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Sample records for carbon 13 reactions

  1. Carbon-13 Labeling Used to Probe Cure and Degradation Reactions of High- Temperature Polymers

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Johnston, J. Christopher

    1998-01-01

    High-temperature, crosslinked polyimides are typically insoluble, intractible materials. Consequently, in these systems it has been difficult to follow high-temperature curing or long-term degradation reactions on a molecular level. Selective labeling of the polymers with carbon-13, coupled with solid nuclear magnetic resonance spectrometry (NMR), enables these reactions to be followed. We successfully employed this technique to provide insight into both curing and degradation reactions of PMR-15, a polymer matrix resin used extensively in aircraft engine applications.

  2. Carbon-13 nuclear magnetic resonance spectroscopic investigation of the Kiliani reaction

    SciTech Connect

    Blazer, R.M.; Whaley, T.W.

    1980-07-16

    The Kiliani reaction of D-arabinose with sodium (/sup 13/C)cyanide (or (/sup 13/C,/sup 15/N)cyanide) was studied by /sup 13/C NMR. The C-1 resonances of intermediates and products were observed as the reaction evolved. Intermediates were identified by addition of authentic samples to reaction solutions, interpretation of chemical shifts and coupling constants, and chemical experiments. Intermediates identified included cyanohydrins, amides, lactones, amidines, and an imidate. A discussion of the course of the reaction over the pH range 5.1 to 12.5 is presented. The final mannonate-to-gluconate ratio was shown to be a function of pH and not associated with the presence of certain metal ions. 2 figures, 1 table.

  3. Implications of the large carbon kinetic isotope effect in the reaction CH4 + Cl for the 13C/12C ratio of stratospheric CH4

    NASA Astrophysics Data System (ADS)

    Bergamaschi, P.; Brühl, C.; Brenninkmeijer, C. A. M.; Saueressig, G.; Crowley, J. N.; Grooß, J. U.; Fischer, H.; Crutzen, P. J.

    Recent investigations of the carbon kinetic isotope effect (KIE) of the reaction CH4 + Cl yielded KIECl = 1.066±0.002 at 297 K (increasing to 1.075±0.005 at 223 K) [Saueressig et al., 1995]. In order to assess the effect of the exceptionally large KIEcl on δ13C of stratospheric CH4 we applied a two-dimensional, time dependent chemical transport model. The model results demonstrate the strong influence of the CH4 + Cl reaction on δ13CH4 in particular in the middle and upper stratosphere, where this reaction contributes several tens of percent to the total CH4 sink. The Cl sink helps to explain the relatively large overall isotope fractionation of 1.010-1.012 observed in the lower stratosphere [Brenninkmeijer et al., 1995; Brenninkmeijer et al., 1996], even though the model results predict a smaller effect than observed.

  4. Catalytic conversion of carbon dioxide into dimethyl carbonate using reduced copper-cerium oxide catalysts as low as 353 K and 1.3 MPa and the reaction mechanism

    PubMed Central

    Wada, Seiki; Oka, Kazuki; Watanabe, Kentaro; Izumi, Yasuo

    2013-01-01

    Synthesis of dimethyl carbonate (DMC) from CO2 and methanol under milder reaction conditions was performed using reduced cerium oxide catalysts and reduced copper-promoted Ce oxide catalysts. Although the conversion of methanol was low (0.005–0.11%) for 2 h of reaction, DMC was synthesized as low as 353 K and at total pressure of as low as 1.3 MPa using reduced Cu–CeO2 catalyst (0.5 wt% of Cu). The apparent activation energy was 120 kJ mol−1 and the DMC synthesis rates were proportional to the partial pressure of CO2. An optimum amount of Cu addition to CeO2 was 0.1 wt% for DMC synthesis under the conditions at 393 K and total pressure of 1.3 MPa for 2 h (conversion of methanol: 0.15%) due to the compromise of two effects of Cu: the activation of H2 during reduction prior to the kinetic tests and the block (cover) of the surface active site. The reduction effects in H2 were monitored through the reduction of Ce4+ sites to Ce3+ based on the shoulder peak intensity at 5727 eV in the Ce L3-edge X-ray absorption near-edge structure (XANES). The Ce3+ content was 10% for reduced CeO2 catalyst whereas it increased to 15% for reduced Cu–CeO2 catalyst (0.5 wt% of Cu). Moreover, the content of reduced Ce3+ sites (10%) associated with the surface O vacancy (defect sites) decreased to 5% under CO2 at 290 K for reduced Cu–CeO2 catalyst (0.1 wt% of Cu). The adsorption step of CO2 on the defect sites might be the key step in DMC synthesis and thus the DMC synthesis rate dependence on the partial pressure of CO2 was proportional. Subsequent H atom subtraction steps from methanol at the neighboring surface Lewis base sites should combine two methoxy species to the adsorbed CO2 to form DMC, water, and restore the surface O vacancy. PMID:24790937

  5. Catalytic conversion of carbon dioxide into dimethyl carbonate using reduced copper-cerium oxide catalysts as low as 353 K and 1.3 MPa and the reaction mechanism

    NASA Astrophysics Data System (ADS)

    Wada, Seiki; Oka, Kazuki; Watanabe, Kentaro; Izumi, Yasuo

    2013-06-01

    Synthesis of dimethyl carbonate (DMC) from CO2 and methanol under milder reaction conditions was performed using reduced cerium oxide catalysts and reduced copper-promoted Ce oxide catalysts. Although the conversion of methanol was low (0.005-0.11%) for 2 h of reaction, DMC was synthesized as low as 353 K and at total pressure of as low as 1.3 MPa using reduced Cu-CeO2 catalyst (0.5 wt% of Cu). The apparent activation energy was 120 kJ mol-1 and the DMC synthesis rates were proportional to the partial pressure of CO2. An optimum amount of Cu addition to CeO2 was 0.1 wt% for DMC synthesis under the conditions at 393 K and total pressure of 1.3 MPa for 2 h (conversion of methanol: 0.15%) due to the compromise of two effects of Cu: the activation of H2 during reduction prior to the kinetic tests and the block (cover) of the surface active site. The reduction effects in H2 were monitored through the reduction of Ce4+ sites to Ce3+ based on the shoulder peak intensity at 5727 eV in the Ce L3-edge X-ray absorption near-edge structure (XANES). The Ce3+ content was 10% for reduced CeO2 catalyst whereas it increased to 15% for reduced Cu-CeO2 catalyst (0.5wt% of Cu). Moreover, the content of reduced Ce3+ sites (10%) associated with the surface O vacancy (defect sites) decreased to 5% under CO2 at 290 K for reduced Cu-CeO2 catalyst (0.1wt% of Cu). The adsorption step of CO2 on the defect sites might be the key step in DMC synthesis and thus the DMC synthesis rate dependence on the partial pressure of CO2 was proportional. Subsequent H atom subtraction steps from methanol at the neighboring surface Lewis base sites should combine two methoxy species to the adsorbed CO2 to form DMC, water, and restore the surface O vacancy.

  6. Carbon-13 variations in the dissolved inorganic carbon in estuarine waters

    NASA Astrophysics Data System (ADS)

    Sackett, William M.; Netratanawong, Toedsit; Holmes, M. Elizabeth

    The stable carbon isotope composition of dissolved inorganic carbon [DIC] was measured in Tampa Bay and Florida Bay. The dependence of isotopic composition was evaluated in terms of atmospheric CO2 exchange, carbon exchange between fresh water and seawater (i.e. salinity) and DIC derived from the reaction between calcium carbonate and organically derived CO2.The extent of organic carbon oxidation and the magnitude of organic carbon loading [pollution] in an estuary have implications for variations in the δ13C of DIC and its use as an indicator of the relative amounts of land and marine derived organic and inorganic carbon in paleogeographic studies.

  7. Cascade enzymatic reactions for efficient carbon sequestration.

    PubMed

    Xia, Shunxiang; Zhao, Xueyan; Frigo-Vaz, Benjamin; Zheng, Wenyun; Kim, Jungbae; Wang, Ping

    2015-04-01

    Thermochemical processes developed for carbon capture and storage (CCS) offer high carbon capture capacities, but are generally hampered by low energy efficiency. Reversible cascade enzyme reactions are examined in this work for energy-efficient carbon sequestration. By integrating the reactions of two key enzymes of RTCA cycle, isocitrate dehydrogenase and aconitase, we demonstrate that intensified carbon capture can be realized through such cascade enzymatic reactions. Experiments show that enhanced thermodynamic driving force for carbon conversion can be attained via pH control under ambient conditions, and that the cascade reactions have the potential to capture 0.5 mol carbon at pH 6 for each mole of substrate applied. Overall it manifests that the carbon capture capacity of biocatalytic reactions, in addition to be energy efficient, can also be ultimately intensified to approach those realized with chemical absorbents such as MEA.

  8. Synthesis of carbon-13 enriched disaccharides: lactose and sucrose

    SciTech Connect

    Walker, T.E.; Unkefer, P.J.; Unkefer, C.J.; Ehler, D.S.

    1986-05-01

    Disaccharides can be prepared enzymatically and by chemical synthesis. Lactose enriched with carbon-13 at C-1 can be synthesized by reacting K/sup 13/CN with a sugar having a one fewer carbon than the desired product. Thus, a mixture of 4-O-..beta..-D-galactopyranosyl-D-(1-/sup 13/C)glucose ((1-/sup 13/C)lactose) and 4-O-..beta..-D-galactopyranosyl-D-(1-/sup 13/C)mannose can be synthesized from 3-O-..beta..-D-galactopyranosyl-D-arabinose and K/sup 13/CN. (/sup 13/C)Sucrose is conveniently prepared in gram quantities from D-(/sup 13/C)fructose and UDP-glucose in a reaction catalyzed by the enzyme sucrose synthetase. This reaction proceeds smoothly at 25/sup 0/ over a period of hours to give an equilibrium mixture which can be separated chromatographically. The glucose portion of sucrose can be labeled using enzymatically-prepared UDP-(/sup 13/C)glucose. Labeled sucrose is important for the preparation of labeled starches to be used for structural and metabolic studies.

  9. A combined crossed beam and ab initio investigation on the reaction of carbon species with C4H6 isomers. I. The 1,3-butadiene molecule, H2CCHCHCH2(X1A')

    NASA Astrophysics Data System (ADS)

    Hahndorf, I.; Lee, H. Y.; Mebel, A. M.; Lin, S. H.; Lee, Y. T.; Kaiser, R. I.

    2000-12-01

    The reaction between ground state carbon atoms, C(3Pj), and 1,3-butadiene, H2CCHCHCH2, was studied at three averaged collision energies between 19.3 and 38.8 kJmol-1 using the crossed molecular beam technique. Our experimental data combined with electronic structure calculations show that the carbon atom adds barrierlessly to the π-orbital of the butadiene molecule via a loose, reactantlike transition state located at the centrifugal barrier. This process forms vinylcyclopropylidene which rotates in a plane almost perpendicular to the total angular momentum vector J around its C-axis. The initial collision complex undergoes ring opening to a long-lived vinyl-substituted triplet allene molecule. This complex shows three reaction pathways. Two distinct H atom loss channels form 1- and 3-vinylpropargyl radicals, HCCCHC2H3(X2A″) and H2CCCC2H3(X2A″), through tight exit transition states located about 20 kJmol-1 above the products; the branching ratio of 1- versus 3-vinylpropargyl radical is about 8:1. A minor channel of less than 10% is the formation of a vinyl, C2H3(X2A'), and propargyl radical C3H3(X2B2). The unambiguous identification of two C5H5 chain isomers under single collision has important implications to combustion processes and interstellar chemistry. Here, in denser media such as fuel flames and in circumstellar shells of carbon stars, the linear structures can undergo a collision-induced ring closure followed by a hydrogen migration to cyclic C5H5 isomers such as the cyclopentadienyl radical—a postulated intermediate in the formation of polycyclic aromatic hydrocarbons (PAHs). 2000 American Institute of Physics.

  10. Carbon-Fixing Reactions of Photosynthesis.

    PubMed

    2016-07-01

    Summaryplantcell;28/7/tpc.116.tt0716/FIG1F1fig1Photosynthesis in plants converts the energy of sunlight into chemical energy. Although photosynthesis involves many proteins and catalytic processes, it often is described as two sets of reactions, the light-dependent reactions and the carbon-fixing reactions. This lesson introduces the core biochemistry of the carbon-fixing reactions of photosynthesis, as well as its variations, C4 and CAM. Finally, it addresses how and why plants are affected by rising atmospheric CO2 levels, and research efforts to increase photosynthetic efficiency in current and future conditions.

  11. Carbon-Fixing Reactions of Photosynthesis.

    PubMed

    2016-07-01

    Summaryplantcell;28/7/tpc.116.tt0716/FIG1F1fig1Photosynthesis in plants converts the energy of sunlight into chemical energy. Although photosynthesis involves many proteins and catalytic processes, it often is described as two sets of reactions, the light-dependent reactions and the carbon-fixing reactions. This lesson introduces the core biochemistry of the carbon-fixing reactions of photosynthesis, as well as its variations, C4 and CAM. Finally, it addresses how and why plants are affected by rising atmospheric CO2 levels, and research efforts to increase photosynthetic efficiency in current and future conditions. PMID:27493209

  12. Optical Excitation of Carbon Nanotubes Drives Localized Diazonium Reactions.

    PubMed

    Powell, Lyndsey R; Piao, Yanmei; Wang, YuHuang

    2016-09-15

    Covalent chemistries have been widely used to modify carbon nanomaterials; however, they typically lack the precision and efficiency required to directly engineer their optical and electronic properties. Here, we show, for the first time, that visible light which is tuned into resonance with carbon nanotubes can be used to drive their functionalization by aryldiazonium salts. The optical excitation accelerates the reaction rate 154-fold (±13) and makes it possible to significantly improve the efficiency of covalent bonding to the sp(2) carbon lattice. Control experiments suggest that the reaction is dominated by a localized photothermal effect. This light-driven reaction paves the way for precise nanochemistry that can directly tailor carbon nanomaterials at the optical and electronic levels. PMID:27588432

  13. Optical Excitation of Carbon Nanotubes Drives Localized Diazonium Reactions.

    PubMed

    Powell, Lyndsey R; Piao, Yanmei; Wang, YuHuang

    2016-09-15

    Covalent chemistries have been widely used to modify carbon nanomaterials; however, they typically lack the precision and efficiency required to directly engineer their optical and electronic properties. Here, we show, for the first time, that visible light which is tuned into resonance with carbon nanotubes can be used to drive their functionalization by aryldiazonium salts. The optical excitation accelerates the reaction rate 154-fold (±13) and makes it possible to significantly improve the efficiency of covalent bonding to the sp(2) carbon lattice. Control experiments suggest that the reaction is dominated by a localized photothermal effect. This light-driven reaction paves the way for precise nanochemistry that can directly tailor carbon nanomaterials at the optical and electronic levels.

  14. Carbon-13 NMR characterization of actinyl(VI) carbonate complexes in aqueous solution

    SciTech Connect

    Clark, D.L.; Hobart, D.E.; Palmer, P.D.; Sullivan, J.C.; Stout, B.E.

    1992-07-01

    The uranyl(VI) carbonate system has been re-examined using {sup 13}C NMR of 99.9% {sup 13}C-enriched U{sup VI}O{sub 2} ({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} in millimolar concentrations. By careful control of carbonate ion concentration, we have confirmed the existence of the trimer, and observed dynamic equilibrium between the monomer and the timer. In addition, the ligand exchange reaction between free and coordinated carbonate on Pu{sup VI}O{sub 2}({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} and Am{sup VI}O{sub 2}({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} systems has been examined by variable temperature {sup 13}C NMR line-broadening techniques {sup 13}C NMR line-broadening techniques. A modified Carr-Purcell-Meiboom-Gill NMR pulse sequence was written to allow for experimental determination of ligand exchange parameters for paramagnetic actinide complexes. Preliminary Eyring analysis has provided activation parameters of {Delta}G{sup {double_dagger}}{sub 295} = 56 kJ/M, {Delta}H{sup {double_dagger}} = 38 kJ/M, and {Delta}S{sup {double_dagger}} = {minus}60 J/M-K for the plutonyl triscarbonate system, suggesting an associative transition state for the plutonyl (VI) carbonate complex self-exchange reaction. Experiments for determination of the activation parameters for the americium (VI) carbonate system are in progress.

  15. Organic syntheses employing supercritical carbon dioxide as a reaction solvent

    NASA Technical Reports Server (NTRS)

    Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

    1991-01-01

    Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

  16. Organic syntheses employing supercritical carbon dioxide as a reaction solvent

    NASA Technical Reports Server (NTRS)

    Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

    1993-01-01

    Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

  17. Chemical reactions confined within carbon nanotubes.

    PubMed

    Miners, Scott A; Rance, Graham A; Khlobystov, Andrei N

    2016-08-22

    In this critical review, we survey the wide range of chemical reactions that have been confined within carbon nanotubes, particularly emphasising how the pairwise interactions between the catalysts, reactants, transition states and products of a particular molecular transformation with the host nanotube can be used to control the yields and distributions of products of chemical reactions. We demonstrate that nanoscale confinement within carbon nanotubes enables the control of catalyst activity, morphology and stability, influences the local concentration of reactants and products thus affecting equilibria, rates and selectivity, pre-arranges the reactants for desired reactions and alters the relative stability of isomeric products. We critically evaluate the relative advantages and disadvantages of the confinement of chemical reactions inside carbon nanotubes from a chemical perspective and describe how further developments in the controlled synthesis of carbon nanotubes and the incorporation of multifunctionality are essential for the development of this ever-expanding field, ultimately leading to the effective control of the pathways of chemical reactions through the rational design of multi-functional carbon nanoreactors.

  18. Structure of 13Be probed via secondary-beam reactions

    NASA Astrophysics Data System (ADS)

    Randisi, G.; Leprince, A.; Al Falou, H.; Orr, N. A.; Marqués, F. M.; Achouri, N. L.; Angélique, J.-C.; Ashwood, N.; Bastin, B.; Bloxham, T.; Brown, B. A.; Catford, W. N.; Curtis, N.; Delaunay, F.; Freer, M.; de Góes Brennand, E.; Haigh, P.; Hanappe, F.; Harlin, C.; Laurent, B.; Lecouey, J.-L.; Ninane, A.; Patterson, N.; Price, D.; Stuttgé, L.; Thomas, J. S.

    2014-03-01

    The low-lying level structure of the unbound neutron-rich nucleus 13Be has been investigated via breakup on a carbon target of secondary beams of 14,15B at 35 MeV/nucleon. The coincident detection of the beam velocity 12Be fragments and neutrons permitted the invariant mass of the 12Be+n and 12Be+n+n systems to be reconstructed. In the case of the breakup of 15B, a very narrow structure at threshold was observed in the 12Be+n channel. Analysis of the 12Be+n+n events demonstrated that this resulted from the sequential decay of the unbound 14Be(2+) state rather than a strongly interacting s-wave virtual state in 13Be, as had been surmised in stable beam fragmentation studies. Single-proton removal from 14B was found to populate a broad low-lying structure some 0.7 MeV above the neutron-decay threshold, in addition to a less prominent feature at around 2.4 MeV. Based on the selectivity of the reaction and a comparison with (0-3)ℏω shell-model calculations, the low-lying structure is concluded to arise from closely spaced Jπ=1/2+ and 5/2+ resonances (Er=0.40±0.03 and 0.85-0.11+0.15 MeV), while the broad higher-lying feature is a second 5/2+ level (Er=2.35±0.14 MeV). Taken in conjunction with earlier studies, the results suggest that the lowest 1/2+ and 1/2- levels lie relatively close together below 1 MeV.

  19. In vivo Carbon-13 Nuclear Magnetic Resonance Studies of Mammals

    NASA Astrophysics Data System (ADS)

    Alger, J. R.; Sillerud, L. O.; Behar, K. L.; Gillies, R. J.; Shulman, R. G.; Gordon, R. E.; Shaw, D.; Hanley, P. E.

    1981-11-01

    Natural abundance carbon-13 nuclear magnetic resonances (NMR) from human arm and rat tissues have been observed in vivo. These signals arise primarily from triglycerides in fatty tissue. Carbon-13 NMR was also used to follow, in a living rat, the conversion of C-1--labeled glucose, which was introduced into the stomach, to C-1--labeled liver glycogen. The carbon-13 sensitivity and resolution obtained shows that natural abundance carbon-13 NMR will be valuable in the study of disorders in fat metabolism, and that experiments with substrates labeled with carbon-13 can be used to study carbohydrate metabolism in vivo.

  20. 1,3-Diferrocenyl-1,3-alkadienes in diene synthesis reactions

    SciTech Connect

    Pushin, A.N.; Klimova, E.I.; Sazanova, V.A.

    1987-11-10

    Stable 1,3-diferrocenyl-1,3-alkadienes, which form Diels-Alder adducts with N-substituted maleimides, have been prepared. Methyldiferrocenylbutadien participates in a cycloaddition reaction less readily than 1,3-diferrocenyl-1,3-butadiene. Adducts of 1,3-diferrocenyl-1,3-butadiene with N-substituted maleimides are dehydrogenated on Al/sub 2/O/sub 3/ or SiO/sub 2/ with subsequent formation of cyclohexadiene and benzene derivatives; protonation-deprotonation induces isomerization with transposition of the double bond.

  1. Synthesis of long-chain polyketide fragments by reaction of 1,3-dioxy-1,3-dienes with allylsilanes: umpolung with sulfur dioxide.

    PubMed

    Turks, Māris; Fonquerne, Freddy; Vogel, Pierre

    2004-03-18

    [reaction: see text] In the presence of a Lewis or protic acid and at low temperature, 1,3-dioxy-1,3-dienes add to sulfur dioxide generating zwitterionic intermediates that can react with carbon nucleophiles such as allylsilanes. After a retro-ene elimination of SO(2), valuable polyketide precursors are obtained.

  2. A slow reaction rate in detonations due to carbon clustering

    SciTech Connect

    Shaw, M.S.; Johnson, J.D.

    1987-07-01

    Theoretical calculations have been made to estimate the rate of heat release due to the carbon clustering process in detonations where elemental carbon is a reaction product. The process is assumed to be diffusion limited. Diffusion constants are determined using modified Enskog theory and the Stokes-Einstein relation. The carbon cluster energy is treated by a surface correction to the bulk. The amount of energy yet to be released has an asymptotic time dependence of t/sup -1/3/. For some explosives, this leads to time dependent detonations where the effective CJ pressure is 10-20% above CJ for run distances of the order of centimeters. 9 refs., 3 figs.

  3. Urea hydrolysis and calcium carbonate reaction fronts

    NASA Astrophysics Data System (ADS)

    Fox, D. T.; Redden, G. D.; Henriksen, J.; Fujita, Y.; Guo, L.; Huang, H.

    2010-12-01

    The mobility of toxic or radioactive metal contaminants in subsurface environments can be reduced by the formation of mineral precipitates that form co-precipitates with the contaminants or that isolate them from the mobile fluid phase. An engineering challenge is to control the spatial distribution of precipitation reactions with respect to: 1) the location of a contaminant, and 2) where reactants are introduced into the subsurface. One strategy being explored for immobilizing contaminants, such as Sr-90, involves stimulating mineral precipitation by forming carbonate ions and hydroxide via the in situ, microbially mediated hydrolysis of urea. A series of column experiments have been conducted to explore how the construction or design of such an in situ reactant production strategy can affect the temporal and spatial distribution of calcium carbonate precipitation, and how the distribution is coupled to changes in permeability. The columns were constructed with silica gel as the porous media. An interval midway through the column contained an adsorbed urease enzyme in order to simulate a biologically active zone. A series of influent solutions were injected to characterize hydraulic properties of the column (e.g., bromide tracer), profiles of chemical conditions and reaction products as the enzyme catalyzes urea hydrolysis (e.g., pH, ammonia, urea), and changes that occur due to CaCO3 precipitation with the introduction of a calcium+urea solutions. In one experiment, hydraulic conductivity was reduced as precipitate accumulated in a layer within the column that had a higher fraction of fine grained silica gel. Subsequent reduction of permeability and flow (for a constant head condition) resulted in displacement of the hydrolysis and precipitation reaction profiles upstream. In another experiment, which lacked the physical heterogeneity (fine grained layer), the precipitation reaction did not result in loss of permeability or flow velocity and the reaction profile

  4. Reaction of dichlorocarbene with 4-phenyl-1,3-dioxane

    SciTech Connect

    Safiev, O.G.; Nazarov, D.V.; Zorin, V.V.; Rakhmankulov, D.L.

    1988-02-20

    The authors have established for the first time that the reaction of 4-phenyl-1,3-dioxane with the dichlorocarbene generated from chloroform by the action of a 50% aqueous solution of sodium hydroxide in the presence of triethylbenzylammonium chloride as phase-transfer catalysis leads to the formation of 4-phenyl-4-dichloromethyl-1,3-dioxane with a yield of 70% on the transformed reagent with 35% conversion with respect to the substrate. The product was isolated by column liquid chromatography. It was identified by means of the PMR and /sup 13/C NMR spectra and by the data from elemental analysis.

  5. Experimental study of the 13C+12C fusion reaction at deep sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Tudor, D.; Chilug, A. I.; Straticiuc, M.; Trache, L.; Chesneanu, D.; Toma, S.; Ghita, D. G.; Burducea, I.; Margineanu, R.; Pantelica, A.; Gomoiu, C.; Zhang, N. T.; Tang, X.; Li, Y. J.

    2016-04-01

    Heavy-ion fusion reactions between light nuclei such as carbon and oxygen isotopes have been studied because of their significance for a wide variety of stellar burning scenarios. One important stellar reaction is 12C+12C, but it is difficult to measure it in the Gamow window because of very low cross sections and several resonances occurring. Hints can be obtained from the study of 13C+12C reaction. We have measured this process by an activation method for energies down to Ecm=2.5 MeV using 13C beams from the Bucharest 3 MV tandetron and gamma-ray deactivation measurements in our low and ultralow background laboratories, the latter located in a salt mine about 100 km north of Bucharest. Results obtained so far are shown and discussed in connection with the possibility to go even further down in energy and with the interpretation of the reaction mechanism at such deep sub-barrier energies.

  6. Polymorphs calcium carbonate on temperature reaction

    SciTech Connect

    Chong, Kai-Yin; Chia, Chin-Hua; Zakaria, Sarani

    2014-09-03

    Calcium carbonate (CaCO{sub 3}) has three different crystal polymorphs, which are calcite, aragonite and vaterite. In this study, effect of reaction temperature on polymorphs and crystallite structure of CaCO{sub 3} was investigated. X-ray powder diffraction (XRD), fourier transform infrared (FTIR), and variable pressure scanning electron microscope (VPSEM) were used to characterize the obtained CaCO{sub 3} particles. The obtained results showed that CaCO{sub 3} with different crystal and particle structures can be formed by controlling the temperature during the synthesis process.

  7. Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions

    NASA Technical Reports Server (NTRS)

    Nuth, J. A.; Johnson, N. M.; Elsila-Cook, J.; Kopstein, M.

    2011-01-01

    Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

  8. CMB-13 research on carbon and graphite

    NASA Technical Reports Server (NTRS)

    Smith, M. C.

    1972-01-01

    The research on graphite and carbon for this period is reported. Topics discussed include: effects of grinding on the Santa Marie graphites, properties and purities of coal-tar, resin-bonded graphite, carbonization of resin components, and glass-like carbon filler.

  9. Redox reactions of actinides in carbonate and alkaline solutions

    NASA Astrophysics Data System (ADS)

    Shilov, Vladimir P.; Yusov, Aleksander B.

    2002-06-01

    Data on redox reactions involving uranium, neptunium, plutonium and americium ions in carbonate and alkaline solutions are generalised. The results of kinetic studies of these reactions are analysed and their mechanisms are discussed. The bibliography includes 169 references.

  10. CMB-13 research on carbon and graphite

    NASA Technical Reports Server (NTRS)

    Smith, M. C.

    1972-01-01

    The effects of grinding on Santa Maria coke are considered, as well as the production of resin-bonded graphite from the coke. Kynol fibers, properties and purities of coal tar pitches, carbonization of resin components, synthesis of gamma BL (4-furfuryl 2-pentenoic acid gamma lactone), and a glass-like carbon powder for use as a filler are also discussed. The hydrogen contents of commercial cokes and graphites are tabulated, and a quantimet image-analyzing computer and its operation are described.

  11. CMB-13 research on carbon and graphite

    NASA Technical Reports Server (NTRS)

    Smith, M. C.

    1972-01-01

    Preliminary results of the research on carbon and graphite accomplished during this report period are presented. Included are: particle characteristics of Santa Maria fillers, compositions and density data for hot-molded Santa Maria graphites, properties of hot-molded Santa Maria graphites, and properties of hot-molded anisotropic graphites. Ablation-resistant graphites are also discussed.

  12. A Short Set of Carbon 13-NMR Correlation Tables.

    ERIC Educational Resources Information Center

    Brown, D. W.

    1985-01-01

    Presents a short set of carbon-13 nuclear magnetic resonance (NMR) tables. These tables not only serve pedagogic purposes but also allow students to do calculations rapidly and with acceptable accuracy for a wide variety of compounds. (JN)

  13. Functionalized multi-walled carbon nanotubes in an aldol reaction

    NASA Astrophysics Data System (ADS)

    Chronopoulos, D. D.; Kokotos, C. G.; Karousis, N.; Kokotos, G.; Tagmatarchis, N.

    2015-01-01

    The covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with a proline-based derivative is reported. Initially, MWCNTs were oxidized in order to introduce a large number of carboxylic units on their tips followed by N-tert-butoxycarbonyl-2,2'(ethylenedioxy)bis-(ethylamine) conjugation through an amide bond. Then, a proline derivative bearing a carboxylic terminal moiety at the 4-position was coupled furnishing proline-modified MWCNTs. This new hybrid material was fully characterized by spectroscopic and microscopy means and its catalytic activity in the asymmetric aldol reaction between acetone and 4-nitrobenzaldehyde was evaluated for the first time, showing to proceed almost quantitatively in aqueous media. Furthermore, several amino-modified MWCNTs were prepared and examined in the particular aldol reaction. These new hybrid materials exhibited an enhanced catalytic activity in water, contrasting with the pristine MWCNTs as well as the parent organic molecule, which failed to catalyze the reaction efficiently. Furthermore, the modified MWCNTs proved to catalyze the aldol reaction even after three repetitive cycles. Overall, a green approach for the aldol reaction is presented, where water can be employed as the solvent and modified MWCNTs can be used as catalysts, which can be successfully recovered and reused, while their catalytic activity is retained.The covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with a proline-based derivative is reported. Initially, MWCNTs were oxidized in order to introduce a large number of carboxylic units on their tips followed by N-tert-butoxycarbonyl-2,2'(ethylenedioxy)bis-(ethylamine) conjugation through an amide bond. Then, a proline derivative bearing a carboxylic terminal moiety at the 4-position was coupled furnishing proline-modified MWCNTs. This new hybrid material was fully characterized by spectroscopic and microscopy means and its catalytic activity in the asymmetric aldol reaction

  14. Quantitative identification of metastable magnesium carbonate minerals by solid-state 13C NMR spectroscopy.

    PubMed

    Moore, Jeremy K; Surface, J Andrew; Brenner, Allison; Wang, Louis S; Skemer, Philip; Conradi, Mark S; Hayes, Sophia E

    2015-01-01

    In the conversion of CO2 to mineral carbonates for the permanent geosequestration of CO2, there are multiple magnesium carbonate phases that are potential reaction products. Solid-state (13)C NMR is demonstrated as an effective tool for distinguishing magnesium carbonate phases and quantitatively characterizing magnesium carbonate mixtures. Several of these mineral phases include magnesite, hydromagnesite, dypingite, and nesquehonite, which differ in composition by the number of waters of hydration or the number of crystallographic hydroxyl groups. These carbonates often form in mixtures with nearly overlapping (13)C NMR resonances which makes their identification and analysis difficult. In this study, these phases have been investigated with solid-state (13)C NMR spectroscopy, including both static and magic-angle spinning (MAS) experiments. Static spectra yield chemical shift anisotropy (CSA) lineshapes that are indicative of the site-symmetry variations of the carbon environments. MAS spectra yield isotropic chemical shifts for each crystallographically inequivalent carbon and spin-lattice relaxation times, T1, yield characteristic information that assist in species discrimination. These detailed parameters, and the combination of static and MAS analyses, can aid investigations of mixed carbonates by (13)C NMR.

  15. Carbon dioxide released from subduction zones by fluid-mediated reactions

    NASA Astrophysics Data System (ADS)

    Ague, Jay J.; Nicolescu, Stefan

    2014-05-01

    The balance between the subduction of carbonate mineral-bearing rocks into Earth's mantle and the return of CO2 to the atmosphere by volcanic and metamorphic degassing is critical to the carbon cycle. Carbon is thought to be released from subducted rocks mostly by simple devolatilization reactions. However, these reactions will also retain large amounts of carbon within the subducting slab and have difficulty in accounting for the mass of CO2 emitted from volcanic arcs. Carbon release may therefore occur via fluid-induced dissolution of calcium carbonate. Here we use carbonate δ18O and δ13C systematics, combined with analyses of rock and fluid inclusion mineralogy and geochemistry, to investigate the alteration of the exhumed Eocene Cycladic subduction complex on the Syros and Tinos islands, Greece. We find that in marble rocks adjacent to two fluid conduits that were active during subduction, the abundance of calcium carbonate drastically decreases approaching the conduits, whereas silicate minerals increase. Up to 60-90% of the CO2 was released from the rocks--far greater than expected via simple devolatilization reactions. The δ18O of the carbonate minerals is 5-10 lighter than is typical for metamorphosed carbonate rocks, implying that isotopically light oxygen was transported by fluid infiltration from the surroundings. We suggest that fluid-mediated carbonate mineral removal, accompanied by silicate mineral precipitation, provides a mechanism for the release of enormous amounts of CO2 from subduction zones.

  16. Current and relic carbon using natural abundance carbon-13

    SciTech Connect

    layse,MF; Clapp,CE; Allmaras,RR; Linden,D.R; Molina, JAE.; Copeland,SM; Dowdy,RH

    2002-05-01

    The role of agricultural practices on soil carbon (C) dynamics is critical to improved soil management. The main objective was to examine the C interactions resulting from crop changes under different tillage and residue treatments.

  17. Organosulfur compounds: electrophilic reagents in transition-metal-catalyzed carbon-carbon bond-forming reactions.

    PubMed

    Dubbaka, Srinivas Reddy; Vogel, Pierre

    2005-12-01

    Transition-metal-catalyzed carbon-carbon bond-forming reactions are among the most powerful methods in organic synthesis and play a crucial role in modern materials science and medicinal chemistry. Recent developments in the area of ligands and additives permit the cross-coupling of a large variety of reactants, including inexpensive and readily available sulfonyl chlorides. Their desulfitative carbon-carbon cross-coupling reactions (Negishi, Stille, carbonylative Stille, Suzuki-Miyaura, and Sonogashira-Hagihara-type cross-couplings and Mizoroki-Heck-type arylations) are reviewed together with carbon-carbon cross-coupling reactions with other organosulfur compounds as electrophilic reagents.

  18. Detection of C-13O radio emission from C-13-rich carbon stars

    NASA Technical Reports Server (NTRS)

    Jura, M.; Kahane, C.; Omont, A.

    1988-01-01

    A high ratio of C-13O radio emission in the J = 1-0 rotational line has been detected from three mass-losing carbon stars which optical data indicate have high C-13/C12 ratios. Since chemical fractionation, isotope-dependent photodissociation and opacity in the rotational and vibrational lines may not raise significantly the C-13O ratio above the actual C-13/C-12 ratio in these circumstellar envelopes, the relative abundance of C-13 in these stars might be even greater by perhaps a factor of two than previously believed. About 15 percent of all luminous carbon stars are C-13-rich, and these stars may play a significant role in the enhancement in the C-13/C12 ratio that has occurred during the past 4.6 billion years since the formation of the sun.

  19. How to identify carbonate rock reactions in concrete

    SciTech Connect

    Katayama, Tetsuya . E-mail: katayamat@kge.co.jp

    2004-11-15

    This paper summarizes the modern petrographic techniques used to diagnose carbonate rock reactions in concrete. Concrete microbar specimens of the prototype RILEM AAR-5 test, provided by the Austrian Cement Research Institute, and typical Canadian concrete that had undergone alkali-carbonate reaction (ACR) were examined. Scanning electron microscopy, element mapping and quantitative analysis using electron-probe microanalyzer with energy-dispersive spectrometry (EPMA/EDS: around x 2000, <0.1 nA) were made of polished thin sections after completing polarizing microscopy. Dedolomitization produced a myrmekitic texture, composed of spotted brucite (<3 {mu}m) and calcite within the reaction rim, along with a carbonate halo of calcite in the surrounding cement paste. However, no evidence was detected that dedolomitization had produced the expansion cracks in the cement paste, while the classical definition of alkali-carbonate reaction postulates their development. It was found that the alkali-silica reaction (ASR) due to cryptocrystalline quartz hidden in the matrix, always associated with dedolomitization in all the carbonate aggregates tested, was responsible for the expansion of both the laboratory and field concretes, even with the Canadian dolomitic limestone from Kingston, the reference material for alkali-carbonate reaction. It is suggested that the term alkali-carbonate reaction is misleading.

  20. Carbon kinetic isotope effect in the reaction of CH4 with HO

    NASA Technical Reports Server (NTRS)

    Davidson, J. A.; Cantrell, C. A.; Tyler, S. C.; Shetter, R. E.; Cicerone, R. J.

    1987-01-01

    The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

  1. Dissociation-excitation reactions of argon metastables with carbon dioxide.

    NASA Technical Reports Server (NTRS)

    Starr, W. L.

    1971-01-01

    Results of a study showing that a metastable argon-carbon dioxide reaction results in dissociation of carbon dioxide and electronic excitation of one of the products, carbon monoxide or oxygen. A flow system using a 2450-MHz discharge was used to produce metastable argon atoms. Metastable argon in the afterglow was confirmed by adding nitrogen to the afterglow. Without addition of carbon dioxide no argon line emission, or any other emission, is observed from the reaction zone. Absence of argon line emission produced by recombination indicates the absence of charged species.

  2. Cycloaddition reactions of allenylphosphonates and related allenes with dialkyl acetylenedicarboxylates, 1,3-diphenylisobenzofuran, and anthracene.

    PubMed

    Sajna, K V; Kotikalapudi, Ramesh; Chakravarty, Manab; Bhuvan Kumar, N N; Swamy, K C Kumara

    2011-02-01

    Cycloaddition reactions of allenylphosphonates [(RO)(2)P(O)[(R(1))C═C═CR(2)(2)] with dialkyl acetylenedicarboxylates, 1,3-diphenylisobenzofuran, and anthracene have been investigated and compared with those of allenoates [(EtO(2)C)RC═C═CH(2)] and allenylphosphine oxides [Ph(2)P(O)(R(1))C═C═CR(2)(2)] in selected cases. Allenylphosphonates (RO)(2)P(O)(Ar)C═C═CH(2) with an α-aryl group preferentially undergo [4 + 2] cycloaddition with DMAD/DEAD under thermal activation, but in addition to the expected 1:1 (allene: DMAD) product, the reaction also leads to 1:2 as well as 2:1 products that were not reported before. When an extra vinyl group is present at the γ-carbon of allenylphosphonate [e.g., (OCH(2)CMe(2)CH(2)O)P(O)(Ph)C═C═CH(C═CHMe)], [4 + 2] cycloaddition takes place utilizing either the vinylic or the aryl end, but additionally a novel cyclization wherein complete opening of the [β,γ] carbon-carbon double bond of the allene is realized. In contrast to these, the reaction of allenylphosphonate (OCH(2)CMe(2)CH(2)O)P(O)(H)C═C═CMe(2) possessing a terminal ═CMe(2) group with DMAD occurs by both [2 + 2] cycloaddition and ene reaction. While the reaction of ═CH(2) terminal allenylphosphonates as well as allenylphosphine oxides with 1,3-diphenylisobenzofuran afforded preferentially endo-[4 + 2] cycloaddition products via [α,β] attack, the analogous allenoates [(EtO(2)C)RC═C═CH(2)] underwent exo-[4 + 2] cyclization. Under similar conditions, allenylphosphonates with a terminal ═CR(2) group gave only [β,γ]-cycloaddition products. An unusual ring-opening of a [4 + 2] cycloaddition product followed by ring-closing via [4 + 4] cycloaddition, as revealed by (31)P NMR spectroscopy, is reported. Anthracene reacted in a manner similar to 1,3-diphenylisobenzofuran, albeit with lower reactivity. Key products, including a set of exo- and endo- [4 + 2] cycloaddition products, have been characterized by single crystal X-ray crystallography.

  3. Regioselective control of aromatic halogenation reactions in carbon nanotube nanoreactors.

    PubMed

    Miners, Scott A; Rance, Graham A; Khlobystov, Andrei N

    2013-06-21

    The use of single-walled carbon nanotubes as effective nanoreactors for preparative chemical reactions has been demonstrated for the first time. Extreme spatial confinement of reactant molecules inside nanotubes has been shown to drastically affect both the regioselectivity and kinetics of aromatic halogenation reactions.

  4. Anomalous 13C enrichment in modern marine organic carbon

    USGS Publications Warehouse

    Arthur, M.A.; Dean, W.E.; Claypool, G.E.

