 (B 12 Cl 12 ) contains discrete [(H 2 O) 2 Na(μ-H 2 O) 2 Na(H 2 O) 2 ] 2+ cations with OH···O hydrogen bonds linking the terminal H 2 O ligands. The structures of the two hydrates and the previously published structure of Na 2 (H 2 O) 4 (B 12 H 12 ) are analyzed with respect to the relative coordinating ability of B 12 F 12 2- , B 12 H 12 2- , and B 12 Cl 12 2- toward Na + ions in the solid state (i.e., the relative ability of these anions to satisfy the valence of Na + ). All three hydrated structures have distorted octahedral NaX 2 (H 2 O) 4 coordination spheres (X = F, H, Cl). The sums of the four Na-O bond valence contributions are 71, 75, and 89% of the total bond valences for the X = F, H, and Cl hydrated compounds, respectively, demonstrating that the relative coordinating ability by this criterion is B 12 Cl 12 2- ≪ B 12 H 12 2- X 12 ) compounds provide additional evidence that B 12 Cl 12 2- is more weakly coordinating than B 12 F 12 2- to Na + in the solid state. Taken together, the results suggest that the anhydrous, halogenated closo-borane compounds Na 2 (B 12 F 12 ) and Na 2 (B 12 Cl 12 ), in appropriately modified forms, may be viable component materials for fast-ion-conducting solid electrolytes in future energy-storage devices.

  1. Characterization of moisture and water content on ignition and combustion of hypergolic propellants

    Science.gov (United States)

    Zarbo, Nicholas D.

    Triethylamine borane (TEAB) and white fuming nitric acid (WFNA) is a promising hypergolic propellant combination being studied as an alternative to monomethylhydrazine (MMH) and red fuming nitric acid (RFNA) or dinitrogen tetroxide (NTO). Nitric acid and MMH are both known to be hygroscopic and their performance is affected by their water content. However, the effect of water on TEAB is yet to be determined. The goal of this research is to characterize the major consequences of water presence on the ignition and combustion performance of TEAB and to compare those results to MMH. To determine the effect of hygroscopic absorption, TEAB samples were put through accelerated aging in humid and dry environments. Along with the aged TEAB, neat TEAB and neat MMH were used in drop on pool tests with WFNA. The drop tests were conducted by controlling the relative humidity in air to either below 24% or above 94% and the water concentration in WFNA to either 0% or 10% by weight. Using the Hypertester, ignition and combustion events were recorded using a photodiode, a microphone, a high speed camera, and a UV streak camera spectrometer. A drop chamber was used to determine the time of gas production onset from the liquid phase reactions. Along with the dry and humid air environments, tests were done in a nitrogen environment in the drop chamber. MMH and RFNA drop tests in a nitrogen environment were completed to replicate the results of Forness. Statistical analysis is applied to the data to determine significant parameters and trends. While relative humidity does not appear to affect the combustion of TEAB with WFNA, water concentration in the oxidizer significantly weakens it. Relative humidity improves MMH ignition delay time and water concentration shows no effect. Water concentration in the oxidizer more than doubles the liquid induction time of both TEAB and MMH with WFNA. The ambient environment does not play a significant role in the onset time of gas production. Both

  2. 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

  3. Deviations from the Most Spherical Deltahedra in Rhenatricarbaboranes Having 2n + 2 Wadean Skeletal Electrons.

    Science.gov (United States)