    1985-01-01

    Marine organic carbon is heavier isotopically (13C enriched) than most land-plant or terrestrial organic C1. Accordingly, ??13C values of organic C in modern marine sediments are routinely interpreted in terms of the relative proportions of marine and terrestrial sources of the preserved organic matter2,3. When independent geochemical techniques are used to evaluate the source of organic matter in Cretaceous or older rocks, those rocks containing mostly marine organic C are found typically to have lighter (more-negative) ??13C values than rocks containing mostly terrestrial organic C. Here we conclude that marine photosynthesis in mid-Cretaceous and earlier oceans generally resulted in a greater fractionation of C isotopes and produced organic C having lighter ??13C values. Modern marine photosynthesis may be occurring under unusual geological conditions (higher oceanic primary production rates, lower PCO2) that limit dissolved CO2 availability and minimize carbon isotope fractionation4. ?? 1985 Nature Publishing Group.

  5. Modeling Corrosion Reactions of Steel in a Dilute Carbonate Solution

    NASA Astrophysics Data System (ADS)

    Eliyan, Faysal Fayez; Alfantazi, Akram

    2016-02-01

    This research models the corrosion reactions of a high-strength steel in an aerated, dilute, carbonate solution during a single-cycle voltammetry. Based on a previous study (Eliyan et al. in J Mater Eng Perform 24(6):1-8, 2015) and a literature survey, the corrosion reactions of the cathodic reduction, anodic dissolution, and passivation, as well as the interfacial interactions and the chemistry of the corrosion products are illustrated in schematics. The paper provides a visual guide on the corrosion reactions for steel in carbonate solutions based on the available mechanistic details that were reported and are still being investigated in literature.

  6. Spectrally edited 2D 13Csbnd 13C NMR spectra without diagonal ridge for characterizing 13C-enriched low-temperature carbon materials

    NASA Astrophysics Data System (ADS)

    Johnson, Robert L.; Anderson, Jason M.; Shanks, Brent H.; Fang, Xiaowen; Hong, Mei; Schmidt-Rohr, Klaus

    2013-09-01

    Two robust combinations of spectral editing techniques with 2D 13Csbnd 13C NMR have been developed for characterizing the aromatic components of 13C-enriched low-temperature carbon materials. One method (exchange with protonated and nonprotonated spectral editing, EXPANSE) selects cross peaks of protonated and nearby nonprotonated carbons, while the other technique, dipolar-dephased double-quantum/single-quantum (DQ/SQ) NMR, selects signals of bonded nonprotonated carbons. Both spectra are free of a diagonal ridge, which has many advantages: Cross peaks on the diagonal or of small intensity can be detected, and residual spinning sidebands or truncation artifacts associated with the diagonal ridge are avoided. In the DQ/SQ experiment, dipolar dephasing of the double-quantum coherence removes protonated-carbon signals; this approach also eliminates the need for high-power proton decoupling. The initial magnetization is generated with minimal fluctuation by combining direct polarization, cross polarization, and equilibration by 13C spin diffusion. The dipolar dephased DQ/SQ spectrum shows signals from all linkages between aromatic rings, including a distinctive peak from polycondensed aromatics. In EXPANSE NMR, signals of protonated carbons are selected in the first spectral dimension by short cross polarization combined with dipolar dephasing difference. This removes ambiguities of peak assignment to overlapping signals of nonprotonated and protonated aromatic carbons, e.g. near 125 ppm. Spin diffusion is enhanced by dipolar-assisted rotational resonance. Before detection, Csbnd H dipolar dephasing by gated decoupling is applied, which selects signals of nonprotonated carbons. Thus, only cross peaks due to magnetization originating from protonated C and ending on nearby nonprotonated C are retained. Combined with the chemical shifts deduced from the cross-peak position, this double spectral editing defines the bonding environment of aromatic, COO, and Cdbnd O carbons

  7. Selective free radical reactions using supercritical carbon dioxide.

    PubMed

    Cormier, Philip J; Clarke, Ryan M; McFadden, Ryan M L; Ghandi, Khashayar

    2014-02-12

    We report herein a means to modify the reactivity of alkenes, and particularly to modify their selectivity toward reactions with nonpolar reactants (e.g., nonpolar free radicals) in supercritical carbon dioxide near the critical point. Rate constants for free radical addition of the light hydrogen isotope muonium to ethylene, vinylidene fluoride, and vinylidene chloride in supercritical carbon dioxide are compared over a range of pressures and temperatures. Near carbon dioxide's critical point, the addition to ethylene exhibits critical speeding up, while the halogenated analogues display critical slowing. This suggests that supercritical carbon dioxide as a solvent may be used to tune alkene chemistry in near-critical conditions.

  8. The reactions of carbon in a hydrogen plasma

    SciTech Connect

    Li, M.; Fan, Y.; Bao, W.; Guan, Y.; Li, S.

    2006-07-01

    Acetylene can be directly produced by coal pyrolysis in hydrogen plasma. A key factor affecting acetylene yield is whether the residue solid carbon is able to react with hydrogen to form acetylene after volatile matters released from coal powders pyrolyzed in hydrogen plasma. Reactions of carbon in hydrogen plasma are studied in this article. The study showed that solid carbon could hardly react with hydrogen at temperatures below the sublimation point, while sublimated carbon could easily react with hydrogen at temperatures above sublimation point, and mainly acetylene and other hydrocarbons can be obtained after quenching process.

  9. Carbon-carbon cross coupling reactions in ionic liquids catalysed by palladium metal nanoparticles.

    PubMed

    Prechtl, Martin H G; Scholten, Jackson D; Dupont, Jairton

    2010-05-12

    A brief summary of selected pioneering and mechanistic contributions in the field of carbon-carbon cross-coupling reactions with palladium nanoparticles (Pd-NPs) in ionic liquids (ILs) is presented. Five exemplary model systems using the Pd-NPs/ILs approach are presented: Heck, Suzuki, Stille, Sonogashira and Ullmann reactions which all have in common the use of ionic liquids as reaction media and the use of palladium nanoparticles as reservoir for the catalytically active palladium species.

  10. Experimental evidence of reaction-induced fracturing during olivine carbonation

    NASA Astrophysics Data System (ADS)

    Zhu, Wenlu; Fusseis, Florian; Lisabeth, Harrison; Xing, Tiange; Xiao, Xianghui; De Andrade, Vincent; Karato, Shun-ichiro

    2016-09-01

    Mineral carbonation, a process that binds CO2 in the form of carbonates by silicate weathering, is widespread on the Earth's surface. Because of the abundance of silicate rocks and the permanence of the carbonated solids, sequestering CO2 via mineral carbonation has generated lots of interests. However, it is unclear how the fluid-rock reaction proceeds to completion in spite of an increasing solid volume. We conducted a mineral carbonation experiment in which a sintered olivine aggregate reacted with a sodium bicarbonate solution at reservoir conditions. Time-resolved synchrotron X-ray microtomographic images show cracks in polygonal patterns arising in the surface layers and propagating into the interior of the olivine aggregate. The nanotomography data reveal that the incipient cracks intersect at right angles. We infer that stretching due to nonuniform volume expansion generates polygonal cracking of the surfaces. Our data shed new lights on the processes that control hydration and carbonation of peridotite.

  11. Radiochemical Reactions Between Tritium Molecule and Carbon Dioxide

    SciTech Connect

    Shu, W.M.; O'Hira, S.; Suzuki, T.; Nishi, M. F.

    2005-07-15

    To have better understanding of radiochemical reactions among oxygen baking products in a fusion reactor, reactions in equimolar tritium molecule (T{sub 2}) and carbon dioxide (CO{sub 2}) were examined by laser Raman spectroscopy and mass spectrometry. After mixing them at room temperature, T{sub 2} and CO{sub 2} decreased rapidly in the first 30 minutes and then the reactions between them became much slower. As the predominant products of the reactions, carbon monoxide (CO) and tritiated water (T{sub 2}O) were found in gaseous phase and condensed phase, respectively. However, there likely existed also some solid products that were thermally decomposed into CO, CO{sub 2}, T{sub 2}, T{sub 2}O, etc. during baking up to 523 K.

  12. Reactions of carbon atoms in pulsed molecular beams

    SciTech Connect

    Reisler, H.

    1993-12-01

    This research program consists of a broad scope of experiments designed to unravel the chemistry of atomic carbon in its two spin states, P and D, by using well-controlled initial conditions and state-resolved detection of products. Prerequisite to the proposed studies (and the reason why so little is known about carbon atom reactions), is the development of clean sources of carbon atoms. Therefore, in parallel with the studies of its chemistry and reaction dynamics, the authors continuously explore new, state-specific and efficient ways of producing atomic carbon. In the current program, C({sup 3}P) is produced via laser ablation of graphite, and three areas of study are being pursued: (i) exothermic reactions with small inorganic molecules (e.g., O{sub 2}, N{sub 2}O, NO{sub 2}) that can proceed via multiple pathways; (ii) the influence of vibrational and translational energy on endothermic reactions involving H-containing reactants that yield CH products (e.g., H{sub 2}O H{sub 2}CO); (iii) reactions of C({sup 3}P) with free radicals (e.g., HCO, CH{sub 3}O). In addition, the authors plan to develop a source of C({sup 1}D) atoms by exploiting the pyrolysis of diazotetrazole and its salts in the ablation source. Another important goal involves collaboration with theoreticians in order to obtain relevant potential energy surfaces, rationalize the experimental results and predict the roles of translational and vibrational energies.

  13. Oxygen electrode reaction in molten carbonate fuel cells

    SciTech Connect

    Appleby, A.J.; White, R.E.

    1992-07-07

    Molten carbonate fuel cell system is a leading candidate for the utility power generation because of its high efficiency for fuel to AC power conversion, capability for an internal reforming, and a very low environmental impact. However, the performance of the molten carbonate fuel cell is limited by the oxygen reduction reaction and the cell life time is limited by the stability of the cathode material. An elucidation of oxygen reduction reaction in molten alkali carbonate is essential because overpotential losses in the molten carbonate fuel cell are considerably greater at the oxygen cathode than at the fuel anode. Oxygen reduction on a fully-immersed gold electrode in a lithium carbonate melt was investigated by electrochemical impedance spectroscopy and cyclic voltammetry to determine electrode kinetic and mass transfer parameters. The dependences of electrode kinetic and mass transfer parameters on gas composition and temperature were examined to determine the reaction orders and the activation energies. The results showed that oxygen reduction in a pure lithium carbonate melt occurs via the peroxide mechanism. A mass transfer parameter, D{sub O}{sup 1/2}C{sub O}, estimated by the cyclic voltammetry concurred with that calculated by the EIS technique. The temperature dependence of the exchange current density and the product D{sub O}{sup 1/2}C{sub O} were examined and the apparent activation energies were determined to be about 122 and 175 kJ/ mol, respectively.

  14. Carbon-13 and proton magnetic resonance of mouse muscle.

    PubMed Central

    Fung, B M

    1977-01-01

    It is shown that roughly 4 mmol carbon atoms/g mouse muscle can give rise to a "high resolution" 13C NMR spectrum. From the 13C spectrum, it is estimated that the protons from mobile organic molecules or molecular segments amount to 6-8%of total nonrigid protons (organic plus water) in muscle. Their spin-spin relaxation times (T2) are of the order of 0.4-2 ms. At 37 degrees C, the proton spin-echo decay of mouse muscle changes rapidly with time after death, while that of mouse brain does not. PMID:890043

  15. Reaction dynamics of carbon-bearing radicals in circumstellar envelopes of carbon stars.

    PubMed

    Gu, Xibin; Guo, Ying; Zhang, Fangtong; Mebel, Alexander M; Kaiser, Ralf I

    2006-01-01

    Crossed molecular beams experiments on dicarbon molecules, C2(X1sigmag+/a3piu), with unsaturated hydrocarbons acetylene (C2H2(X1sigmag+), ethylene (C2H4(X1Ag)), methylacetylene (CH3CCH(X1A1)), and allene (H2CCCH2 (X1A1)) were carried out at 18 collision energies between 10.6 and 50.3 kJ mol(-1) utilizing a universal crossed beams machine to untangle the reaction dynamics forming hydrogen deficient hydrocarbon radicals in circumstellar envelopes of carbons stars and in cold molecular clouds. We find that all reactions proceed without the entrance barrier through indirect (complex forming) scattering dynamics. Each bimolecular collision is initiated by an addition of the dicarbon molecule to the pi bond of the unsaturated hydrocarbon molecule yielding initially acyclic (triplet) and three- or four-membered cyclic collision complexes (triplet and singlet surface). On the singlet surface, the cyclic structures isomerize to form eventually diacetylene (HCCCCH; C2/C2H2), butatriene (H2CCCCH2; C2/C2H4), methyldiacetylene (CH3CCCCH; C2/CH3CCH), and pentatetraene (H2CCCCCH2; C2/H2CCCH2) intermediates. The latter were found to decompose via atomic hydrogen loss yielding the buta-1,3-diynyl [C4H(X2sigma+) HCCCC], 1-butene-3-yne-2-yl [i-C4H3(X2A') H2CCCCH], penta-2,4-diynyl-1 [C5H3(X2B1) HCCCCCH2], and penta-1,4-diynyl-3 radical [C5H3(X2B1) HCCCHCCH] under single collision conditions. The underlying characteristics of these dicarbon versus atomic hydrogen replacement pathways (indirect scattering dynamics; no entrance barrier; isomerization barriers below the energy of the separated reactants; exoergic reactions) suggest the enormous potential of the dicarbon plus unsaturated hydrocarbon reaction class to form highly hydrogen-deficient carbonaceous molecules in cold molecular clouds and in circumstellar envelopes of carbon stars. The studies therefore present an important advancement in establishing a comprehensive database of reaction intermediates and products involved in

  16. The delta 13C record of Devonian to Permian carbonates

    NASA Astrophysics Data System (ADS)

    Buggisch, W.

    2003-04-01

    A δ13Ccarb curve will be presented for samples spanning the time interval from the Silurian/Devonian to the Permian/Triassic boundary. Reliable data are usually based on analyses of brachiopod shells. Because of the huge reservoir of carbon in carbonates, also whole rock samples are suitable for stable carbon isotope analyses if they are not altered by meteoric water or by incorporation of re-oxidized organic carbon during diagenesis. There are several possibilities to test the quality of the data: (1) comparison of the δ13C record of whole rock samples with samples from brachiopod shells, (2) with the organic record, (3) analyses of the same time interval in different sections. If the same pattern of isotope data is observed in separa-ted palaeogeographic settings, it is probably caused by a change in the global carbon reservoir. Reliable δ13C data will be presented for the Devonian, Mississippian and Middle to Late Permian. During Pennsylvanian and Early Permian most carbonates were affected by meteoric diagenesis due to the large glacio-eustatic sea level changes of the Permo-Carboniferous glaciation. Long term variations (mean values for 10 Ma) are known from literature. Devonian δ13C values are about 0 to 2 ppm (V-PDB) they increase up to 5 to 6 ppm during the Mississippian - Pennsylvanian transition and drop sharply at the Permian Triassic boundary. The Devonian - Carboniferous trend is probably at least partly due to the evolution of land plants. Short term variations in the range of 0.1 to 1 Ma modify the long term trend significantly. Large positive excursions of δ13C up to 5 or 6 ppm are known from the Silurian - Devonian boundary and during the Middle Tournaisian of Laurentia and Europe. Many positive excursions of a magnitude of 2 to 3 ppm are observed, some are verified worldwide as for instance at the Frasnian - Famennian boundary which coincides with one of the largest extinction events in earth history. Short time variations in the isotopic

  17. Lithological influence of aggregate in the alkali-carbonate reaction

    SciTech Connect

    Lopez-Buendia, A.M. . E-mail: angel.lopez@aidico.es; Climent, V. . E-mail: vcliment@grupogla.com; Verdu, P.

    2006-08-15

    The reactivity of carbonate rock with the alkali content of cement, commonly called alkali-carbonate reaction (ACR), has been investigated. Alkali-silica reaction (ASR) can also contribute in the alkali-aggregate reaction (AAR) in carbonate rock, mainly due to micro- and crypto-crystalline quartz or clay content in carbonate aggregate. Both ACR and ASR can occur in the same system, as has been also evidenced on this paper. Carbonate aggregate samples were selected using lithological reactivity criteria, taking into account the presence of dedolomitization, partial dolomitization, micro- and crypto-crystalline quartz. Selected rocks include calcitic dolostone with chert (CDX), calcitic dolostone with dedolomitization (CDD), limestone with chert (LX), marly calcitic dolostone with partial dolomitization (CD), high-porosity ferric dolostone with clays (FD). To evaluate the reactivity, aggregates were studied using expansion tests following RILEM AAR-2, AAR-5, a modification using LiOH AAR-5Li was also tested. A complementary study was done using petrographic monitoring with polarised light microscopy on aggregates immersed in NaOH and LiOH solutions after different ages. SEM-EDAX has been used to identify the presence of brucite as a product of dedolomitization. An ACR reaction showed shrinkage of the mortar bars in alkaline solutions explained by induced dedolomitization, while an ASR process typically displayed expansion. Neither shrinkage nor expansion was observed when mortar bars were immersed in solutions of lithium hydroxide. Carbonate aggregate classification with AAR pathology risk has been elaborated based on mechanical behaviours by expansion and shrinkage. It is proposed to be used as a petrographic method for AAR diagnosis to complement the RILEM AAR1 specifically for carbonate aggregate. Aggregate materials can be classified as I (non-reactive), II (potentially reactive), and III (probably reactive), considering induced dedolomitization ACR

  18. Production of carbon-13-labeled cadaverine by engineered Corynebacterium glutamicum using carbon-13-labeled methanol as co-substrate.

    PubMed

    Leßmeier, Lennart; Pfeifenschneider, Johannes; Carnicer, Marc; Heux, Stephanie; Portais, Jean-Charles; Wendisch, Volker F

    2015-12-01

    Methanol, a one-carbon compound, can be utilized by a variety of bacteria and other organisms as carbon and energy source and is regarded as a promising substrate for biotechnological production. In this study, a strain of non-methylotrophic Corynebacterium glutamicum, which was able to produce the polyamide building block cadaverine as non-native product, was engineered for co-utilization of methanol. Expression of the gene encoding NAD+-dependent methanol dehydrogenase (Mdh) from the natural methylotroph Bacillus methanolicus increased methanol oxidation. Deletion of the endogenous aldehyde dehydrogenase genes ald and fadH prevented methanol oxidation to carbon dioxide and formaldehyde detoxification via the linear formaldehyde dissimilation pathway. Heterologous expression of genes for the key enzymes hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase of the ribulose monophosphate (RuMP) pathway in this strain restored growth in the presence of methanol or formaldehyde, which suggested efficient formaldehyde detoxification involving RuMP key enzymes. While growth with methanol as sole carbon source was not observed, the fate of 13C-methanol added as co-substrate to sugars was followed and the isotopologue distribution indicated incorporation into central metabolites and in vivo activity of the RuMP pathway. In addition, 13C-label from methanol was traced to the secreted product cadaverine. Thus, this synthetic biology approach led to a C. glutamicum strain that converted the non-natural carbon substrate methanol at least partially to the non-native product cadaverine.

  19. Pattern Formation and Reaction Textures during Dunite Carbonation

    NASA Astrophysics Data System (ADS)

    Lisabeth, H. P.; Zhu, W.

    2015-12-01

    Alteration of olivine-bearing rocks by fluids is one of the most pervasive geochemical processes on the surface of the Earth. Serpentinized and/or carbonated ultramafic rocks often exhibit characteristic textures on many scales, from polygonal mesh textures on the grain-scale to onion-skin or kernel patterns on the outcrop scale. Strong disequilibrium between pristine ultramafic rocks and common geological fluids such as water and carbon dioxide leads to rapid reactions and coupled mechanical and chemical feedbacks that manifest as characteristic textures. Textural evolution during metasomatic reactions can control effective reaction rates by modulating dynamic porosity and therefore reactant supply and reactive surface area. We run hydrostatic experiments on thermally cracked dunites saturated with carbon dioxide bearing brine at 15 MPa confining pressure and 150°C to explore the evolution of physical properties and reaction textures as carbon mineralization takes place in the sample. Compaction and permeability reduction are observed throughout experiments. Rates of porosity and permeability changes are sensitive to pore fluid chemistry. After reaction, samples are imaged in 3-dimension (3D) using a dual-beam FIB-SEM. Analysis of the high resolution 3D microstructure shows that permeable, highly porous domains are created by olivine dissolution at a characteristic distance from pre-existing crack surfaces while precipitation of secondary minerals such as serpentine and magnesite is limited largely to the primary void space. The porous dissolution channels provide an avenue for fluid ingress, allow reactions to continue and could lead to progressive hierarchical fracturing. Initial modeling of the system indicates that this texture is the result of coupling between dissolution-precipitation reactions and the local stress state of the sample.

  20. Heat of Combustion of the Product Formed by the Reaction of Diborane with 1,3-Butadiene

    NASA Technical Reports Server (NTRS)

    Tannenbaum, Stanley; Allen, Harrison, Jr.

    1953-01-01

    The net heat of combustion of the product formed by the reaction of diborane with 1,3-butadiene was found to be 18,700+/-150 Btu per pound for the reaction of liquid fuel to gaseous carbon dioxide, gaseous water, and solid boric oxide. The measurements were made in a Parr oxygen-bomb calorimeter, and the combustion was believed to be 98 percent complete. The estimated net heat of combustion for complete combustion would therefore be 19,075+/-150 Btu per pound. Since this value is approximately the same as the heat of combustion of butadiene, it seems certain that the material is partially oxidized.

  1. Impacts of diffusive transport on carbonate mineral formation from magnesium silicate-CO2-water reactions.

    PubMed

    Giammar, Daniel E; Wang, Fei; Guo, Bin; Surface, J Andrew; Peters, Catherine A; Conradi, Mark S; Hayes, Sophia E

    2014-12-16

    Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated.

  2. Effects of hydrolysis and carbonization reactions on hydrochar production.

    PubMed

    Fakkaew, K; Koottatep, T; Polprasert, C

    2015-09-01

    Hydrothermal carbonization (HTC) is a thermal conversion process which converts wet biomass into hydrochar. In this study, a low-energy HTC process named "Two-stage HTC" comprising of hydrolysis and carbonization stages using faecal sludge as feedstock was developed and optimized. The experimental results indicated the optimum conditions of the two-stage HTC to be; hydrolysis temperature of 170 °C, hydrolysis reaction time of 155 min, carbonization temperature of 215 °C, and carbonization reaction time of 100 min. The hydrolysis reaction time and carbonization temperature had a statistically significant effect on energy content of the produced hydrochar. Energy input of the two-stage HTC was about 25% less than conventional HTC. Energy efficiency of the two-stage HTC for treating faecal sludge was higher than that of conventional HTC and other thermal conversion processes such as pyrolysis and gasification. The two-stage HTC could be considered as a potential technology for treating FS and producing hydrochar.

  3. Effects of hydrolysis and carbonization reactions on hydrochar production.

    PubMed

    Fakkaew, K; Koottatep, T; Polprasert, C

    2015-09-01

    Hydrothermal carbonization (HTC) is a thermal conversion process which converts wet biomass into hydrochar. In this study, a low-energy HTC process named "Two-stage HTC" comprising of hydrolysis and carbonization stages using faecal sludge as feedstock was developed and optimized. The experimental results indicated the optimum conditions of the two-stage HTC to be; hydrolysis temperature of 170 °C, hydrolysis reaction time of 155 min, carbonization temperature of 215 °C, and carbonization reaction time of 100 min. The hydrolysis reaction time and carbonization temperature had a statistically significant effect on energy content of the produced hydrochar. Energy input of the two-stage HTC was about 25% less than conventional HTC. Energy efficiency of the two-stage HTC for treating faecal sludge was higher than that of conventional HTC and other thermal conversion processes such as pyrolysis and gasification. The two-stage HTC could be considered as a potential technology for treating FS and producing hydrochar. PMID:26051497

  4. Investigation of thermochemistry associated with the carbon-carbon coupling reactions of furan and furfural using ab initio methods.

    PubMed

    Liu, Cong; Assary, Rajeev S; Curtiss, Larry A

    2014-06-26

    Upgrading furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan can be coupled with various C1 to C4 low molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase to produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (∼25 kcal/mol) are lower than the cellulose activation or decomposition reactions (∼50 kcal/mol). Cycloaddition of C5-C8 cyclo ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products, and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ∼20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons. PMID:24902118

  5. Investigation of thermochemistry associated with the carbon-carbon coupling reactions of furan and furfural using ab initio methods.

    PubMed

    Liu, Cong; Assary, Rajeev S; Curtiss, Larry A

    2014-06-26

    Upgrading furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan can be coupled with various C1 to C4 low molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase to produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (∼25 kcal/mol) are lower than the cellulose activation or decomposition reactions (∼50 kcal/mol). Cycloaddition of C5-C8 cyclo ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products, and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ∼20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.

  6. Determination of the astrophysical 12N(p,γ)13O reaction rate from the 2H(12N,13O)n reaction and its astrophysical implications

    NASA Astrophysics Data System (ADS)

    Guo, B.; Su, J.; Li, Z. H.; Wang, Y. B.; Yan, S. Q.; Li, Y. J.; Shu, N. C.; Han, Y. L.; Bai, X. X.; Chen, Y. S.; Liu, W. P.; Yamaguchi, H.; Binh, D. N.; Hashimoto, T.; Hayakawa, S.; Kahl, D.; Kubono, S.; He, J. J.; Hu, J.; Xu, S. W.; Iwasa, N.; Kume, N.; Li, Z. H.

    2013-01-01

    The evolution of massive stars with very low-metallicities depends critically on the amount of CNO nuclides which they produce. The 12N(p,γ)13O reaction is an important branching point in the rap processes, which are believed to be alternative paths to the slow 3α process for producing CNO seed nuclei and thus could change the fate of massive stars. In the present work, the angular distribution of the 2H(12N, 13O)n proton transfer reaction at Ec.m.=8.4 MeV has been measured for the first time. Based on the Johnson-Soper approach, the square of the asymptotic normalization coefficient (ANC) for the virtual decay of 13Og.s. → 12N+p was extracted to be 3.92±1.47 fm-1 from the measured angular distribution and utilized to compute the direct component in the 12N(p,γ)13O reaction. The direct astrophysical S factor at zero energy was then found to be 0.39±0.15 keV b. By considering the direct capture into the ground state of 13O, the resonant capture via the first excited state of 13O and their interference, we determined the total astrophysical S factors and rates of the 12N(p,γ)13O reaction. The new rate is two orders of magnitude slower than that from the REACLIB compilation. Our reaction network calculations with the present rate imply that 12N(p,γ)13O will only compete successfully with the β+ decay of 12N at higher (˜2 orders of magnitude) densities than initially predicted.

  7. Chemical reaction equilibrium in nanoporous materials: NO dimerization reaction in carbon slit nanopores.

    PubMed

    Lísal, Martin; Brennan, John K; Smith, William R

    2006-02-14

    We present a molecular-level simulation study of the effects of confinement on chemical reaction equilibrium in nanoporous materials. We use the reaction ensemble Monte Carlo (RxMC) method to investigate the effects of temperature, nanopore size, bulk pressure, and capillary condensation on the nitric oxide dimerization reaction in a model carbon slit nanopore in equilibrium with a bulk reservoir. In addition to the RxMC simulations, we also utilize the molecular-dynamics method to determine self-diffusion coefficients for confined nonreactive mixtures of nitric oxide monomers and dimers at compositions obtained from the RxMC simulations. We analyze the effects of the temperature, nanopore width, bulk pressure, and capillary condensation on the reaction equilibrium with respect to the reaction conversion, fluid structure, and self-diffusion coefficients. We show that the influence of the temperature, nanopore size, and capillary condensation on the confined reaction equilibrium is quite dramatic while the effect of the bulk pressure on the reaction equilibrium in the carbon slit nanopore is only moderate. This work is an extension of previous work by Turner et al. [J. Chem. Phys. 114, 1851 (2001)] on the confined reactive nitric oxide system.

  8. New study of the astrophysical reaction 13C(a,n)16O via the 13C(7Li,t)17O transfer reaction

    NASA Astrophysics Data System (ADS)

    Pellegriti, Maria Grazia; Hammache, F.; Roussel, P.; Audouin, L.; Beaumel, D.; Fortier, S.; Gaudefroy, L.; Kiener, J.; Lefebvre-Schujl, A.; Stanoiu, M.; Tatischeff, V.; Vilmay, M.

    PoS(NIC-IX)161 , , [1] , L. Gaudefroy[2] , J. Kiener[3] , A. Lefebvre-Schuhl[3] , M. Stanoiu[4] , V. The cross section of the 13 C(α,n)16 O reaction is a key ingredient for the comprehension of the s-process (slow neutron captures) in stars. This reaction is considered as the main neutron source for the s-process in low-mass Asymptotic Giant Branch (AGB) stars (1-3 solar mass) [1, 2, 3]. At the α-13 C energies of astrophysical interest (Ecm around 190 keV, corresponding to a tem- perature of 108 K) the contribution of the 17 O α-decay subthreshold resonance at 6.356 MeV to the 13 C(α,n)16 O cross section should be taken into account. The effect of this resonance is controversial after the different analyses of the Kubono et al. measurement [4] of the 6.356 MeV α-spectroscopic factor (Sα ) via the transfer reaction 13 C(6 Li,d)17 O . In order to further investigate the contribution of the 6.356 MeV resonance to the 13 C(α,n)16 O cross section, we performed a new measurement of its Sα factor via a different α-transfer reac- tion, namely the 13 C(7 Li,t)17 O reaction. The experiment was performed at the Orsay Tandem by using a 7 Li beam of 28 and 34 MeV on a 13C target. The angular distribution for the transfer dif- ferential cross section was measured by detecting the tritons at the focal plane of the SPLITPOLE spectrometer. The analysis procedure used in order to extract the yield of the 6.356 MeV level will be described. Preliminary results of the angular distribution will be shown.

  9. Follow the Carbon: Laboratory Studies of 13C-Labeled Early Earth Haze Analogs

    NASA Astrophysics Data System (ADS)

    Hicks, R. K.; Day, D. A.; Mojzsis, S. J.; Jimenez, J. L.; Tolbert, M. A.

    2013-12-01

    While the Sun was still young and faint before the rise of molecular oxygen 2.4 Ga, early Earth might have been kept warm by an atmosphere containing the greenhouse gases methane and carbon dioxide in abundances greater than what is found on Earth today. It has been suggested that an atmosphere containing approximately 1000 ppmv methane and carbon dioxide could provided the needed greenhouse warming for liquid water to exist at the surface. Laboratory and modeling studies suggest that an atmosphere containing methane and carbon dioxide could lead to the formation of significant amounts of organic haze due to photochemical reactions initiated by Lyman-α (121.6 nm) excitation. Chemical mechanisms proposed to explain the chemistry rely on methane as the source of carbon in these hazes and treat carbon dioxide as a source of oxygen only. In the present work, we use isotopically labelled precursor gases to examine the source of carbon in photochemical haze formed in a CH4/CO2/N2 atmosphere. We generate haze analogs in the laboratory by far-UV irradiation of analog atmospheres containing permutations of 1,000 ppmv unlabeled and 13C-labeled methane and carbon. Products in the particle phase were analyzed by both unit mass resolution and high-resolution (m/Δm=5,000) aerosol mass spectrometry. Results indicate that carbon from carbon dioxide accounts for 20% (×5%) of the total carbon contained in the hazes. These results have implications for the geochemical interpretations of inclusions found in Archaean rocks on Earth, and for the astrobiological potential of other planetary atmospheres.

  10. ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter

    2001-10-01

    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation, before and/or during carbonation, may provide an important parameter for enhancing carbonation reaction processes. Mg(OH){sub 2} was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (i) its structural and chemical simplicity, (ii) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (iii) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO{sub 2} sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for minimizing the cost of any lamellar-hydroxide-based mineral carbonation sequestration process. This report covers the third year progress of this grant, as well as providing an integrated overview of the progress in years 1-3, as we have been granted a one-year no-cost extension to wrap up a few studies and publications to optimize project impact.

  11. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    NASA Astrophysics Data System (ADS)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  12. Anion Effects in Oxidative Aliphatic Carbon-Carbon Bond Cleavage Reactions of Cu(II) Chlorodiketonate Complexes.

    PubMed

    Saraf, Sushma L; Miłaczewska, Anna; Borowski, Tomasz; James, Christopher D; Tierney, David L; Popova, Marina; Arif, Atta M; Berreau, Lisa M

    2016-07-18

    Aliphatic oxidative carbon-carbon bond cleavage reactions involving Cu(II) catalysts and O2 as the terminal oxidant are of significant current interest. However, little is currently known regarding how the nature of the Cu(II) catalyst, including the anions present, influence the reaction with O2. In previous work, we found that exposure of the Cu(II) chlorodiketonate complex [(6-Ph2TPA)Cu(PhC(O)CClC(O)Ph)]ClO4 (1) to O2 results in oxidative aliphatic carbon-carbon bond cleavage within the diketonate unit, leading to the formation of benzoic acid, benzoic anhydride, benzil, and 1,3-diphenylpropanedione as organic products. Kinetic studies of this reaction revealed a slow induction phase followed by a rapid decay of the absorption features of 1. Notably, the induction phase is not present when the reaction is performed in the presence of a catalytic amount of chloride anion. In the studies presented herein, a combination of spectroscopic (UV-vis, EPR) and density functional theory (DFT) methods have been used to examine the chloride and benzoate ion binding properties of 1 under anaerobic conditions. These studies provide evidence that each anion coordinates in an axial position of the Cu(II) center. DFT studies reveal that the presence of the anion in the Cu(II) coordination sphere decreases the barrier for O2 activation and the formation of a Cu(II)-peroxo species. Notably, the chloride anion more effectively lowers the barrier associated with O-O bond cleavage. Thus, the nature of the anion plays an important role in determining the rate of reaction of the diketonate complex with O2. The same type of anion effects were observed in the O2 reactivity of the simple Cu(II)-bipyridine complex [(bpy)Cu(PhC(O)C(Cl)C(O)Ph)ClO4] (3). PMID:27377103

  13. Hydrothermal carbon from biomass: structural differences between hydrothermal and pyrolyzed carbons via 13C solid state NMR.

    PubMed

    Falco, Camillo; Perez Caballero, Fernando; Babonneau, Florence; Gervais, Christel; Laurent, Guillaume; Titirici, Maria-Magdalena; Baccile, Niki

    2011-12-01

    The objective of this paper is to better describe the structure of the hydrothermal carbon (HTC) process and put it in relationship with the more classical pyrolytic carbons. Indeed, despite the low energetic impact and the number of applications described so far for HTC, very little is known about the structure, reaction mechanism, and the way these materials relate to coals. Are HTC and calcination processes equivalent? Are the structures of the processed materials related to each other in any way? Which is the extent of polyaromatic hydrocarbons (PAH) inside HTC? In this work, the effect of hydrothermal treatment and pyrolysis are compared on glucose, a good model carbohydrate; a detailed single-quantum double-quantum (SQ-DQ) solid state (13)C NMR study of the HTC and calcined HTC is used to interpret the spectral region corresponding to the signal of furanic and arene groups. These data are compared to the spectroscopic signatures of calcined glucose, starch, and xylose. A semiquantitative analysis of the (13)C NMR spectra provides an estimation of the furanic-to-arene ratio which varies from 1:1 to 4:1 according to the processing conditions and carbohydrate employed. In addition, we formulate some hypothesis, validated by DFT (density functional theory) modeling associated with (13)C NMR chemical shifts calculations, about the possible furan-rich structural intermediates that occur in the coalification process leading to condensed polyaromatic structures. In combination with a broad parallel study on the HTC processing conditions effect on glucose, cellulose, and raw biomass (Falco, C.; Baccile, N.; Titirici, M.-M. Green Chem., 2011, DOI: 10.1039/C1GC15742F), we propose a broad reaction scheme and in which we show that, through HTC, it is possible to tune the furan-to-arene ratio composing the aromatic core of the produced HTC carbons, which is not possible if calcination is used alone, in the temperature range below 350 °C. PMID:22050004

  14. Diethers enriched in 13C suggest carbon-limitation at the Lost City Hydrothermal Field

    NASA Astrophysics Data System (ADS)

    Bradley, A. S.; Hayes, J. M.; Summons, R. E.

    2004-12-01

    Active and inactive carbonate vent structures from the Lost City Hydrothermal Field (LCHF) contain up to 0.6% organic carbon including diverse lipids. Values of δ 13C for total organic carbon (TOC) range from -18.7‰ vs. VPDB at the active, high-temperature vent known as "The Beehive" (90° C), to -3.1‰ at Marker 7 (active, 70° C). Samples with relatively high levels of 13C also contained high amounts of isoprenoidal and nonisoprenoidal diethers. Samples more depleted in 13C lacked or contained low amounts of these diethers. The correlation between high 13C and abundant diethers is supported by compound-specific isotopic analyses. Archaeal and bacterial diethers are enriched in 13C relative to photosynthetically derived marine carbon. The biomarkers sn-2 hydroxyarchaeol, sn-3 hydroxyarchaeol, and dihydroxyarchaeol - considered diagnostic for methane-cycling archaea - had δ values ranging from -8.5 to +4.8‰ . Phylogenetic data confirms the presence at these vents of a single group of methanogens, related to the Methanosarcinales (Schrenk et al., 2004). Diethers with non-isoprenoidal alkyl chains are also present, are of presumed bacterial origin, and may indicated the presence of sulfate-reducing bacteria. Values of δ for these compounds range from -7.3 to +1.0‰ . At the Beehive vent, diether lipids are absent and the TOC is depleted in 13C. Coexistence of isotopically similar hydroxyarchaeols and nonisoprenoidal glycerol diethers is typical of marine, cold-seep environments at which concentrations of H2 are low and methane is oxidized anaerobically. At the LCHF, however, concentrations of H2 in pore waters reach 15 mM (Proskurowski et al., 2003). This H2, produced by serpentinization reactions, drives production (rather than oxidation) of methane. Simultaneously, sulfate-reducing bacteria can flourish as carbon-fixing autotrophs. Under such conditions, carbon may be the limiting substrate, its nearly complete consumption accounting for the enrichment of

  15. Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

    SciTech Connect

    Um, Wooyong; Jung, Hun Bok; Martin, Paul F.; McGrail, B. Peter

    2011-11-01

    Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C) for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron

  16. Diastereoselective Ugi reaction of chiral 1,3-aminoalcohols derived from an organocatalytic Mannich reaction

    PubMed Central

    Caputo, Samantha; Basso, Andrea; Moni, Lisa; Riva, Renata; Rocca, Valeria

    2016-01-01

    Summary Enantiomerically pure β-aminoalcohols, produced through an organocatalytic Mannich reaction, were subjected to an Ugi multicomponent reaction under classical or Lewis acid-promoted conditions with diastereoselectivities ranging from moderate to good. This approach represents a step-economical path to enantiomerically pure, polyfunctionalized peptidomimetics endowed with three stereogenic centers, allowing the introduction of five diversity inputs. PMID:26877816

  17. Chemical Reactions in the Processing of Mosi2 + Carbon Compacts

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Lee, Kang N.; Maloy, Stuart A.; Heuer, Arthur H.

    1993-01-01

    Hot-pressing of MoSi2 powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

  18. Controlling the regioselectivity of the hydrosilylation reaction in carbon nanoreactors.

    PubMed

    Solomonsz, William A; Rance, Graham A; Suyetin, Mikhail; La Torre, Alessandro; Bichoutskaia, Elena; Khlobystov, Andrei N

    2012-10-01

    Hollow graphitized carbon nanofibres (GNF) are employed as nanoscale reaction vessels for the hydrosilylation of alkynes. The effects of confinement in GNF on the regioselectivity of addition to triple carbon-carbon bonds are explored. A systematic comparison of the catalytic activities of Rh and RhPt nanoparticles embedded in a nanoreactor with free-standing and surface-adsorbed nanoparticles reveals key mechanisms governing the regioselectivity. Directions of reactions inside GNF are largely controlled by the non-covalent interactions between reactant molecules and the nanofibre channel. The specific π-π interactions increase the local concentration of the aromatic reactant and thus promote the formation of the E isomer of the β-addition product. In contrast, the presence of aromatic groups on both reactants (silane and alkyne) reverses the effect of confinement and favours the formation of the Z isomer due to enhanced interactions between aromatic groups in the cis-orientation with the internal graphitic step-edges of GNF. The importance of π-π interactions is confirmed by studying transformations of aliphatic reactants that show no measurable changes in regioselectivity upon confinement in carbon nanoreactors.

  19. Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene.