    Attia, Amr A A; Lupan, Alexandru; King, R Bruce

    2017-12-18

    Density functional theory studies on the rhenatricarbaboranes C 3 B n-4 H n-1 Re(CO) 3 (n = 7-12) show that the lowest energy polyhedra for n-vertex metallaboranes having 2n + 2 skeletal electrons and sufficiently dissimilar vertex atoms can deviate from the most spherical closo deltahedra predicted by application of the Wade-Mingos rules. Furthermore, the lowest energy structures of these rhenatricarbaboranes are found to avoid C-C edges and have carbon atoms located at degree 4 rather than degree 5 vertices. The lowest energy structures for the 7-vertex C 3 B 3 H 6 Re(CO) 3 system all have a central C 3 B 3 Re closo deltahedron, namely the pentagonal bipyramid with the rhenium atom at a degree 5 axial vertex and all three carbon atoms at degree 4 equatorial vertices. However, the lowest energy structure for the 8-vertex C 3 B 4 H 7 Re(CO) 3 is not the most spherical closo 8-vertex deltahedron, namely the bisdisphenoid, but instead a central C 3 B 4 Re hexagonal bipyramid with mutually nonadjacent degree 4 vertices for the carbon atoms. Similarly, the lowest energy 10-vertex C 3 B 6 H 9 Re(CO) 3 structures are derived from isocloso deltahedra having three degree 4 vertices for all three carbon atoms rather than from the most spherical 10-vertex closo deltahedron, namely the bicapped square antiprism with only two degree 4 vertices. However, for the 9-vertex C 3 B 5 H 8 Re(CO) 3 system, the most spherical closo deltahedron, namely the tricapped trigonal prism, has three mutually nonadjacent degree 4 vertices, which is ideal for the three carbon atoms and thus is the preferred deltahedron. The preferred deltahedron for the 11-vertex C 3 B 7 H 10 Re(CO) 3 remains the most spherical closo deltahedron despite having only two degree 4 vertices for the carbon atoms. Furthermore, the six lowest energy 12-vertex C 3 B 8 H 11 Re(CO) 3 structures are all based on the regular icosahedron generally favored in polyhedral borane chemistry despite its complete lack of degree 4

  4. Inhibition of hepatitis C viral RNA-dependent RNA polymerase by α-P-boranophosphate nucleotides: exploring a potential strategy for mechanism-based HCV drug design.

    Science.gov (United States)

    Cheek, Marcus Adrian; Sharaf, Mariam L; Dobrikov, Mikhail I; Shaw, Barbara Ramsay

    2013-05-01

    Improved treatments for chronic HCV infections remain a challenge, and new chemical strategies are needed to expand the current paradigm. The HCV RNA polymerase (RdR(P)) has been a target for antiviral development. For the first time we show that the boranophosphate (BP) modification increases the substrate efficiency of ATP analogs into HCV NS5BΔ55 RdRP-catalyzed RNA. Boranophosphate nucleotides contain a borane (BH₃) group substituted for a non-bridging phosphoryl oxygen of a normal phosphate group, resulting in a class of modified isoelectronic DNA and RNA mimics capable of modulating the reading and writing of genetic information. We determine that HCV NS5BΔ55, being a stereospecific enzyme, incorporates the Rp isomer of both ATPαB and the two boranophosphate analogs: 2'-O-methyladenosine 5'-(α-P-borano) triphosphate (2'-OMe ATPαB, 5a) and 3'-deoxyadenosine 5'-(α-P-borano) triphosphate (3'-dATPαB, 5b). The R(p) diastereomer of ATPαB (6), having no ribose modifications, was found to be a slightly better substrate than natural ATP, showing a 42% decrease in the apparent Michaelis-Menten constant (K(m)). The IC₅₀ of both 2'-O-Me and 3'-deoxy ATP was decreased with the boranophosphate modification up to 16-fold. This "borano effect" was further confirmed by determining the steady-state inhibitory constant (K(i)), showing a comparable potency shift (21-fold). These experiments also indicate that the boranophosphate analogs 5a and 5b inhibit HCV NS5B through a competitive mode of inhibition. This evidence, together with previous crystal structure data, further supports the idea that HCV NS5B (in a similar manner to HIV-1 RT) discriminates against the 3'-deoxy modification via lost interactions between the 3'-OH on the ribose and the active site residues, or lost intramolecular hydrogen bonding interactions between the 3'-OH and the pyrophosphate leaving group during phosphoryl transfer. To our knowledge, these data represent the first time a phosphate

  5. 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

  6. Low-Cost Precursors to Novel Hydrogen Storage Materials

    International Nuclear Information System (INIS)

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

    2010-01-01

    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 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 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 2 ) for on-board hydrogen storage systems and an overall 60% energy efficiency. With the September 2007 No-Go decision for NaBH 4 as an on-board hydrogen storage medium, focus was shifted to ammonia borane (AB) for on-board hydrogen storage and delivery. However, NaBH 4 is a key building block to most boron-based fuels, and the ability to produce NaBH 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 project utilized an engineering

  7. 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

  8. Hydrogen storage materials at INCDTIM Cluj - Napoca. Achievements and outlook

    International Nuclear Information System (INIS)

    Lupu, D.; Biris, A.R.; Misan, I.