    PubMed

    Baker, Jillian; Arey, Janet; Atkinson, Roger

    2005-06-01

    1,3-Butadiene and isoprene (2-methyl-1,3-butadiene) are emitted into the atmosphere in vehicle exhaust and, in the case of isoprene, from vegetation. We have investigated the formation and further reaction of products of their hydroxyl radical-initiated reactions using atmospheric pressure ionization mass spectrometry (API-MS) and solid-phase microextraction fibers precoated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl compounds, with subsequent analysis by thermal desorption and gas chromatography with flame ionization detection (SPME/GC-FID) or MS detection. Products attributed as HOCH2CH=CHCHO and HOCH2CH=CHCH2ONO2 (and isomers) from 1,3-butadiene; HOCD2CD=CDCDO and HOCD2CD=CDCD2ONO2 (and isomers) from 1,3-butadiene-d6; HOCH2C(CH3)=CHCHO and/or HOCH2CH=C(CH3)CHO, and HOCH2C(CH3)=CHCH2ONO2 (and isomers) from isoprene; and HOCD2C(CD3)=CDCDO and/or HOCD2CD=C(CD3)CDO, and HOCD2C(CD3)=CDCD2ONO2 (and isomers) from isoprene-d8 were observed as their NO2- adducts in the API-MS analyses. The hydroxycarbonyls were observed from SPME/GC-FID analyses of the 1,3-butadiene and isoprene reactions as their oximes, together with acrolein, glycolaldehyde, and glyoxal from the 1,3-butadiene reaction. A rate constant for the reaction of OH radicals with 4-hydroxy-2-butenal of (5.7 +/- 1.4) x 10(-11) cm3 molecule(-1) s(-1) at 298 +/- 2 K was derived, and formation yields of acrolein and 4-hydroxy-2-butenal from the 1,3-butadiene reaction of 58 +/- 10% and 25 (+15/-10)%, respectively, were determined. Analogous experiments showed that the two C5-hydroxycarbonyls formed from isoprene have rate constants for their reactions with OH radicals of (1.0 +/- 0.3) x 10(-10) cm3 molecule(-1) s(-1) and (4 +/- 2) x 10(-11) cm3 molecule(-1) s(-1) and a combined yield of approximately 15%, although isomer-specific identification of the hydroxycarbonyls was not achieved.

  20. Effect of partial carbonation on the cyclic CaO carbonation reaction

    SciTech Connect

    Grasa, G.; Abanades, J.C.; Anthony, E.J.

    2009-10-15

    CaO particles from the calcination of natural limestones can be used as regenerable solid sorbents in some CO{sub 2} capture systems. Their decay curves in terms of CO{sub 2} capture capacity have been extensively studied in the literature, always in experiments allowing particles to reach their maximum carbonation conversion for a given cycle. However, at the expected operating conditions in a CO{sub 2} capture system using the carbonation reaction, a relevant fraction of the CaO particles will not have time to fully convert in the carbonator reactor. This work investigates if there is any effect on the decay curves when CaO is only partially converted in each cycle. Experiments have been conducted in a thermobalance arranged to interrupt the carbonation reaction in each cycle before the end of the fast reaction period typical in the CaO-CO{sub 2} reaction. It is shown that, after the necessary normalization of results, the effective capacity of the sorbent to absorb CO{sub 2} during particle lifetime in the capture system slightly increases and CaO particles partially converted behave 'younger' than particles fully converted after every calcination. This has beneficial implications for the design of carbonation/calcination loops.

  1. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    DOEpatents

    Cortright, Randy D.; Dumesic, James A.

    2013-04-02

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  2. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    DOEpatents

    Cortright, Randy D.; Dumesic, James A.

    2012-04-10

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  3. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    DOEpatents

    Cortright, Randy D.; Dumesic, James A.

    2011-01-18

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  4. PHOTOCHEMICALLY-INDUCED ALTERATION OF STABLE CARBON ISOTOPE RATIOS (DELTA C-13) IN TERRIGENOUS DISSOLVED ORGANIC CARBON

    EPA Science Inventory

    Exposure of riverine waters to natural sunlight initiated alterations in stable carbon isotope ratios (delta C-13) of the associated dissolved organic carbon (DOC). Water samples were collected from two compositionally distinct coastal river systems in the southeastern United Sta...

  5. Calcium carbonate phase transformations during the carbonation reaction of calcium heavy alkylbenzene sulfonate overbased nanodetergents preparation.

    PubMed

    Chen, Zhaocong; Xiao, Shan; Chen, Feng; Chen, Dongzhong; Fang, Jianglin; Zhao, Min

    2011-07-01

    The preparation and application of overbased nanodetergents with excess alkaline calcium carbonate is a good example of nanotechnology in practice. The phase transformation of calcium carbonate is of extensive concern since CaCO(3) serves both as an important industrial filling material and as the most abundant biomineral in nature. Industrially valuable overbased nanodetergents have been prepared based on calcium salts of heavy alkylbenzene sulfonate by a one-step process under ambient pressure, the carbonation reaction has been monitored by the instantaneous temperature changes and total base number (TBN). A number of analytical techniques such as TGA, DLS, SLS, TEM, FTIR, and XRD have been utilized to explore the carbonation reaction process and phase transformation mechanism of calcium carbonate. An enhanced understanding on the phase transformation of calcium carbonate involved in calcium sulfonate nanodetergents has been achieved and it has been unambiguously demonstrated that amorphous calcium carbonate (ACC) transforms into the vaterite polymorph rather than calcite, which would be of crucial importance for the preparation and quality control of lubricant additives and greases. Our results also show that a certain amount of residual Ca(OH)(2) prevents the phase transformation from ACC to crystalline polymorphs. Moreover, a vaterite nanodetergent has been prepared for the first time with low viscosity, high base number, and uniform particle size, nevertheless a notable improvement on its thermal stability is required for potential applications.

  6. Somewhere beyond the sea? The oceanic - carbon dioxide - reactions

    NASA Astrophysics Data System (ADS)

    Meisinger, Philipp; Wittlich, Christian

    2014-05-01

    In correlation to climate change and CO2 emission different campaigns highlight the importance of forests and trees to regulate the concentration of carbon dioxide in the earths' atmosphere. Seeing millions of square miles of rainforest cut down every day, this is truly a valid point. Nevertheless, we often tend to forget what scientists like Spokes try to raise awareness for: The oceans - and foremost deep sea sections - resemble the second biggest deposit of carbon dioxide. Here carbon is mainly found in form of carbonate and hydrogen carbonate. The carbonates are needed by corals and other sea organisms to maintain their skeletal structure and thereby to remain vital. To raise awareness for the protection of this fragile ecosystem in schools is part of our approach. Awareness is achieved best through understanding. Therefore, our approach is a hands-on activity that aims at showing students how the carbon dioxide absorption changes in relation to the water temperature - in times of global warming a truly sensitive topic. The students use standard syringes filled with water (25 ml) at different temperatures (i.e. 10°C, 20°C, 40°C). Through a connector students inject carbon dioxide (25ml) into the different samples. After a fixed period of time, students can read of the remaining amount of carbon dioxide in relation to the given water temperature. Just as with every scientific project, students need to closely monitor their experiments and alter their setups (e.g. water temperature or acidity) according to their initial planning. A digital template (Excel-based) supports the analysis of students' experiments. Overview: What: hands-on, minds -on activity using standard syringes to exemplify carbon dioxide absorption in relation to the water temperature (Le Chatelier's principle) For whom: adjustable from German form 11-13 (age: 16-19 years) Time: depending on the prior knowledge 45-60 min. Sources (extract): Spokes, L.: Wie Ozeane CO2 aufnehmen. Environmental

  7. Carbon Nanowalls for oxygen reduction reaction in Bio Fuel Cells

    NASA Astrophysics Data System (ADS)

    Lehmann, K.; Yurchenko, O.; Urban, G.

    2014-11-01

    We report on the usage of Carbon Nanowalls (CNW) synthesized by a PECVD process as electrode material for oxygen reduction reaction (ORR). In order to substitute the platinum based catalysts in fuel cells, graphene is a promising candidate. Carbon Nanowalls are a graphene modification with good accessibility and a controllable morphology. By controlling height and pore size, they can be optimized for different applications. A ID/IG ratio around 2.5 and the SEM images indicate vertical nanocrystallin graphene sheets. Tests with ferrocene as electroactive compound verify CNW suitability as electrode material. Cyclic voltammetry measurements in oxygen saturated PBS prove the catalytic activity of CNW towards ORR. The results support the feasibility of CNW as cathode in Bio Fuel Cells.

  8. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1979-01-01

    The heavy isotopic anomalies observed recently in the fractionation and unknown nuclear inclusions from the Allende meteorite are explained by neutron reactions during the explosive carbon burning (ECB). This model produces heavy anomalies in the same zone where Al-26 and O-16 are produced, thus reducing the number of source zones required for the isotopic anomalies. Unlike the classical r-process, the ECB n-process avoids the problem with the Sr anomaly and may resolve the problem of conflicting time scales between Al-26 and the r-process isotopes I-129 and Pu-244. Experimental studies of Zr and Ce isotopic composition are proposed to test this model.

  9. Study of redox reactions to split water and carbon dioxide

    NASA Astrophysics Data System (ADS)

    Arifin, Darwin

    The development of carbon-neutral, environmentally-sustainable energy carrier is a technological imperative necessary to mitigate the impact of anthropogenic carbon dioxide on earth's climate. One compelling approach rapidly gaining international attention is the conversion of solar energy into renewable fuels, such as H2 or CO, via a two-step thermochemical cycle driven by concentrated solar power. In accordance with the increased interest in this process, there is a need to better understand the gas splitting chemistry on the metal oxide intermediates encountered in such solar-driven processes. Here we measured the H2 and CO production rates during oxidation by H2O and CO2 in a stagnation flow reactor. Redox cycles were performed over various metal oxide chemistries such as hercynite and ceria based materials that are thermally reduced by laser irradiation. In addition to cycle capacity evaluation, reaction kinetics intrinsic to the materials were extracted using a model-based analytical approach to account for the effects of mixing and dispersion in the reactor. Investigation of the "hercynite chemistry" with raman spectroscopy verifies that, at the surface, the cycle proceeds by stabilizing the reduced and oxidized moieties in two different compounds, which allows the thermal reduction reaction to occur to a greater extent at a temperature 150 °C lower than a similarly prepared CoFe2O4-coated m-ZrO2. Investigation of the ceria cycle shows that the water splitting reaction, in the range of 750 - 950 °C and 20 - 40 vol.% H2O, can best be described by a first-order kinetic model with low apparent activation energy (29 kJ/mol). The carbon dioxide splitting reaction, in the range of 650 - 875 °C and 10 - 40 vol.% CO2, is a more complex surface-mediated phenomena that is controlled by a temperature-dependent surface site blocking mechanism involving adsorbed carbon. Moreover, we find that lattice substitution of ceria with zirconium can increase H2 production by

  10. Synthesis of deleobuvir, a potent hepatitis C virus polymerase inhibitor, and its major metabolites labeled with carbon-13 and carbon-14.

    PubMed

    Latli, Bachir; Hrapchak, Matt; Chevliakov, Maxim; Li, Guisheng; Campbell, Scot; Busacca, Carl A; Senanayake, Chris H

    2015-05-30

    Deleobuvir, (2E)-3-(2-{1-[2-(5-bromopyrimidin-2-yl)-3-cyclopentyl-1-methyl-1H-indole-6-carboxamido]cyclobutyl}-1-methyl-1H-benzimidazol-6-yl)prop-2-enoic acid (1), is a non-nucleoside, potent, and selective inhibitor of hepatitis C virus NS5B polymerase. Herein, we describe the detailed synthesis of this compound labeled with carbon-13 and carbon-14. The synthesis of its three major metabolites, namely, the reduced double bond metabolite (2) and the acyl glucuronide derivatives of (1) and (2), is also reported. Aniline-(13) C6 was the starting material to prepare butyl (E)-3-(3-methylamino-4-nitrophenyl-(13) C6 )acrylate [(13) C6 ]-(11) in six steps. This intermediate was then used to obtain [(13) C6 ]-(1) and [(13) C6 ]-(2) in five and four more steps, respectively. For the radioactive synthesis, potassium cyanide-(14) C was used to prepare 1-cylobutylaminoacid [(14) C]-(23) via Buchrer-Bergs reaction. The carbonyl chloride of this acid was then used to access both [(14) C]-(1) and [(14) C]-(2) in four steps. The acyl glucuronide derivatives [(13) C6 ]-(3), [(13) C6 ]-(4) and [(14) C]-(3) were synthesized in three steps from the acids [(13) C6 ]-(1), [(13) C6 ]-(2) and [(14) C]-(1) using known procedures. PMID:25964148

  11. Water, hydrogen, deuterium, carbon, carbon-13, and oxygen-18 content of selected lunar material

    USGS Publications Warehouse

    Friedman, I.; O'Neil, J.R.; Adami, L.H.; Gleason, J.D.; Hardcastle, K.

    1970-01-01

    The water content of the breccia is 150 to 455 ppm, with a ??D from -580 to -870 per mil. Hydrogen gas content is 40 to 53 ppm with a ??D of -830 to -970 per mil. The CO2 is 290 to 418 ppm with S 13C = + 2.3 to + 5.1 per mil and ??18O = 14.2 to 19.1 per mil. Non-CO2 carbon is 22 to 100 ppm, ??18C = -6.4 to -23.2 per mil. Lunar dust is 810 ppm H2O (D = 80 ppm) and 188 ppm total carbon (??13C = -17.6 per mil). The 18O analyses of whole rocks range from 5.8 to 6.2 per mil. The temperature of crystallization of type B rocks is 1100?? to 1300??C, based on the oxygen isotope fractionation between coexisting plagioclase and ilmenite.

  12. The Reaction of Carbon Dioxide with Palladium Allyl Bonds

    PubMed Central

    Wu, Jianguo; Green, Jennifer C.; Hruszkewycz, Damian P.; Incarvito, Christopher D.; Schmeier, Timothy J.

    2010-01-01

    A family of palladium allyl complexes of the type bis(2-methylallyl)Pd(L) (L = PMe3 (1), PEt3 (2), PPh3 (3) or NHC (4); NHC = 1,3-Bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene) have been prepared through the reaction of bis(2-methylallyl)Pd with the appropriate free ligand. Compounds 1–4 contain one η1 and one η3-2-methylallyl ligand and 3 was characterized by X-ray crystallography. These complexes react rapidly with CO2 at low temperature to form well defined unidentate palladium carboxylates of the type (η3-2-methylallyl)Pd(OC(O)C4H7)(L) (L = PMe3 (6), PEt3 (7), PPh3 (8) or NHC (9). The structure of 9 was elucidated using X-ray crystallography. The mechanism of the reaction of 1–4 with CO2 was probed using a combination of experimental and theoretical (density functional theory) studies. The coordination mode of the allyl ligand is crucial and whereas nucleophilic η1-allyls react rapidly with CO2, η3-allyls do not react. We propose that the reaction of η1-palladium allyls with CO2 does not proceed via direct insertion of CO2 into the Pd-C bond but through nucleophilic attack of the terminal olefin on electrophilic CO2, followed by an associative substitution at palladium. PMID:21218132

  13. In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

    PubMed

    Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

    2013-01-01

    We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions. PMID:22676479

  14. Determination of 13C/ 12C ratios with (d, p) nuclear reactions

    NASA Astrophysics Data System (ADS)

    Wang, Y. Q.; Zhang, J.; Tesmer, J. R.; Li, Y. H.; Greco, R.; Grim, G. P.; Obst, A. W.; Rundberg, R. S.; Wilhelmy, J. B.

    2010-06-01

    Stable isotope ratios such as 13C/ 12C play an important role in many applications including environment and energy research. Since many surface analysis techniques are plagued with unavoidable hydrocarbon contamination issues during analysis, it is highly desirable that 13C and 12C isotopes be measured simultaneously especially in specimens with a minute amount of 13C, in order to reliably determine 13C/ 12C ratios. In this paper, we report that deuterium induced proton particle reactions, 13C(d, p) 14C and 12C(d, p) 13C, provide a convenient and reliable approach for 13C/ 12C ratio determination. Optimizations on experimental considerations and potential interferences from other common light isotopes are discussed as well as results from the application of this technique to diagnose the performance of a target debris collection in an inertial confinement fusion (ICF) experiment.

  15. The use of the polymerase chain reaction for the detection of human papillomavirus type 13.

    PubMed

    Williamson, A L; Dennis, S J

    1991-01-01

    Human papillomavirus type 13 (HPV-13) is associated with oral focal epithelial hyperplasia (FEH). The purpose of this study was to establish conditions for the application of polymerase chain reaction (PCR) to the specific detection and amplification of HPV-13 DNA. To design primers for HPV-13 a part of the HPV-13 genome was sequenced first: the smallest BamHI fragment (597 bp) of HPV-13 was subcloned and sequenced. The sequence was found to be part of a large open reading frame and had significant homology with the L1 gene of other HPVs. HPV-13 specific primers were designed to amplify a 240 bp fragment from the L1 gene by PCR. Conditions for PCR were standardized for this set of primers.

  16. Sulfuric acid as an agent of carbonate weathering constrained by δ13C DIC: Examples from Southwest China

    NASA Astrophysics Data System (ADS)

    Li, Si-Liang; Calmels, Damien; Han, Guilin; Gaillardet, Jérôme; Liu, Cong-Qiang

    2008-06-01

    Rock weathering by carbonic acid is thought to play an important role in the global carbon cycle because it can geologically sequestrate atmospheric CO 2. Current model of carbon cycle evolution usually assumes that carbonic acid is the major weathering agent and that other acids are not important. Here, we use carbon isotopic evidence and water chemistry of springs and rivers from the Beipanjiang River basin (Guizhou Province, Southwest China) to demonstrate that sulfuric acid is also an important agent of rock weathering. The δ13C of dissolved inorganic carbon (DIC) in the water samples ranges from - 13.1‰ to - 2.4‰, and correlates negatively to [HCO 3-]/([Ca 2+] + [Mg 2+]) ratios and positively to [SO 42-]/([Ca 2+] + [Mg 2+]) ratios. These relationships are interpreted as mixing diagrams between two reactions of carbonate weathering, using carbonic acid and sulfuric acid as a proton donor, respectively. Mixing proportions show that around 42% of the divalent cations in the spring water from Guizhou are originated from the interaction between carbonate minerals and sulfuric acid. It is shown that 40% of this sulfuric acid is derived from the atmosphere and has an anthropogenic origin. The remaining 60% are derived from the oxidative weathering of sulfide minerals in sedimentary rocks. Our results show the positive action of sulfuric acid on the chemical weathering of carbonate. Particularly, we show that sulfuric acid generated by coal combustion has increased by almost 20% the weathering rates of carbonate in Southwest China. This is a clear evidence that human activities are changing the weathering rates of rocks and demonstrates a negative feedback on the acidification of the ocean by greenhouse gases. Because of the involvement of sulfuric acid in weathering reactions, 63% of the alkalinity exported by rivers is derived from carbonate, instead of 50% when atmospheric CO 2 is the only acid involved in chemical weathering of carbonate. In the Guizhou

  17. Synthesis of nanocrystals of gadolinium carbonate by reaction crystallization.

    PubMed

    He, Xin-Kuai; Shin, Dongmin; Kim, Woo-Sik

    2012-03-01

    The formation of nano-sized crystals of gadolinium carbonate via reaction crystallization was studied in a semi-batch crystallizer using gadolinium chloride and ammonium hydrogen carbonate as the reactants. The gadolinium carbonate crystals were formed by the aggregation of primary particles sized about 5 nm. Thereby, the crystallization parameters acting directly on the aggregation of the primary particles, such as the reactant concentrations, non-stoichiometry of the reactants, solution pH, acoustic energy, and agitation speed, were mechanistically investigated. As such, increasing the reactant concentrations enhanced the crystal size due to higher nucleation of the primary particles for the aggregation. Non-stoichiometric reactant concentrations resulted in a significant reduction of the crystal size, due to the adsorption of the excess species on the primary particles. Similarly, the surface charge of the primary particles depended on the solution pH. Thus, the crystal size was reduced when the pH deviated from the neutral point. The acoustic cavitation of the ultrasound was much more effective than the turbulent fluid motion of the agitation in inhibiting the primary particle aggregation. Thus, the crystal size was remarkably reduced, even at a low acoustic energy of 6 watts.

  18. Mineral carbonation of gaseous carbon dioxide using a clay-hosted cation exchange reaction.

    PubMed

    Kang, Il-Mo; Roh, Ki-Min

    2013-01-01

    The mineral carbonation method is still a challenge in practical application owing to: (1) slow reaction kinetics, (2) high reaction temperature, and (3) continuous mineral consumption. These constraints stem from the mode of supplying alkaline earth metals through mineral acidification and dissolution. Here, we attempt to mineralize gaseous carbon dioxide into calcium carbonate, using a cation exchange reaction of vermiculite (a species of expandable clay minerals). The mineralization is operated by draining NaCI solution through vermiculite powders and continuously dropping into the pool of NaOH solution with CO2 gas injected. The mineralization temperature is regulated here at 293 and 333 K for 15 min. As a result of characterization, using an X-ray powder diffractometer and a scanning electron microscopy, two types of pure CaCO3 polymorphs (vaterite and calcite) are identified as main reaction products. Their abundance and morphology are heavily dependent on the mineralization temperature. Noticeably, spindle-shaped vaterite, which is quite different from a typical vaterite morphology (polycrystalline spherulite), forms predominantly at 333 K (approximately 98 wt%).

  19. Iridium-catalyzed reductive carbon-carbon bond cleavage reaction on a curved pyridylcorannulene skeleton.

    PubMed

    Tashiro, Shohei; Yamada, Mihoko; Shionoya, Mitsuhiko

    2015-04-27

    The cleavage of CC bonds in π-conjugated systems is an important method for controlling their shape and coplanarity. An efficient way for the cleavage of an aromatic CC bond in a typical buckybowl corannulene skeleton is reported. The reaction of 2-pyridylcorannulene with a catalytic amount of IrCl3 ⋅n H2 O in ethylene glycol at 250 °C resulted in a structural transformation from the curved corannulene skeleton to a strain-free flat benzo[ghi]fluoranthene skeleton through a site-selective CC cleavage reaction. This cleavage reaction was found to be driven by both the coordination of the 2-pyridyl substituent to iridium and the relief of strain in the curved corannulene skeleton. This finding should facilitate the design of carbon nanomaterials based on CC bond cleavage reactions.

  20. Hydrogen storage reactions on titanium decorated carbon nanocones theoretical study

    NASA Astrophysics Data System (ADS)

    Shalabi, A. S.; Taha, H. O.; Soliman, K. A.; Abeld Aal, S.

    2014-12-01

    Hydrogen storage reactions on Ti decorated carbon nanocones (CNC) are investigated by using the state of the art density functional theory calculations. The single Ti atom prefers to bind at the bridge site between two hexagonal rings, and can bind up to 6 hydrogen molecules with average adsorption energies of -1.73, -0.74, -0.57, -0.45, -0.42, and -0.35 eV per hydrogen molecule. No evidence for metal clustering in the ideal circumstances, and the hydrogen storage capacity is expected to be as large as 14.34 wt%. Two types of interactions are recognized. While the interaction of 2H2 with Ti-CNC is irreversible at 532 K, the interaction of 3H2 with Ti-CNC is reversible at 392 K. Further characterizations of the former two reactions are considered in terms of projected densities of states, simulated infrared and proton magnetic resonance spectra, electrophilicity, and statistical thermodynamic stability. The free energy of the highest hydrogen storage capacity reaction between 6H2 and Ti-CNC meets the ultimate targets of department of energy at (233.15 K) and (11.843 atm) with surface coverage (0.941) and (direct/inverse) rate constants ratio (1.35).

  1. Structural snapshots of the SCR reaction mechanism on Cu-SSZ-13.

    PubMed

    Günter, Tobias; Carvalho, Hudson W P; Doronkin, Dmitry E; Sheppard, Thomas; Glatzel, Pieter; Atkins, Andrew J; Rudolph, Julian; Jacob, Christoph R; Casapu, Maria; Grunwaldt, Jan-Dierk

    2015-06-01

    The structure of copper sites in Cu-SSZ-13 during NH3-SCR was unravelled by a combination of novel operando X-ray spectroscopic techniques. Strong adsorption of NH3 on Cu, its reaction with weakly adsorbed NO from the gas phase, and slow re-oxidation of Cu(I) were proven. Thereby the SCR reaction mechanism is significantly different to that observed for Fe-ZSM-5. PMID:25951966

  2. Structural snapshots of the SCR reaction mechanism on Cu-SSZ-13.

    PubMed

    Günter, Tobias; Carvalho, Hudson W P; Doronkin, Dmitry E; Sheppard, Thomas; Glatzel, Pieter; Atkins, Andrew J; Rudolph, Julian; Jacob, Christoph R; Casapu, Maria; Grunwaldt, Jan-Dierk

    2015-06-01

    The structure of copper sites in Cu-SSZ-13 during NH3-SCR was unravelled by a combination of novel operando X-ray spectroscopic techniques. Strong adsorption of NH3 on Cu, its reaction with weakly adsorbed NO from the gas phase, and slow re-oxidation of Cu(I) were proven. Thereby the SCR reaction mechanism is significantly different to that observed for Fe-ZSM-5.

  3. SN1 reactions in supercritical carbon dioxide in the presence of alcohols: the role of preferential solvation.

    PubMed

    Delgado-Abad, Thais; Martínez-Ferrer, Jaime; Acerete, Rafael; Asensio, Gregorio; Mello, Rossella; González-Núñez, María Elena

    2016-07-01

    Ethanol () inhibits SN1 reactions of alkyl halides in supercritical carbon dioxide (scCO2) and gives no ethers as products. The unexpected behaviour of alcohols in the reaction of alkyl halides with 1,3-dimethoxybenzene () in scCO2 under different conditions is rationalised in terms of Brønsted and Lewis acid-base equilibria of reagents, intermediates, additives and products in a singular solvent characterised by: (i) the strong quadrupole and Lewis acid character of carbon dioxide, which hinders SN2 paths by strongly solvating basic solutes; (ii) the weak Lewis base character of carbon dioxide, which prevents it from behaving as a proton sink; (iii) the compressible nature of scCO2, which enhances the impact of preferential solvation on carbon dioxide availability for the solvent-demanding rate determining step.

  4. Preparation and Reaction Chemistry of Novel Silicon-Substituted 1,3-Dienes.

    PubMed

    Choudhury, Partha P; Welker, Mark E

    2015-01-01

    2-Silicon-substituted 1,3-dienes containing non transferrable groups known to promote transmetallation were prepared by Grignard chemistry and enyne metathesis. These dienes participated in one pot metathesis/Diels-Alder reactions in regio- and diastereoselective fashions. Electron-rich alkenes showed the fastest rates in metathesis reactions, and ethylene, a commonly used metathesis promoter slowed enyne metathesis. 2-Pyridyldimethylsilyl and 2-thienyldimethylsilyl substituted Diels-Alder cycloadducts participated in cross-coupling chemistry and the 2-thienyldimethylsilyl substituted cycloadducts underwent cross-coupling under very mild reaction conditions. PMID:26389877

  5. Measurement of pion double charge exchange on carbon-13, carbon-14, magnesium-26, and iron-56

    SciTech Connect

    Seidl, P.A.

    1985-02-01

    Cross sections for the /sup 13,14/C,/sup 26/Mg,/sup 56/Fe(..pi../sup +/,..pi../sup -/)/sup 13,14/O,/sup 26/Si,/sup 56/Ni reactions were measured with the Energetic Pion Channel and Spectrometer at the Clinton P. Anderson Meson Physics Facility for 120 less than or equal to T/sub ..pi../ less than or equal to 292 MeV and 0 less than or equal to theta less than or equal to 50. The double isobaric analog states (DIAS) are of primary interest. In addition, cross sections for transitions to /sup 14/O(0/sup +/, 5.92 MeV), /sup 14/O(2/sup +/, 7.77 MeV), /sup 56/Ni(gs), /sup 13/O(gs), and /sup 13/O(4.21 MeV) are presented. The /sup 13/O(4.21 MeV) state is postulated to have J/sup ..pi../ = 1/2/sup -/. The data are compared to previously measured double-charge-exchange cross sections on other nuclei, and the systematics of double charge exchange on T greater than or equal to 1 target nuclei leading to the DIAS are studied. Near the ..delta../sub 33/ resonance, cross sections for the DIAS transitions are in disagreement with calculations in which the reaction is treated as sequential charge exchange through the free pion-nucleon amplitude, while for T/sub ..pi../ > 200 MeV the anomalous features of the 164 MeV data are not apparent. This is evidence for significant higher order contributions to the double-charge-exchange amplitude near the reasonable energy. Two theoretical approaches that include two nucleon processes are applied to the DIAS data. 64 references.

  6. Base-Promoted Tandem Reaction Involving Insertion into Carbon-Carbon σ-Bonds: Synthesis of Xanthone and Chromone Derivatives.

    PubMed

    Cheng, Xingcan; Zhou, Yuanyuan; Zhang, Fangfang; Zhu, Kai; Liu, Yuanyuan; Li, Yanzhong

    2016-08-26

    Tandem reactions using base-promoted processes have been developed for the synthesis of xanthone and chromone derivatives. The first examples of base-promoted insertion reactions of isolated carbon-carbon triple bonds into carbon-carbon σ-bonds have been reported. Using these approaches, polycyclic structures can be prepared. This reaction has the potential to become a general synthetic protocol for the preparation of multi-substituted xanthones and chromones due to the abundance of easily accessible starting materials possessing diverse substituent groups. PMID:27460875

  7. Expanding Stereochemical and Skeletal Diversity Using Petasis Reactions and 1,3-Dipolar Cycloadditions

    PubMed Central

    2010-01-01

    A short and modular synthetic pathway using intramolecular 1,3-dipolar cycloaddition reactions and yielding functionalized isoxazoles, isoxazolines, and isoxazolidines is described. The change in shape of previous compounds and those in this study is quantified and compared using principal moment-of-inertia shape analysis. PMID:20977261

  8. Electrochemical device for converting carbon dioxide to a reaction product

    DOEpatents

    Masel, Richard I.; Chen, Qingmei; Liu, Zengcai; Kutz, Robert

    2016-11-01

    An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potential of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.

  9. Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.

    EPA Science Inventory

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

  10. Complete reaction mechanisms of mercury oxidation on halogenated activated carbon.

    PubMed

    Rungnim, Chompoonut; Promarak, Vinich; Hannongbua, Supa; Kungwan, Nawee; Namuangruk, Supawadee

    2016-06-01

    The reaction mechanisms of mercury (Hg) adsorption and oxidation on halogenated activated carbon (AC) have been completely studied for the first time using density functional theory (DFT) method. Two different halogenated AC models, namely X-AC and X-AC-X (X=Cl, Br, I), were adopted. The results revealed that HgX is found to be stable-state on the AC edge since its further desorption from the AC as HgX, or further oxidation to HgX2, are energetically unfavorable. Remarkably, the halide type does not significantly affect the Hg adsorption energy but it strongly affects the activation energy barrier of HgX formation, which obviously increases in the order HgIBr-AC>Cl-AC. Thus, the study of the complete reaction mechanism is essential because the adsorption energy can not be used as a guideline for the rational material design in the halide impregnated AC systems. The activation energy is an important descriptor for the predictions of sorbent reactivity to the Hg oxidation process. PMID:26943019

  11. Fractional enrichment of proteins using [2-(13)C]-glycerol as the carbon source facilitates measurement of excited state 13Cα chemical shifts with improved sensitivity.

    PubMed

    Ahlner, Alexandra; Andresen, Cecilia; Khan, Shahid N; Kay, Lewis E; Lundström, Patrik

    2015-07-01

    A selective isotope labeling scheme based on the utilization of [2-(13)C]-glycerol as the carbon source during protein overexpression has been evaluated for the measurement of excited state (13)Cα chemical shifts using Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion (RD) experiments. As expected, the fractional incorporation of label at the Cα positions is increased two-fold relative to labeling schemes based on [2-(13)C]-glucose, effectively doubling the sensitivity of NMR experiments. Applications to a binding reaction involving an SH3 domain from the protein Abp1p and a peptide from the protein Ark1p establish that accurate excited state (13)Cα chemical shifts can be obtained from RD experiments, with errors on the order of 0.06 ppm for exchange rates ranging from 100 to 1000 s(-1), despite the small fraction of (13)Cα-(13)Cβ spin-pairs that are present for many residue types. The labeling approach described here should thus be attractive for studies of exchanging systems using (13)Cα spin probes.

  12. Reaction of 2-acetyl-indane-1,3-dione with aniline - Schiff base or enamine?

    NASA Astrophysics Data System (ADS)

    Enchev, Venelin; Ivanova, Galya; Pavlović, Gordana; Rogojerov, Marin; Ahmedova, Anife; Mitewa, Mariana

    2003-06-01

    The structure of the product of the condensation reaction between 2-acetylindan-1,3-dione and aniline has been investigated in the gas phase, solution and solid state using a combination of quantum-chemical calculations, NMR and IR spectroscopies, and X-ray crystallography. Energetics of both isomers and all tautomers of the product of the reaction are predicted at HF/3-21G//HF/3-21G and HF/6-31G**//HF/3-21G levels. Geometric optimizations at HF/6-31G** level are also performed for favorable tautomers. Quantum-chemical calculations indicate that the enamine isomer, 2-[1-( N-phenylamino)-1-ethylidene]-indane-1,3-dione is favored. This is confirmed by 13C NMR spectroscopy in non-polar and polar solvents, and in the solid state by X-ray crystallography.

  13. Investigation on biological properties of tacrolimus-loaded poly(1,3-trimethylene carbonate) in vitro

    NASA Astrophysics Data System (ADS)

    Hou, Ruixia; Wu, Leigang; Wang, Jin; Huang, Nan

    2010-06-01

    The drug-eluting stents have been regarded as a milestone in inhibiting the restenosis of coronary arteries. However, adverse reactions caused by bare-metal stents and non-biodegradable polymer coatings may result in some clinical problems. In this study, a new tacrolimus-eluting stent coated with biodegradable poly(1,3-trimethylene carbonate) (PTMC) is developed. The structures are characterized by Fourier transform infrared (FTIR) analysis, and the wettability is measured by contact angle assay. The biological behaviors are evaluated by the in vitro platelets adhesion test, APTT test, the human umbilical cord artery smooth muscle cells (HUCASMCs), 4',6-diamidine-2-phenylindole (DAPI) and actin immunofluorescence staining, MTT colorimetric assay. These results show that after blending tacrolimus into PTMC, the anticoagulant behavior is improved, and the adhesion and proliferation of HUCASMCs on samples are inhibited. This work aims to find one kind of surface erosion biodegradable polymers that can be applied as drug-eluting stent coatings.

  14. "Homeopathic" palladium nanoparticle catalysis of cross carbon-carbon coupling reactions.

    PubMed

    Deraedt, Christophe; Astruc, Didier

    2014-02-18

    Catalysis by palladium derivatives is now one of the most important tools in organic synthesis. Whether researchers design palladium nanoparticles (NPs) or nanoparticles occur as palladium complexes decompose, these structures can serve as central precatalysts in common carbon-carbon bond formation. Palladium NPs are also valuable alternatives to molecular catalysts because they do not require costly and toxic ligands. In this Account, we review the role of "homeopathic" palladium catalysts in carbon-carbon coupling reactions. Seminal studies from the groups of Beletskaya, Reetz, and de Vries showed that palladium NPs can catalyze Heck and Suzuki-Miyaura reactions with aryl iodides and, in some cases, aryl bromides at part per million levels. As a result, researchers coined the term "homeopathic" palladium catalysis. Industry has developed large-scale applications of these transformations. In addition, chemists have used Crooks' concept of dendrimer encapsulation to set up efficient nanofilters for Suzuki-Miyaura and selective Heck catalysis, although these transformations required high PdNP loading. With arene-centered, ferrocenyl-terminated dendrimers containing triazolyl ligands in the tethers, we designed several generations of dendrimers to compare their catalytic efficiencies, varied the numbers of Pd atoms in the PdNPs, and examined encapsulation vs stabilization. The catalytic efficiencies achieved "homeopathic" (TON = 540 000) behavior no matter the PdNP size and stabilization type. The TON increased with decreasing the Pd/substrate ratio, which suggested a leaching mechanism. Recently, we showed that water-soluble arene-centered dendrimers with tri(ethylene glycol) (TEG) tethers stabilized PdNPs involving supramolecular dendritic assemblies because of the interpenetration of the TEG branches. Such PdNPs are stable and retain their "homeopathic" catalytic activities for Suzuki-Miyaura reactions for months. (TONs can reach 2.7 × 10(6) at 80 °C for aryl

  15. Reaction of uranium oxides with chlorine and carbon or carbon monoxide to prepare uranium chlorides

    SciTech Connect

    Haas, P.A.; Lee, D.D.; Mailen, J.C.

    1991-11-01

    The preferred preparation concept of uranium metal for feed to an AVLIS uranium enrichment process requires preparation of uranium tetrachloride (UCI{sub 4}) by reacting uranium oxides (UO{sub 2}/UO{sub 3}) and chlorine (Cl{sub 2}) in a molten chloride salt medium. UO{sub 2} is a very stable metal oxide; thus, the chemical conversion requires both a chlorinating agent and a reducing agent that gives an oxide product which is much more stable than the corresponding chloride. Experimental studies in a quartz reactor of 4-cm ID have demonstrated the practically of some chemical flow sheets. Experimentation has illustrated a sequence of results concerning the chemical flow sheets. Tests with a graphite block at 850{degrees}C demonstrated rapid reactions of Cl{sub 2} and evolution of carbon dioxide (CO{sub 2}) as a product. Use of carbon monoxide (CO) as the reducing agent also gave rapid reactions of Cl{sub 2} and formation of CO{sub 2} at lower temperatures, but the reduction reactions were slower than the chlorinations. Carbon powder in the molten salt melt gave higher rates of reduction and better steady state utilization of Cl{sub 2}. Addition of UO{sub 2} feed while chlorination was in progress greatly improved the operation by avoiding the plugging effects from high UO{sub 2} concentrations and the poor Cl{sub 2} utilizations from low UO{sub 2} concentrations. An UO{sub 3} feed gave undesirable effects while a feed of UO{sub 2}-C spheres was excellent. The UO{sub 2}-C spheres also gave good rates of reaction as a fixed bed without any molten chloride salt. Results with a larger reactor and a bottom condenser for volatilized uranium show collection of condensed uranium chlorides as a loose powder and chlorine utilizations of 95--98% at high feed rates. 14 refs., 7 figs., 14 tabs.

  16. Actinide cross sections from the reaction of sup 13 C with sup 254 Es sup g

    SciTech Connect

    Moody, K.J.; Lougheed, R.W.; Dougan, R.J.; Hulet, E.K.; Wild, J.F.; Summerer, K.; Hahn, R.L.; Aarle, J.v.; Bethune, G.R. )

    1990-01-01

    We have measured cross sections for the formation of actinide transfer products in the reaction of 72-MeV {sup 13}C projectiles with {sup 254}Es{sup {ital g}} targets. The pattern of nuclide yields is similar to those observed in the reactions of heavier ions with {sup 254}Es{sup {ital g}}. We have constructed the primary element yields from these results and show that the total cross section for transfer reactions is 58 mb. The total reaction cross section is about 300 mb. Lawrencium isotopes are formed with larger cross sections than are consistent with the trends of the transfer-product distributions; we explain this in terms of massive transfer, and model the lawrencium yields with an evaporation code.

  17. Template-free synthesis of porous graphitic carbon nitride/carbon composite spheres for electrocatalytic oxygen reduction reaction.

    PubMed

    Fu, Xiaorui; Hu, Xiaofei; Yan, Zhenhua; Lei, Kaixiang; Li, Fujun; Cheng, Fangyi; Chen, Jun

    2016-01-28

    Porous graphitic carbon nitride/carbon composite spheres were synthesized using melamine and cyanuric acid, and glucose as the carbon nitride and carbon precursor, respectively. The 3D hierarchical composites efficiently catalyzed the oxygen reduction reaction with an onset potential of 0.90 V and a kinetic current density of 23.92 mA cm(-2). These merit their promising applications in fuel cells and metal-air batteries.

  18. Preparation of 13C/15N-labeled oligomers using the polymerase chain reaction

    DOEpatents

    Chen, Xian; Gupta, Goutam; Bradbury, E. Morton

    2001-01-01

    Preparation of .sup.13 C/.sup.15 N-labeled DNA oligomers using the polymerase chain reaction (PCR). A PCR based method for uniform (.sup.13 C/.sup.15 N)-labeling of DNA duplexes is described. Multiple copies of a blunt-ended duplex are cloned into a plasmid, each copy containing the sequence of interest and restriction Hinc II sequences at both the 5' and 3' ends. PCR using bi-directional primers and uniformly .sup.13 C/.sup.15 N-labeled dNTP precursors generates labeled DNA duplexes containing multiple copies of the sequence of interest. Twenty-four cycles of PCR, followed by restriction and purification, gave the uniformly .sup.13 C/.sup.15 N-labeled duplex sequence with a 30% yield. Such labeled duplexes find significant applications in multinuclear magnetic resonance spectroscopy.

  19. 1,3-Dipolar Cycloaddition Reactions of Azomethine Ylides with Carbonyl Dipolarophiles Yielding Oxazolidine Derivatives.