    2005-01-01

    Introducing hydrogen fuel to the transportation area poses key challenges for research on hydrogen storage materials. As one of the most promising alternative fuels for transport, hydrogen offers the long-term potential for an energy system that produces near-zero emissions and can be based on renewable energy sources. The Joint Research Centre (JRC), a Directorate-General of the European Commission fosters research for safe methods for storing hydrogen, for use in fuel cells or modified combustion engines in cars and other road vehicles. Hydrogen storage materials focused, in the last 30 years, the attention of the research programs in the many countries. Due to the fast development of the fuel cell technologies, the subject is much more stringent now. For mobile applications to fuel cell powered vehicles, on-board storage materials with hydrogen absorption/desorption capacities of at least 6.5%H are needed. For an efficient storage system the goal is to pack hydrogen as close as possible. Hydrogen storage implies the reduction of an enormous volume of H 2 gas (1 kg of gas has a volume of 11 m 3 at ambient temperature and pressure). To reach the high volumetric and gravimetric density suitable for mobile applications, basically six reversible storage methods are known today according to A. Zuettel: 1) high-pressure gas cylinders, 2) liquid in cryogenic tanks, 3) physisorbed on a solid surface e.g. carbon-nanotubes 4) metal hydrides of the metals or intermetallic compounds. 5) complex hydrides of light elements such as alanates and boranates, 6) storage via chemical reactions. Recently, the storage as hydrogen hydrates at 50 bar using promoters has been reported by F. Peetom. The paper discusses the feasibility of each of these storing alternatives. The authors presents their experience and results of the work in the field of metal hydrides and application obtained since 1975. All classes of hydrogen absorbing intermetallic compounds were studied: LaNi 5 , FeTi, Ti

  9. 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.

  10. 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

  11. Once-monthly paliperidone palmitate in early stage schizophrenia – a retrospective, non-interventional 1-year study of patients with newly diagnosed schizophrenia

    Directory of Open Access Journals (Sweden)

    Emsley R

    2017-08-01

    Full Text Available Robin Emsley,1 Ludger Hargarter,2 Paul Bergmans,3 Boran Uglešić,4 Abdullah Cem Sengül,5 Antonino Petralia,6 Angelina Khannanova,7 Pierre Cherubin,8 Andreas Schreiner2 1Stellenbosch University, Tygerberg Campus, Cape Town, South Africa; 2Janssen Cilag EMEA, Neuss, Germany, 3Janssen Cilag, Clinical Biostatistics, Breda, Netherlands; 4Department of Psychiatry, University Hospital Centre Split, Split, Croatia; 5Özel Antalya Likya Hastanesi, Antalya, Turkey; 6Department of Clinical and Experimental Medicine, School of Medicine, University of Catania, Catania, Italy; 7State Budgetary Healthcare Institution, Psychiatrc Clinical Hospital N3 named after VA Giliarovskiy, Moscow, Russia; 8Janssen Cilag EMEA, Issy-les-Moulineaux, France Background: Long-acting antipsychotic therapy may be best suited for patients in the early stage of schizophrenia, when the most can be done before disease progression associated with poor adherence occurs. We explored the patterns of use of once-monthly paliperidone palmitate (PP1M, concomitant medication use, hospitalization, and clinical outcomes of adult, newly diagnosed patients with schizophrenia receiving continuous treatment with PP1M for at least 12 months. Methods: This was an international, multicenter, exploratory, retrospective chart review of medical records of adult patients who were newly diagnosed (not more than 1 year before initiation of PP1M treatment with schizophrenia and who had received continuous treatment with PP1M for ≥12 months in naturalistic clinical settings. Results: A total of 84 (93.3% patients were included in the analysis. All but one patient (98.8%, n=83 had received oral antipsychotic medication at least during the last month before the first PP1M administration. Three patients (3.6% were newly hospitalized during the 12-month documentation period. The reason for hospitalization for all three was management of episode/relapse. A total of 79.2% of patients had a ≥20% improvement

  12. Development of group IV molecular catalysts for high temperature ethylene-α-olefin copolymerization reactions.

    Science.gov (United States)

    Klosin, Jerzy; Fontaine, Philip P; Figueroa, Ruth

    2015-07-21

    polymerization reactions were conducted in the presence of diethylzinc, an essential requirement for use in the production of olefin block copolymers via chain shuttling polymerization. Overall, the excellent characteristics of imino-amido-type catalysts, including high catalytic activities and ultrahigh molecular weight capabilities, make them good candidates for high temperature syntheses of block and random ethylene-α-olefin copolymers. Additionally, trialkyl imino-enamido complexes react quickly with various protic and unsaturated organic fragments, leading to a library of dialkyl precatalysts that, in several instances, resulted in superior catalysts. In conjunction with the development of transition metal catalysts, we also synthesized and evaluated activators for olefin polymerization. We found, for example, that, when conducted in coordinating solvents, the reaction between aluminum alkyls and tris(pentafluorophenyl)borane leads to the exclusive formation of alumenium borates, which are excellent activators for CGC complexes. Additionally, we developed a series of highly effective new activators featuring a very weakly coordinating anion composed of two Lewis acids coordinated to an imidazole fragment.

  13. Chemical Modification of Cellulose Esters for Oral Drug Delivery

    Science.gov (United States)

    Meng, Xiangtao

    with carboxylic acid/carbonyl during a typical esterification reaction or ring opening of lactones, producing cellulose-g-polyester and homopolyester. We demonstrated the viability of chemoselective olefin hydroboration-oxidation in the synthesis of cellulose o-hydroxyesters in the presence of ester groups. Cellulose esters with terminally olefinic side chains were transformed to the target products by two-step, one-pot hydroborationoxidation reactions, using 9-borabicyclo[3.3.1]nonane (9-BBN) as hydroboration agent, followed by oxidizing the organoborane intermediate to a primary alcohol using mildly alkaline H2O2. The use of 9-BBN as hydroboration agent and sodium acetate as base catalyst in oxidation successfully avoided cleavage of ester linkages by borane reduction and base catalyzed hydrolysis. With the impetus of modular and efficient synthesis, we introduced olefin crossmetathesis (CM) in polysaccharide functionalization. Using Grubbs type catalyst, cellulose esters with terminally olefinic side chains were reacted with various CM partners including acrylic acid, acrylates and acrylamides to afford families of functionalized cellulose esters. Molar excesses of CM partners were used in order to suppress potential crosslinking caused by self-metathesis between terminally olefinic side chains. Amide CM partners can chelate with the ruthenium catalyst and cause low conversions in conventional solvents such as THF. While the inherent reactivity toward CM and tendency of acrylamides to chelate Ru is influenced by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides. We observed that the CM products are prone to crosslinking during storage, and found that the crosslinking is likely caused by free radical abstraction of gamma-hydrogen of the alpha,beta-unsaturation and subsequent recombination. We further demonstrated successful hydrogenation of these alpha,beta-unsaturated acids, esters, and

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

    International Nuclear Information System (INIS)

    Hawthorne, M. Frederick

    2005-01-01

    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 amphiphilic

  15. 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

  16. 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

  17. Investigations into Chemical Hydrogen Storage and the anti-Markovnikov Hydroamination of Alkenes

    Science.gov (United States)

    St. John, Anthony J.