    PubMed

    Meyer, Adam G; Ryan, John H

    2016-01-01

    We provide a comprehensive account of the 1,3-dipolar cycloaddition reactions of azomethine ylides with carbonyl dipolarophiles. Many different azomethine ylides have been studied, including stabilized and non-stabilized ylides. Of the carbonyl dipolarophiles, aldehydes including formaldehyde are the most studied, although there are now examples of cycloadditions with ketones, ketenes and carboxyl systems, in particular isatoic anhydrides and phthalic anhydrides. Intramolecular cycloadditions with esters can also occur under certain circumstances. The oxazolidine cycloadducts undergo a range of reactions triggered by the ring-opening of the oxazolidine ring system. PMID:27455230

  20. Stereoselective α,α'-annelation reactions of 1,3-dioxan-5-ones.

    PubMed

    Casey, Tyrone C; Carlisle, Julie; Tisselli, Patrizia; Male, Louise; Spencer, Neil; Grainger, Richard S

    2010-11-01

    Pyrrolidine enamines derived from three 1,3-dioxan-5-ones undergo α,α'-annelation reactions with methyl α-(bromomethyl)acrylate to produce bridged 2,4-dioxabicyclo[3.3.1]nonane ring systems with complete stereocontrol. Stereochemical outcomes have been rationalized based on steric and stereoelectronic interactions in intermediate boat-like conformations of the 1,3-dioxane ring and subsequent kinetic protonation to set an axial ester group on the cyclohexanone ring. Base-mediated ester epimerization provides the stereochemical array found in the highly oxygenated cyclohexane ring of phyllaemblic acid and glochicoccins B and D. PMID:20936869

  1. Reaction of dialkyltin methoxide with carbon dioxide relevant to the mechanism of catalytic carbonate synthesis

    SciTech Connect

    Choi, J.C.; Sakakura, Toshiyasu; Sako, Takeshi

    1999-04-21

    Conversion of carbon dioxide to industrially useful compounds has been a challenge for synthetic chemists and has recently attracted much interest. One of the most attractive synthetic goals starting from CO{sub 2} is dimethyl carbonate (DMC). Indeed, the straightforward reaction of methanol and CO{sub 2} catalyzed by R{sub 2}Sn(OMe){sub 2} leading to DMC has been intensively studied although catalytic performance is still far from satisfactory. The authors have recently enhanced the catalytic efficiency of R{sub 2}Sn(OMe){sub 2} using dehydrated derivatives of methanol (e.g., ortho esters and acetals) as a starting material under supercritical CO{sub 2} conditions.

  2. The 1,3-dipolar cycloaddition reaction of chiral carbohydrate-derived nitrone and olefin: towards long-chain sugars.

    PubMed

    Oukani, Hassan; Pellegrini-Moïse, Nadia; Jackowski, Olivier; Chrétien, Françoise; Chapleur, Yves

    2013-11-15

    The thermal and microwave-activated 1,3-dipolar cycloadditions of several α,β-unsaturated esters derived from d-mannose and chiral nitrones derived from threitol have been studied as a model reaction en route to eleven carbon long chain carbohydrates. Very high facial selectivity is observed for the chiral nitrones whereas the olefin facial selectivity varies with the substrate. The presence of a dioxolane ring α to the olefinic bond is beneficial to the facial selectivity of the olefin whereas a pyranose ring is not. The combination of a d-mannose derivative and a l-threitol-derived nitrone is a matched pair suitable for the synthesis of long chain sugars with nine contiguous chiral centres. Finally complete facial selectivity was observed with exo-glycals which gave a single cycloadduct.

  3. A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

    SciTech Connect

    Young, Alan; Colbow, Vesna; Harvey, David; Rogers, Erin; Wessel, Silvia

    2013-01-01

    The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

  4. The US nuclear reaction data network. Summary of the first meeting, March 13 & 14 1996

    SciTech Connect

    1996-03-01

    The first meeting of the US Nuclear Reaction Data Network (USNRDN) was held at the Colorado School of Mines, March 13-14, 1996 chaired by F. Edward Cecil. The Agenda of the meeting is attached. The Network, its mission, products and services; related nuclear data and data networks, members, and organization are described in Attachment 1. The following progress reports from the members of the USNRDN were distributed prior to the meeting and are given as Attachment 2. (1) Measurements and Development of Analytic Techniques for Basic Nuclear Physics and Nuclear Applications; (2) Nuclear Reaction Data Activities at the National Nuclear Data Center; (3) Studies of nuclear reactions at very low energies; (4) Nuclear Reaction Data Activities, Nuclear Data Group; (5) Progress in Neutron Physics at Los Alamos - Experiments; (6) Nuclear Reaction Data Activities in Group T2; (7) Progress Report for the US Nuclear Reaction Data Network Meeting; (8) Nuclear Astrophysics Research Group (ORNL); (9) Progress Report from Ohio University; (10) Exciton Model Phenomenology; and (11) Progress Report for Coordination Meeting USNRDN.

  5. Theoretical Studies on the Dynamics of the Fluorine Atom Reaction with trans-1,3-butadiene

    NASA Astrophysics Data System (ADS)

    Song, Hui; Wang, Xiu-yan; Yang, Xue-ming

    2006-08-01

    Theoretical studies of F atom reaction with trans-1,3-butadiene were carried out at the CCSD(T)/6-311G(d,p)/B3LYP/6-311G(d,p) levels. Energies and structures for all reactants, products and transition states were determined. Two reaction pathways involving the formation of the complexes CH2CHCHFCH2 and CH2CHCHCH2F were found in this reaction. Theoretical results suggest that the H atom channel observed in previous crossed beam experiment occurs likely via these two long-lived complex formation pathways. For the complex CH2CHCHFCH2 pathway, another reaction channel (C2H3+C2H3F) is also accessible. Relative importance of the C2H3+C2H3F channel versus the H formation channel via the same reaction pathway has also been estimated, suggesting that it would be di±cult to observe the C2H3+C2H3F channel in a crossed molecular beam experiment. Theoretical analysis also shows that the HF formation proceeds via direct abstraction mechanisms, though it is likely a minor process in this reaction.

  6. Study of Nuclear Structure of 13C and 20Ne by Low Energy Nuclear Reactions

    NASA Astrophysics Data System (ADS)

    Lombardo, I.; Campajola, L.; Dell'Aquila, D.; La Commara, M.; Ordine, A.; Rosato, E.; Spadaccini, G.; Vigilante, M.

    2014-12-01

    We report some recent experimental results on the spectroscopy of 13C and 20Ne nuclei by means of low energy nuclear reactions carried out with high resolution electrostatic accelerators. In the case of 13C we investigated the possible existence of a-cluster states above the a emission threshold by means of low energy elastic resonant scattering α+9Be in direct kinematics. Excitation functions show the presence of various resonances that have been reproduced by R-matrix fit. We studied also the structure of 20Ne by means of the 19F(p,α0) reaction at sub-barrier energies. The spectroscopy of 20Ne excited states in the region Ex ≈ 13.5-14.0 MeV can be probed by analyzing experimental angular distributions and excitation functions. This reaction plays an important role also in the CNOF cycle and is an important ingredient to describe hydrogen-induced destruction of fluorine in massive stars. For this reason we investigated the trend of S-factor, that has been compared with results previously reported in the literature.

  7. Carbon dioxide sequestration via olivine carbonation: Examining the formation of reaction products

    NASA Astrophysics Data System (ADS)

    King, H. E.; Plümper, O.; Putnis, A.

    2009-04-01

    Due to its abundance and natural ability to sequester CO2, olivine has been proposed as one mineral that could be used in the control of CO2 emissions into the atmosphere (Metz, 2005). Large scale peridotite deposits found in locations such as the Western Gneiss Region in Norway could provide in-situ sites for sequestration or the raw materials for ex-situ mineral carbonation. Determining the conditions under which magnesite (MgCO3) forms most efficiently is crucial to conduct a cost effective process. Understanding the development of secondary minerals is particularly important for in-situ methods as these phases can form passivating layers and affect the host rock porosity. The final solution of flow-through experiments conducted at alkaline pH have been shown to be supersaturated with respect to talc and chrysotile (Giammer et al., 2005), although these phases were not found to have precipitated the formation of a passivating, amorphous silica layer has been observed on reacted olivine surfaces (Bearat et al., 2006). By studying magnesite and other products produced during the carbonation of olivine within Teflon lined steel autoclaves we have begun to form a more comprehensive understanding of how these reactions would proceed during sequestration processes. We have performed batch experiments using carbonated saline solutions in the presence of air or gaseous CO2 from 80 to 200 ˚ C. X-ray powder diffraction was used to identify magnesite within the reaction products. Crystals of magnesite up to 20 m in diameter can be observed on olivine grain surfaces with scanning electron microscopy. Secondary reaction products formed a platy layer on olivine surfaces in reactions above 160 ˚ C and below pH 12. Energy dispersive X-ray analysis of the platy layer revealed an increase in Fe concentration. The macroscopically observable red colouration of the reaction products and Raman spectroscopy indicate that hematite is present in these layers. For experiments with

  8. Sc3CH@C80: selective (13)C enrichment of the central carbon atom.

    PubMed

    Junghans, Katrin; Rosenkranz, Marco; Popov, Alexey A

    2016-05-01

    Sc3CH@C80 is synthesized and characterized by (1)H, (13)C, and (45)Sc NMR. A large negative chemical shift of the proton, -11.73 ppm in the Ih and -8.79 ppm in the D5h C80 cage isomers, is found. (13)C satellites in the (1)H NMR spectrum enabled indirect determination of the (13)C chemical shift for the central carbon at 173 ± 1 ppm. Intensity of the satellites allowed determination of the (13)C content for the central carbon atom. This unique possibility is applied to analyze the cluster/cage (13)C distribution in mechanistic studies employing either (13)CH4 or (13)C powder to enrich Sc3CH@C80 with (13)C. PMID:27109443

  9. Sc3CH@C80: selective 13C enrichment of the central carbon atom†

    PubMed Central

    Junghans, Katrin; Rosenkranz, Marco; Popov, Alexey A.

    2016-01-01

    Sc3CH@C80 is synthesized and characterized by 1H, 13C, and 45Sc NMR. A large negative chemical shift of the proton, −11.73 ppm in the Ih and −8.79 ppm in the D5h C80 cage isomers, is found. 13C satellites in the 1H NMR spectrum enabled indirect determination of the 13C chemical shift for the central carbon at 173 ± 1 ppm. Intensity of the satellites allowed determination of the 13C content for the central carbon atom. This unique possibility is applied to analyze the cluster/cage 13C distribution in mechanistic studies employing either 13CH4 or 13C powder to enrich Sc3CH@C80 with 13C. PMID:27109443

  10. Interleukin-13 Activates Distinct Cellular Pathways Leading to Ductular Reaction, Steatosis, and Fibrosis.

    PubMed

    Gieseck, Richard L; Ramalingam, Thirumalai R; Hart, Kevin M; Vannella, Kevin M; Cantu, David A; Lu, Wei-Yu; Ferreira-González, Sofía; Forbes, Stuart J; Vallier, Ludovic; Wynn, Thomas A

    2016-07-19

    Fibroproliferative diseases are driven by dysregulated tissue repair responses and are a major cause of morbidity and mortality because they affect nearly every organ system. Type 2 cytokine responses are critically involved in tissue repair; however, the mechanisms that regulate beneficial regeneration versus pathological fibrosis are not well understood. Here, we have shown that the type 2 effector cytokine interleukin-13 simultaneously, yet independently, directed hepatic fibrosis and the compensatory proliferation of hepatocytes and biliary cells in progressive models of liver disease induced by interleukin-13 overexpression or after infection with Schistosoma mansoni. Using transgenic mice with interleukin-13 signaling genetically disrupted in hepatocytes, cholangiocytes, or resident tissue fibroblasts, we have revealed direct and distinct roles for interleukin-13 in fibrosis, steatosis, cholestasis, and ductular reaction. Together, these studies show that these mechanisms are simultaneously controlled but distinctly regulated by interleukin-13 signaling. Thus, it may be possible to promote interleukin-13-dependent hepatobiliary expansion without generating pathological fibrosis. VIDEO ABSTRACT. PMID:27421703

  11. Role of organic carbon in heterogeneous reaction of NO2 with soot.

    PubMed

    Han, Chong; Liu, Yongchun; He, Hong

    2013-04-01

    A large uncertainty among the reported uptake coefficients of NO2 on soot highlights the importance of the composition of soot in this reaction. Soot samples with different fractions of organic carbon (OC) were prepared by combusting n-hexane under controlled conditions. The heterogeneous reaction of NO2 on soot was investigated using a flow tube reactor at ambient pressure. The soot with the highest fuel/oxygen ratio showed the largest uptake coefficient (γ(initial)) of NO2 and yield of HONO (yHONO). Compared to fresh soot samples, preheated samples exhibited a great decrease in uptake coefficient of NO2 and HONO yield due to the removal of OC from soot. Ozonized soot also showed a lower reactivity toward NO2 than fresh soot, which can be ascribed to the consumption of OC with a reduced state (OCR). A linear dependence of the NO2 uptake coefficient and yields of HONO and NO on the OCR content of the soot was established, with γ(initial)(NO2) = (1.54 ± 1.39) × 10(-6) + (1.96 ± 0.35) × 10(-7) × OCR, yHONO = (11.6 ± 16.1) + (1.3 ± 0.40) × OCR, and yNO = (13.1 ± 1.9) - (0.2 ± 0.05) × OCR, respectively.

  12. Carbon-sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE

    NASA Astrophysics Data System (ADS)

    Rohac, Roman; Amara, Patricia; Benjdia, Alhosna; Martin, Lydie; Ruffié, Pauline; Favier, Adrien; Berteau, Olivier; Mouesca, Jean-Marie; Fontecilla-Camps, Juan C.; Nicolet, Yvain

    2016-05-01

    Carbon-sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5‧-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate.

  13. Belowground carbon allocation in a temperate beech forest: new insight into carbon residence time using whole tree 13C labelling

    NASA Astrophysics Data System (ADS)

    Epron, D.; Ngao, J.; Plain, C.; Longdoz, B.; Granier, A.

    2011-12-01

    Belowground carbon allocation is an important component of forest carbon budget, affecting tree growth (competition between aboveground and belowground carbon sinks), acquisition of belowground resources (nutrients and water) that are often limiting forest ecosystems and soil carbon sequestration. Total belowground carbon flow can be estimated using a mass-balance approach as cumulative soil CO2 efflux minus the carbon input from aboveground litter plus the changes in the C stored in roots, in the forest floor, and in the soil, and further compared to gross annual production. While this approach is useful for understanding the whole ecosystem carbon budget, uncertainties remain about the contribution of the different belowground pools of carbon to ecosystem respiration and carbon sequestration. New insights into transfer rate and residence time of carbon in belowground compartments can be gained from in situ whole-crown 13C labelling experiments. We combined both approaches in a young temperate beech forest in north-eastern France where ecosystem carbon fluxes are recorded since a decade. Carbon allocated belowground represented less than 40% of gross primary production in this young beech forest. Autotrophic respiration assessed by comparing soil CO2 efflux measured on normal and on root exclusion plots, accounted for 60% of the total belowground carbon flow. This indicated a rather short mean residence time of carbon allocated belowground in the soil compartments. The recovery of 13C in soil CO2 efflux after pulse-labelling entire crowns of tree with 13CO2 at several occasions during the growing season was observed a few couple of hours after the labelling. That indicates a rapid transfer of 13C belowground with a maximum occurring within 2 to 4 days after labelling. Label was recovered at the same time in the respiration and in the biomass of both fine roots and soil microbes. Allocation of recently assimilated carbon to soil microbial respiration was greater in

  14. Automated determination of the stable carbon isotopic composition (δ13C) of total dissolved inorganic carbon (DIC) and total nonpurgeable dissolved organic carbon (DOC) in aqueous samples: RSIL lab codes 1851 and 1852

    USGS Publications Warehouse

    Révész, Kinga M.; Doctor, Daniel H.

    2014-01-01

    The purposes of the Reston Stable Isotope Laboratory (RSIL) lab codes 1851 and 1852 are to determine the total carbon mass and the ratio of the stable isotopes of carbon13C) for total dissolved inorganic carbon (DIC, lab code 1851) and total nonpurgeable dissolved organic carbon (DOC, lab code 1852) in aqueous samples. The analysis procedure is automated according to a method that utilizes a total carbon analyzer as a peripheral sample preparation device for analysis of carbon dioxide (CO2) gas by a continuous-flow isotope ratio mass spectrometer (CF-IRMS). The carbon analyzer produces CO2 and determines the carbon mass in parts per million (ppm) of DIC and DOC in each sample separately, and the CF-IRMS determines the carbon isotope ratio of the produced CO2. This configuration provides a fully automated analysis of total carbon mass and δ13C with no operator intervention, additional sample preparation, or other manual analysis. To determine the DIC, the carbon analyzer transfers a specified sample volume to a heated (70 °C) reaction vessel with a preprogrammed volume of 10% phosphoric acid (H3PO4), which allows the carbonate and bicarbonate species in the sample to dissociate to CO2. The CO2 from the reacted sample is subsequently purged with a flow of helium gas that sweeps the CO2 through an infrared CO2 detector and quantifies the CO2. The CO2 is then carried through a high-temperature (650 °C) scrubber reactor, a series of water traps, and ultimately to the inlet of the mass spectrometer. For the analysis of total dissolved organic carbon, the carbon analyzer performs a second step on the sample in the heated reaction vessel during which a preprogrammed volume of sodium persulfate (Na2S2O8) is added, and the hydroxyl radicals oxidize the organics to CO2. Samples containing 2 ppm to 30,000 ppm of carbon are analyzed. The precision of the carbon isotope analysis is within 0.3 per mill for DIC, and within 0.5 per mill for DOC.

  15. The 13Carbon footprint of B[e] supergiants

    NASA Astrophysics Data System (ADS)

    Liermann, A.; Kraus, M.; Schnurr, O.; Fernandes, M. Borges

    2010-10-01

    We report on the first detection of 13C enhancement in two B[e] supergiants (B[e]SGs) in the Large Magellanic Cloud. Stellar evolution models predict the surface abundance in 13C to strongly increase during main-sequence and post-main-sequence evolution of massive stars. However, direct identification of chemically processed material on the surface of B[e]SGs is hampered by their dense, disc-forming winds, hiding the stars. Recent theoretical computations predict the detectability of enhanced 13C via the molecular emission in 13CO arising in the circumstellar discs of B[e]SGs. To test this potential method and to unambiguously identify a post-main-sequence B[e] SG by its 13CO emission, we have obtained high-quality K-band spectra of two known B[e] SGs in the Large Magellanic Cloud, using the Very Large Telescope's Spectrograph for INtegral Field Observation in the Near-Infrared (VLT/SINFONI). Both stars clearly show the 13CO band emission, whose strength implies a strong enhancement of 13C, in agreement with theoretical predictions. This first ever direct confirmation of the evolved nature of B[e]SGs thus paves the way to the first identification of a Galactic B[e]SG. Based on observations collected with the ESO VLT Paranal Observatory under programme 384.D-1078(A). E-mail: liermann@mpifr-bonn.mpg.de (AL); kraus@sunstel.asu.cas.cz (MK); oschnurr@aip.de (OS); borges@on.br (MBF)

  16. Metal amides as the simplest acid/base catalysts for stereoselective carbon-carbon bond-forming reactions.

    PubMed

    Yamashita, Yasuhiro; Kobayashi, Shū

    2013-07-15

    In this paper, new possibilities for metal amides are described. Although typical metal amides are recognized as strong stoichiometric bases for deprotonation of inert or less acidic hydrogen atoms, transition-metal amides, namely silver and copper amides, show interesting abilities as one of the simplest acid/base catalysts in stereoselective carbon-carbon bond-forming reactions.

  17. Carbon-carbon bond cleavage and formation reactions in drug metabolism and the role of metabolic enzymes.

    PubMed

    Bolleddula, Jayaprakasam; Chowdhury, Swapan K

    2015-01-01

    Elimination of xenobiotics from the human body is often facilitated by a transformation to highly water soluble and more ionizable molecules. In general, oxidation-reduction, hydrolysis, and conjugation reactions are common biotransformation reactions that are catalyzed by various metabolic enzymes including cytochrome P450s (CYPs), non-CYPs, and conjugative enzymes. Although carbon-carbon (C-C) bond formation and cleavage reactions are known to exist in plant secondary metabolism, these reactions are relatively rare in mammalian metabolism and are considered exceptions. However, various reactions such as demethylation, dealkylation, dearylation, reduction of alkyl chain, ring expansion, ring contraction, oxidative elimination of a nitrile through C-C bond cleavage, and dimerization, and glucuronidation through C-C bond formation have been reported for drug molecules. Carbon-carbon bond cleavage reactions for drug molecules are primarily catalyzed by CYP enzymes, dimerization is mediated by peroxidases, and C-glucuronidation is catalyzed by UGT1A9. This review provides an overview of C-C bond cleavage and formation reactions in drug metabolism and the metabolic enzymes associated with these reactions.

  18. Carbon catalysis of reactions in the lithium SOCl2 and SO2 systems

    NASA Technical Reports Server (NTRS)

    Kilroy, W. P.

    1981-01-01

    Certain hazards associated with lithium batteries have delayed widespread acceptance of these power sources. The reactivity of ground lithium carbon mixtures was examined. The effect of carbon types on this reactivity was determined. The basic reaction involved mixtures of lithium and carbon with battery electrolyte. The various parameters that influenced this reactivity included: the nature and freshness of the carbon; the freshness, the purity, and the conductive salt of the electrolyte; and the effect of Teflon or moisture.

  19. 1,3-Dehydro-o-carborane: generation and reaction with arenes.

    PubMed

    Zhao, Da; Zhang, Jiji; Xie, Zuowei

    2014-08-01

    Like the importance of benzyne, witnessed in modern arene chemistry for decades, 1,2-dehydro-o-carborane (o-carboryne), a three-dimensional relative of benzyne, has been used as a synthon for generating a wide range of cage, carbon-functionalized carboranes over the past 20 years. However, the selective B functionalization of the cage still represents a challenging task. Disclosed herein is the first example of 1,3-dehydro-o-carborane featuring a cage C-B bond having multiple bonding characters, and is successfully generated by treatment of 3-diazonium-o-carborane tetrafluoroborate with non-nucleophilic bases. This presents a new methodology for simultaneous functionalization of both cage carbon and boron vertices.

  20. Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

    PubMed

    Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-01-01

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

  1. Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

    PubMed

    Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-05-07

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.

  2. Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

    PubMed Central

    Drake, Henrik; Åström, Mats E.; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-01-01

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

  3. Amidation reaction of eugenyl oxyacetate ethyl ester with 1,3 diaminopropane

    NASA Astrophysics Data System (ADS)

    Suryanti, V.; Wibowo, F. R.; Kusumaningsih, T.; Wibowo, A. H.; Khumaidah, S. A.; Wijayanti, L. A.

    2016-04-01

    Eugenol having various substituents on the aromatic ring (hydroxy, methoxy and allyl) are useful for starting material in synthesizing of its derivatives. Eugenol derivatives have shown wide future potential applications in many areas, especially as future drugs against many diseases. The aim of this work was to synthesize an amide of eugenol derivative. The starting material used was eugenol from clove oil and the reaction was conducted in 3 step reactions to give the final product. Firstly, eugenol was converted into eugenyl oxyacetate [2-(4-allyl-2-methoxyphenoxy) acetic acid] as a white crystal with 70.5% yield, which was then esterified with ethanol to have eugenyl oxyacetate ethyl ester [ethyl 2-(4-allyl-2-methoxyphenoxy) acetate] as brown liquid in 75.7%. The last step was the reaction between eugenyl oxyacetate ethyl ester and 1,3 diaminopropane to give 2-(4-allyl-2-methoxyphenoxy)-N-(3-aminopropyl) acetamide as a brown powder with 71.6% yield, where the amidation reaction was occurred.

  4. Enhanced biosynthetically directed fractional carbon-13 enrichment of proteins for backbone NMR assignments.

    PubMed

    Wenrich, Broc R; Sonstrom, Reilly E; Gupta, Riju A; Rovnyak, David

    2015-11-01

    Routes to carbon-13 enrichment of bacterially expressed proteins include achieving uniform or positionally selective (e.g. ILV-Me, or (13)C', etc.) enrichment. We consider the potential for biosynthetically directed fractional enrichment (e.g. carbon-13 incorporation in the protein less than 100%) for performing routine n-(D)dimensional NMR spectroscopy of proteins. First, we demonstrate an approach to fractional isotope addition where the initial growth media containing natural abundance glucose is replenished at induction with a small amount (e.g. 10%(w/w)u-(13)C-glucose) of enriched nutrient. The approach considered here is to add 10% (e.g. 200mg for a 2g/L culture) u-(13)C-glucose at the induction time (OD600=0.8), resulting in a protein with enhanced (13)C incorporation that gives almost the same NMR signal levels as an exact 20% (13)C sample. Second, whereas fractional enrichment is used for obtaining stereospecific methyl assignments, we find that (13)C incorporation levels no greater than 20%(w/w) yield (13)C and (13)C-(13)C spin pair incorporation sufficient to conduct typical 3D-bioNMR backbone experiments on moderate instrumentation (600 MHz, RT probe). Typical 3D-bioNMR experiments of a fractionally enriched protein yield expected backbone connectivities, and did not show amino acid biases in this work, with one exception. When adding 10% u-(13)C glucose to expression media at induction, there is poor preservation of (13)Cα-(13)Cβ spin pairs in the amino acids ILV, leading to the absence of Cβ signals in HNCACB spectra for ILV, a potentially useful editing effect. Enhanced fractional carbon-13 enrichment provides lower-cost routes to high throughput protein NMR studies, and makes modern protein NMR more cost-accessible.

  5. Investigating 13C +12C reaction by the activation method. Sensitivity tests

    NASA Astrophysics Data System (ADS)

    Chesneanu, Daniela; Trache, L.; Margineanu, R.; Pantelica, A.; Ghita, D.; Straticiuc, M.; Burducea, I.; Blebea-Apostu, A. M.; Gomoiu, C. M.; Tang, X.

    2015-02-01

    We have performed experiments to check the limits of sensitivity of the activation method using the new 3 MV Tandetron accelerator and the low and ultra-low background laboratories of the "Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH). We have used the 12C +13C reaction at beam energies Elab= 6, 7 and 8 MeV. The knowledge of this fusion cross section at deep sub-barrier energies is of interest for astrophysical applications, as it provides an upper limit for the fusion cross section of 12C +12C over a wide energy range. A 13C beam with intensities 0.5-2 particleμA was provided by the accelerator and used to bombard graphite targets, resulting in activation with 24Na from the 12C (13C ,p) reaction. The 1369 and 2754 keV gamma-rays from 24Na de-activation were clearly observed in the spectra obtained in two different laboratories used for measurements at low and ultralow background: one at the surface and one located underground in the Unirea salt mine from Slanic Prahova, Romania. In the underground laboratory, for Elab = 6 MeV we have measured an activity of 0.085 ± 0.011 Bq, corresponding to cross sections of 1-3 nb. This demonstrates that it is possible to measure 12C targets irradiated at lower energies for at least 10 times lower cross sections than before β-γ coincidences will lead us another factor of 10 lower, proving that this installations can be successfully used for nuclear astrophysics measurements.

  6. Formation of 6-methyl-1,4-dihydronaphthalene in the reaction of the p-tolyl radical with 1,3-butadiene under single-collision conditions.

    PubMed

    Parker, Dorian S N; Dangi, Beni B; Kaiser, Ralf I; Jamal, Adeel; Ryazantsev, Mikhail; Morokuma, Keiji

    2014-12-26

    Crossed molecular beam reactions of p-tolyl (C7H7) plus 1,3-butadiene (C4H6), p-tolyl (C7H7) plus 1,3-butadiene-d6 (C4D6), and p-tolyl-d7 (C7D7) plus 1,3-butadiene (C4H6) were carried out under single-collision conditions at collision energies of about 55 kJ mol(-1). 6-Methyl-1,4-dihydronaphthalene was identified as the major reaction product formed at fractions of about 94% with the monocyclic isomer (trans-1-p-tolyl-1,3-butadiene) contributing only about 6%. The reaction is initiated by barrierless addition of the p-tolyl radical to the terminal carbon atom of the 1,3-butadiene via a van der Waals complex. The collision complex isomerizes via cyclization to a bicyclic intermediate, which then ejects a hydrogen atom from the bridging carbon to form 6-methyl-1,4-dihydronaphthalene through a tight exit transition state located about 27 kJ mol(-1) above the separated products. This is the dominant channel under the present experimental conditions. Alternatively, the collision complex can also undergo hydrogen ejection to form trans-1-p-tolyl-1,3-butadiene; this is a minor contributor to the present experiment. The de facto barrierless formation of a methyl-substituted aromatic hydrocarbons by dehydrogenation via a single event represents an important step in the formation of polycyclic aromatic hydrocarbons (PAHs) and their partially hydrogenated analogues in combustion flames and the interstellar medium. PMID:25407848

  7. The reaction of lithium with dimethyl carbonate and diethyl carbonate in ultrahigh vacuum studied by X-ray photoemission spectroscopy

    SciTech Connect

    Zhuang, G.; Chen, Y.; Ross, P.N. Jr.

    1999-02-16

    The reaction of dimethyl carbonate (DMC) and diethyl carbonate (DEC) with clean metallic lithium in ultrahigh vacuum was studied by the use of X-ray photoelectron spectroscopy with the temperature-programmed reaction methodology. Both molecules are of interest as solvents in ambient-temperature lithium batteries. The solvent molecules were condensed onto the surface of an evaporated lithium film at 120 K, and spectra were collected as the sample was warmed in ca. 25 to 30-K increments. The reaction of either DMC or DEC with lithium was initiated at 180 K, a temperature much lower than their bulk melting temperatures, producing lithium methyl carbonate, methyllithium and lithium ethyl carbonate, and ethyllithium, respectively. At temperatures greater than 270--300 K, the lithium alkyl carbonates start to decompose with Li{sub 2}O, elemental carbon, and alkyllithium as products on the surface. Both DMC and DEC are more reactive toward metallic Li than another carbonate solvent, propylene carbonate, which the authors have studied by the same methodology. Because methyl and ethyllithium are highly soluble in the parent solvent, electrodeposited Li is predicted to have poor stability in an electrolyte composed of either DMC or DEC.

  8. An unusual carbon-carbon bond cleavage reaction during phosphinothricin biosynthesis

    SciTech Connect

    Cicchillo, Robert M; Zhang, Houjin; Blodgett, Joshua A.V.; Whitteck, John T; Li, Gongyong; Nair, Satish K; van derDonk, Wilfred A; Metcalf, William W

    2010-01-12

    Natural products containing phosphorus-carbon bonds have found widespread use in medicine and agriculture. One such compound, phosphinothricin tripeptide, contains the unusual amino acid phosphinothricin attached to two alanine residues. Synthetic phosphinothricin (glufosinate) is a component of two top-selling herbicides (Basta and Liberty), and is widely used with resistant transgenic crops including corn, cotton and canola. Recent genetic and biochemical studies showed that during phosphinothricin tripeptide biosynthesis 2-hydroxyethylphosphonate (HEP) is converted to hydroxymethylphosphonate (HMP). Here we report the in vitro reconstitution of this unprecedented C(sp{sup 3})-C(sp{sup 3}) bond cleavage reaction and X-ray crystal structures of the enzyme. The protein is a mononuclear non-haem iron(II)-dependent dioxygenase that converts HEP to HMP and formate. In contrast to most other members of this family, the oxidative consumption of HEP does not require additional cofactors or the input of exogenous electrons. The current study expands the scope of reactions catalysed by the 2-His-1-carboxylate mononuclear non-haem iron family of enzymes.

  9. The Path of Carbon in Photosynthesis IX. Photosynthesis, Photoreduction, and the Hydrogen-Oxygen-Carbon Dioxide Dark Reaction

    DOE R&D Accomplishments Database

    Badin, E. J.; Calvin, M.

    1950-02-01

    A comparison of the rates of fixation of Carbon 14 dioxide in algae for the processes of photosynthesis, photoreduction and the hydrogen-oxygen-carbon dioxide dark reaction has been made. For the same series of experiments, rates of incorporation of tracer carbon into the separate soluble components using the radiogram method have been determined. The mechanism of carbon dioxide uptake has been shown to occur via two distinct paths. In all cases studied, essentially the same compounds appear radioactive. The distribution with time, however, differs markedly.

  10. Kinetics of the carbon monoxide oxidation reaction under microwave heating

    SciTech Connect

    Perry, W.L.; Katz, J.D.; Rees, D.; Paffett, M.T.; Datye, A.

    1996-06-01

    915 MHz microwave heating has been used to drive the CO oxidation reaction over Pd/Al{sub 2}O{sub 3} with out significantly affecting the reaction kinetics. As compared to an identical conventionally heated system, the activation energy, pre-exponential factor, and reaction order with respect to CO were unchanged. Temperature was measured using a thermocouple extrapolation technique. Microwave-induced thermal gradients were found to play a significant role in kinetic observations. The authors chose the CO oxidation reaction over a supported metal catalyst because the reaction kinetics are well known, and because of the diverse dielectric properties of the various elements in the system: CO is a polar molecule, O{sub 2} and CO{sub 2} are non-polar, Al{sub 2}O{sub 3} is a dielectric, and Pt and Pd are conductors.

  11. 13C NMR spectroscopy of the insoluble carbon of carbonaceous chondrites.

    PubMed

    Cronin, J R; Pizzarello, S; Frye, J S

    1987-01-01

    13C NMR spectra have been obtained of the insoluble carbon residues resulting from HF-digestion of three carbonaceous chondrites, Orgueil (C1), Murchison (CM2), and Allende (CV3). Spectra obtained using the cross polarization magic-angle spinning technique show two major features attributable respectively to carbon in aliphatic/olefinic structures. The spectrum obtained from the Allende sample was weak, presumably as a consequence of its low hydrogen content. Single pulse excitation spectra, which do not depend on 1H-13C polarization transfer for signal enhancement were also obtained. These spectra, which may be more representative of the total carbon in the meteorite samples, indicate a greater content of carbon in aromatic/olefinic structures. These results suggest that extensive polycyclic aromatic sheets are important structural features of the insoluble carbon of all three meteorites. The Orgueil and Murchison materials contain additional hydrogenated aromatic/olefinic and aliphatic groups.

  12. 13C NMR spectroscopy of the insoluble carbon of carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Cronin, J. R.; Pizzarello, S.; Frye, J. S.

    1987-01-01

    13C NMR spectra have been obtained of the insoluble carbon residues resulting from HF-digestion of three carbonaceous chondrites, Orgueil (C1), Murchison (CM2), and Allende (CV3). Spectra obtained using the cross polarization magic-angle spinning technique show two major features attributable respectively to carbon in aliphatic/olefinic structures. The spectrum obtained from the Allende sample was weak, presumably as a consequence of its low hydrogen content. Single pulse excitation spectra, which do not depend on 1H-13C polarization transfer for signal enhancement were also obtained. These spectra, which may be more representative of the total carbon in the meteorite samples, indicate a greater content of carbon in aromatic/olefinic structures. These results suggest that extensive polycyclic aromatic sheets are important structural features of the insoluble carbon of all three meteorites. The Orgueil and Murchison materials contain additional hydrogenated aromatic/olefinic and aliphatic groups.

  13. Elementary reactions of nitrogen and oxygen with boron and carbon at high pressures and temperatures

    SciTech Connect

    Yoo, C.S.; Cynn, H.; Nicol, M.F.

    1997-08-01

    The direct elementary reactions among the first and second row elements often yield novel super hard, high energy density, and wide band-gap optical materials. The reactions of oxygen and nitrogen with boron and carbon have been investigated at high pressures and temperatures by using an integrated technique of diamond-anvil cell, laser-heating, x-ray diffraction, Raman spectroscopy. A wide range of products has been synthesized and characterized in-situ at high pressures, including {alpha}-CO{sub 2}, B{sub 2}0{sub 3}-I,B{sub 2}0{sub 3}-II, c-BN, h-BN, h{sup `}-B, amorphous carbon nitrides. The elementary reactions occur exothermically and result in highly polycrystallized products with an exception in carbon-nitrogen reactions. The implication of the elementary reactions to energetic materials applications is discussed.

  14. Investigating {sup 13}C+{sup 12}C reaction by the activation method. Sensitivity tests

    SciTech Connect

    Chesneanu, Daniela Trache, L.; Margineanu, R.; Pantelica, A.; Ghita, D.; Straticiuc, M.; Burducea, I.; Blebea-Apostu, A. M.; Gomoiu, C. M.; Tang, X.

    2015-02-24

    We have performed experiments to check the limits of sensitivity of the activation method using the new 3 MV Tandetron accelerator and the low and ultra-low background laboratories of the “Horia Hulubei” National Institute of Physics and Nuclear Engineering (IFIN-HH). We have used the {sup 12}C+{sup 13}C reaction at beam energies E{sub lab}= 6, 7 and 8 MeV. The knowledge of this fusion cross section at deep sub-barrier energies is of interest for astrophysical applications, as it provides an upper limit for the fusion cross section of {sup 12}C+{sup 12}C over a wide energy range. A {sup 13}C beam with intensities 0.5–2 particleμA was provided by the accelerator and used to bombard graphite targets, resulting in activation with {sup 24}Na from the {sup 12}C({sup 13}C,p) reaction. The 1369 and 2754 keV gamma-rays from {sup 24}Na de-activation were clearly observed in the spectra obtained in two different laboratories used for measurements at low and ultralow background: one at the surface and one located underground in the Unirea salt mine from Slanic Prahova, Romania. In the underground laboratory, for E{sub lab} = 6 MeV we have measured an activity of 0.085 ± 0.011 Bq, corresponding to cross sections of 1–3 nb. This demonstrates that it is possible to measure {sup 12}C targets irradiated at lower energies for at least 10 times lower cross sections than before β–γ coincidences will lead us another factor of 10 lower, proving that this installations can be successfully used for nuclear astrophysics measurements.

  15. Simulation of soil organic carbon in different soil size fractions using 13Carbon measurement data

    NASA Astrophysics Data System (ADS)

    Gottschalk, P.; Bellarby, J.; Chenu, C.; Foereid, B.; Wattenbach, M.; Zingore, S.; Smith, J.

    2009-04-01

    We simulate the soil organic carbon (SOC) dynamics at a chronoseqeunce site in France, using the Rothamsted Carbon model. The site exhibits a transition from C3 plants, dominated by pine forest, to a conventional C4 maize rotation. The different 13C signatures of the forest plants and maize are used to distinguish between the woodland derived carbon (C) and the maize derived C. The model is evaluated against total SOC and C derived from forest and maize, respectively. The SOC dynamics of the five SOC pools of the model, decomposable plant material (DPM), resistant plant material (RPM), biomass, humus and inert C, are also compared to the SOC dynamics measured in different soil size fractions. These fractions are > 50 μm (particulate organic matter), 2-50 μm (silt associated SOC) and <2 μm (clay associated SOC). Other authors had shown that the RPM pool of the model corresponds well to SOC measured in the soil size fraction > 50 μm and the sum of the other pools corresponds well to the SOC measured in the soil size fraction < 50 μm. Default model applications show that the model underestimates the fast drop in forest C stocks in the first 20 years after land-use change and overestimates the C accumulation of maize C. Several hypotheses were tested to evaluate the simulations. Input data and internal model parameter uncertainties had minor effects on the simulations results. Accounting for erosion and implementing a simple tillage routine did not improve the simulation fit to the data. We therefore hypothesize that a generic process that is not yet explicitly accounted for in the ROTHC model could explain the loss in soil C after land use change. Such a process could be the loss of the physical protection of soil organic matter as would be observed following cultivation of a previously uncultivated soil. Under native conditions a fraction of organic matter is protected in stable soil aggregates. These aggregates are physically disrupted by continuous and

  16. Spectroscopy of {sup 13}B via the {sup 13}C(t,{sup 3}He) reaction at 115A MeV

    SciTech Connect

    Guess, C. J.; Zegers, R. G. T.; Brown, B. A.; Deaven, J. M.; Hitt, G. W.; Meharchand, R.; Austin, Sam M.; Perdikakis, G.; Tur, C.; Bazin, D.; Grinyer, G. F.; Caesar, C.; Herlitzius, C.; Noji, S.; Sakai, H.; Shimbara, Y.

    2009-08-15

    Gamow-Teller and dipole transitions to final states in {sup 13}B were studied via the {sup 13}C(t,{sup 3}He) reaction at E{sub t}=115A MeV. In addition to the strong Gamow-Teller transition to the {sup 13}B ground state, a weaker Gamow-Teller transition to a state at 3.6 MeV was found. This state was assigned a spin-parity of 3/2{sup -} by comparison with shell-model calculations using the WBP and WBT interactions which were modified to allow for mixing between n({Dirac_h}/2{pi}){omega} and (n+2)({Dirac_h}/2{pi}){omega} configurations. This assignment agrees with a recent result from a lifetime measurement of excited states in {sup 13}B. The shell-model calculations also explained the relatively large spectroscopic strength measured for a low-lying 1/2{sup +} state at 4.83 MeV in {sup 13}B. The cross sections for dipole transitions up to E{sub x}({sup 13}B)=20 MeV excited via the {sup 13}C(t,{sup 3}He) reaction were also compared with the shell-model calculations. The theoretical cross sections exceeded the data by a factor of about 1.8, which might indicate that the dipole excitations are ''quenched''. Uncertainties in the reaction calculations complicate that interpretation.

  17. Asymmetric catalytic hydrogenation reactions in supercritical carbon dioxide

    SciTech Connect

    Burk, M.J.; Gross, M.F.; Feng, S.; Tumas, W.

    1995-08-09

    We demonstrate that asymmetric catalytic hydrogenation reactions can be conducted in supercritical CO{sub 2} and that, in some cases, higher enantioselectivities can be achieved in this solvent relative to conventional solvents. These preliminary studies effectively demonstrate the feasibility of conducting highly enantioselective hydrogenation reactions in supercritical CO{sub 2}. Importantly, we have shown that higher enantioselectivities may be achieved in supercritical CO{sub 2} relative to conventional solvents. 16 refs., 2 tabs.