    The known carbon-boron-nitrogen (CBN) material ethylenediamine bisborane (EDBB) has been prepared and tested as a potential hydrogen storage material. Dehydrogenation of EDBB was achieved using the (t BuPOCOP)Ir(H)2 (t BuPOCOP = 2,6-bis(OPtBu2)C 6H3) catalyst. This reaction results in the release of two equivalents of hydrogen per molecule of EDBB. The product of this reaction is an insoluble, likely oligomeric, species. Heating the reaction mixture does not result in the release of additional equivalents of hydrogen. A new CBN material, 1,2-B,N-cyclohexane, was targeted as a potential hydrogen storage material. The enthalpy of dehydrogenation of 1,2-B,N-cyclohexane to 1,2-dihydro-1,2-azaborine was calculated to be 23.5 kcal/mol at 298 K using the B3LYP basis set. Ultimately, our collaborators at the University of Oregon prepared 1,2-B,N-cyclohexane. This molecule is a stable solid and undergoes thermal dehydrogenation of the B-N bond at 150 °C. The dehydrogenation of a variety of cyclic CBN materials was studied with the ( tBuPOCOP)Ir(H)2 catalyst. A number of cobalt-pincer complexes were tested as ammonia borane (AB) dehydrogenation catalysts. (PhPSiNSiP)CoCl (PhPSiNSiP = (N(SiMe2CH2PPh 2)2) was found to be a very active precatalyst for AB dehydrogenation, releasing 1 equivalent of hydrogen at 2.0 mol % catalyst loading within 5 minutes. The product of this reaction was characterized as cyclopentaborazane. The catalyst lifetime is limited and the identity of the active species remains unknown. A novel [(tBuPOCOP)Co] 2Hg complex was synthesized by reaction of (t BuPOCOP)CoI with Na/Hg. This complex was fully characterized by 1H NMR spectroscopy, elemental analysis, and X-ray crystallography. A new catalytic pathway for the anti-Markovnikov hydroamination of alkenes is proposed. The individual steps of this pathway were studied with the [(MTPA)Rh(propene)][BPh 4] (MTPA = tris((6-methyl-2-pyridyl)methyl)amine) complex. Protonation of this complex with anilinium

  18. Ferrocene-fused derivatives of acenes, tropones and thiepins

    Science.gov (United States)

    Maharjan, Bidhya Laxmi

    This research project is concentrated on tuning the properties of small organic molecules, namely polyacenes, tropones and thiepins, by incorporating redox-active transition metal centers pi-bonded to terminal cyclopentadienyl ligands. Organometallicfused acenequinones, tropones, thiepins and cyclopentadiene-capped polyacenes were synthesized and characterized. This work was divided into three parts: first, the synthesis of ferrocene-fused acenequinones, cyclopentadiene-capped acenequinones and their subsequent aromatization to polyacenes; second, the synthesis of ferrocene-fused tropones, thiotropones and tropone oxime; and third, the synthesis of ferrocene-fused thiepins. Ferrocene-fused quinones are the precursors to our target complexes. Our synthetic route to ferrocenequinones involved two-fold aldol condensation between 1,2- diformylferrocene and naphthalene-1,4-diol or anthracene-1,4-diol, and four-fold condensation between 1,2-diformylferrocene and 1,4-cyclohexanedione. Reduction of ferrocene-fused quinones with borane in THF resulted in ferrocene-fused dihydroacenes. Attempts to reduce ferrocene-fused acenequinones with sodium dithionite led to metalfree cyclopentadiene- (Cp-) capped acenequinones. Cp-capped acenequinones were aromatized to bis(triisopropylsilyl)ethynyl polyacenes by using lithium (triisopropylsilyl)acetylide (TIPSC≡CLi) with subsequent dehydroxylation by stannous chloride. The compounds were characterized by using spectroscopic methods and X-ray crystallography. Further, the electronic properties of these compounds were studied by using cyclic voltammetry and UV-visible spectroscopy. Cyclic voltammetry showed oxidation potentials of Cp-capped TIPS-tetracene and bis-Cp-capped TIPS-anthracene as 0.49 V and 0.61 V, respectively (vs. ferrocene/ferrocenium). The electrochemical band gaps were 2.15 eV and 2.58 eV, respectively. Organic thin-film transistor device performance of Cp-capped polyacenes was studied using solution deposition

  19. Variance Components and Genetic Parameters for Milk Production and Lactation Pattern in an Ethiopian Multibreed Dairy Cattle Population

    Directory of Open Access Journals (Sweden)

    Gebregziabher Gebreyohannes

    2013-09-01

    Full Text Available The objective of this study was to estimate variance components and genetic parameters for lactation milk yield (LY, lactation length (LL, average milk yield per day (YD, initial milk yield (IY, peak milk yield (PY, days to peak (DP and parameters (ln(a and c of the modified incomplete gamma function (MIG in an Ethiopian multibreed dairy cattle population. The dataset was composed of 5,507 lactation records collected from 1,639 cows in three locations (Bako, Debre Zeit and Holetta in Ethiopia from 1977 to 2010. Parameters for MIG were obtained from regression analysis of monthly test-day milk data on days in milk. The cows were purebred (Bos indicus Boran (B and Horro (H and their crosses with different fractions of Friesian (F, Jersey (J and Simmental (S. There were 23 breed groups (B, H, and their crossbreds with F, J, and S in the population. Fixed and mixed models were used to analyse the data. The fixed model considered herd-year-season, parity and breed group as fixed effects, and residual as random. The single and two-traits mixed animal repeatability models, considered the fixed effects of herd-year-season and parity subclasses, breed as a function of cow H, F, J, and S breed fractions and general heterosis as a function of heterozygosity, and the random additive animal, permanent environment, and residual effects. For the analysis of LY, LL was added as a fixed covariate to all models. Variance components and genetic parameters were estimated using average information restricted maximum likelihood procedures. The results indicated that all traits were affected (p<0.001 by the considered fixed effects. High grade B×F cows (3/16B 13/16F had the highest least squares means (LSM for LY (2,490±178.9 kg, IY (10.5±0.8 kg, PY (12.7±0.9 kg, YD (7.6±0.55 kg and LL (361.4±31.2 d, while B cows had the lowest LSM values for these traits. The LSM of LY, IY, YD, and PY tended to increase from the first to the fifth parity. Single-trait analyses

  20. Variance components and genetic parameters for milk production and lactation pattern in an ethiopian multibreed dairy cattle population.

    Science.gov (United States)

    Gebreyohannes, Gebregziabher; Koonawootrittriron, Skorn; Elzo, Mauricio A; Suwanasopee, Thanathip

    2013-09-01

    The objective of this study was to estimate variance components and genetic parameters for lactation milk yield (LY), lactation length (LL), average milk yield per day (YD), initial milk yield (IY), peak milk yield (PY), days to peak (DP) and parameters (ln(a) and c) of the modified incomplete gamma function (MIG) in an Ethiopian multibreed dairy cattle population. The dataset was composed of 5,507 lactation records collected from 1,639 cows in three locations (Bako, Debre Zeit and Holetta) in Ethiopia from 1977 to 2010. Parameters for MIG were obtained from regression analysis of monthly test-day milk data on days in milk. The cows were purebred (Bos indicus) Boran (B) and Horro (H) and their crosses with different fractions of Friesian (F), Jersey (J) and Simmental (S). There were 23 breed groups (B, H, and their crossbreds with F, J, and S) in the population. Fixed and mixed models were used to analyse the data. The fixed model considered herd-year-season, parity and breed group as fixed effects, and residual as random. The single and two-traits mixed animal repeatability models, considered the fixed effects of herd-year-season and parity subclasses, breed as a function of cow H, F, J, and S breed fractions and general heterosis as a function of heterozygosity, and the random additive animal, permanent environment, and residual effects. For the analysis of LY, LL was added as a fixed covariate to all models. Variance components and genetic parameters were estimated using average information restricted maximum likelihood procedures. The results indicated that all traits were affected (pIY (10.5±0.8 kg), PY (12.7±0.9 kg), YD (7.6±0.55 kg) and LL (361.4±31.2 d), while B cows had the lowest LSM values for these traits. The LSM of LY, IY, YD, and PY tended to increase from the first to the fifth parity. Single-trait analyses yielded low heritability (0.03±0.03 and 0.08±0.02) and repeatability (0.14±0.01 to 0.24±0.02) estimates for LL, DP and parameter c

  1. 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

  2. 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

  3. 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.)

  4. 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

  5. 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