  18. Properties of ionic liquids on Au surfaces: non-conventional anion exchange reactions with carbonate.

    PubMed

    Ratel, Mathieu; Branca, Mathieu; Breault-Turcot, Julien; Zhao, Sandy Shuo; Chaurand, Pierre; Schmitzer, Andreea R; Masson, Jean-Francois

    2011-10-14

    A simple anion metathesis in diluted aqueous carbonate at room temperature affords 1-(12-mercaptododecyl)-3-methyl-imidazolium carbonate (MDMI-HCO(3)) from MDMI salts self-assembled on gold films and nanoparticles. The properties of MDMI-SAM differ from MDMI in solution, for which the anion exchange reaction does not proceed. PMID:21879044

  19. Biocatalytic carbon capture via reversible reaction cycle catalyzed by isocitrate dehydrogenase.

    PubMed

    Xia, Shunxiang; Frigo-Vaz, Benjamin; Zhao, Xueyan; Kim, Jungbae; Wang, Ping

    2014-09-12

    The practice of carbon capture and storage (CCS) requires efficient capture and separation of carbon dioxide from its gaseous mixtures such as flue gas, followed by releasing it as a pure gas which can be subsequently compressed and injected into underground storage sites. This has been mostly achieved via reversible thermochemical reactions which are generally energy-intensive. The current work examines a biocatalytic approach for carbon capture using an NADP(H)-dependent isocitrate dehydrogenase (ICDH) which catalyzes reversibly carboxylation and decarboxylation reactions. Different from chemical carbon capture processes that rely on thermal energy to realize purification of carbon dioxide, the biocatalytic strategy utilizes pH to leverage the reaction equilibrium, thereby realizing energy-efficient carbon capture under ambient conditions. Results showed that over 25 mol of carbon dioxide could be captured and purified from its gas mixture for each gram of ICDH applied for each carboxylation/decarboxylation reaction cycle by varying pH between 6 and 9. This work demonstrates the promising potentials of pH-sensitive biocatalysis as a green-chemistry route for carbon capture.

  20. Computational studies of gas phase reactions of carbon chain anions with N and O atoms.

    PubMed

    Yang, Zhibo; Snow, Theodore P; Bierbaum, Veronica M

    2010-10-28

    Experimental studies of gas phase reactions of carbanions with N and O atoms have been reported previously to understand ion chemistry relevant to the interstellar medium. In all cases reactions of anions with O atoms exhibit larger reaction rate constants compared to the corresponding N atom reactions. In addition, the open-shell carbon chain anions exhibit higher reactivities than the corresponding closed-shell species in N atom reactions, whereas similar reactivities were observed for both open and closed-shell anions in O atom reactions. These trends are investigated by the current theoretical study of the reactions of HC(n)(-)(n = 2, 4, and 6) and C(n)(-) (n = 2, 4-7) with N and O atoms. Our results indicate that spin-forbidden processes are the probable pathways in reactions of closed-shell anions HC(n)(-) with N atoms, and spin conversion limits the reaction efficiency. In reactions of open-shell anions C(n)(-) with N atoms, about 50% of the collisions may proceed through spin-allowed barrierless pathways, which results in relatively higher reaction efficiencies than for the closed-shell reactions. For reactions of all anions with O atoms, the spin-allowed barrierless pathways are the only channels, such that all reactions occur with very high efficiencies. This work provides a greater understanding of the influence of spin effects on the reactivities of anion reactions involving N and O atoms that may be important in the interstellar medium.

  1. Systematic R -matrix analysis of the 13C(p ,γ )14N capture reaction

    NASA Astrophysics Data System (ADS)

    Chakraborty, Suprita; deBoer, Richard; Mukherjee, Avijit; Roy, Subinit

    2015-04-01

    Background: The proton capture reaction 13C(p ,γ )14N is an important reaction in the CNO cycle during hydrogen burning in stars with mass greater than the mass of the Sun. It also occurs in astrophysical sites such as red giant stars: the asymptotic giant branch (AGB) stars. The low energy astrophysical S factor of this reaction is dominated by a resonance state at an excitation energy of around 8.06 MeV (Jπ=1-,T =1 ) in 14N. The other significant contributions come from the low energy tail of the broad resonance with Jπ=0-,T =1 at an excitation of 8.78 MeV and the direct capture process. Purpose: Measurements of the low energy astrophysical S factor of the radiative capture reaction 13C(p ,γ )14N reported extrapolated values of S (0 ) that differ by about 30 % . Subsequent R -matrix analysis and potential model calculations also yielded significantly different values for S (0 ) . The present work intends to look into the discrepancy through a detailed R -matrix analysis with emphasis on the associated uncertainties. Method: A systematic reanalysis of the available decay data following the capture to the Jπ=1-,T =1 resonance state of 14N around 8.06 MeV excitation had been performed within the framework of the R -matrix method. A simultaneous analysis of the 13C(p ,p0 ) data, measured over a similar energy range, was carried out with the capture data. The data for the ground state decay of the broad resonance state (Jπ=0-,T =1 ) around 8.78 MeV excitations was included as well. The external capture model along with the background poles to simulate the internal capture contribution were used to estimate the direct capture contribution. The asymptotic normalization constants (ANCs) for all states were extracted from the capture data. The multichannel, multilevel R -matrix code azure2 was used for the calculation. Results: The values of the astrophysical S factor at zero relative energy, resulting from the present analysis, are found to be consistent within the

  2. Deglacial change in terrestrial carbon storage estimated by benthic δ13C

    NASA Astrophysics Data System (ADS)

    Peterson, C. D.; Lisiecki, L. E.

    2012-12-01

    Terrestrial carbon storage is dramatically decreased during glacial periods due to cold temperatures, increased aridity, and the presence of large ice sheets on land. Most of the carbon released by the terrestrial biosphere is stored in the glacial ocean, where the isotopic signature of terrestrial carbon13C terrestrial carbon = -25‰) is observed as a 0.32-0.7‰ depletion in benthic foraminiferal δ13C. The wide range in estimated δ13C change is due to different subsets of benthic δ13C data and different methods of weighting the mean δ13C by volume. We estimate the glacial-interglacial δ13C change of marine DIC using benthic Cibicides spp. δ13C records from 356 core sites (five to eight times as many as previous studies). We divide the ocean into 9 regions to generate linear regressions of regional δ13C versus depth (0.5-5 km) for the late Holocene (0-6 ka) and LGM (18-21 ka) and estimate a mean δ13C decrease of 0.53 +/-0.06‰ (2σ), equivalent to 715-885 Pg C. Our estimate is in good agreement with a vegetation reconstruction estimate of ~750-1050 Pg C [Crowley, 1995] and a recent model estimate of ~670 Pg C [Kohler, 2010] and is ~66% larger than the previous whole ocean δ13C estimate of 0.32‰ [Duplessy et al., 1988]. To evaluate the uncertainty of our estimate, we used a bootstrapping approach (100,000 iterations) to generate realistic error estimates for our different regional line-fits of δ13C vs. depth for both the LGM and Holocene time slices. We propagated the bootstrapped linear regressions through all of our calculations to estimate a 95% confidence interval for global δ13C change (+/-0.06‰) and the uncertainty contribution from each region. The largest sources of uncertainty in our estimate are the South Pacific (35% of variance) and Indian Ocean (36% of variance) because they are the regions with the largest volumes and sparsest δ13C data. Additionally, we note that mean benthic δ13C change could in part reflect glacial

  3. Silicate or Carbonate Weathering: Fingerprinting Sources of Dissolved Inorganic Carbon Using δ13C in a Tropical River, Southern India

    NASA Astrophysics Data System (ADS)

    Bhagat, H.; Ghosh, P.

    2015-12-01

    Rivers are an inherently vital resource for the development of any region and their importance is highlighted by the presence of many ancient human civilizations adjacent to river systems. δ13C - Si/HCO3 systematics has been applied to large south Indian rivers which drain the Deccan basaltic traps in order to quantify their relative contributions from silicate and carbonate weathering. This study investigates δ13C - Si/HCO3 systematics of the Cauvery River basin which flows through silicate lithology in the higher reaches and carbonate lithology with pedogenic and marine carbonates dominating the terrain in the lower reaches of the basin. The samples for the present study were collected at locations within the watershed during Pre-Monsoon and Monsoon Season 2014. The measurements of stable isotope ratios of δ13CDIC and were accomplished through a Thermo Scientific GasBench II interface connected to a MAT 253 IRMS. We captured a large spatial variation in δ13C and Si/HCO3 values during both seasons; Pre-Monsoon δ13C values ranges between -17.57‰ to -4.02‰ and during Monsoon it varies between -9.19‰ to +0.61‰. These results indicate a two end-member mixing component i.e. a silicate and a carbonate end member; governing the weathering interactions of the Cauvery River. Within the drainage basin, we identified silicate and carbonate dominating sources by using contributions of DIC and δ13C. Si/HCO3 values for Pre-Monsoon ranges between 0.028 - 0.67 and for Monsoon it varies between 0.073 - 0.80. Lighter δ13C composition was observed at sampling sites at higher altitude in contrast to sampling sites at flood plain which show relatively enriched δ13C which indicate mixing of soil derived CO2 with C4 plants. Result suggests dominance of carbonate weathering during the Monsoon Period, while silicate weathering is pronounced during Pre- Monsoon period.

  4. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1978-01-01

    The possibility that the newly discovered correlated isotopic anomalies for heavy elements in the Allende meteorite were synthesized in the secondary neutron capture episode during the explosive carbon burning, the possible source of the O-16 and Al-26 anomalies, is examined. Explosive carbon burning calculations under typical conditions were first performed to generate time profiles of temperature, density, and free particle concentrations. These quantities were inputted into a general neutron capture code which calculates the resulting isotopic pattern from exposing the preexisting heavy seed nuclei to these free particles during the explosive carbon burning conditions. The interpretation avoids the problem of the Sr isotopic data and may resolve the conflict between the time scales inferred from 1-129, Pu-244, and Al-26.

  5. Transition-Metal-Catalyzed Laboratory-Scale Carbon–Carbon Bond-Forming Reactions of Ethylene

    PubMed Central

    Saini, Vaneet; Stokes, Benjamin J.; Sigman, Matthew S.

    2014-01-01

    Ethylene, the simplest alkene, is the most abundantly synthesized organic molecule by volume. It is readily incorporated into transitionmetal–catalyzed carbon-carbon bond-forming reactions through migratory insertions into alkylmetal intermediates. Because of its D2h symmetry, only one insertion outcome is possible. This limits byproduct formation and greatly simplifies analysis. As described within this Minireview, many carbon–carbon bond-forming reactions incorporate a molecule (or more) of ethylene at ambient pressure and temperature. In many cases, a useful substituted alkene is incorporated into the product. PMID:24105881

  6. Mechanistic aspects of the copolymerization reaction of carbon dioxide and epoxides, using a chiral salen chromium chloride catalyst.

    PubMed

    Darensbourg, Donald J; Yarbrough, Jason C

    2002-06-01

    The air-stable, chiral (salen)Cr(III)Cl complex (3), where H(2)salen = N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexene diamine, has been shown to be an effective catalyst for the coupling of cyclohexene oxide and carbon dioxide to afford poly(cyclohexenylene carbonate), along with a small quantity of its trans-cyclic carbonate. The thus produced polycarbonate contained >99% carbonate linkages and had a M(n) value of 8900 g/mol with a polydispersity index of 1.2 as determined by gel permeation chromatography. The turnover number (TON) and turnover frequency (TOF) values of 683 g of polym/g of Cr and 28.5 g of polym/g of Cr/h, respectively for reactions carried out at 80 degrees C and 58.5 bar pressure increased by over 3-fold upon addition of 5 equiv of the Lewis base cocatalyst, N-methyl imidazole. Although this chiral catalyst is well documented for the asymmetric ring-opening (ARO) of epoxides, in this instance the copolymer produced was completely atactic as illustrated by (13)C NMR spectroscopy. Whereas the mechanism for the (salen)Cr(III)-catalyzed ARO of epoxides displays a squared dependence on [catalyst], which presumably is true for the initiation step of the copolymerization reaction, the rate of carbonate chain growth leading to copolymer or cyclic carbonate formation is linearly dependent on [catalyst]. This was demonstrated herein by way of in situ measurements at 80 degrees C and 58.5 bar pressure. Hence, an alternative mechanism for copolymer production is operative, which is suggested to involve a concerted attack of epoxide at the axial site of the chromium(III) complex where the growing polymer chain for epoxide ring-opening resides. Preliminary investigations of this (salen)Cr(III)-catalyzed system for the coupling of propylene oxide and carbon dioxide reveal that although cyclic carbonate is the main product provided at elevated temperatures, at ambient temperature polycarbonate formation is dominant. A common reaction pathway for

  7. REACTION MECHANISMS OF MAGNESIUM SILICATES WITH CARBON DIOXIDE IN MICROWAVE FIELDS

    SciTech Connect

    William B. White; Michael R. Silsbee; B. Joe Kearns

    2004-02-18

    The objective of the investigation was to determine whether microwave fields would enhance the reactions of CO{sub 2} with silicates that are relevant to the sequestration of carbon dioxide. Three sets of experiments were conducted. (1) Serpentine and CO{sub 2} were reacted directly at one atmosphere pressure in a microwave furnace. Little reaction was observed. (2) Serpentine was dehydroxylated in a microwave furnace. The reaction was rapid, reaching completion in less than 30 minutes. A detailed investigation of this reaction produced an S-shaped kinetics curve, similar to the kinetics from dehydroxylating serpentine in a resistance furnace, but offset to 100 C lower temperature. This set of experiments clearly demonstrates the effect of microwaves for enhancing reaction kinetics. (3) Reactions of serpentine with alkaline carbonates and in acid solution were carried out in a microwave hydrothermal apparatus. There was a greatly enhanced decomposition of the serpentine in acid solution but, at the temperature and pressure of the reaction chamber (15 bars; 200 C) the carbonates did not react. Overall, microwave fields, as expected, enhance silicate reaction kinetics, but higher CO{sub 2} pressures are needed to accomplish the desired sequestration reactions.

  8. Chemo- and stereoselective reaction between alkyl isocyanides and dimethyl 1,3-acetonedicarbocxylate in the presence of acetylenic esters.

    PubMed

    Nasiri, Farogh; Nazem, Fatemeh; Pourdavaie, Kourosh

    2007-05-01

    The reaction of alkyl isocyanides with dimethyl 1,3-acetonedicarboxylate in the presence of dialkyl acetylenedicarboxylates in CH(2)Cl(2) at ambient temperature leads to highly functionalized 2-amino-4H-pyrans and 1,2-dialkyl 4,6-dimethyl-(1E, 3E)-3 (alkylamino)-5-oxo-1,3-hexadiene-1,2,4,6-tetracarboxylates.

  9. Dual template synthesis of a highly mesoporous SSZ-13 zeolite with improved stability in the methanol-to-olefins reaction.

    PubMed

    Wu, Leilei; Degirmenci, Volkan; Magusin, Pieter C M M; Szyja, Bartłomiej M; Hensen, Emiel J M

    2012-10-01

    The dual template synthesis of zeolite SSZ-13 by use of trimethyl-adamantanammonium hydroxide and a diquaternary-ammonium mesoporogen induces considerable mesoporosity without impeding zeolite microporosity. The strongly improved accessibility of Brønsted sites in mesoporous SSZ-13 increases its stability during application as an acid catalyst in the methanol-to-olefins reaction. PMID:22896837

  10. Intramolecular 1,3-dipolar cycloaddition reactions in the synthesis of complex annelated quinolines, α-carbolines and coumarins.

    PubMed

    Majumder, Swarup; Borah, Pallabi; Bhuyan, Pulak J

    2012-05-01

    In this study, we report the synthesis of several novel dihydroisoxazole-, tetrahydroisoxazole- and dihydropyrazole-fused pyrido[2,3-b]quinolines, α-carbolines, and pyrido[2,3-c]coumarins, respectively, from simple precursors and by exploring intramolecular 1,3-dipolar cycloaddition reactions involving nitrile oxides, nitrones, and nitrile imines as 1,3-dipoles. PMID:22374452

  11. A Large Metabolic Carbon Ccontribution to the δ13C Record in Marine Aragonitic Bivalve Shells

    NASA Astrophysics Data System (ADS)

    Gillikin, D. P.; Lorrain, A.; Dehairs, F.

    2006-12-01

    The stable carbon isotopic signature archived in bivalve shells was originally thought to record the δ13C of seawater dissolved inorganic carbon13C-DIC). However, more recent studies have shown that the incorporation of isotopically light metabolic carbon (M) significantly affects the δ13C signal recorded in biogenic carbonates. To assess the M contribution to Mercenaria mercenaria shells collected in North Carolina, USA, we sampled seawater δ13C-DIC, tissue, hemolymph and shell δ13C. We found up to a 4‰ decrease through ontogeny in shell δ13C in a 23 year old individual. There was no correlation between shell height or age and tissue δ13C. Thus, the ontogenic decrease observed in the shell δ13C could not be attributed to changes in food sources as the animal ages leading to more negative metabolic CO2, since this would require a negative relationship between tissue δ13C and shell height. Hemolymph δ13C, on the other hand, did exhibit a negative relationship with height, but the δ13C values were more positive than expected, indicating that hemolymph may not be a good proxy of extrapallial fluid δ13C. Nevertheless, the hemolymph data indicate that respired CO2 does influence the δ13C of internal fluids and that the amount of respired CO2 is related to the age of the bivalve. The percent metabolic C incorporated into the shell (%M) was significantly higher (up to 37%) than has been found in other bivalve shells, which usually contain less than 10 %M. Attempts to use shell biometrics to predict %M could not explain more than ~60% of the observed variability. Moreover, there were large differences in the %M between different sites. Thus, the metabolic effect on shell δ13C cannot easily be accounted for to allow reliable δ13C-DIC reconstructions. However, there does seem to be a common effect of size, as all sites had indistinguishable slopes between the %M and shell height (+0.19% per mm of shell height).

  12. Carbon isotope ratio (13C/12C) of pine honey and detection of HFCS adulteration.

    PubMed

    Çinar, Serap B; Ekşi, Aziz; Coşkun, İlknur

    2014-08-15

    Carbon isotope ratio ((13)C/(12)C=δ(13)C) of 100 pine honey samples collected from 9 different localities by Mugla region (Turkey) in years 2006, 2007 and 2008 were investigated. The δ(13)Cprotein value of honey samples ranged between -23.7 and -26.6‰, while the δ(13)Choney value varied between -22.7 and -27‰. For 90% of the samples, the difference in the C isotope ratio of protein and honey fraction (δ(13)Cpro-δ(13)Chon) was -1.0‰ and/or higher. Therefore, it can be said that the generally anticipated minimum value of C isotope difference (-1.0‰) for honey is also valid for pine honey. On the other hand, C4 sugar value (%), which was calculated from the δ(13)Cpro-δ(13)Chon difference, was found to be linearly correlated with the amount of adulterant (HFCS) in pine honey. These results indicate that C4 sugar value is a powerful criteria for detecting HFCS adulteration in pine honey. The δ(13)Choney and δ(13)Cprotein-δ(13)Choney values of the samples did not show any significant differences in terms of both year and locality (P>0.05), while the δ(13)Cprotein values showed significant differences due to year (P<0.05) but not due to locality (P>0.05). PMID:24679745

  13. Carbon isotope ratio (13C/12C) of pine honey and detection of HFCS adulteration.

    PubMed

    Çinar, Serap B; Ekşi, Aziz; Coşkun, İlknur

    2014-08-15

    Carbon isotope ratio ((13)C/(12)C=δ(13)C) of 100 pine honey samples collected from 9 different localities by Mugla region (Turkey) in years 2006, 2007 and 2008 were investigated. The δ(13)Cprotein value of honey samples ranged between -23.7 and -26.6‰, while the δ(13)Choney value varied between -22.7 and -27‰. For 90% of the samples, the difference in the C isotope ratio of protein and honey fraction (δ(13)Cpro-δ(13)Chon) was -1.0‰ and/or higher. Therefore, it can be said that the generally anticipated minimum value of C isotope difference (-1.0‰) for honey is also valid for pine honey. On the other hand, C4 sugar value (%), which was calculated from the δ(13)Cpro-δ(13)Chon difference, was found to be linearly correlated with the amount of adulterant (HFCS) in pine honey. These results indicate that C4 sugar value is a powerful criteria for detecting HFCS adulteration in pine honey. The δ(13)Choney and δ(13)Cprotein-δ(13)Choney values of the samples did not show any significant differences in terms of both year and locality (P>0.05), while the δ(13)Cprotein values showed significant differences due to year (P<0.05) but not due to locality (P>0.05).

  14. Removable well in reaction flask facilitates carbon dioxide collection

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Removable plastic well with a flange that seats on the rim of an Erlenmeyer screwcap flask aids quantitative collection of carbon dioxide liberated in the flask. The well can be removed without danger of cross-contamination. It can collect other gases using appropriate absorbents.

  15. Quantitative and mechanistic studies using the oxygen-18 isotope shift in carbon-13 nuclear magnetic resonance spectroscopy

    SciTech Connect

    Mega, T.L.

    1989-01-01

    The {sup 18}O-isotope shift in {sup 13}C NMR spectroscopy was used to study the kinetics of oxygen exchange at the anomeric carbon atoms of several ketoses and aldoses. At 25-26{degree}C and over the pH range from 2 to 10, the relative rates of oxygen exchange for the aldoses studied increased in the following sequence: D-glucose, D-mannose, D-ribose, D-2-deoxyribose. The hydration rates for the open chain forms of the sugars were calculated and the results were analyzed in terms of steric and inductive effects by drawing analogies with the hydration kinetics of simple aldehydes and ketones. Effective molarities associated with ring closure reactions of common monosaccharides are calculated. The position of bond cleavage in the acid-catalyzed hydrolysis of sucrose was elucidated by hydrolyzing the sugar in {sup 18}O-water and assaying the incorporation of {sup 18}O into the several anomeric products using {sup 13}C NMR. Independents supporting experimental evidence was obtained using {sup 1}H NMR. A detailed investigation was made of the complex {sup 13}C NMR spectrum arising from the various {sup 18}O-isotopomers in a solution of {sup 18}O-labeled (1,4-{sup 13}C{sub 2}) succinic acid. The quantitative use of the {sup 18}O isotope shift in {sup 13}C NMR was assessed.

  16. Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

    NASA Technical Reports Server (NTRS)

    Johnson, Natasha M; Elsila, Jamie E.; Kopstein, Mickey; Nuth, Joseph A., III

    2012-01-01

    Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

  17. Preparation of 2-BF3-substituted 1,3-dienes and their Diels-Alder/cross-coupling reactions.

    PubMed

    De, Subhasis; Welker, Mark E

    2005-06-01

    [reaction: see text] 2-BF3-substituted 1,3-butadienes with potassium and tetrabutylammonium counterions have been prepared in gram quantities from chloroprene via a simple synthetic procedure. The potassium salt of this new main group element substituted diene has been characterized by 1H, 13C, 11B, and 19F NMR. Diels-Alder reactions of these dienes with ethyl acrylate and methyl vinyl ketone are reported, as well as subsequent Pd-catalyzed cross-coupling reactions of those Diels-Alder adducts. PMID:15932228

  18. Tracing photosynthetic carbon in leaves with nanoSIMS after 13CO2 labelling

    NASA Astrophysics Data System (ADS)

    Dannoura, Masako; Takeuchi, Miyuki; Kominami, Yuji; Takanashi, Satoru; Kenichi, Yoshimura; Ataka, Mioko

    2015-04-01

    To understand the carbon allocation of the tree and forest ecosystem, it is important to consider the residence time of carbon in different pools at suitable time scales. For example the carbon used for respiration will stay a few minutes to a few days in the tree, the carbon used for storage or structure of leaves will stay months to years, and the carbon used for wood structure, it will stay over the whole lifespan of the tree. The leaves are the entrance of carbon in trees where it can be used for foliage growth and maintenance or exported to the other organs or the other forest ecosystem compartments. Tracing carbon isotope using NanoSIMS technique is one of useful methods to estimate where and how long the carbon stay in the tree organs. In this study, 13CO2 pulse labelling were conducted and 13C was measured by IRMS to see the amount of C remaining in the leaves with time.NanoSIMS was used to localize where the labelled C remained within the leaf tissue. Twice labelling were done on branches of Quercus serrata at FFPRI(Forest and Forest Products research Institute) in Kyoto, Japan. The first labelling was in 30 April 2012 when the leaves start flushing and the second one was in 29 May 2012 when the leaves were completely deployed. For both labelling experiment, one branch was selected and covered with transparent plastic bag. CO2 concentration was recorded with IRGA and air temperature inside the chamber was monitored. Then 13CO2 was injected into the bag, and after 1 hour, the bag was removed and the branch was again exposed to ambient air. Leaves were collected before and 10-12 times after labelling and their isotope compositions were measured by IRMS. The leaf collected just after labelling and 6 days after labelling were used for NanoSIMS observation. Samples for nanoSIMS were preserved in glutaraldehyde and then embed in epoxy resin. The sliced sample were placed on the silicon wafer and observed by NanoSIMS 50L(Cameca, France). The 13C was highest just

  19. ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter

    2000-08-01

    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation before and/or during carbonation may provide an important parameter for enhancing carbonation reaction processes. Mg(OH){sub 2} was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (i) its structural and chemical simplicity, (ii) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (iii) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO{sub 2} sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for cost optimization of any lamellar-hydroxide-based mineral carbonation sequestration process.

  20. Cyanobacterial production of 1,3-propanediol directly from carbon dioxide using a synthetic metabolic pathway.

    PubMed

    Hirokawa, Yasutaka; Maki, Yuki; Tatsuke, Tsuneyuki; Hanai, Taizo

    2016-03-01

    Production of chemicals directly from carbon dioxide using light energy is an attractive option for a sustainable future. The 1,3-propanediol (1,3-PDO) production directly from carbon dioxide was achieved by engineered Synechococcus elongatus PCC 7942 with a synthetic metabolic pathway. Glycerol dehydratase catalyzing the conversion of glycerol to 3-hydroxypropionaldehyde in a coenzyme B12-dependent manner worked in S. elongatus PCC 7942 without addition of vitamin B12, suggesting that the intrinsic pseudovitamin B12 served as a substitute of coenzyme B12. The highest titers of 1,3-PDO (3.79±0.23 mM; 288±17.7 mg/L) and glycerol (12.62±1.55 mM; 1.16±0.14 g/L), precursor of 1,3-PDO, were reached after 14 days of culture under optimized conditions in this study. PMID:26769097

  1. Thermodynamics and high-pressure kinetics of a fast carbon dioxide fixation reaction by a (2,6-pyridinedicarboxamidato-hydroxo)nickel(II) complex.

    PubMed

    Troeppner, O; Huang, D; Holm, R H; Ivanović-Burmazović, I

    2014-04-14

    The previously reported carbon dioxide fixation reaction by the planar terminal hydroxide complex [Ni(pyN2(Me2))(OH)](1-) in DMF has been further characterized by determination of the equilibrium constants K(eq)²⁹⁸ = 2.4 ± 0.2 × 10(5) M(-1) and K(eq)²²³ = 1.3 ± 0.1 × 10(7) M(-1), as well as the volume of activation for the CO2 binding (ΔV(on)(≠223) = -21 ± 3 cm(3) mol(-1)) and back decarboxylation (ΔV(off)(≠223) = -13 ± 1 cm(3) mol(-1)) by high-pressure kinetics. The data are consistent with an earlier DFT computation, including the probable nature of the transition state, and support designating the reaction as one of the most completely investigated carbon dioxide fixation reactions of any type.

  2. Buffering dissociation/formation reaction of biogenic calcium carbonate.

    PubMed

    Ichikawa, Kazuhiko

    2007-01-01

    The oscillating stability of coral reef seawater pH has been maintained at around physiological pH values over the past 300 years (Pelejero et al., 2005). The stability mechanism of its pH has been interpreted in terms of the buffering dissolution/formation reaction of CaCO(3) as well as the proton consumption/generation reaction in CaCO(3)-saturated water. Here the pH-dependent solubility product [HCO(3)(-)][Ca(2+)] has been derived on the basis of the actual pH-dependent reactions for the atmospheric CO(2)/CO(2 (aq.))/HCO(3)(-)/CO(3)(2-)/Ca(2+)/CaCO(3) system. Overbasic pH peaks appeared between pH approximately 8 and approximately 9.5 during sodium hydroxide titration, as a result of simultaneous CaCO(3) formation and proton generation. The spontaneous and prompt water pH recovery from the acidic to the physiological range has been confirmed by the observation of acid/base time evolution, because of simultaneous CaCO(3) dissolution and proton consumption. The dissolution/formation of CaCO(3) in water at pH 7.5-9 does not take place without a proton consumption/generation reaction, or a buffering chemical reaction of HCO(3)(-)+Ca(2+)right arrow over left arrowCaCO(3)+H(+). SEM images of the CaCO(3) fragments showed that the acid water ate away at the CaCO(3) formed at physiological pH values. Natural coral reefs can thus recover the physiological pH levels of seawater from the acidic range through partial dissolution of their own skeletons.

  3. 13C Incorporation into Signature Fatty Acids as an Assay for Carbon Allocation in Arbuscular Mycorrhiza

    PubMed Central

    Olsson, Pål Axel; van Aarle, Ingrid M.; Gavito, Mayra E.; Bengtson, Per; Bengtsson, Göran

    2005-01-01

    The ubiquitous arbuscular mycorrhizal fungi consume significant amounts of plant assimilated C, but this C flow has been difficult to quantify. The neutral lipid fatty acid 16:1ω5 is a quantitative signature for most arbuscular mycorrhizal fungi in roots and soil. We measured carbon transfer from four plant species to the arbuscular mycorrhizal fungus Glomus intraradices by estimating 13C enrichment of 16:1ω5 and compared it with 13C enrichment of total root and mycelial C. Carbon allocation to mycelia was detected within 1 day in monoxenic arbuscular mycorrhizal root cultures labeled with [13C]glucose. The 13C enrichment of neutral lipid fatty acid 16:1ω5 extracted from roots increased from 0.14% 1 day after labeling to 2.2% 7 days after labeling. The colonized roots usually were more enriched for 13C in the arbuscular mycorrhizal fungal neutral lipid fatty acid 16:1ω5 than for the root specific neutral lipid fatty acid 18:2ω6,9. We labeled plant assimilates by using 13CO2 in whole-plant experiments. The extraradical mycelium often was more enriched for 13C than was the intraradical mycelium, suggesting rapid translocation of carbon to and more active growth by the extraradical mycelium. Since there was a good correlation between 13C enrichment in neutral lipid fatty acid 16:1ω5 and total 13C in extraradical mycelia in different systems (r2 = 0.94), we propose that the total amount of labeled C in intraradical and extraradical mycelium can be calculated from the 13C enrichment of 16:1ω5. The method described enables evaluation of C flow from plants to arbuscular mycorrhizal fungi to be made without extraction, purification and identification of fungal mycelia. PMID:15870350

  4. Determination of carbon by the oxidation reduction reaction with chromium

    NASA Technical Reports Server (NTRS)

    Mashkovich, L.; Kuteynikov, A. F.

    1978-01-01

    Free carbon was determined in silicon and boron carbides in ash, oxides, and other materials by oxidation to carbon dioxide with a mixture of K2Cr2O7 + H2SO4. The determination was made from the amount of CR(6) consumed, by adding excess Mohr's salt and titrating with a standard solution of KMnO4. The amount of Cr(6) self reduced was determined in a blank test. Optimum oxidation and conditions were achieved when the volumes of 5% k2Cr2Oz and H2SO4 were equal. The mixture was boiled for 1-2 hours using a reflex condenser. The volume should not be reduced, in order to avoid an increase in the sulfuric acid concentration. The relative error was 4-7% for 0.005-0.04 g C and less than or equal to 3.5% for 0.1 g C.

  5. sup 13 C and sup 18 O isotopic disequilibrium in biological carbonates: I. Patterns

    SciTech Connect

    McConnaughey, T. )

    1989-01-01

    Biological carbonates frequently precipitate out of {sup 18}O and {sup 13}C equilibrium with ambient waters. Two patterns of isotopic disequilibrium are particularly common. Kinetic disequilibria, so designated because they apparently result from kinetic isotope effects during CO{sub 2} hydration and hydroxylation, involve simultaneous depletions of {sup 18}O and {sup 13}C as large as 4{per thousand} and 10 to 15{per thousand}, respectively. Rapid skeletogenesis favors strong kinetic effects, and approximately linear correlations between skeletal {delta}{sup 18}O and {delta}{sup 13}C are common in carbonates showing mainly the kinetic pattern. Metabolic effects involve additional positive or negative modulation of skeletal {delta}{sup 13}C, reflecting changes in the {delta}{sup 13}C of dissolved inorganic carbon, caused mainly by photosynthesis and respiration. Kinetic isotope disequilibria tend to be fairly consistent in rapidly growing parts of photosynthetic corals, and time dependent isotopic variations therefore reflect changes in environmental conditions. {delta}{sup 18}O variations from Galapagos corals yields meaningful clues regarding seawater temperature, while {delta}{sup 13}C variations reflect changes in photosynthesis, modulated by cloudiness.

  6. Application of the random pore model to the carbonation cyclic reaction

    SciTech Connect

    Grasa, G.; Murillo, R.; Alonso, M.; Abanades, J.C.

    2009-05-15

    Calcium oxide has been proved to be a suitable sorbent for high temperature CO{sub 2} capture processes based on the cyclic carbonation-calcination reaction. It is important to have reaction rate models that are able to describe the behavior of CaO particles with respect to the carbonation reaction. Fresh calcined lime is known to be a reactive solid toward carbonation, but the average sorbent particle in a CaO-based CO{sub 2} capture system experiences many carbonation-calcination cycles and the reactivity changes with the number of cycles. This study applies the random pore model (RPM) to estimate the intrinsic rate parameters for the carbonation reaction and develops a simple model to calculate particle conversion with time as a function of the number of cycles, partial pressure of CO{sub 2}, and temperature. This version of the RPM model integrates knowledge obtained in earlier works on intrinsic carbonation rates, critical product layer thickness, and pore structure evolution in highly cycled particles.

  7. Characteristics of 14C and 13C of carbonate aerosols in dust storm events in China

    NASA Astrophysics Data System (ADS)

    Chen, Bing; Jie, Dongmei; Shi, Meinan; Gao, Pan; Shen, Zhenxing; Uchida, Masao; Zhou, Liping; Liu, Kexin; Hu, Ke; Kitagawa, Hiroyuki

    2015-10-01

    In contrast with its decrease in western China deserts, the dust storm event in eastern China, Korea, and Japan shows an increase in frequency. Although the drylands in northeastern China have been recognized as an important dust source, the relative contributions of dust transport from the drylands and deserts are inconclusive, thus the quantification of dust storm sources in downwind area remains a challenge. We measured the 14C and 13C contents in carbonates of dust samples from six sites in China, which were collected for the duration of dust storm events in drylands, deserts, and urban areas. The δ13C of the dryland dust samples considerably varied in a range of - 9.7 to - 5.0‰, which partly overlapped the desert dust carbonate δ13C ranges. The 14C content of the dryland dust carbonates showed a narrow range of 60.9 ± 4.0 (as an average and 1 SD of five samples) percent modern carbon (pMC), indicating the enrichment of modern carbonate. Dust samples in desert regions contained relatively aged carbonates with the depleting 14C showing of 28.8 ± 3.3 pMC. After the long-range transport of the western China desert dust plume, the carbonates collected at the southern China remained the depletion of 14C (33.5 ± 5.3 pMC) as in the desert regions. On the other hand, the samples of dust storm events at the urban areas of eastern China showed an enrichment of 14C contents (46.2 ± 5.0 pMC, n = 7), which might be explained by the stronger contribution of modern-carbonate-rich dryland dust.

  8. Brown carbon formation by aqueous-phase carbonyl compound reactions with amines and ammonium sulfate.

    PubMed

    Powelson, Michelle H; Espelien, Brenna M; Hawkins, Lelia N; Galloway, Melissa M; De Haan, David O

    2014-01-21

    Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV-vis and fluorescence spectroscopy monitoring. Glycolaldehyde-glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Å(abs)) of 2 to 11, overlapping the Å(abs) range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl-AS-amine reactions of ≤ 10% of global light absorption by brown carbon. PMID:24351110

  9. The role of carbon dioxide in free radical reactions of the organism.

    PubMed

    Veselá, A; Wilhelm, J

    2002-01-01

    Carbon dioxide interacts both with reactive nitrogen species and reactive oxygen species. In the presence of superoxide, NO reacts to form peroxynitrite that reacts with CO2 to give nitrosoperoxycarbonate. This compound rearranges to nitrocarbonate which is prone to further reactions. In an aqueous environment, the most probable reaction is hydrolysis producing carbonate and nitrate. Thus the net effect of CO2 is scavenging of peroxynitrite and prevention of nitration and oxidative damage. However, in a nonpolar environment of membranes, nitrocarbonate undergoes other reactions leading to nitration of proteins and oxidative damage. When NO reacts with oxygen in the absence of superoxide, a nitrating species N2O3 is formed. CO2 interacts with N2O3 to produce a nitrosyl compound that, under physiological pH, is hydrolyzed to nitrous and carbonic acid. In this way, CO2 also prevents nitration reactions. CO2 protects superoxide dismutase against oxidative damage induced by hydrogen peroxide. However, in this reaction carbonate radicals are formed which can propagate the oxidative damage. It was found that hypercapnia in vivo protects against the damaging effects of ischemia or hypoxia. Several mechanisms have been suggested to explain the protective role of CO2 in vivo. The most significant appears to be stabilization of the iron-transferrin complex which prevents the involvement of iron ions in the initiation of free radical reactions. PMID:12449430

  10. Evaluation of 1,3-butadiene dimerization and secondary reactions in the presence and absence of oxygen.

    PubMed

    Aldeeb, A A; Rogers, W J; Mannan, M S

    2004-11-11

    Thermal stability evaluation of exothermic chemical reactions is of great importance to the safer design and operation of chemical processes. Dominant reaction stoichiometries and their thermochemistry parameters are key elements in the evaluation process. Identification of significant reaction pathways under possible process conditions will lead to an understanding of the overall thermodynamic and kinetic behavior. The kinetics of 1,3-butadiene (BD) is an excellent example of conjugated dienes that undergo addition reactions. At elevated temperatures, 1,3-butadiene monomers can dimerize exothermally, and as temperature increases, secondary exothermic reactions will take place. The very high temperature and pressure rates that these reactions can attain may lead to a reaction runaway or even a thermal explosion. BD is a vapor at ambient conditions, usually stored as a pressurized liquid, and is a carcinogen, so the experimental evaluation is potentially difficult and hazardous. In this paper, the thermal stability of BD is evaluated. Dimerization and other secondary reactions are investigated by experimental thermal analysis using an automatic pressure adiabatic calorimeter (APTAC), by theoretical computational quantum chemistry methods, and empirical thermodynamic-energy correlations. A theoretical approach is conducted to predict some of the BD reaction behavior. Results are compared to other literature data obtained using different experimental methods. PMID:15518964

  11. Reaction of folic acid with single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Ellison, Mark D.; Chorney, Matthew

    2016-10-01

    The oxygen-containing functional groups on oxidized single-walled carbon nanotubes (SWNTs) are used to covalently bond folic acid molecules to the SWNTs. Infrared spectroscopy confirms intact molecular binding to the SWNTs through the formation of an amide bond between a carboxylic acid group on an SWNT and the primary amine group of folic acid. The folic acid-functionalized SWNTs are readily dispersible in water and phosphate-buffered saline, and the dispersions are stable for a period of two weeks or longer. These folic acid-functionalized SWNTs offer potential for use as biocompatible SWNTs.

  12. Determination of the δ13C of dissolved inorganic carbon in water; RSIL lab code 1710

    USGS Publications Warehouse

    Singleton, Glenda L.; Revesz, Kinga; Coplen, Tyler B.

    2012-01-01

    The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1710 is to present a method to determine the δ13C of dissolved inorganic carbon (DIC) of water. The DIC of water is precipitated using ammoniacal strontium chloride (SrCl2) solution to form strontium carbonate (SrCO3). The δ13C is analyzed by reacting SrCO3 with 100-percent phosphoric acid (H3PO4) to liberate carbon quantitatively as carbon dioxide (CO2), which is collected, purified by vacuum sublimation, and analyzed by dual inlet isotope-ratio mass spectrometry (DI-IRMS). The DI-IRMS is a DuPont double-focusing mass spectrometer. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other measurable ion beams are collected in the front collector. By changing the ion-accelerating voltage under computer control, the instrument is capable of measuring mass/charge (m/z) 45 or 46 in the rear collector and m/z 44 and 46 or 44 and 45, respectively, in the front collector. The ion beams from these m/z values are as follows: m/z 44 = CO2 = 12C16O16O, m/z 45 = CO2 = 13C16O16O primarily, and m/z 46 = CO2 = 12C16O18O primarily. The data acquisition and control software calculates δ13C values.

  13. Carbon fluxes to the soil in a mature temperate forest assessed by 13C isotope tracing.

    PubMed

    Steinmann, Katharina; Siegwolf, Rolf T W; Saurer, Matthias; Körner, Christian

    2004-11-01

    Photosynthetic carbon uptake and respiratory C release from soil are major components of the global carbon balance. The use of 13C depleted CO2)(delta13C = -30 per thousand) in a free air CO2 enrichment experiment in a mature deciduous forest permitted us to trace the carbon transfer from tree crowns to the rhizosphere of 100-120 years old trees. During the first season of CO2 enrichment the CO2 released from soil originated substantially from concurrent assimilation. The small contribution of recent carbon in fine roots suggests a much slower fine root turnover than is often assumed. 13C abundance in soil air correlated best with temperature data taken from 4 to 10 days before air sampling time and is thus rapidly available for root and rhizosphere respiration. The spatial variability of delta13C in soil air showed relationships to above ground tree types such as conifers versus broad-leaved trees. Considering the complexity and strong overlap of roots from different individuals in a forest, this finding opens an exciting new possibility of associating respiration with different species. What might be seen as signal noise does in fact contain valuable information on the spatial heterogeneity of tree-soil interaction.

  14. Carbonation of steel slag for CO{sub 2} sequestration: leaching of products and reaction mechanisms

    SciTech Connect

    Wouter J.J. Huijgen; Rob N.J. Comans

    2006-04-15

    Carbonation of industrial alkaline residues can be used as a CO{sub 2} sequestration technology to reduce carbon dioxide emissions. In this study, steel slag samples were carbonated to a varying extent. Leaching experiments and geochemical modeling were used to identify solubility-controlling processes of major and trace elements, both with regard to carbonation mechanisms and the environmental properties of the (carbonated) steel slag. Carbonation was shown to reduce the leaching of alkaline earth metals (except Mg) by conversion of Ca-phases, such as portlandite, ettringite, and Ca-(Fe)-silicates into calcite, possibly containing traces of Ba and Sr. The leaching of vanadium increased substantially upon carbonation, probably due to the dissolution of a Ca-vanadate. The reactive surface area of Al- and Fe-(hydr)oxides increased with the carbonation degree, which tends to reduce the leaching of sorption-controlled trace elements. Sorption on Mn-(hydr)oxides was found to be required to adequately model the leaching of divalent cations, but was not influenced by carbonation. Consideration of these three distinct reactive surfaces and possible (surface) precipitation reactions resulted in adequate modeling predictions of oxyanion and trace metal leaching from (carbonated) steel slag. Hence, these surfaces exert a major influence on the environmental properties of both fresh and carbonated steel slag. 24 refs., 1 fig., 2 tabs.

  15. Carbonation of steel slag for CO2 sequestration: leaching of products and reaction mechanisms.

    PubMed

    Huijgen, Wouter J J; Comans, Rob N J

    2006-04-15

    Carbonation of industrial alkaline residues can be used as a CO2 sequestration technology to reduce carbon dioxide emissions. In this study, steel slag samples were carbonated to a varying extent. Leaching experiments and geochemical modeling were used to identify solubility-controlling processes of major and trace elements, both with regard to carbonation mechanisms and the environmental properties of the (carbonated) steel slag. Carbonation was shown to reduce the leaching of alkaline earth metals (except Mg) by conversion of Ca-phases, such as portlandite, ettringite, and Ca-(Fe)-silicates into calcite, possibly containing traces of Ba and Sr. The leaching of vanadium increased substantially upon carbonation, probably due to the dissolution of a Ca-vanadate. The reactive surface area of Al- and Fe-(hydr)oxides increased with the carbonation degree, which tends to reduce the leaching of sorption-controlled trace elements. Sorption on Mn- (hydr)oxides was found to be required to adequately model the leaching of divalent cations, but was not influenced by carbonation. Consideration of these three distinct reactive surfaces and possible (surface) precipitation reactions resulted in adequate modeling predictions of oxyanion and trace metal leaching from (carbonated) steel slag. Hence, these surfaces exert a major influence on the environmental properties of both fresh and carbonated steel slag.

  16. The Measurement of Pion Double Charge Exchange on CARBON-13, CARBON-14, MAGNESIUM-26 and IRON-56.

    NASA Astrophysics Data System (ADS)

    Seidl, Peter Anthony

    Cross sections for the ('13,14)C,('26)Mg,('56)Fe((pi)('+),(pi)(' -))('13,14)O,('26)Si,('56)Ni reactions were measured with the Energetic Pion Channel and Spectrometer at the Clinton P. Anderson Meson Physics Facility for 120 (LESSTHEQ) T(,(pi)) (LESSTHEQ) 292 MeV and 0 (LESSTHEQ) (theta) (LESSTHEQ) 50. The double isobaric analog states (DIAS) were of primary interest, and in addition, cross sections for transitions to ('14)O(0('+), 5.92 MeV), ('14)O(2('+), 7.77 MeV), ('56)Ni(gs), ('13)O(gs), and ('13)O(4.21 MeV) are presented. The ('13)O(4.21 MeV) state is postulated to have J('(pi)) = 1/2('-). The data are compared to previously measured double-charge -exchange cross sections on other nuclei, and the systematics of double charge exchange on T (GREATERTHEQ) 1 target nuclei leading to DIAS are studied. Near the (DELTA)(,33) resonance, cross section for the DIAS transitions are in disagreement with calculations in which the reaction is treated as sequential charge exchange through the free pion-nucleon amplitude, while for T(,(pi)) > 200 MeV the anomalous features of the 164 MeV data are not apparent. This is evidence for significant higher order contributions to the double-charge -exchange amplitude near the resonance energy. Two theoretical approaches that include two nucleon processes are applied to the DIAS data.

  17. Protein carbon-13 spin systems by a single two-dimensional nuclear magnetic resonance experiment

    SciTech Connect

    Oh, B.H.; Westler, W.M.; Darba, P.; Markley, J.L.

    1988-05-13

    By applying a two-dimensional double-quantum carbon-13 nuclear magnetic resonance experiment to a protein uniformly enriched to 26% carbon-13, networks of directly bonded carbon atoms were identified by virtue of their one-bond spin-spin couplings and were classified by amino acid type according to their particular single- and double-quantum chemical shift patterns. Spin systems of 75 of the 98 amino acid residues in a protein, oxidized Anabaena 7120 ferredoxin (molecular weight 11,000), were identified by this approach, which represents a key step in an improved methodology for assigning protein nuclear magnetic resonance spectra. Missing spin systems corresponded primarily to residues located adjacent to the paramagnetic iron-sulfur cluster. 25 references, 2 figures.

  18. Inhomogeneity of C13 isotope distribution in isotope engineered carbon nanotubes: Experiment and theory

    NASA Astrophysics Data System (ADS)

    Zólyomi, V.; Simon, F.; Rusznyák, Á.; Pfeiffer, R.; Peterlik, H.; Kuzmany, H.; Kürti, J.

    2007-05-01

    Vibrational modes of C13 isotope enriched single-walled carbon nanotubes are inhomogeneously broadened due to the random distribution of isotopes. We study this effect on the radial breathing mode theoretically using density-functional theory within the local-density approximation and compare the result with experiments on inner tubes in double-walled carbon nanotubes grown from C13 -enriched fullerenes. Increased inhomogeneity was achieved by growing inner tubes from a mixture of enriched and natural fullerenes, which is explained by the calculations. This shows the absence of carbon diffusion along the tube axis during inner tube growth, supporting the theory of inner tube growth by Stone-Wales transformations from interconnected fullerenes.

  19. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    DOEpatents

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  20. 13C MAS NMR evidence for a homogeneously ordered environment of tyrosine M210 in reaction centres of Rhodobacter sphaeroides

    NASA Astrophysics Data System (ADS)

    Shochat, S.; Gast, P.; Hoff, A. J.; Boender, G. J.; van Leeuwen, S.; van Liemt, W. B. S.; Vijgenboom, E.; Raap, J.; Lugtenburg, J.; de Groot, H. J. M.

    1995-01-01

    The initial electron transfer time in the photosynthetic reaction centre of Rhodobacter sphaeroides is highly sensitive to the replacement of tyrosine M210 by a tryptophan residue. Low-temperature magic angle spinning 13C NMR is used to study Rhodobacter sphaeroides 2.4.1 (M)Y210W mutant reaction centres that are labelled with [4'- 13C]tyrosine. The response of (M)Y210 in R26 is assigned unambiguously to the most upfield narrow signal (linewidth 34 Hz) at σi = 152.2 ppm, in the region where non-hydrogen bonded tyrosine signals are expected. From the comparison with the signal of labelled R26 it follows that the chemical environment of the (M)Y210 label is unique. The Y(M)210 is in a structurally and electrostatically homogeneous region on the sensitivity scale of the MAS NMR technique. The environment of M210 is structurally stable and the observation of a narrow line shows that the (M)Y210 side chain can be considered static with respect to rotational diffusion on time scales as long as 10 -2s. The narrow signals from the remaining labels in the protein interior for the 2.4.1 (M)Y210W mutant are remarkably similar to those observed for R26. Using a commonly accepted ratio of 150 ppm shift per positive charge equivalent for aromatic carbons, the chemical shift differences between mutant and R26 translate into small variations of the order of 10 -3 electronic equivalents of charge polarization. Also the linewidths are similar, except for a narrow response at σi = 156.4 ppm that sharpens slightly in the (M)Y210W mutant. Thus, the influence of the (M)Y210W mutation on the global electrostatic properties and structure of the protein, as probed by the tyrosine labels, is minimal. This strongly argues against an explanation of slow and non-exponential electron transfer kinetics in the (M)Y210W RC in terms of loss of structural integrity upon mutation. In contrast, the NMR results strongly support current opinions that (M)Y210 contributes to the fine-tuning of the

  1. On the use of phloem sap δ13C to estimate canopy carbon discrimination

    NASA Astrophysics Data System (ADS)

    Rascher, Katherine; Máguas, Cristina; Werner, Christiane

    2010-05-01

    Although the carbon stable isotope composition (d13C) of bulk leaf material is a good integrative parameter of photosynthetic discrimination and can be used as a reliable ecological index of plant functioning; it is not a good tracer of short-term changes in photosynthetic discrimination. In contrast, d13C of phloem sap is potentially useful as an indicator of short-term changes in canopy photosynthetic discrimination. However, recent research indicates that d13C signatures may be substantially altered by metabolic processes downstream of initial leaf-level carbon fixation (e.g. post-photosynthetic fractionation). Accordingly, before phloem sap d13C can be used as a proxy for canopy level carbon discrimination an understanding of factors influencing the degree and magnitude of post-photosynthetic fractionation and how these vary between species is of paramount importance. In this study, we measured the d13C signature along the basipetal transport pathway in two co-occurring tree species in the field - an understory invasive exotic legume, Acacia longifolia, and a native pine, Pinus pinaster. We measured d13C of bulk leaf and leaf water soluble organic matter (WSOM), phloem sap sampled at two points along the plant axis and leaf and root dark respiration. In general, species differences in photosynthetic discrimination resulted in more enriched d13C values in the water-conserving P. pinaster relative to the water-spending A. longifolia. Post-photosynthetic fractionation led to differences in d13C of carbon pools along the plant axis with progressively more depleted d13C from the canopy to the trunk (~6.5 per mil depletion in A. longifolia and ~0.8per mil depletion in P. pinaster). Leaf and root respiration, d13C, were consistently enriched relative to putative substrates. We hypothesize that the pronounced enrichment of leaf respired CO2 relative to leaf WSOM may have left behind relatively depleted carbon to be loaded into the phloem resulting in d13C depletion

  2. Neoproterozoic diamictite-cap carbonate succession and δ13C chemostratigraphy from eastern Sonora, Mexico

    USGS Publications Warehouse

    Corsetti, Frank A.; Stewart, John H.; Hagadorn, James W.

    2007-01-01

    Despite the occurrence of Neoproterozoic strata throughout the southwestern U.S. and Sonora, Mexico, glacial units overlain by enigmatic cap carbonates have not been well-documented south of Death Valley, California. Here, we describe in detail the first glaciogenic diamictite and cap carbonate succession from Mexico, found in the Cerro Las Bolas Group. The diamictite is exposed near Sahuaripa, Sonora, and is overlain by a 5 m thick very finely-laminated dolostone with soft sediment folds. Carbon isotopic chemostratigraphy of the finely-laminated dolostone reveals a negative δ13C anomaly (down to − 3.2‰ PDB) characteristic of cap carbonates worldwide. Carbon isotopic values rise to + 10‰ across ∼ 400 m of section in overlying carbonates of the Mina el Mezquite and Monteso Formations. The pattern recorded here is mostly characteristic of post-Sturtian (ca. ≤ 700 Ma), but pre-Marinoan (ca. ≥ 635 Ma) time. However, the Cerro Las Bolas Group shares ambiguity common to most Neoproterozoic successions: it lacks useful radiometric age constraints and biostratigraphically useful fossils, and its δ13C signature is oscillatory and therefore somewhat equivocal.

  3. Tracing solid waste leachate in groundwater using δ13 C from dissolved inorganic carbon.

    PubMed

    Haarstad, Ketil; Mæhlum, Trond

    2013-01-01

    Tracers can be used to monitor emissions of leachate from landfills in order to detect hydrological pathways and to evaluate environmental pollution. We investigated the stable carbon isotope ratio (δ(13)C-Σ CO (2)) in dissolved inorganic carbon and tritium ((3)H) in water, in addition to the tracers of pollution commonly found in relatively high concentrations in leachate, such as chloride (Cl), organic matter (COD), nitrogen (total and NH(4)-N), iron (Fe), electrical conductivity (EC) and pH. The sampling was performed at seven landfills in the south-eastern part of Norway during a period of 5 years. The objective was to evaluate the potential for tracing leachate in the environment with emphasis on groundwater pollution. By measuring the δ(13)C-Σ CO (2) in leachates, groundwaters and surface waters, the influence of leachate can be identified. The value of δ(13)C-Σ CO (2) varied from-5.5 to 25.9 ‰ in leachate, from-25.4 to 14.7 ‰ in groundwater and from-19.7 to-13.1 ‰ in creeks. A comparison of the carbon isotope ratio with COD, EC and the concentrations of total and NH (4)-N, Cl and Fe showed that δ(13)C-Σ CO (2) is a good tracer for leachate due to higher sensitivity compared to other parameters. The mean concentrations of all the studied parameters were higher in the leachate samples; however, only the carbon isotope ratio showed significant differences between all the groups with strong and middle pollution and samples with low pollution, showing that it can be used as a convenient tracer for leachate in groundwater and surface water. The carbon isotope ratio showed strong correlation between nitrogen, EC and bicarbonate, but not with pH. Tritium was only sporadically found in measureable concentrations and is not considered as a suitable tracer at the sampled locations.

  4. Synthesis of carbon-11, fluorine-18, and nitrogen-13 labeled radiotracers for biomedical applications

    SciTech Connect

    Fowler, J.S.; Wolf, A.P.

    1981-01-01

    A number of reviews, many of them recent, have appeared on various aspects of /sup 11/C, /sup 18/F and /sup 13/N-labeled radiotracers. This monograph treats the topic principally from the standpoint of synthetic organic chemistry while keeping in perspective the necessity of integrating the organic chemistry with the design and ultimate application of the radiotracer. Where possible, recent examples from the literature of organic synthesis are introduced to suggest potentially new routes which may be applied to problems in labeling organic molecules with the short-lived positron emitters, carbon-11, fluorine-18, and nitrogen-13. The literature survey of carbon-11, fluorine-18 and nitrogen-13 labeled compounds presented are of particular value to scientists working in this field. Two appendices are also included to provide supplementary general references. A subject index concludes this volume.

  5. In Situ Evaluation of Water-Rock Reactions during Carbon Dioxide Injection in Basaltic and Metasedimentary Rocks

    NASA Astrophysics Data System (ADS)

    Matter, J. M.; Assayag, N.; Goldberg, D.; Takahashi, T.

    2006-12-01

    Large differences between laboratory and field derived mineral reaction rates underscore the importance of evaluating mineral-fluid reactions under in situ conditions in a natural environment. This study investigates the extent of in situ water-rock reactions in basaltic and metasedimentary rocks (rich in Ca, Mg silicates) after the injection of CO2 enriched water, with the objective of providing information pertinent to permanent storage of anthropogenic CO2 in geologic reservoirs. CO2 injections were conducted using a single-well push-pull testing strategy. CO2 saturated water (pH 3.5) was injected into a hydraulically isolated and permeable aquifer in a 300-m experimental borehole. Water samples were retrieved after the CO2 injection. Mass transfer terms for Ca, Mg, Na, and Si were determined by using the measured ion concentrations. Using the mass balance, the weeks-long incubation time of the injected solution, and geometric estimates of the reactive surface area of the host rocks, in situ bulk rock dissolution rates of aquifer material were estimated. In addition, δ13C data coupled with total CO2 concentration were used as a tracer to quantitatively evaluate processes such as carbonate dissolution and precipitation, oxidation of organic matter and biological activity within the aquifer. Results show that the injected CO2 was neutralized within several days by two processes; mixing with aquifer water, and rock-water reactions. Calculated bulk rock dissolution rates decrease with increasing pH. The pH dependence of the dissolution rate for Ca is twice as large as for Mg, strongly favoring Ca release and possibly suggesting an additional source of Ca besides silicate minerals. Analyses of δ13C on water and rock samples confirm dissolution of calcium carbonates within the aquifer.

  6. Reactions involving the heterolytic cleavage of carbon-element σ-bonds by Grignard reagents

    NASA Astrophysics Data System (ADS)

    Polivin, Yurii N.; Karakhanov, Robert A.; Postnov, Victor N.

    1990-03-01

    The reactions involving the heterolysis of the C-O, C-C, C-N, C-S, C-Cl, etc. bonds by organomagnesium compounds are examined and the nature of this interesting phenomenon is analysed. On the basis of the analysis of the characteristic features of the cleavage under discussion, it is shown that the heterolysis of the carbon-element bond is, firstly, a general reaction for all classes of organic compounds (provided that two conditions are observed: the substrate molecule must fragment into two stable species — a carbonium ion and an anion — and the strength of the Lewis acid properties should be adequate for the occurrence of the above reaction) and, secondly, the heterolysis of the carbon-element bond is one of the independent pathways in the reactions of the Grignard reagents. The bibliography includes 158 references.

  7. Graphitic-Carbon Layers on Oxides: Toward Stable Heterogeneous Catalysts for Biomass Conversion Reactions.

    PubMed

    Xiong, Haifeng; Schwartz, Thomas J; Andersen, Nalin I; Dumesic, James A; Datye, Abhaya K

    2015-06-26

    Conversion of biomass-derived molecules involves catalytic reactions under harsh conditions in the liquid phase (e.g., temperatures of 250 °C and possibly under either acidic or basic conditions). Conventional oxide-supported catalysts undergo pore structure collapse and surface area reduction leading to deactivation under these conditions. Here we demonstrate an approach to deposit graphitic carbon to protect the oxide surface. The heterogeneous catalysts supported on the graphitic carbon/oxide composite exhibit excellent stability (even under acidic conditions) for biomass conversion reactions. PMID:25973732

  8. Graphitic-Carbon Layers on Oxides: Toward Stable Heterogeneous Catalysts for Biomass Conversion Reactions.

    PubMed

    Xiong, Haifeng; Schwartz, Thomas J; Andersen, Nalin I; Dumesic, James A; Datye, Abhaya K

    2015-06-26

    Conversion of biomass-derived molecules involves catalytic reactions under harsh conditions in the liquid phase (e.g., temperatures of 250 °C and possibly under either acidic or basic conditions). Conventional oxide-supported catalysts undergo pore structure collapse and surface area reduction leading to deactivation under these conditions. Here we demonstrate an approach to deposit graphitic carbon to protect the oxide surface. The heterogeneous catalysts supported on the graphitic carbon/oxide composite exhibit excellent stability (even under acidic conditions) for biomass conversion reactions.

  9. Apparent equilibrium constants and standard transformed Gibbs energies of biochemical reactions involving carbon dioxide.

    PubMed

    Alberty, R A

    1997-12-01

    When carbon dioxide is produced in a biochemical reaction, the expression for the apparent equilibrium constant K' can be written in terms of the partial pressure of carbon dioxide in the gas phase or the total concentration of species containing CO2 in the aqueous phase, referred to here as [TotCO2]. The values of these two apparent equilibrium constants are different because they correspond to different ways of writing the biochemical equations. Their dependencies on pH and ionic strength are also different. The ratio of these two apparent equilibrium constants is equal to the apparent Henry's law constant K'H. This article provides derivations of equations for the calculation of the standard transformed Gibbs energies of formation of TotCO2 and values of the apparent Henry's law constant at various pH levels and ionic strengths. These equations involve the four equilibrium constants interconnecting the five species [CO2(g), CO2(aq), H2CO3, HCO3-, and CO3(2-)] of carbon dioxide. In the literature there are many errors in the treatment of equilibrium data on biochemical reactions involving carbon dioxide, and so several examples are discussed here, including calculation of standard transformed Gibbs energies of formation of reactants. This approach also applies to net reactions, and the net reaction for the oxidation of glucose to carbon dioxide and water is discussed.

  10. The Reaction of Carbonates in Contact with Superheated Silicate Melts: New Insights from MEMIN Laser Melting Experiments

    NASA Astrophysics Data System (ADS)

    Hamann, C.; Hecht, L.; Schäffer, S.; Deutsch, A.; Lexow, B.

    2016-08-01

    The reaction of carbonates in contact with silicate impact melts is discussed quite controversially in the impact community. Here, we discuss four MEMIN laser melting experiments involving carbonates in contact with superheated silicate melts.

  11. Antihydrophobic cosolvent effects for alkylation reactions in water solution, particularly oxygen versus carbon alkylations of phenoxide ions.

    PubMed

    Breslow, Ronald; Groves, Kevin; Mayer, M Uljana

    2002-04-10

    Antihydrophobic cosolvents such as ethanol increase the solubility of hydrophobic molecules in water, and they also affect the rates of reactions involving hydrophobic surfaces. In simple reactions of hydrocarbons, such as the Diels-Alder dimerization of 1,3-cyclopentadiene, the rate and solubility data directly reflect the geometry of the transition state, in which some hydrophobic surface becomes hidden. In reactions involving polar groups, such as alkylations of phenoxide ions or S(N)1 ionizations of alkyl halides, cosolvents in water can have other effects as well. However, solvation of hydrophobic surfaces is still important. By the use of structure-reactivity relationships, and comparing the effects of ethanol and DMSO as solvents, it has been possible to sort out these effects. The conclusions are reinforced by an ab initio computer model for hydrophobic solvation. The result is a sensible transition state for phenoxide ion as a nucleophile, using its oxygen n electrons to avoid loss of conjugation. The geometry of alkylation of aniline is very different, involving packing (stacking) of the aniline ring onto the phenyl ring of a benzyl group in the benzylation reaction. The alkylation of phenoxide ions by benzylic chlorides can occur both at the phenoxide oxygen and on ortho and para positions of the ring. Carbon alkylation occurs in water, but not in nonpolar organic solvents, and it is observed only when the phenoxide has at least one methyl substituent ortho, meta, or para. The effects of phenol substituents and of antihydrophobic cosolvents on the rates of the competing alkylation processes indicate that in water the carbon alkylation involves a transition state with hydrophobic packing of the benzyl group onto the phenol ring. The results also support our conclusion that oxygen alkylation uses the n electrons of the phenoxide oxygen as the nucleophile and does not have hydrophobic overlap in the transition state. The mechanisms and explanations for

  12. The Prevalence of Carbon-13 in Respiratory Carbon Dioxide As an Indicator of the Type of Endogenous Substrate

    PubMed Central

    Jacobson, Bruce S.; Smith, Bruce N.; Epstein, Samuel; Laties, George G.

    1970-01-01

    Isotope discrimination is a common feature of biosynthesis in nature, with the result that different classes of carbon compounds frequently display different 13C/12C ratios. The 13C/12C ratio of lipid in potato tuber tissue is considerably lower than that for starch or protein. We have collected respiratory CO2 from potato discs in successive periods through 24 hr from the time of cutting—an interval in which the respiration rate rises 3–5-fold. The 13C/12C ratio of the evolved CO2 was determined for each period, and compared with the 13C/12C ratios of the major tissue metabolites. In the first hours the carbon isotope ratio of the CO2 matches that of lipid. With time, the ratio approaches that typical of starch or protein. An estimation has been made of the contribution of lipid and carbohydrate to the total respiration at each juncture. In connection with additional observations, it was deduced that the basal, or initial, respiration represents lipid metabolism—possibly the α-oxidation of long chain fatty acids—while the developed repiration represents conventional tricarboxylic acid cycle oxidation of the products of carbohydrate glycolysis. The true isotopic composition of the respiratory CO2 may be obscured by fractionation attending the refixation of CO2 during respiration, and by CO2 arising from dissolved CO2 and bicarbonate preexisting in the tuber. Means are described for coping with both pitfalls. PMID:5415043

  13. Al13@Pt42 Core-Shell Cluster for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Xiao, B. B.; Zhu, Y. F.; Lang, X. Y.; Wen, Z.; Jiang, Q.

    2014-06-01

    To increase Pt utilization for oxygen reduction reaction (ORR) in fuel cells, reducing particle sizes of Pt is a valid way. However, poisoning or surface oxidation limits the smallest size of Pt particles at 2.6 nm with a low utility of 20%. Here, using density functional theory calculations, we develop a core-shell Al13@Pt42 cluster as a catalyst for ORR. Benefit from alloying with Al in this cluster, the covalent Pt-Al bonding effectively activates the Pt atoms at the edge sites, enabling its high utility up to 70%. Valuably, the adsorption energy of O is located at the optimal range with 0.0-0.4 eV weaker than Pt(111), while OH-poisoning does not observed. Moreover, ORR comes from O2 dissociation mechanism where the rate-limiting step is located at OH formation from O and H with a barrier of 0.59 eV, comparable with 0.50 eV of OH formation from O and H2O on Pt(111).

  14. Al13@Pt42 core-shell cluster for oxygen reduction reaction.

    PubMed

    Xiao, B B; Zhu, Y F; Lang, X Y; Wen, Z; Jiang, Q

    2014-01-01

    To increase Pt utilization for oxygen reduction reaction (ORR) in fuel cells, reducing particle sizes of Pt is a valid way. However, poisoning or surface oxidation limits the smallest size of Pt particles at 2.6 nm with a low utility of 20%. Here, using density functional theory calculations, we develop a core-shell Al13@Pt42 cluster as a catalyst for ORR. Benefit from alloying with Al in this cluster, the covalent Pt-Al bonding effectively activates the Pt atoms at the edge sites, enabling its high utility up to 70%. Valuably, the adsorption energy of O is located at the optimal range with 0.0-0.4 eV weaker than Pt(111), while OH-poisoning does not observed. Moreover, ORR comes from O2 dissociation mechanism where the rate-limiting step is located at OH formation from O and H with a barrier of 0.59 eV, comparable with 0.50 eV of OH formation from O and H2O on Pt(111). PMID:24902886

  15. Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen

    DOEpatents

    Werpy, Todd A [West Richland, WA; Zacher, Alan H [Kennewick, WA

    2002-11-12

    Methods and compositions for reactions of hydrogen over a Re-containing catalyst with compositions containing a 5-carbon sugar, sugar alcohol, or lactic acid are described. It has been surprisingly discovered that reaction with hydrogen over a Re-containing multimetallic catalyst resulted in superior conversion and selectivity to desired products such as propylene glycol. A process for the synthesis of PG from lactate or lactic acid is also described.

  16. Hydrogenolysis Of 5-Carbon Sugars, Sugar Alcohols And Compositions For Reactions Involving Hydrogen

    DOEpatents

    Werpy, Todd A.; Frye, Jr., John G.; Zacher, Alan H.; Miller, Dennis J.

    2004-01-13

    Methods and compositions for reactions of hydrogen over a Re-containing catalyst with compositions containing a 5-carbon sugar, sugar alcohol, or lactic acid are described. It has been surprisingly discovered that reaction with hydrogen over a Re-containing multimetallic catalyst resulted in superior conversion and selectivity to desired products such as propylene glycol. A process for the synthesis of PG from lactate or lactic acid is also described.

  17. Oxygen electrode reaction in molten carbonate fuel cells. Final report, September 15, 1987--September 14, 1990

    SciTech Connect

    Appleby, A.J.; White, R.E.

    1992-07-07

    Molten carbonate fuel cell system is a leading candidate for the utility power generation because of its high efficiency for fuel to AC power conversion, capability for an internal reforming, and a very low environmental impact. However, the performance of the molten carbonate fuel cell is limited by the oxygen reduction reaction and the cell life time is limited by the stability of the cathode material. An elucidation of oxygen reduction reaction in molten alkali carbonate is essential because overpotential losses in the molten carbonate fuel cell are considerably greater at the oxygen cathode than at the fuel anode. Oxygen reduction on a fully-immersed gold electrode in a lithium carbonate melt was investigated by electrochemical impedance spectroscopy and cyclic voltammetry to determine electrode kinetic and mass transfer parameters. The dependences of electrode kinetic and mass transfer parameters on gas composition and temperature were examined to determine the reaction orders and the activation energies. The results showed that oxygen reduction in a pure lithium carbonate melt occurs via the peroxide mechanism. A mass transfer parameter, D{sub O}{sup 1/2}C{sub O}, estimated by the cyclic voltammetry concurred with that calculated by the EIS technique. The temperature dependence of the exchange current density and the product D{sub O}{sup 1/2}C{sub O} were examined and the apparent activation energies were determined to be about 122 and 175 kJ/ mol, respectively.

  18. Effect of reaction temperature on structure and fluorescence properties of nitrogen-doped carbon dots

    NASA Astrophysics Data System (ADS)

    Zhang, Yi; Wang, Yaling; Feng, Xiaoting; Zhang, Feng; Yang, Yongzhen; Liu, Xuguang

    2016-11-01

    To investigate the effect of reaction temperature and nitrogen doping on the structure and fluorescence properties of carbon dots (CDs), six kinds of nitrogen-doped CDs (NCDs) were synthesized at reaction temperatures of 120, 140, 160, 180, 200 and 220 °C, separately, by using citric acid as carbon source and ammonia solution as nitrogen source. Nitrogen-free CDs (N-free CDs-180) was also prepared at 180 °C by using citric acid as the only carbon source for comparison. Results show that reaction temperature has obvious effect on carbonization degree, quantum yield (QY), ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) spectra but less effect on functional groups, nitrogen doping degree and fluorescence lifetime of NCDs. Compared with N-free CDs-180, NCDs-180 possesses enchanced QY and longer fluorescence lifetime. Doping nitrogen has obvious effect on UV-vis absorption and PL spectra but less effect on particles sizes and carbonization degree. The formation mechanism of NCDs is explored: QY of NCDs depends largely on the number of fluorescent polymer chains (FPC), the competition between FPC formation on the surface of NCDs and carbon core growth leads to the change in number of FPC, and consequently to the NCDs with highest QY at appropriate hydrothermal temperature.

  19. Reaction Kinetics of CO2 Carbonation with Mg-Rich Minerals

    SciTech Connect

    Kwon, Dr. Soonchul; Fan, Maohong; DaCosta, Dr. Herbert F.M.; Russell, Dr. Armistead; Tsouris, Costas

    2011-01-01

    Due to their low price, wide availability, and stability of the resulting carbonates, Mg-rich minerals are promising materials for carbonating CO{sub 2}. Direct carbonation of CO{sub 2} with Mg-rich minerals reported in this research for the first time could be considerably superior to conventional liquid extraction processes from an energy consumption perspective due to its avoidance of the use of a large amount of water with high specific heat capacity and latent heat of vaporization. Kinetic models of the reactions of the direct CO{sub 2} carbonation with Mg-rich minerals and within simulated flue gas environments are important to the scale-up of reactor designs. Unfortunately, such models have not been made available thus far. This research was initiated to fill that gap. Magnesium silicate (Mg{sub 2}SiO{sub 4}), a representative compound in Mg-rich minerals, was used to study CO{sub 2} carbonation reaction kinetics under given simulated flue gas conditions. It was found that the chosen sorbent deactivation model fits well the experimental data collected under given conditions. A reaction order of 1 with respect to CO{sub 2} is obtained from experimental data. The Arrhenius form of CO{sub 2} carbonation with Mg{sub 2}SiO{sub 4} is established based on changes in the rate constants of the chosen deactivation model as a function of temperature.

  20. Selenium-ligated palladium(II) complexes as highly active catalysts for carbon-carbon coupling reactions: the Heck reaction.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Zheng, Chong

    2004-08-19

    Three selenium-ligated Pd(II) complexes were readily synthesized and shown to be extremely active catalysts for the Heck reaction of various aryl bromides, including deactivated and heterocyclic ones. The catalytic activity of the selenide-based Pd(II) complexes not only rivals but vastly outperforms that of the corresponding phosphorus and sulfur analogues. Practical advantages of the selenium-based catalysts include their straightforward synthesis and high activity in the absence of any additives as well as the enhanced stability of the selenide ligands toward air oxidation. PMID:15330667

  1. Selenium-ligated palladium(II) complexes as highly active catalysts for carbon-carbon coupling reactions: the Heck reaction.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Zheng, Chong

    2004-08-19

    Three selenium-ligated Pd(II) complexes were readily synthesized and shown to be extremely active catalysts for the Heck reaction of various aryl bromides, including deactivated and heterocyclic ones. The catalytic activity of the selenide-based Pd(II) complexes not only rivals but vastly outperforms that of the corresponding phosphorus and sulfur analogues. Practical advantages of the selenium-based catalysts include their straightforward synthesis and high activity in the absence of any additives as well as the enhanced stability of the selenide ligands toward air oxidation.

  2. Spherical carbon particles and carbon nanotubes prepared by autogenic reactions : evaluation as anodes in lithium electrochemical cells.

    SciTech Connect

    Pol, V. G.; Thackeray, M. M.

    2011-05-01

    Autogenic reactions, based on the decomposition of one or more precursors at elevated temperatures with self generated pressures can be used to prepare a wide range of materials with interesting structural, morphological and technological properties. Recent reports that spherical carbon particles and carbon nanotubes can be prepared by this technique from waste products, such as used plastic bags, have highlighted this environmentally-attractive approach to synthesize new or modified carbon-based materials. In this paper, we report the synthesis of spherical carbon particles and carbon nanotubes and their evaluation as negative electrodes (anodes) in lithium electrochemical cells. A steady reversible capacity of approximately 240 mAh/g for hundreds of cycles was achieved from both types of carbon, when cycled at a 1C rate between 1.5 V and 5 mV. A reversible capacity of 372 mAh/g, i.e., the theoretical value for graphite, was obtained from the carbon nanotube electrodes by raising the upper voltage limit to 3 V. To increase the graphitic order in the carbon spheres, the particles were heated to 2400 C in an inert atmosphere. This treatment reduced the first cycle irreversible capacity loss of Li/C half cells from 60 to 20%, the spherical carbon electrodes yielding a stable 252 mAh/g discharge capacity for numerous cycles. Structural and morphological information about the parent and cycled carbon electrodes, obtained by powder X-ray diffraction, Raman spectroscopy, high-resolution scanning electron microscopy, and electron dispersive analysis of X-rays is provided.

  3. Spherical Carbon Particles and Carbon Nanotubes Prepared by Autogenic Reactions: Evaluation as Anodes in Lithium Electrochemical Cells

    SciTech Connect

    Pol, Vilas G.; Thackeray, Michael M.

    2010-01-01

    Autogenic reactions, based on the decomposition of one or more precursors at elevated temperatures with self generated pressures can be used to prepare a wide range of materials with interesting structural, morphological and technological properties. Recent reports that spherical carbon particles and carbon nanotubes can be prepared by this technique from waste products, such as used plastic bags, have highlighted this environmentally-attractive approach to synthesize new or modified carbon-based materials. In this paper, we report the synthesis of spherical carbon particles and carbon nanotubes and their evaluation as negative electrodes (anodes) in lithium electrochemical cells. A steady reversible capacity of approximately 240 mAh/g for hundreds of cycles was achieved from both types of carbon, when cycled at a 1C rate between 1.5 V and 5 mV. A reversible capacity of 372 mAh/g, i.e., the theoretical value for graphite, was obtained from the carbon nanotube electrodes by raising the upper voltage limit to 3 V. To increase the graphitic order in the carbon spheres, the particles were heated to 2400 °C in an inert atmosphere. This treatment reduced the first cycle irreversible capacity loss of Li/C half cells from 60 to 20%, the spherical carbon electrodes yielding a stable 252 mAh/g discharge capacity for numerous cycles. Structural and morphological information about the parent and cycled carbon electrodes, obtained by powder X-ray diffraction, Raman spectroscopy, high-resolution scanning electron microscopy, and electron dispersive analysis of X-rays is provided.

  4. Alpha Resonances in {sup 13}C Excited by the {sup 9}Be ({sup 6}Li,d) Reaction

    SciTech Connect

    Rodrigues, M. R. D.; Borello-Lewin, T.; Horodynski-Matsushigue, L. B.; Duarte, J. L. M.; Rodrigues, C. L.; Souza, M. A.; Miyake, H.; Cunsolo, A.; Cappuzzello, F.; Ukita, G. M.

    2010-05-21

    The {sup 9}Be({sup 6}Li,d){sup 13}C reaction was used to investigate alpha resonant states in {sup 13}C up to 13 MeV of excitation. The reaction was measured at a bombarding energy of 25.5 MeV employing the Sao Paulo Pelletron-Enge-Spectrograph facility and the nuclear emulsion detection technique. The resolution of 50 keV allowed for the separation of the resonant contributions to the known 7/2{sup -} at 10.753 MeV and (5/2{sup -}) at 10.818 MeV {sup 13}C states. The alpha resonance seen at the (3alpha+n) threshold was not previously reported. The experimental angular distributions are presented in comparison with DWBA predictions.

  5. A high-precision carbon-13 shift thermometer for the temperature range 100-300 K

    PubMed

    Quast; Heubes; Dunger; Limbach

    1998-10-01

    The first carbon-13 shift thermometer for the temperature range of 100-300 K is based on the very rapid equilibration of a pair of semibullvalene valence tautomers. The temperature dependence of the equilibrium constant is reflected in strongly temperature-dependent shift differences Deltadelta between averaged signals, e.g., d(Deltadelta)/dT = 0.051 ppm K-1 at 300, 0.087 ppm K-1 at 200, and 0. 175 ppm K-1 at 110 K for the quaternary carbon atoms C2 and C6. At 37 temperatures T, which were measured with calibrated platinum resistance thermometers, shift differences Deltadelta were taken from nondecoupled carbon-13 spectra recorded from solutions of 1 in mixtures of chlorodifluoromethane and deuterated dimethyl ether without spinning. The least-squares fit of these Deltadelta vs T data to a polynomial equation of the fourth degree (Eq. [5], r2 = 0. 9999) allows the calculation of temperatures from measured shift differences with a standard deviation of 0.46 K and an estimated error of about 1 K. The heating effects of WALTZ-16 decoupling and the influence of solvents on Deltadelta are investigated. A comparison with existing NMR thermometers demonstrates the superior performance of the new carbon-13 shift thermometer with respect to precision and the accessible temperature range. Copyright 1998 Academic Press.

  6. A High-Precision Carbon-13 Shift Thermometer for the Temperature Range 100 300 K

    NASA Astrophysics Data System (ADS)

    Quast, Helmut; Heubes, Markus; Dunger, Anita; Limbach, Hans-Heinrich

    1998-10-01

    The first carbon-13 shift thermometer for the temperature range of 100-300 K is based on the very rapid equilibration of a pair of semibullvalene valence tautomers. The temperature dependence of the equilibrium constant is reflected in strongly temperature-dependent shift differences Δδ between averaged signals, e.g.,d(Δδ)/dT= 0.051 ppm K-1at 300, 0.087 ppm K-1at 200, and 0.175 ppm K-1at 110 K for the quaternary carbon atoms C2 and C6. At 37 temperaturesT, which were measured with calibrated platinum resistance thermometers, shift differences Δδ were taken from nondecoupled carbon-13 spectra recorded from solutions of 1 in mixtures of chlorodifluoromethane and deuterated dimethyl ether without spinning. The least-squares fit of these Δδ vsTdata to a polynomial equation of the fourth degree (Eq. [5],r2= 0.9999) allows the calculation of temperatures from measured shift differences with a standard deviation of 0.46 K and an estimated error of about 1 K. The heating effects of WALTZ-16 decoupling and the influence of solvents on Δδ are investigated. A comparison with existing NMR thermometers demonstrates the superior performance of the new carbon-13 shift thermometer with respect to precision and the accessible temperature range.

  7. ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter; K. Streib

    1999-09-01

    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg(OH){sub 2} carbonation is a leading process candidate, which generates the stable naturally occurring mineral magnesite (MgCO{sub 3}) and water. Key to process cost and viability are the carbonation reaction rate and its degree of completion. This process, which involves simultaneous dehydroxylation and carbonation is very promising, but far from optimized. In order to optimize the dehydroxylation/carbonation process, an atomic-level understanding of the mechanisms involved is needed. Since Mg(OH){sub 2} dehydroxylation is intimately associated with the carbonation process, its mechanisms are also of direct interest in understanding and optimizing the process. In the first project year, our investigations have focused on developing an atomic-level understanding of the dehydroxylation/carbonation reaction mechanisms that govern the overall carbonation reaction process in well crystallized material. In years two and three, we will also explore the roles of crystalline defects and impurities. Environmental-cell, dynamic high-resolution transmission electron microscopy has been used to directly observe the dehydroxylation process at the atomic-level for the first time. These observations were combined with advanced computational modeling studies to better elucidate the atomic-level process. These studies were combined with direct carbonation studies to better elucidate dehydroxylation/carbonation reaction mechanisms. Dehydroxylation follows a lamellar nucleation and growth process involving oxide layer formation. These layers form lamellar oxyhydroxide regions, which can

  8. Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

    USGS Publications Warehouse

    McMahon, Peter B.; Chapelle, Francis H.

    1991-01-01

    Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO2 to respiration CO2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO2 to respiration CO2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was

  9. The chemistry of subcritical water reactions of a hardwood derived lignin and lignin model compounds with nitrogen, hydrogen, carbon monoxide and carbon dioxide

    NASA Astrophysics Data System (ADS)

    Hill Bembenic, Meredith A.

    collected solids from the CO reactions appeared to be the most reacted (i.e., the most changed from the unreacted lignin) according to solid state 13C-NMR analysis, and the widest variety of products (methoxy-substituted phenolic compounds) were obtained when using CO according to GC/MS analysis. Therefore, reactions with CO were completed that varied the initial reaction pressure (300, 500 and 800 psi) in order to elucidate the effects of CO pressure. Similar conversion (≈54--58%) and DCM-soluble liquid product yields (≈53--62%) were obtained for the different pressure reactions, but the reactions with an initial pressure of 500 psi had the greatest change in aromaticity from the unreacted lignin. Additional reactions between Organosolv lignin and H2O with CO (initial pressure of 500 psi) were conducted where the reaction time was varied (15, 30 and 60 min.) to determine the effect of reaction time. Longer reaction time (60 min.) appeared to inhibit conversion to low molecular weight compounds (i.e., conversion and DCM-soluble yields were lower at ≈53% and ≈28%, respectively). Solid state 13C-NMR of collected residues also showed that there are losses in carbons representative of both guaiacyl and syringyl components as reaction time increases, which may indicate that methoxy groups are being cleaved or the products are reacting with each other (i.e., repolymerization) to form high molecular weight compounds as reaction time is increased. The role of H2O and the gases during the baseline reactions and the expanded CO reactions is not intuitive based on the results, so reactions with lignin model compounds (i.e., aromatic aldehydes represented by vanillin and syringaldehyde, aromatic ketones represented by acetovanillone and acetosyringone, and aromatic ethers represented by dibenzyl ether and 2-phenethyl phenyl ether) were completed to study this. From these results, the suggested reaction pathway of Organosolv lignin reactions in subcritical H2O with and without

  10. Modeling reaction-driven cracking during mineral carbonation in peridotite for CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Paukert, A. N.; Sonnenthal, E. L.; Matter, J.; Kelemen, P. B.

    2013-12-01

    In situ mineral carbonation in mantle peridotite has been proposed as a mechanism for long-term, environmentally benign CO2 sequestration1,2. This process converts peridotite and CO2 to carbonate minerals, like magnesite, in the subsurface, providing permanent and safe storage of the CO2. The volume that can be sequestered in this manner is an open question as peridotite carbonation involves a positive volume change and peridotite aquifers have limited porosity and permeability to accommodate the addition of solid volume. Conversion of peridotite to magnesite results in a volume increase of ~44%, which will fill the existing pore space and could limit the extent of carbonation by reducing porosity and permeability, clogging fluid flow paths, and armoring the reactive surface area. Alternatively, the force of crystallization and changes in fluid pressure from carbonation could act as driving forces for mechanical deformation and fracture propagation within the peridotite, creating new porosity, permeability, and reactive surface area, allowing carbonation to continue3. Natural examples of peridotite that have been entirely converted to magnesite suggest that reactive cracking from mineral carbonation is possible given the right conditions, such as elevated temperature and pCO2 2. Results will be presented from a reactive transport model that has been developed for peridotite carbonation using TOUGHREACT v.24. This model evaluates water and CO2 flow through peridotite fractured at different scales using a multiple continuum mesh. The effect of fluid flow, chemical reactions, and porosity and permeability feedbacks on carbonation rate and extent are explored, as is the effect of temperature. Peridotite carbonation is exothermic, so the release of heat of reaction could be balanced with the fluid injection temperature to maintain the 185oC conditions that facilitate the fastest carbonation rate2. The effect of fluid temperature and flow rate on the rate of carbonation

  11. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOEpatents

    Bamberger, Carlos E.; Robinson, Paul R.

    1980-01-01

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  12. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOEpatents

    Bamberger, C.E.; Robinson, P.R.

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  13. Method of carbon chain extension using novel aldol reaction

    DOEpatents

    Silks, Louis A; Gordon, John C; Wu, Ruilan; Hanson, Susan Kloek

    2013-07-30

    Method of producing C.sub.8-C.sub.15 hydrocarbons. comprising providing a ketone starting material; providing an aldol starting material comprising chloromethylfurfural; mixing the ketone starting material and the aldol starting material in a reaction in the presence of a proline-containing catalyst selected from the group consisting of Zn(Pro).sub.2, Yb(Pro).sub.3, and combinations thereof, or a catalyst having one of the structures (I), (II) or (III), and in the presence of a solvent, wherein the solvent comprises water and is substantially free of organic solvents, where (I), (II) and (III) respectively are: ##STR00001## where R.sub.1 is a C.sub.1-C.sub.6 alkyl moiety, X=(OH) and n=2. ##STR00002## In (III), X may be CH.sub.2, sulfur or selenium, M may be Zn, Mg, or a lanthanide, and R.sub.1 and R.sub.2 each independently may be a methyl, ethyl, phenyl moiety.

  14. Method of carbon chain extension using novel aldol reaction

    DOEpatents

    Silks, Louis A; Gordon, John C; Wu, Ruilan; Hangson, Susan Kloek

    2013-08-13

    Method of producing C.sub.8-C.sub.15 hydrocarbons comprising providing a ketone starting material; providing an aldol starting material comprising hydroxymethylfurfural; mixing the ketone starting material and the aldol starting material in a reaction in the presence of a proline-containing catalyst selected from the group consisting of Zn(Pro).sub.2, Yb(Pro).sub.2, and combinations thereof, or a catalyst having one of the structures (I), (II) or (III), and in the presence of a solvent, wherein the solvent comprises water and is substantially free of organic solvents, where (I), (II) and (III) respectively are: ##STR00001## where R.sub.1 is a C.sub.1-C.sub.6 alkyl moiety, X=(OH) and n=2. ##STR00002## In (III), X may be CH.sub.2, sulfur or selenium, M may be Zn, Mg, or a lanthanide, and R.sub.1 and R.sub.2 each independently may be a methyl, ethyl, phenyl moiety.

  15. Reaction of matrix-isolated iron atoms with carbon disulfide

    SciTech Connect

    Doeff, M.M.

    1986-07-02

    This study was undertaken to determine the type of bonding, as well as the extent of reactivity between CS/sub 2/ and iron atoms. The results of several matrix isolation experiments in which either pure CS/sub 2/ or SC/sub 2//Ar and CS/sub 2//Kr mixtures were condensed with iron atoms and studied by infrared and Moessbauer spectroscopy are presented. All the spectra indicate the presence of only one product of the reaction between Fe and CS/sub 2/ no matter what the composition of the matrix. Conditions were also such that only monomeric Fe complexes were expected; therefore, it is concluded that the complex formed in these matrices has a composition of Fe(CS/sub 2/). Results of annealing experiments carried out to determine the stability of the complex were interpreted to mean that the Fe(CS/sub 2/) formed in a 100% CS/sub 2/ matrix is stable to at least 60 K, begins to decompose between 60 and 80 K to form a new iron-containing species, and forms a very stable, nonvolatile residue at room temperature. 22 references, 1 figure.

  16. Carbon-Supported Copper Nanomaterials: Recyclable Catalysts for Huisgen [3+2] Cycloaddition Reactions.

    PubMed

    Shaygan Nia, Ali; Rana, Sravendra; Döhler, Diana; Jirsa, Franz; Meister, Annette; Guadagno, Liberata; Koslowski, Eik; Bron, Michael; Binder, Wolfgang H

    2015-07-20

    Highly disperse copper nanoparticles immobilized on carbon nanomaterials (CNMs; graphene/carbon nanotubes) were prepared and used as a recyclable and reusable catalyst to achieve Cu(I) -catalyzed [3+2] cycloaddition click chemistry. Carbon nanomaterials with immobilized N-heterocyclic carbene (NHC)-Cu complexes prepared from an imidazolium-based carbene and Cu(I) show excellent stability including high efficiency at low catalyst loading. The catalytic performance evaluated in solution and in bulk shows that both types of Cu-CNMs can function as an effective recyclable catalysts (more than 10 cycles) for click reactions without decomposition and the use of external additives.

  17. The Development and Application of Two-Chamber Reactors and Carbon Monoxide Precursors for Safe Carbonylation Reactions.

    PubMed

    Friis, Stig D; Lindhardt, Anders T; Skrydstrup, Troels

    2016-04-19

    , an array of low-pressure carbonylations were developed applying only near stoichiometric amounts of carbon monoxide. Importantly, carbon isotope variants of the CO precursors, such as (13)COgen, Sila(13)COgen, or even (14)COgen, provide a simple means for performing isotope-labeling syntheses. Finally, the COware applicability has been extended to reactions with other gases, such as hydrogen, CO2, and ethylene including their deuterium and (13)C-isotopically labeled versions where relevant. The COware system has been repeatedly demonstrated to be a valuable reactor for carrying out a wide number of transition metal-catalyzed transformations, and we believe this technology will have a significant place in many organic research laboratories. PMID:26999377

  18. The Development and Application of Two-Chamber Reactors and Carbon Monoxide Precursors for Safe Carbonylation Reactions.

    PubMed

    Friis, Stig D; Lindhardt, Anders T; Skrydstrup, Troels

    2016-04-19

    , an array of low-pressure carbonylations were developed applying only near stoichiometric amounts of carbon monoxide. Importantly, carbon isotope variants of the CO precursors, such as (13)COgen, Sila(13)COgen, or even (14)COgen, provide a simple means for performing isotope-labeling syntheses. Finally, the COware applicability has been extended to reactions with other gases, such as hydrogen, CO2, and ethylene including their deuterium and (13)C-isotopically labeled versions where relevant. The COware system has been repeatedly demonstrated to be a valuable reactor for carrying out a wide number of transition metal-catalyzed transformations, and we believe this technology will have a significant place in many organic research laboratories.

  19. Mesoporous nitrogen-doped carbon derived from carp with high electrocatalytic performance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Rongfang; Song, Huihui; Li, Hao; Wang, Hui; Mao, Xuefeng; Ji, Shan

    2015-03-01

    In this work, a low-cost and nitrogen-containing carbon material with mesopores and high surface area is synthesized by carbonizing carp with SiO2 nanoparticles as template. It is found that pyridinic-N dominates the N species on the surface of obtained carbon material, which can act as active sites for oxygen reduction reaction (ORR). The BET surface area of obtained carbon material is 401.7 m2 g-1 and the pore size is ca. 11.1 nm. Due to its high pyridinic-N content and mesoporous architecture, the ORR activity of obtained carbon material in alkaline media is comparable to that of commercial Pt/C catalyst. In addition, it shows a higher methanol tolerance than Pt/C catalyst, making it a potential alternative to Pt-based catalysts.

  20. Ambient solid-state mechano-chemical reactions between functionalized carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Kabbani, Mohamad A.; Tiwary, Chandra Sekhar; Autreto, Pedro A. S.; Brunetto, Gustavo; Som, Anirban; Krishnadas, K. R.; Ozden, Sehmus; Hackenberg, Ken P.; Gong, Yongi; Galvao, Douglas S.; Vajtai, Robert; Kabbani, Ahmad T.; Pradeep, Thalappil; Ajayan, Pulickel M.

    2015-06-01

    Carbon nanotubes can be chemically modified by attaching various functionalities to their surfaces, although harsh chemical treatments can lead to their break-up into graphene nanostructures. On the other hand, direct coupling between functionalities bound on individual nanotubes could lead to, as yet unexplored, spontaneous chemical reactions. Here we report an ambient mechano-chemical reaction between two varieties of nanotubes, carrying predominantly carboxyl and hydroxyl functionalities, respectively, facilitated by simple mechanical grinding of the reactants. The purely solid-state reaction between the chemically differentiated nanotube species produces condensation products and unzipping of nanotubes due to local energy release, as confirmed by spectroscopic measurements, thermal analysis and molecular dynamic simulations.

  1. Ambient solid-state mechano-chemical reactions between functionalized carbon nanotubes.

    PubMed

    Kabbani, Mohamad A; Tiwary, Chandra Sekhar; Autreto, Pedro A S; Brunetto, Gustavo; Som, Anirban; Krishnadas, K R; Ozden, Sehmus; Hackenberg, Ken P; Gong, Yongi; Galvao, Douglas S; Vajtai, Robert; Kabbani, Ahmad T; Pradeep, Thalappil; Ajayan, Pulickel M

    2015-01-01

    Carbon nanotubes can be chemically modified by attaching various functionalities to their surfaces, although harsh chemical treatments can lead to their break-up into graphene nanostructures. On the other hand, direct coupling between functionalities bound on individual nanotubes could lead to, as yet unexplored, spontaneous chemical reactions. Here we report an ambient mechano-chemical reaction between two varieties of nanotubes, carrying predominantly carboxyl and hydroxyl functionalities, respectively, facilitated by simple mechanical grinding of the reactants. The purely solid-state reaction between the chemically differentiated nanotube species produces condensation products and unzipping of nanotubes due to local energy release, as confirmed by spectroscopic measurements, thermal analysis and molecular dynamic simulations.

  2. Structure and Reactions of Carbon and Hydrogen on Ru(0001): A Scanning Tunneling Microscopy Study

    SciTech Connect

    Shimizu, Tomoko K.; Mugarza, Aitor; Cerda, Jorge; Salmeron, Miquel

    2008-09-09

    The interaction between carbon and hydrogen atoms on a Ru(0001) surface was studied using scanning tunneling microscopy (STM), Density Functional Theory (DFT) and STM image calculations. Formation of CH species by reaction between adsorbed H and C was observed to occur readily at 100 K. When the coverage of H increased new complexes of the form CH+nH (n = 1, 2 and 3) were observed. These complexes, never observed before, might be precursors for further hydrogenation reactions. DFT analysis reveals that a considerable energy barrier exists for the CH+H {yields} CH{sub 2} reaction.

  3. Quantifying the metabolic contribution to δ13C of shell carbonate of Arctica islandica: an experimental calibration

    NASA Astrophysics Data System (ADS)

    Beirne, E. C.; Wanamaker, A. D.

    2010-12-01

    The stable isotopic composition of dissolved inorganic carbon of seawater (δ13CDIC) can provide a powerful means to investigate atmospheric and oceanic carbon dynamics. Records of past δ13CDIC values of seawater, especially from the extratropical oceans, are needed to better understand how recent climate change and anthropogenic activity (namely fossil fuel emissions) have impacted the global carbon cycle. However, long-term reconstructions of marine δ13CDIC are limited (both spatially and temporally) by a lack of suitable proxy archives, which have undergone a rigorous calibration process. Marine mollusks represent a potential δ13CDIC archive given that the primary source of carbon to their shell material is ambient dissolved inorganic carbon. However, interpretation of this archive is confounded by the additional contribution of respired (or metabolic) carbon to the carbon isotope ratio of shell material (δ13Cshell). Although theoretical models predict that less than 10% of δ13Cshell of marine mollusks is attributable to metabolic carbon, several studies have reported significantly larger contributions of respired carbon (CM) to shell material depending upon the species in question, and in some cases, ontogenetic age. Therefore, species-specific calibrations must be conducted to establish metabolic contribution to δ13Cshell at different stages of ontogeny. The central objective of this study was to quantify the metabolic contribution to the shell carbonate of Arctica islandica L., juveniles and adults, to determine the viability of this species as a paleo-δ13CDIC archive. Results will be presented from an 8-month experimental calibration between δ13CDIC and δ13Cshell of the species Arctica islandica. Adults (25 to 55 years old) and juveniles (<3 years old) were collected and cultured in the Gulf of Maine, both in situ and in the laboratory environment. Relatively high growth rates in juveniles (>1mm/month) allowed for the measurement of three distinct

  4. ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter

    2002-11-01

    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation, before and/or during carbonation, may provide an important parameter for enhancing carbonation reaction processes. Mg(OH){sub 2} was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (1) its structural and chemical simplicity, (2) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (3) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO{sub 2} sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for minimizing the cost of any lamellar-hydroxide-based mineral carbonation sequestration process. This final report covers the overall progress of this grant.

  5. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  6. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  7. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  8. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  9. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  10. Microwave Plasma Chemical Vapor Deposition of Carbon Coatings on LiNi1/3Co1/3Mn1/3O2 for Li-Ion Battery Composite Cathodes

    SciTech Connect

    Doeff, M.M.; Kostecki, R.; Marcinek, M.; Wilcoc, J.D.

    2008-12-10

    In this paper, we report results of a novel synthesis method of thin film conductive carbon coatings on LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} cathode active material powders for lithium-ion batteries. Thin layers of graphitic carbon were produced from a solid organic precursor, anthracene, by a one-step microwave plasma chemical vapor deposition (MPCVD) method. The structure and morphology of the carbon coatings were examined using SEM, TEM, and Raman spectroscopy. The composite LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} electrodes were electrochemically tested in lithium half coin cells. The composite cathodes made of the carbon-coated LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} powder showed superior electrochemical performance and increased capacity compared to standard composite LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} electrodes.

  11. Magnetic moment of the 13 /2 + isomeric state in 69Cu: Spin alignment in the one-nucleon removal reaction

    NASA Astrophysics Data System (ADS)

    Kusoglu, A.; Georgiev, G.; Sotty, C.; Balabanski, D. L.; Goasduff, A.; Ishii, Y.; Abe, Y.; Asahi, K.; Bostan, M.; Chevrier, R.; Chikamori, M.; Daugas, J. M.; Furukawa, T.; Nishibata, H.; Ichikawa, Y.; Ishibashi, Y.; Lozeva, R.; Miyatake, H.; Nagae, D.; Nanao, T.; Niikura, M.; Niwa, T.; Okada, S.; Ozawa, A.; Saito, Y.; Shirai, H.; Ueno, H.; Yordanov, D. T.; Yoshida, N.

    2016-05-01

    We report on a new measurement of the g factor of the (13 /2 + ) isomeric state in the neutron-rich nucleus 69Cu. This study demonstrates the possibility of obtaining considerable nuclear spin alignment for multi-quasiparticle states in single-nucleon removal reactions. The time-dependent perturbed angular distribution (TDPAD) method was used to extract the gyromagnetic factor of the (13 /2+ ) [T1 /2=351 (14 ) ns] isomeric state of 69Cu. Its g factor was obtained as g (13 /2+) =0.248 (9 ) . The experimentally observed spin alignment for the state of interest was deduced as A =-3.3 (9 )% .

  12. Carboxylic Group Embedded Carbon Balls as a New Supported Catalyst for Hydrogen Economic Reactions.

    PubMed

    Bordoloi, Ankur

    2016-03-01

    Carboxylic group functionalized carbon balls have been successfully synthesized by using a facile synthesis method and well characterized with different characterization techniques such as XPS, MAS NMR, SEM, ICP and N2 physi-sorption analysis. The synthesized material has been effectively utilized as novel support to immobilized ruthenium catalyst for hydrogen economic reactions.

  13. Quantitative carbon-13 nuclear magnetic resonance spectroscopic study of mobile residues in bacteriorhodopsin

    SciTech Connect

    Bowers, J.L.; Oldfield, E.

    1988-07-12

    The authors have used quantitative carbon-13 nuclear magnetic resonance (NMR) spectroscopy to study the dynamic structure of the backbone of bacteriorhodopsin in the purple membrane of Halobacterium halobium R/sub 1/ and JW-3. NMR experiments were performed using an internal sucrose quantitation standard on purple membranes in which one of the following /sup 13/C'-labeled amino acids had been biosynthetically incorporated: glycine, isoleucine, lysine, phenylalanine, and valine. The results suggest that the C-terminus of the polypeptide chain backbone, and possibly one of the connecting loops, undergoes rapid, large angle fluctuations. The results are compared with previous NMR and fluorescence spectroscopic data obtained on bacteriorhodopsin.

  14. On calculating the transfer of carbon-13 in reservoir models of the carbon cycle

    SciTech Connect

    TANS, PIETER P.

    1980-10-01

    An approach to calculating the transfer of isotopic tracers in reservoir models is outlined that takes into account the effects of isotopic fractionation at phase boundaries without any significant approximations. Simultaneous variations in both the rare isotopic tracer and the total elemental (the sum of its isotopes) concentration are considered. The proposed procedure is applicable to most models of the carbon cycle and a four-box model example is discussed. Although the exact differential equations are non-linear, a simple linear approximation exists that gives insight into the nature of the solution. The treatment will be in terms of isotopic ratios which are the directly measured quantities.

  15. Coke formation and carbon atom economy of methanol-to-olefins reaction.

    PubMed

    Wei, Yingxu; Yuan, Cuiyu; Li, Jinzhe; Xu, Shutao; Zhou, You; Chen, Jingrun; Wang, Quanyi; Xu, Lei; Qi, Yue; Zhang, Qing; Liu, Zhongmin

    2012-05-01

    The methanol-to-olefins (MTO) process is becoming the most important non-petrochemical route for the production of light olefins from coal or natural gas. Maximizing the generation of the target products, ethene and propene, and minimizing the production of byproducts and coke, are major considerations in the efficient utilization of the carbon resource of methanol. In the present work, the heterogeneous catalytic conversion of methanol was evaluated by performing simultaneous measurements of the volatile products generated in the gas phase and the confined coke deposition in the catalyst phase. Real-time and complete reaction profiles were plotted to allow the comparison of carbon atom economy of methanol conversion over the catalyst SAPO-34 at varied reaction temperatures. The difference in carbon atom economy was closely related with the coke formation in the SAPO-34 catalyst. The confined coke compounds were determined. A new type of confined organics was found, and these accounted for the quick deactivation and low carbon atom economy under low-reaction-temperature conditions. Based on the carbon atom economy evaluation and coke species determination, optimized operating conditions for the MTO process are suggested; these conditions guarantee high conversion efficiency of methanol.

  16. Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

    USGS Publications Warehouse

    Rosenbauer, Robert J.; Thomas, Burt; Bischoff, James L.; Palandri, James

    2012-01-01

    Basaltic rocks are potential repositories for sequestering carbon dioxide (CO2) because of their capacity for trapping CO2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO2-charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO2, an average basaltic MgO content of 8% is equivalent to 2.6 × 108 metric ton CO2/km3 basalt.

  17. Mineral carbonation: energy costs of pretreatment options and insights gained from flow loop reaction studies

    SciTech Connect

    Penner, Larry R.; O'Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.; Rush, Gilbert E.

    2004-01-01

    Sequestration of carbon as a stable mineral carbonate has been proposed to mitigate environmental concerns that carbon dioxide may with time escape from its sequestered matrix using alternative sequestration technologies. A method has been developed to prepare stable carbonate products by reacting CO2 with magnesium silicate minerals in aqueous bicarbonate/chloride media at high temperature and pressure. Because this approach is inherently expensive due to slow reaction rates and high capital costs, studies were conducted to improve the reaction rates through mineral pretreatment steps and to cut expenses through improved reactor technology. An overview is given for the estimated cost of the process including sensitivity to grinding and heating as pretreatment options for several mineral feedstocks. The energy costs are evaluated for each pretreatment in terms of net carbon avoided. New studies with a high-temperature, high-pressure flow-loop reactor have yielded information on overcoming kinetic barriers experienced with processing in stirred autoclave reactors. Repeated tests with the flow-loop reactor have yielded insights on wear and failure of system components, on challenges to maintain and measure flow, and for better understanding of the reaction mechanism.

  18. Lithium Methyl Carbonate as a Reaction Product of Metallic Lithiumand Dimethyl Carbonate

    SciTech Connect

    Zhuang, Guorong V.; Yang, Hui; Ross Jr., Philip N.; Xu, Kang; Jow, T. Richard

    2005-10-16

    To improve the understanding of passive film formation on metallic lithium in organic electrolyte, we synthesized and characterized lithium methyl carbonate (LiOCO{sub 2}CH{sub 3}), a prototypical component of the film. The chemical structure of this compound was characterized with Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Spectroscopy (FTIR), and its thermal stability and decomposition pathway was studied by thermo-gravimetric analysis (TGA). The FTIR spectrum of chemically synthesized compound enabled us to resolve multiple products in the passive film on lithium in dimethyl carbonate (DMC). Lithium methyl carbonate is only one of the components, the others being lithium oxalate and lithium methoxide.

  19. Stable Carbon Isotopes (δ 13C) in Coral Skeletons: Experimental Approach and Applications for Paleoceanography

    NASA Astrophysics Data System (ADS)

    Grottoli, A. G.

    2004-12-01

    Scleractinian corals obtain fixed carbon via photosynthesis by their endosymbiotic algae (zooxanthellae) and via hetertrophy (injestion of zooplankton, δ 13C ≈ -17 to -22‰ ). Carbon dioxide (CO2) used for photosynthesis is obtained from seawater (δ 13C ≈ 0%) or from respired CO2 within the coral host. The δ 13C of the carbon used in the formation of the underlying coral skeleton is fractionated as a result of both of these metabolic processes. Here I have pooled evidence from several field and tank experiments on the effect of photosynthesis and heterotrophy of coral skeletal δ 13C. In the experiments, decreases in light levels due to shading or depth resulted in a significant decrease in skeletal δ 13C in all species studied (Pavona gigantea, Pavona clavus, Porites compressa). Decreases in photosynthesis in bleached corals also resulted in a decrease in skeletal δ 13C compared to non-bleached corals growing under the same conditions and at the same location. Skeletal δ 13C also decreased at higher than normal light levels most likely due to photoinhibition. Thus, decreases in photosynthesis due to reduced light levels, due to bleaching-induced decreases in chlorophyll a concentrations, or due to photodamage-induced decreases in functional cholorphyll a, results in significant δ 13C decreases. Comprehensive interpretation of all of the data showed that changes in photosynthesis itself can drive the changes in δ 13C. In field experiments, the addition of natural concentrations of zooplankton to the diet resulted in decreases in skeletal δ 13C. Such a decrease was more pronounced with depth and in P. gigantea compared to P. clavus. In situ feeding experiments have since confirmed these findings. However under tank conditions with unaturally high feeding rates, enhanced nitrogen supply in the diet can disrupt the coral-algal symbiosis, stimlate zooxanthellae growth and photosynthesis, and cause an incrase in skeletal δ 13C. It is proposed that under

  20. Carbon-13 NMR of glycogen: Hydration response studied by using solids methods

    SciTech Connect

    Jackson, C.L.; Bryant, R.G. )

    1989-06-13

    The carbon-13 NMR spectra of glycogen are reported by using the methods of magic-angle sample spinning and high-power proton decoupling to provide a dynamic report on the glucose monomer behavior as a function of hydration. Although the glycogen behaves as a typical polymer in the dry state, addition of water makes a significant difference in the spectral appearance. Water addition decreases the carbon spin-lattice relaxation times by 2 orders of magnitude over the range from 7% to 70% water by weight. The proton-carbon dipole-dipole coupling, which broadens the carbon spectrum and permits cross-polarization spectroscopy, is lost with increasing hydration over this range. By 60% water by weight, scalar decoupling methods are sufficient to achieve a reasonably high-resolution spectrum. Further, at this concentration, the carbon spin-lattice relaxation times are near their minimum values at a resonance frequency of 50.3 MHz, making acquisition of carbon spectra relatively insensitive to intensity distortions associated with saturation effects. Though motional averaging places the spectrum in the solution phase limit, the static spectrum shows a residual broader component that would not necessarily be detected readily by using high-resolution liquid-state experiments.

  1. THE GAS PHASE REACTION OF OZONE WITH 1,3-BUTADIENE: FORMATION YIELDS OF SOME TOXIC PRODUCTS. (R826236)

    EPA Science Inventory

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separa...

  2. Arylpalladium Phosphonate Complexes as Reactive Intermediates in Phosphorus-Carbon Bond Forming Reactions

    SciTech Connect

    Kohler, Mark C.; Grimes, Thomas V.; Wang, Xiaoping; Cundari, Thomas R.; Stockland, Robert A. Jr.

    2009-01-01

    Phosphorus-carbon bond formation from discrete transition metal complexes have been investigated through a combination of synthetic, spectroscopic, crystallographic, and computational methods. Reactive intermediates of the type (diphosphine)Pd(aryl)(P(O)(OEt)(2)) have been prepared, characterized, and studied as possible intermediates in metal-mediated coupling reactions. Several of the reactive intermediates were characterized crystallographicaliy, and a discussion of the solid state structures is presented. In contrast to other carbon-heteroelement bond forming reactions, palladium complexes containing electron-donating substituents on the aromatic fragment exhibited faster rates of reductive elimination. Large bite angle diphosphine ligands induced rapid rates of elimination, while bipyridine and small bite angle diphosphine ligands resulted in much slower rates of elimination. An investigation of the effect of typical impurities on the elimination reaction was carried out. While excess diphosphine, pyridine, and acetonitrile had little effect on the observed rate, the addition of water slowed the phosphorus-carbon bond forming reaction. Coordination of water to the complex was observed spectroscopically and crystallographically. Computational studies were utilized to probe the reaction pathways for P-C bond formation via Pd catalysis.

  3. The complete set of spin observables for the (13)C(polarized proton, polarized neutron)(13)N and (15)N(polarized proton, polarized neutron)(15)O reactions

    NASA Astrophysics Data System (ADS)

    Du, Qun Qun

    1998-12-01

    The 13C(p,n)13N and 15N(p,n)15O reactions have been a puzzle for more than ten years. The ground state transitions are Jπ=1/2- to Jπ=1/2-. These are 'mixed' transitions because they can involve quantum number changes either (/Delta T=1,/ /Delta J=0,/ /Delta/pi=0,/ /Delta S=0), or (/Delta T=1,/ /Delta J=1,/ /Delta/pi=0,/ /Delta S=1); these quantum number changes are refered to as 'Fermi' and 'Gamow-Teller' respectively. Because the quantum number changes are the same as for Fermi and Gamow-Teller beta decay. From the systematics of (p,n) and (n,p) reactions on pure Fermi transitions (e.g. 0 + to 0+) and pure Gamow-Teller transitions (e.g. 0+ to 1+), calibrations have been established of cross section per unit B(F) or unit B(GT), where 'B' refers to doubly reduced matrix elements extracted from beta decay. However, cross sections for the 13C(p,n)13N(g.s.) and 15N(p,n)15O(g.s.) reactions are substantially larger than one would then predict from the known B(F)s and B(GT)s for these transitions. To explore this anomaly, spin observables were used to extract separately the Fermi and Gamow-Teller cross sections for these reactions. To acquire the complete sets of polarization- transfer observables, a new neutron polarimeter was designed, built, commissioned and calibrated. This polarimeter, call the '2π polarimeter' because of its complete azimuthal coverage for scattered neutrons, has very good position and timing resolution (354 ps). The complete sets of spin-transfer coefficients Dij for 13C(p,n)13N (at 0o , 5.5o , and 11o ) and 15N(p,n)15O (at 0o ) at 135 MeV were measured. Following the formalism of Ichimura and Kawahigashi, we extracted the spin-longitudinal, and spin-transverse and spin-independent responses D0,/ Dq,/ Dn and Dp from the measured Dijs. The F and GT fractions of the (p,n) cross sections are then extracted as f F=D0 and fGT=Dn+Dp+Dq=1- d0. Values of Dk for both the 13C(p,n)13N(g.s) and 15N(p,n)15O(g.s.) were extracted. From these responses, we

  4. Metal Carbonation of Forsterite in Wet Supercritical CO2: The Role of H2O Studied by Solid State C-13 and Si-29 NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hu, J.; Kwak, J.; Turcu, R. V.; Rosso, K. M.; Ilton, E. S.; Wang, C.; Sears, J. A.; Felmy, A. R.; Hoyt, D. W.

    2010-12-01

    Selected as a model mineral carbonation system for geological carbon sequestration in mafic host rocks, chemical mechanisms of forsterite carbonation in supercritical CO2 containing water varied from dry to well above saturation, including at saturation, were investigated by a combination of solid state NMR (C-13 SP-, CP-MAS, Si-29 SP-, CP-MAS), XRD, TEM and XPS. Run conditions were 80 degrees (C) and 75 bars. Major findings are as follows. At high water contents where a bulk aqueous solution coexisted with water-saturated scCO2, forsterite was converted into magnesite and a separate Mg-free amorphous SiO2 reaction product characterized by highly polymerized oligomeric Q4, and to a lesser extent by Q3 silica species. As the amount of added water was reduced, hydrated intermediate reaction products that did not evolve to magnesite could be identified until at zero water no reaction intermediates or magnesite carbonation products were observed. The intermediate reaction products identified were a complex mixture of partially hydrated/hydroxylated magnesium carbonate species and a variety of surface silica species with low polymerization extent. The intermediates were mainly in an amorphous state, forming a thin layer on the surface. Formation of these intermediate species consumes water by hydrolysis of Mg-O-Si linkages at the forsterite surface as well as by incorporation of water in the lattice. If insufficient water is available, the reaction is found not to proceed far enough to form magnesite and amorphous SiO2. Water in excess of this limit appears necessary for the intermediates to evolve to anhydrous magnesite, a process that is expected to liberate water for continued reaction. Hence, for a given fluid/forsterite ratio there appears to be a water threshold (i.e., the formation of H2O film with sufficient thickness estimated to be between 3.2 and 18.4 nm) above which a significant portion of the water is recycled in an apparent quasi-catalytic role for the

  5. Reactions of the Carbon Anode in Alternative Battery and Fuel Cell Configurations

    SciTech Connect

    Cooper, J F; Krueger, R

    2003-10-01

    A model is formulated by combining carbonate dissociation with pre-existing anode mechanisms involving heterogeneous reaction kinetics. The proposed model accounts for both the observed preponderance of CO{sub 2} evolution and dependence of rate on carbon anode microstructure. Implications of the model for the design of carbon batteries and fuel cells are discussed, and the laboratory cells used in earlier research are described. High coulombic efficiencies for the net reaction C + O{sub 2} = CO{sub 2} require severely limiting the thickness of paste anodes in powder-fed fuel cells while the unreacting surfaces of solid prismatic anodes must be isolated from the CO{sub 2} product atmosphere to prevent Boudouard corrosion, according to C + CO{sub 2} = 2CO.

  6. A novel one-pot and one-step microwave-assisted cyclization-methylation reaction of amino alcohols and acetylated derivatives with dimethyl carbonate and TBAC.

    PubMed

    Ochoa-Terán, Adrián; Guerrero, Leticia; Rivero, Ignacio A

    2014-01-01

    A simple and efficient microwave-assisted methodology for the synthesis of 4-substituted-3-methyl-1,3-oxazolidin-2-ones from amino alcohols catalyzed by a ionic liquid was developed. This novel one-pot and one-step cyclization-methylation reaction represents an easier and faster method than any other reported protocols that can be used to obtain the desired products in good yields and high purity. Applying microwave irradiation at 130°C in the presence of TBAC, dimethyl carbonate acts simultaneously as carbonylating and methylating agent and surprisingly promotes an in situ basic trans esterification when a N-acetylated amino alcohol is used as starting material. Furthermore, dimethyl carbonate worked better than diethyl carbonate in performing this reaction. PMID:25692177

  7. A Novel One-Pot and One-Step Microwave-Assisted Cyclization-Methylation Reaction of Amino Alcohols and Acetylated Derivatives with Dimethyl Carbonate and TBAC

    PubMed Central

    Ochoa-Terán, Adrián; Guerrero, Leticia; Rivero, Ignacio A.

    2014-01-01

    A simple and efficient microwave-assisted methodology for the synthesis of 4-substituted-3-methyl-1,3-oxazolidin-2-ones from amino alcohols catalyzed by a ionic liquid was developed. This novel one-pot and one-step cyclization-methylation reaction represents an easier and faster method than any other reported protocols that can be used to obtain the desired products in good yields and high purity. Applying microwave irradiation at 130°C in the presence of TBAC, dimethyl carbonate acts simultaneously as carbonylating and methylating agent and surprisingly promotes an in situ basic trans esterification when a N-acetylated amino alcohol is used as starting material. Furthermore, dimethyl carbonate worked better than diethyl carbonate in performing this reaction. PMID:25692177

  8. Carbon-13 CP-MAS nuclear magnetic resonance studies of teas.

    PubMed

    Martínez-Richa, Antonio; Joseph-Nathan, Pedro

    2003-05-01

    13C CP-MAS NMR spectra of green and black tea were obtained and assigned based on the solid-state NMR spectra of tropolone, (+)-catechin hydrate, gallic acid, caffeine and flavone derivatives. The peak shape and chemical shifts observed for carbonyl carbons in CP-MAS spectra of teas indicate the existence of different chemical species, mainly free phenollic acids and ester derivatives of flavonoids. The peak patterns allow to establish differences between both teas.

  9. Reaction of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithiethane with N-vinyl compounds

    PubMed Central

    Marshall, Will

    2013-01-01

    Summary The reaction of hexafluorothioacetone dimer (2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithiethane, 1) with vinylamides leads to the rapid formation of [2 + 2] cycloadducts: 4-amino-2,2-bis(trifluoromethyl)thietanes. The reaction proceeds in polar solvents (DMF, DMSO) in the absence of a catalyst at elevated temperature producing the corresponding cycloadducts in 47–86% yield. The reaction of N-vinylimidazole unexpectedly led to the formation of the corresponding 1-(hexafluoroisopropyl)-3-vinyl-1,3-dihydro-2H-imidazole-2-thione (5). The structure of this compound, along with the structures of two new thietanes was confirmed by single crystal X-ray diffraction. PMID:24367424

  10. Astrophysical reaction rate for the neutron-generator reaction 13C(alpha,n)16O in asymptotic giant branch stars.

    PubMed

    Johnson, E D; Rogachev, G V; Mukhamedzhanov, A M; Baby, L T; Brown, S; Cluff, W T; Crisp, A M; Diffenderfer, E; Goldberg, V Z; Green, B W; Hinners, T; Hoffman, C R; Kemper, K W; Momotyuk, O; Peplowski, P; Pipidis, A; Reynolds, R; Roeder, B T

    2006-11-10

    The reaction 13C(alpha,n) is considered to be the main source of neutrons for the s process in asymptotic giant branch stars. At low energies, the cross section is dominated by the 1/2+ 6.356 MeV subthreshold resonance in (17)O whose contribution at stellar temperatures is uncertain by a factor of 10. In this work, we performed the most precise determination of the low-energy astrophysical S factor using the indirect asymptotic normalization (ANC) technique. The alpha-particle ANC for the subthreshold state has been measured using the sub-Coulomb alpha-transfer reaction ((6)Li,d). Using the determined ANC, we calculated S(0), which turns out to be an order of magnitude smaller than in the nuclear astrophysics compilation of reaction rates.

  11. Surface reactions of molecular and atomic oxygen with carbon phosphide films.

    PubMed

    Gorham, Justin; Torres, Jessica; Wolfe, Glenn; d'Agostino, Alfred; Fairbrother, D Howard

    2005-11-01

    The surface reactions of atomic and molecular oxygen with carbon phosphide films have been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Carbon phosphide films were produced by ion implantation of trimethylphosphine into polyethylene. Atmospheric oxidation of carbon phosphide films was dominated by phosphorus oxidation and generated a carbon-containing phosphate surface film. This oxidized surface layer acted as an effective diffusion barrier, limiting the depth of phosphorus oxidation within the carbon phosphide film to < 3 nm. The effect of atomic oxygen (AO) exposure on this oxidized carbon phosphide layer was subsequently probed in situ using XPS. Initially AO exposure resulted in a loss of carbon atoms from the surface, but increased the surface concentration of phosphorus atoms as well as the degree of phosphorus oxidation. For more prolonged AO exposures, a highly oxidized phosphate surface layer formed that appeared to be inert toward further AO-mediated erosion. By utilizing phosphorus-containing hydrocarbon thin films, the phosphorus oxides produced during exposure to AO were found to desorb at temperatures >500 K under vacuum conditions. Results from this study suggest that carbon phosphide films can be used as AO-resistant surface coatings on polymers.

  12. Exploration of the Role of Heat Activation in Enhancing Serpentine Carbon Sequestration Reactions

    SciTech Connect

    McKelvy, M.J.; Chizmeshya, A.V.G.; Diefenbacher, J.; Bearat, H.; Wolf, G.

    2005-03-29

    As compared with other candidate carbon sequestration technologies, mineral carbonation offers the unique advantage of permanent disposal via geologically stable and environmentally benign carbonates. The primary challenge is the development of an economically viable process. Enhancing feedstock carbonation reactivity is key. Heat activation dramatically enhances aqueous serpentine carbonation reactivity. Although the present process is too expensive to implement, the materials characteristics and mechanisms that enhance carbonation are of keen interest for further reducing cost. Simultaneous thermogravimetric and differential thermal analysis (TGA/DTA) of the serpentine mineral lizardite was used to isolate a series of heat-activated materials as a function of residual hydroxide content at progressively higher temperatures. Their structure and composition are evaluated via TGA/DTA, X-ray powder diffraction (including phase analysis), and infrared analysis. The meta-serpentine materials that were observed to form ranged from those with longer range ordering, consistent with diffuse stage-2 like interlamellar order, to an amorphous component that preferentially forms at higher temperatures. The aqueous carbonation reaction process was investigated for representative materials via in situ synchrotron X-ray diffraction. Magnesite was observed to form directly at 15 MPa CO{sub 2} and at temperatures ranging from 100 to 125 C. Carbonation reactivity is generally correlated with the extent of meta-serpentine formation and structural disorder.

  13. Preparation of 13X from Waste Quartz and Photocatalytic Reaction of Methyl Orange on TiO2/ZSM-5, 13X and Y-Zeolite.

    PubMed

    Wang, Jia-Jie; Jing, You-Hai; Ouyang, Tong; Chang, Chang-Tang

    2015-08-01

    TiO2 photocatalytic reactions not only remove a variety of organic pollutants via complete mineralization, but also destroy the bacterial cell wall and cell membrane, thus playing an important bactericidal role. However, the post-filtration procedures to separate nanometer-levels of TiO2 and the gradual inactivity of photocatalyst during continuous use are defects that limit its application. In this case, we propose loading TiO2 on zeolite for easy separation and 13X is considered as a promising one. In our study, 13X-zeolite was prepared by a hydrothermal method and the source of Si was extracted from waste quartz sand. For comparison, commercial zeolite with different microporous and mesoporous diameters (ZSM-5 and Y-zeolites) were also used as TiO2 supports. The pore size of the three kinds of zeolites are as follows: Y-zeolite > 13X > ZSM-5. Different TiO2 loading content over ZSM-5, 13X and Y-zeolite were prepared by the sol-gel method. XRD, FTIR, BET, UV-vis, TGA and SEM were used for investigation of material characteristics. In addition, the efficiencies of mineralization and photodegradation were studied in this paper. The effects of the loading ratio of TiO2 over zeolites, initial pH, and concentration on photocatalytic performance are investigated. The relationship between best loading content of TiO2 and pore size of the zeolite was studied. The possible roles of the ZSM-5, 13X-zeolites and Y-zeolites support on the reactions and the possible mechanisms of effects were also explored. The best loading content of TiO2 over ZSM-5, 13X and Y-zeolite was found to be 50 wt%, 12.5 wt% and 7 wt%, respectively. The optimum pH condition is 3 with TiO2 over ZSM-5, 13X-zeolites and Y-zeolites. The results showed that the degradation and mineralization efficiency of 12.5 wt%GT13X (TiO2 over 13X) after 90 min irradiation reached 57.9% and 22.0%, which was better than that of 7 wt%GTYZ (TiO2 over Y-zeolites) while much lower than that of 50 wt%GTZ (TiO2 over ZSM-5

  14. Preparation of 13X from Waste Quartz and Photocatalytic Reaction of Methyl Orange on TiO2/ZSM-5, 13X and Y-Zeolite.

    PubMed

    Wang, Jia-Jie; Jing, You-Hai; Ouyang, Tong; Chang, Chang-Tang

    2015-08-01

    TiO2 photocatalytic reactions not only remove a variety of organic pollutants via complete mineralization, but also destroy the bacterial cell wall and cell membrane, thus playing an important bactericidal role. However, the post-filtration procedures to separate nanometer-levels of TiO2 and the gradual inactivity of photocatalyst during continuous use are defects that limit its application. In this case, we propose loading TiO2 on zeolite for easy separation and 13X is considered as a promising one. In our study, 13X-zeolite was prepared by a hydrothermal method and the source of Si was extracted from waste quartz sand. For comparison, commercial zeolite with different microporous and mesoporous diameters (ZSM-5 and Y-zeolites) were also used as TiO2 supports. The pore size of the three kinds of zeolites are as follows: Y-zeolite > 13X > ZSM-5. Different TiO2 loading content over ZSM-5, 13X and Y-zeolite were prepared by the sol-gel method. XRD, FTIR, BET, UV-vis, TGA and SEM were used for investigation of material characteristics. In addition, the efficiencies of mineralization and photodegradation were studied in this paper. The effects of the loading ratio of TiO2 over zeolites, initial pH, and concentration on photocatalytic performance are investigated. The relationship between best loading content of TiO2 and pore size of the zeolite was studied. The possible roles of the ZSM-5, 13X-zeolites and Y-zeolites support on the reactions and the possible mechanisms of effects were also explored. The best loading content of TiO2 over ZSM-5, 13X and Y-zeolite was found to be 50 wt%, 12.5 wt% and 7 wt%, respectively. The optimum pH condition is 3 with TiO2 over ZSM-5, 13X-zeolites and Y-zeolites. The results showed that the degradation and mineralization efficiency of 12.5 wt%GT13X (TiO2 over 13X) after 90 min irradiation reached 57.9% and 22.0%, which was better than that of 7 wt%GTYZ (TiO2 over Y-zeolites) while much lower than that of 50 wt%GTZ (TiO2 over ZSM-5

  15. Combined crossed molecular beam and ab initio investigation of the reaction of boron monoxide (BO; X(2)Σ(+)) with 1,3-butadiene (CH2CHCHCH2; X(1)Ag) and its deuterated counterparts.

    PubMed

    Maity, Surajit; Dangi, Beni B; Parker, Dorian S N; Kaiser, Ralf I; Lin, Hong-Mao; E, Hai-Ping; Sun, Bing-Jian; Chang, A H H

    2015-02-19

    The reactions of the boron monoxide ((11)BO; X(2)Σ(+)) radical with 1,3-butadiene (CH2CHCHCH2; X(1)Ag) and its partially deuterated counterparts, 1,3-butadiene-d2 (CH2CDCDCH2; X(1)Ag) and 1,3-butadiene-d4 (CD2CHCHCD2; X(1)Ag), were investigated under single collision conditions exploiting a crossed molecular beams machine. The experimental data were combined with the state-of-the-art ab initio electronic structure calculations and statistical RRKM calculations to investigate the underlying chemical reaction dynamics and reaction mechanisms computationally. Our investigations revealed that the reaction followed indirect scattering dynamics through the formation of (11)BOC4H6 doublet radical intermediates via the barrierless addition of the (11)BO radical to the terminal carbon atom (C1/C4) and/or the central carbon atom (C2/C3) of 1,3-butadiene. The resulting long-lived (11)BOC4H6 intermediate(s) underwent isomerization and/or unimolecular decomposition involving eventually at least two distinct atomic hydrogen loss pathways to 1,3-butadienyl-1-oxoboranes (CH2CHCHCH(11)BO) and 1,3-butadienyl-2-oxoboranes (CH2C ((11)BO)CHCH2) in overall exoergic reactions via tight exit transition states. Utilizing partially deuterated 1,3-butadiene-d2 and -d4, we revealed that the hydrogen loss from the methylene moiety (CH2) dominated with 70 ± 10% compared to an atomic hydrogen loss from the methylidyne group (CH) of only 30 ± 10%; these data agree nicely with the theoretically predicted branching ratio of 80% versus 19%. PMID:25626151

  16. Modeling of Sheath Ion-Molecule Reactions in Plasma Enhanced Chemical Vapor Deposition of Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Hash, David B.; Govindan, T. R.; Meyyappan, M.

    2004-01-01

    In many plasma simulations, ion-molecule reactions are modeled using ion energy independent reaction rate coefficients that are taken from low temperature selected-ion flow tube experiments. Only exothermic or nearly thermoneutral reactions are considered. This is appropriate for plasma applications such as high-density plasma sources in which sheaths are collisionless and ion temperatures 111 the bulk p!asma do not deviate significantly from the gas temperature. However, for applications at high pressure and large sheath voltages, this assumption does not hold as the sheaths are collisional and ions gain significant energy in the sheaths from Joule heating. Ion temperatures and thus reaction rates vary significantly across the discharge, and endothermic reactions become important in the sheaths. One such application is plasma enhanced chemical vapor deposition of carbon nanotubes in which dc discharges are struck at pressures between 1-20 Torr with applied voltages in the range of 500-700 V. The present work investigates The importance of the inclusion of ion energy dependent ion-molecule reaction rates and the role of collision induced dissociation in generating radicals from the feedstock used in carbon nanotube growth.

  17. High-Temperature and Pressure Aluminum Reactions in Carbon Dioxide Rich Post-Detonation Environments

    NASA Astrophysics Data System (ADS)

    Tappan, Bryce; Manner, Virginia; Pemberton, Steven; Lieber, Mark; Johnson, Carl; Sanders, Eric

    2013-06-01

    Powdered aluminum is a common additive to energetic materials, but little is understood regarding its reaction rate at very high temperatures and pressures in specific oxidizing gases such as carbon dioxide. Aluminum reaction kinetics in carbon dioxide have been studied in various reaction conditions, but difficulties arise in the more specific study of Al oxidation at the high pressures and temperatures in detonation reactions. To study these reactions, small particle size Al or the inert surrogate, LiF, was added to the energetic material benzotrifuroxan (BTF). BTF is a hydrogen-free material that selectively forms CO2 as the major oxidizing species for post-detonation Al oxidation. High-fidelity PDV measurements were utilized for early wall velocity expansion measurements in 12.7 mm copper cylinders. The JWL equation of state was solved to determine temperature, pressure and energies at specific time periods. A genetic algorithm was used in conjunction with a numerical simulation hydrocode, ALE3D, which enables the elucidation of aluminum reaction extent. By comparison of the Al oxidation with LiF, data indicate that Al oxidation occurs on an extremely fast time scale, beginning and completing between 1 and 25 microseconds. Unconfined, 6.4 mm diameter rate-sticks were also utilized to determine the effect of Al compared to LiF on detonation velocity.

  18. High-temperature and pressure aluminum reactions in carbon dioxide rich post-detonation environments

    NASA Astrophysics Data System (ADS)

    Tappan, B. C.; Hill, L. G.; Manner, V. W.; Pemberton, S. J.; Lieber, M. A.; Johnson, C. E.; Sanders, V. E.

    2014-05-01

    Powdered aluminum is a common additive to energetic materials, but little is understood regarding its reaction rate at very high temperatures and pressures in specific oxidizing gases such as carbon dioxide. Aluminum reaction kinetics in carbon dioxide have been studied in various reaction conditions, but difficulties arise in the more specific study of Al oxidation at the high pressures and temperatures in detonation reactions. To study these reactions, small particle size Al or the inert surrogate, LiF, was added to the energetic material benzotrifuroxan (BTF). BTF is a hydrogen-free material that selectively forms CO2 as the major oxidizing species for post-detonation Al oxidation. High-fidelity PDV measurements were utilized for early wall velocity expansion measurements in 12.7 mm copper cylinders. The JWL equation of state was solved to determine temperature, pressure and energies at specific time periods. A genetic algorithm was used in conjunction with a numerical simulation hydrocode, ALE3D, which enables the elucidation of aluminum reaction extent. By comparison of the Al oxidation with LiF, data indicate that Al oxidation occurs on an extremely fast time scale, beginning and completing between 1 and 25 microseconds. Unconfined, 6.4 mm diameter rate-sticks were also utilized to determine the effect of Al compared to LiF on detonation velocity.

  19. Extraordinary 13C enrichment of diether lipids at the Lost City Hydrothermal Field indicates a carbon-limited ecosystem

    NASA Astrophysics Data System (ADS)

    Bradley, Alexander S.; Hayes, John M.; Summons, Roger E.

    2009-01-01

    Active and inactive carbonate chimneys from the Lost City Hydrothermal Field contain up to 0.6% organic carbon with diverse lipid assemblages. The δ 13C values of total organic carbon range from -21.5‰ vs. VPDB at an extinct carbonate chimney to -2.8‰ at a 70 °C, actively venting carbonate chimney. Samples collected at locations with total organic carbon with δ 13C > -15‰ also contained high abundances of isoprenoidal and nonisoprenoidal diether lipids. Samples with TOC more depleted in 13C lacked or contained lower amounts of these diethers. Isoprenoidal diethers, including sn-2 hydroxyarchaeol, sn-3 hydroxyarchaeol, and putative dihydroxyarchaeol, are likely to derive from methanogenic archaea. These compounds have δ 13C values ranging from -2.9 to +6.7‰ vs. VPDB. Nonisoprenoidal diethers and monoethers are presumably derived from bacteria, and have structures similar to those produced by sulfate-reducing bacteria in culture and at cold seeps. In samples that also contained abundant hydroxyarchaeols, these diethers have δ 13C values between -11.8 and +3.6‰. In samples without abundant hydroxyarchaeols, the nonisoprenoidal diethers were typically more depleted in 13C, with δ 13C as low as -28.7‰ in chimneys and -45‰ in fissures. The diethers at Lost City are probably derived from hydrogen-consuming methanogens and bacteria. High hydrogen concentrations favor methanogenesis over methanotrophy and allow the concurrent growth of methanogens and sulfate-reducing bacteria. The unusual enrichment of 13C in lipids can be attributed to nearly complete consumption of bioavailable carbon in vent fluids. Under carbon-limited conditions, the isotope effects that usually lead to 13C-depletion in organic material cannot be expressed. Consequently, metabolic products such as lipids and methane have δ 13C values typical of abiotic carbon.

  20. Carbon kinetic isotope effect in the reaction of CH{sub 4} with Cl atoms

    SciTech Connect

    Saueressig, G.; Bergamaschi, P.; Crowley, J.N.

    1995-05-15

    The authors report laser absorption spectroscopy measurements of the carbon kinetic isotope effect involving chlorine reacting with methane under stratospheric type conditions. The authors find a slight isotope effect of 1.066 {+-} 0.002 at 297 K for the ratio of {sup 13}CH{sub 4}/{sup 12}CH{sub 4}. There was also a slight temperature dependence observed.

  1. Assessing offsets between the δ13C of sedimentary components and the global exogenic carbon pool across early Paleogene carbon cycle perturbations

    NASA Astrophysics Data System (ADS)

    Sluijs, Appy; Dickens, Gerald R.

    2012-12-01

    Negative stable carbon isotope excursions (CIEs) across the Paleocene-Eocene thermal maximum (PETM; ˜56 Ma) range between 2‰ and 7‰, even after discounting sections with truncated records. Individual carbon isotope records differ in shape and magnitude from variations in the global exogenic carbon cycle through changes in (1) the relative abundance of mixed components with different δ13C within a measured substrate, (2) isotope fractionation through physiological change, and (3) the isotope composition of the carbon source. All three factors likely influence many early Paleogene δ13C records, especially across the PETM and other hyperthermal events. We apply these concepts to late Paleocene-early Eocene (˜58-52 Ma) records from Lomonosov Ridge, Arctic Ocean. Linear regression analyses show correlations between the δ13C of total organic carbon (TOC) and two proxies for the relative contribution of terrestrial organic components to sediment TOC: the branched and isoprenoid tetraether index and palynomorphs. We use these correlations to subtract the terrestrial component from δ13CTOC and calculate marine organic matter δ13C. The results show that the magnitude of the CIE in δ13CTOC across the PETM is exaggerated relative to the magnitude of the CIE in δ13CMOM by ˜3‰ due to increased contributions of terrestrial organic carbon during the event. Collectively, all carbon isotope records across the PETM and other major climate-carbon cycle perturbations in Earth's history are potentially biased through one or more of the above factors. Indeed, it is highly unlikely that any δ13C record shows the true shape and magnitude of the CIE for the global exogenic carbon cycle. For the PETM, we conclude that CIE in the exogenic carbon cycle is likely <4‰, but it will take additional analyses and modeling to obtain an accurate value for this CIE.

  2. Temperature-mediated changes in microbial carbon use efficiency and 13C discrimination

    NASA Astrophysics Data System (ADS)

    Lehmeier, Christoph A.; Ballantyne, Ford, IV; Min, Kyungjin; Billings, Sharon A.

    2016-06-01

    Understanding how carbon dioxide (CO2) flux from ecosystems feeds back to climate warming depends in part on our ability to quantify the efficiency with which microorganisms convert organic carbon (C) into either biomass or CO2. Quantifying ecosystem-level respiratory CO2 losses often also requires assumptions about stable C isotope fractionations associated with the microbial transformation of organic substrates. However, the diversity of organic substrates' δ13C and the challenges of measuring microbial C use efficiency (CUE) in their natural environment fundamentally limit our ability to project ecosystem C budgets in a warming climate. Here, we quantify the effect of temperature on C fluxes during metabolic transformations of cellobiose, a common microbial substrate, by a cosmopolitan microorganism growing at a constant rate. Biomass C specific respiration rate increased by 250 % between 13 and 26.5 °C, decreasing CUE from 77 to 56 %. Biomass C specific respiration rate was positively correlated with an increase in respiratory 13C discrimination from 4.4 to 6.7 ‰ across the same temperature range. This first demonstration of a direct link between temperature, microbial CUE, and associated isotope fluxes provides a critical step towards understanding δ13C of respired CO2 at multiple scales, and towards a framework for predicting future ecosystem C fluxes.

  3. Effect of reaction temperature on carbon films prepared by a hydrothermal electrochemical method

    NASA Astrophysics Data System (ADS)

    Tao, Y.; Yi, D.; Zhu, B.

    2012-03-01

    Carbon films were synthesized under hydrothermal electrochemical conditions using sugar as the carbon source at temperature ranging from 170 °C to 180 °C. The reaction temperature affects the degree of sugar decomposition, the concentration of carbon ions, supersaturation and overpotential of the solution, thereby affecting the morphology, orientation, and crystallinity of the films. The graphitic content (sp2) increases with increasing the processing temperature and vice versa. The higher the synthesizing temperature the less the amount of amorphous carbon (sp3). The graphite in thin films prepared at 170 °C and 175 °C shows a (101) preferred orientation, whereas those prepared at 180 °C show a fairly random orientation. The mechanism of this synthesizing process seems to consist of three stages.

  4. Ecosystem Carbon-13 Isoscapes and Uncertainty Estimates for Africa: Integrating Remote Sensing and Field Isotope Measurements

    NASA Astrophysics Data System (ADS)

    Powell, R. L.; Yoo, E.; Still, C. J.

    2012-12-01

    The carbon isotope composition (δ13C) of terrestrial vegetation and soils is required for a diverse set of carbon cycle research, including inversion studies that use global CO2 and δ13C atmospheric data, as well as work that requires the carbon isotope composition of biomass burning emissions. Spatial representation of plant photosynthetic pathways is also necessary for mapping plant functional types needed to accurately simulate biosphere-atmosphere exchanges and for understanding the response of vegetation to global change. Here, we present continental maps of leaf and soil δ13C for Africa corresponding to approximately the year 2000, based upon predictions of the abundance and distribution of C3 and C4 vegetation and the δ13C values of various plant leaf endmembers. Our approach is based on the near-universal restriction of C4 photosynthesis to the herbaceous growth form and the differing performance of C3 and C4 plants in various climates, along with land-cover and crop-type distributions. We predict the percentage of C3 and C4 vegetation in each 5-minute grid cell (~10 km) by merging freely available, global-scale datasets of vegetation-growth-form fractional cover, crop-area/crop-type distribution, and fine-spatial-resolution climate data. We develop a consistent set of rules to harmonize the different data layers. The δ13C of vegetation is then estimated based on the relative C3/C4 composition of each terrestrial grid cell, assuming constant mean δ13C values for closed tropical forest, open forest/shrub ecosystems, C3 herbaceous cover, and C4 herbaceous cover. By integrating the reported standard deviations for each vegetation category, we generate additional layers that represent the lower and upper values for expected leaf δ13C (μ ± 1σ). Soil δ13C is estimated for regions in C4-favored climates using two different approaches: the first is derived from our vegetation δ13C prediction, and the second is based on a previously published

  5. Shrinkage Cracking: A mechanism for self-sustaining carbon mineralization reactions in olivine rocks

    NASA Astrophysics Data System (ADS)

    Zhu, W.; Fusseis, F.; Lisabeth, H. P.; Xing, T.; Xiao, X.; De Andrade, V. J. D.; Karato, S. I.

    2015-12-01

    The hydration and carbonation of olivine results in an up to ~44% increase in solid molar volume, which may choke off of fluid supply and passivate reactive surfaces, thus preventing further carbonation reactions. The carbonation of olivine has ben studied extensively in the laboratory. To date, observations from these experimental studies indicate that carbonation reaction rates generally decrease with time and the extent of carbonation is limited in olivine rocks. Field studies, however, show that 100% hydration and carbonation occur naturally in ultramafic rocks. The disagreement between the laboratory results under controlled conditions and the field observations underlines the lack of understanding of the mechanisms responsible for the self-sustaining carbonation interaction in nature. We developed a state-of-the-art pressurized hydrothermal cell that is transparent to X-rays to characterize the real-time evolution of pore geometry during fluid-rock interaction using in-situ synchrotron-based X-ray microtomography. Through a time series of high-resolution 3-dimensional images, we document the microstructural evolution of a porous olivine aggregate reacting with a sodium bicarbonate solution at elevated pressure and temperature conditions. We observed porosity increases, near constant rate of crystal growth, and pervasive reaction-induced fractures. Based on the nanometer scale tomography data, we propose that shrinkage cracking is the mechanism responsible for producing new reactive surface and keep the carbonation reaction self-sustaining in our experiment. Shrinkage cracks are commonly observed in drying mud ponds, cooling lava flows and ice wedge fields. Stretching of a contracting surface bonded to a substrate of nearly constant dimensions leads to a stress buildup in the surface layer. When the stress exceeds the tensile strength, polygonal cracks develop in the surface layer. In our experiments, the stretching mismatch between the surface and interior of

  6. Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8 + 2] Isomers via Tandem [4 + 2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms.

    PubMed

    Chen, Kai; Wu, Feng; Ye, Lijuan; Tian, Zi-You; Yu, Zhi-Xiang; Zhu, Shifa

    2016-09-16

    An experimental test of designed [8 + 2] reaction of vinylphenylfuran and dimethyl acetylenedicarboxylate (DMAD) has been carried out, showing that the reaction gave unexpected addition products under different conditions. When the reaction was conducted under thermal conditions in toluene, expoxyphenanthrene, which was named as a [8 + 2] isomer, was generated. The scope of this reaction has been investigated in the present study. In addition, experiments and DFT calculations have been conducted to investigate how the reaction between vinylphenylfuran and DMAD took place. Surprisingly, the reaction did not involve the expected [8 + 2] intermediate, o-quinodimethane. Instead, the reaction starts from intermolecular Diels-Alder reactions between DMAD and the furan moiety of vinylphenylfuran, followed by unexpected intramolecular alkene-alkene coupling. This step generates a diradical species, which then undergoes [1,3]-H shift to give the experimentally observed expoxyphenanthrene. DFT calculations revealed that, the [8 + 2] cycloadduct cannot be obtained because the [1,5]-H shift process from the [1,5]-vinyl shift intermediate is disfavored kinetically compared to the [1,3]-H shift to the [8 + 2] isomer.

  7. Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8 + 2] Isomers via Tandem [4 + 2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms.

    PubMed

    Chen, Kai; Wu, Feng; Ye, Lijuan; Tian, Zi-You; Yu, Zhi-Xiang; Zhu, Shifa

    2016-09-16

    An experimental test of designed [8 + 2] reaction of vinylphenylfuran and dimethyl acetylenedicarboxylate (DMAD) has been carried out, showing that the reaction gave unexpected addition products under different conditions. When the reaction was conducted under thermal conditions in toluene, expoxyphenanthrene, which was named as a [8 + 2] isomer, was generated. The scope of this reaction has been investigated in the present study. In addition, experiments and DFT calculations have been conducted to investigate how the reaction between vinylphenylfuran and DMAD took place. Surprisingly, the reaction did not involve the expected [8 + 2] intermediate, o-quinodimethane. Instead, the reaction starts from intermolecular Diels-Alder reactions between DMAD and the furan moiety of vinylphenylfuran, followed by unexpected intramolecular alkene-alkene coupling. This step generates a diradical species, which then undergoes [1,3]-H shift to give the experimentally observed expoxyphenanthrene. DFT calculations revealed that, the [8 + 2] cycloadduct cannot be obtained because the [1,5]-H shift process from the [1,5]-vinyl shift intermediate is disfavored kinetically compared to the [1,3]-H shift to the [8 + 2] isomer. PMID:27541179

  8. Reaction engineering for materials processing in space: Reduction of ilmenite by hydrogen and carbon monoxide

    NASA Technical Reports Server (NTRS)

    Zhao, Y.; Shadman, F.

    1991-01-01

    Oxygen is a consumable material which needs to be produced continuously in most space missions. Its use for propulsion as well as life support makes oxygen one of the largest volume chemicals to be produced in space. Production of oxygen from lunar materials is of particular interest and is very attractive possibility. The kinetics and mechanism of reduction of ilmenite by carbon monoxide and hydrogen at 800 to 1100 C were investigated. The temporal profiles of conversion for carbon monoxide have a sigmoidal shape and indicate the presence of three different stages (induction, acceleration, and deceleration) during the reduction reaction. The apparent activation energy decreases from 18 kcal/mole at 10 percent conversion to 10 kcal/mole at 50 percent conversion. The reaction is first order with respect to carbon monoxide under the experimental conditions studied. Both SEM and EDX analysis show that the diffusion of Fe product away from the reaction front and through the TiO2 phase, followed by the nucleation and growth of a separate Fe phase are important steps affecting the process kinetics. The results from hydrogen reduction show that the mechanism of ilmenite reduction by hydrogen is similar to that by carbon monoxide. However, the titanium dioxide can be further reduced by hydrogen at 800 to 1000 C. The detailed comparison and theoretical modeling of both reduction processes is presented.

  9. Racing carbon atoms. Atomic motion reaction coordinates and structural effects on Newtonian kinetic isotope effects.

    PubMed

    Andujar-De Sanctis, Ivonne L; Singleton, Daniel A

    2012-10-19

    Intramolecular (13)C kinetic isotope effects were determined for the dimerization of methacrolein. Trajectory studies accurately predict the isotope effects and support an origin in Newton's second law of motion, with no involvement of zero-point energy or transition state recrossing. Atomic motion reaction coordinate diagrams are introduced as a way to qualitatively understand the selectivity.

  10. Synthesis and polymerization of renewable 1,3-cyclohexadiene using metathesis, isomerization, and cascade reactions with late-metal catalysts.

    PubMed

    Mathers, Robert T; Shreve, Michael J; Meyler, Etan; Damodaran, Krishnan; Iwig, David F; Kelley, Diana J

    2011-09-01

    Synthesis and subsequent polymerization of renewable 1,3-cyclohexadiene (1,3-CHD) from plant oils is reported via metathesis and isomerization reactions. The metathesis reaction required no plant oil purification, minimal catalyst loading, no organic solvents, and simple product recovery by distillation. After treating soybean oil with a ruthenium metathesis catalyst, the resulting 1,4-cyclohexadiene (1,4-CHD) was isomerized with RuHCl(CO)(PPh3)3. The isomerization reaction was conducted for 1 h in neat 1,4-CHD with [1,4-CHD]/[RuHCl(CO)(PPh3)3] ratios as high as 5000. The isomerization and subsequent polymerization of the renewable 1,3-CHD was examined as a two-step sequence and as a one-step cascade reaction. The polymerization was catalyzed with nickel(II)acetylacetonate/methaluminoxane in neat monomer, hydrogenated d-limonene, and toluene. The resulting polymers were characterized by FTIR, DSC, and TGA. PMID:21648003

  11. Cutting the Gordian Knot: Identifiability of anaplerotic reactions in Corynebacterium glutamicum by means of (13) C-metabolic flux analysis.

    PubMed

    Kappelmann, Jannick; Wiechert, Wolfgang; Noack, Stephan

    2016-03-01

    Corynebacterium glutamicum is the major workhorse for the microbial production of several amino and organic acids. As long as these derive from tricarboxylic acid cycle intermediates, the activity of anaplerotic reactions is pivotal for a high biosynthetic yield. To determine single anaplerotic activities (13) C-Metabolic Flux Analysis ((13) C-MFA) has been extensively used for C. glutamicum, however with different network topologies, inconsistent or poorly determined anaplerotic reaction rates. Therefore, in this study we set out to investigate whether a focused isotopomer model of the anaplerotic node can at all admit a unique solution for all fluxes. By analyzing different scenarios of active anaplerotic reactions, we show in full generality that for C. glutamicum only certain anaplerotic deletion mutants allow to uniquely determine the anaplerotic fluxes from (13) C-isotopomer data. We stress that the result of this analysis for different assumptions on active enzymes is directly transferable to other compartment-free organisms. Our results demonstrate that there exist biologically relevant metabolic network topologies for which the flux distribution cannot be inferred by classical (13) C-MFA. PMID:26375179

  12. The Precise Radio Observation of the 13C Isotopic Fractionation for Carbon Chain Molecule HC3N in the Low-Mass Star Forming Region L1527

    NASA Astrophysics Data System (ADS)

    Araki, Mitsunori; Takano, Shuro; Sakai, Nami; Yamamoto, Satoshi; Oyama, Takahiro; Kuze, Nobuhiko; Tsukiyama, Koichi

    2016-06-01

    We observed the three 13C isotopic species of HC3N with the high signal-to-noise ratios in L1527 using Green Bank 100 m telescope and Nobeyama 45 m telescope to explore the production scheme of HC3N, where L1527 is the low-mass star forming region in the phase of a warm carbon chain chemistry region. The spectral lines of the J = 5--4, 9--8, 10--9, and 12--11 transitions in the 44-109 GHz region were used to measure isotopic ratios. The abundance of HCCCN was determined from the line intensities of the two weak hyperfine components of the J = 5-4 transition. The isotopic ratios were precisely determined to be 1.00 : 1.01 : 1.35 : 86.4 for [H13CCCN] : [HC13CCN] : [HCC13CN] : [HCCCN]. It was found that the abundance of H13CCCN is equal to that of HC13CCN, and it was implied that HC3N is mainly formed by the reaction schemes via C2H2 and C2H2+ in L1527. This would suggest a universality of dicarbide chemistry producing HC3N irrespective of evolutional phases from a starless dark cloud to a warm carbon chain chemistry region. Sakai, N., Sakai, T., Hirota, T., & Yamamoto, S. 2008, ApJ, 672, 371 Takano, S., Masuda, A., Hirahara, Y., et al. 1998, A&A, 329, 1156

  13. Carbon Transfer from the Host to Tuber melanosporum Mycorrhizas and Ascocarps Followed Using a 13C Pulse-Labeling Technique

    PubMed Central

    Le Tacon, François; Zeller, Bernd; Plain, Caroline; Hossann, Christian; Bréchet, Claude; Robin, Christophe

    2013-01-01

    Truffles ascocarps need carbon to grow, but it is not known whether this carbon comes directly from the tree (heterotrophy) or from soil organic matter (saprotrophy). The objective of this work was to investigate the heterotrophic side of the ascocarp nutrition by assessing the allocation of carbon by the host to Tuber melanosporum mycorrhizas and ascocarps. In 2010, a single hazel tree selected for its high truffle (Tuber melanosporum) production and situated in the west part of the Vosges, France, was labeled with 13CO2. The transfer of 13C from the leaves to the fine roots and T. melanosporum mycorrhizas was very slow compared with the results found in the literature for herbaceous plants or other tree species. The fine roots primarily acted as a carbon conduit; they accumulated little 13C and transferred it slowly to the mycorrhizas. The mycorrhizas first formed a carbon sink and accumulated 13C prior to ascocarp development. Then, the mycorrhizas transferred 13C to the ascocarps to provide constitutive carbon (1.7 mg of 13C per day). The ascocarps accumulated host carbon until reaching complete maturity, 200 days after the first labeling and 150 days after the second labeling event. This role of the Tuber ascocarps as a carbon sink occurred several months after the end of carbon assimilation by the host and at low temperature. This finding suggests that carbon allocated to the ascocarps during winter was provided by reserve compounds stored in the wood and hydrolyzed during a period of frost. Almost all of the constitutive carbon allocated to the truffles (1% of the total carbon assimilated by the tree during the growing season) came from the host. PMID:23741356

  14. Sulfur reactions and cryptic cross-linkages to oxygen, iron, and carbon cyclin

    NASA Astrophysics Data System (ADS)

    Druschel, G.; Kafantaris, F. C. A.; Fike, D. A.; Schmitt-Kopplin, P.; Dvorski, S.; Oduro, H.

    2014-12-01

    Sulfur speciation in any setting is controlled by a complex series of redox reactions, polymerization, and complexation reactions that are affected by both biotic and abiotic processes. Additionally there are several crossroads of reactions with oxygen, carbon, and iron in which polysulfide molecules serve as a key reaction component that affects not only sulfur speciation, but the speciation, solubility, and bioavailability of these elements as well. Utilizing a combination of analytical approaches including electrochemistry, spectroscopy, mass spectrometry, and chromatography, we have started to unravel the interconnections between sulfur and other key elements, and how microorganisms may be either direct or indirect contributors to these chemical and mineralogical signatures. In microbial mats, we have observed microbial production of significant hydrogen peroxide under UV-stressed conditions. This peroxide interaction with hydrogen sulfide changes the kinetics and the pathways of abiotic sulfur reactions, potentially affecting the overall bioavailability and isotopic fractionations for specific reactions via a change in the linkage between oxygen and sulfur cycling. In systems containing significant iron, we have observed the production of an electroactive form of ferrous iron and sulfide (FeS(aq)) that is of a size that can be described between a dissolved molecular cluster and a small nanoparticle. This FeS(aq) can be a significant fraction of the dissolved iron or sulfide in a system, and is a key part of both the solubility of iron and sulfur and the pathways potentially important for pyritization reactions. In systems where we investigate the links between sulfur and carbon, laboratory and field experiments indicate a wide range of large and more reduced organic compounds are highly reactive towards polysulfide. Utilizing Fourier-transform ion cyclotron resonance mass spectrometry in conjunction with electrochemistry and chromatography, we are seeing a

  15. Effect of carbon on the Ni catalyzed methane cracking reaction: A DFT study

    NASA Astrophysics Data System (ADS)

    Li, Jingde; Croiset, Eric; Ricardez-Sandoval, Luis

    2014-08-01

    To understand the effects of carbon atoms on the Ni catalyzed methane cracking reactions, methane dissociation on clean, surface-carbon-covered, and subsurface-carbon-accumulated Ni(1 1 1) surfaces were investigated using density functional theory (DFT). The results show that the existence of surface and subsurface C atoms destabilized the adsorption of the surface hydrocarbon species when compared to the clean Ni(1 1 1) surface. The projected density state (PDOS) analysis shows that the deposition of C atoms on and into the Ni surface modified the electronic structure of the Ni surface, and thus reduced the catalytic activity of the bonded Ni atoms. Moreover, it was found that the presence carbon atoms increase the CHx (x = 4-1) species activation barriers especially on the surface carbon covered (1/4 ML) Ni(1 1 1) surface, where CHx (x = 4-1) species encounter highest energy barrier for dissociation due to the electronic deactivation induced by Csbnd Ni bonding and the strong repulsive carbon sbnd CHx interaction. The calculations also show that CHx dissociation barriers are not affected by its neighboring C atom at low surface carbon coverage (1/9 ML). This work can be used to estimate more realistic kinetic parameters for this system.

  16. CaCO3, its reaction and carbonate rocks: terahertz spectroscopy investigation

    NASA Astrophysics Data System (ADS)

    Zhan, Honglei; Wu, Shixiang; Zhao, Kun; Bao, Rima; Xiao, Lizhi

    2016-10-01

    Carbonate-rich rocks cover a primary part of the earth’s petroleum geology reservoir. The study of carbonate has special significance and more effective study methods are now needed. In order to improve the availability of carbonate rock detection, terahertz (THz) spectroscopy was employed to investigate relevant materials in Na2CO3  +  CaCl2  =  CaCO3  +  2NaCl, which is often used to generate CaCO3. By comparing the materials composited with different ions, it can be revealed that Ca2+, \\text{CO}32- , Na+ and Cl- have respective absorption features at different frequencies. Furthermore, by utilizing a conservation equation it can be observed that the average refractive indices of Na2CO3 as well as CaCl2 equal those of CaCO3 and NaCl in the entire range. Combining the absorption and refractive effect of the materials in the reaction can comprehensively characterize the different substances and reveal the inner interaction during the reaction. THz spectra can deduce the process of molecule rearrangement in the chemical reaction of long-term rock evolution. Besides, the absorption features of the real carbonate rock collected from the nearest town of Sinan county, Guizhou province in Yunnan-Guizhou plateau validate the peaks’ central frequencies of ions and the principal components of carbonates, which can be in agreement with the SEM-EDS analysis. This research will supply a spectral tool to identify the particles in the rock and deduce an evolution of petroleum carbonate reservoir.

  17. Asymmetric Synthesis of α-Amino 1,3-Dithianes via Chiral N-Phosphonyl Imine-based Umpolung Reaction

    PubMed Central

    Kattamuri, Padmanabha V.; Ai, Teng; Pindi, Suresh; Sun, Yinwei; Gu, Peng; Shi, Min; Li, Guigen

    2011-01-01

    A series of α-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The addition manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (Group-Assistant-Purification chemistry) process which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral α-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or the mixture of hexane-ethyl acetate. PMID:21405041

  18. Products of the gas-phase reactions of 1,3-butadiene with OH and NO{sub 3} radicals

    SciTech Connect

    Tuazon, E.C.; Alvarado, A.; Aschmann, S.M.; Atkinson, R.; Arey, J.

    1999-10-15

    1,3-Butadiene is emitted into the atmosphere from a number of sources including combustion sources and is listed in the US as a hazardous air pollutant. In the atmosphere, 1,3-butadiene reacts with OH radicals, NO{sub 3} radicals, and O{sub 3} with the dominant tropospheric removal processes being daytime reaction with the OH radical and nighttime reaction with the NO{sub 3} radical. The authors have used gas chromatography, in situ Fourier transform infrared (FT-IR) absorption spectroscopy, and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS) to identify and quantify the products formed from the reactions of 1,3-butadiene with OH radicals (in the presence of NO) and NO{sub 3} radicals. Acrolein, formaldehyde, and furan were identified and quantified from the OH radical-initiated reaction, with formation yields of 0.58 {+-} 0.04, 0.62 {+-} 0.05, and 0.03--0.04, respectively. Organic nitrates were observed by FT-IR spectroscopy with an estimated yield of 0.07 {+-} 0.03, and the API-MS analyses indicated that these organic nitrates are mainly the hydroxynitrate HOCH{sub 2}CH=CHCH{sub 2}ONO{sub 2} and/or its isomers. API-MS analyses showed the formation of a hydroxycarbonyl with the formula C{sub 4}H{sub 6}O{sub 2}, attributed to HOCH{sub 2}CH=CHCHO and/or its isomers. The major products of the NO{sub 3} radical-initiated reaction were organic nitrates; the API-MS analyses indicated the formation of acrolein, 1,2-epoxy-3-butene, and unsaturated C{sub 4}-hydroxycarbonyls, hydroxynitrates, carbonyl nitrates, and nitrooxyhydroperoxides. Acrolein, HCHO, and furan were again quantified by gas chromatographic and FT-IR analyses. The data is compared with previous literature studies, and detailed reaction mechanisms are presented and discussed.

  19. Enantioselective TADMAP-Catalyzed Carboxyl Migration Reactions for the Synthesis of Stereogenic Quaternary Carbon

    PubMed Central

    Shaw, Scott A.; Aleman, Pedro; Christy, Justin; Kampf, Jeff W.; Va, Porino

    2008-01-01

    The chiral, nucleophilic catalyst TADMAP (1) has been prepared from 3-lithio-4-dimethylamino-pyridine (5) and triphenylacetaldehyde (3), followed by acylation and resolution. TADMAP catalyzes the carboxyl migration of oxazolyl, furanyl, and benzofuranyl enol carbonates with good to excellent levels of enantioselection. The oxazole reactions are especially efficient, and are used to prepare chiral lactams (23) and lactones (30) containing a quaternary asymmetric carbon. TADMAP-catalyzed carboxyl migrations in the indole series are relatively slow and proceed with inconsistent enantioselectivity. Modeling studies (B3LYP/6-31G*) have been used in qualitative correlations of catalyst conformation, reactivity, and enantioselectivity. PMID:16417383

  20. Facile synthesis of nitrogen and sulfur codoped carbon from ionic liquid as metal-free catalyst for oxygen reduction reaction.

    PubMed

    She, Yiyi; Lu, Zhouguang; Ni, Meng; Li, Li; Leung, Michael K H

    2015-04-01

    Developing metal-free catalysts for oxygen reduction reaction (ORR) is a great challenge in the development of fuel cells. Nitrogen and sulfur codoped carbon with remarkably high nitrogen content up to 13.00 at % was successfully fabricated by pyrolysis of homogeneous mixture of exfoliated graphitic flakes and ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bimi][Tf2N]). The exfoliated graphite flakes served as a structure-directing substance as well as additional carbon source in the fabrication. It was demonstrated that the use of graphite flakes increased the nitrogen doping level, optimized the composition of active nitrogen configurations, and enlarged the specific surface area of the catalysts. Electrochemical characterizations revealed that the N and S codoped carbon fabricated by this method exhibited superior catalytic activities toward ORR under both acidic and alkaline conditions. Particularly in alkaline solution, the current catalyst compared favorably to the conventional 20 wt % Pt/C catalyst via four-electron transfer pathway with better ORR selectivity. The excellent catalytic activity was mainly ascribed to high nitrogen doping content, appropriate constitution of active nitrogen configurations, large specific surface area, and synergistic effect of N and S codoping. PMID:25781628

  1. Role of Carbon-Addition and Hydrogen-Migration Reactions in Soot Surface Growth.

    PubMed

    Zhang, Hong-Bo; Hou, Dingyu; Law, Chung K; You, Xiaoqing

    2016-02-11

    Using density functional theory and master equation modeling, we have studied the kinetics of small unsaturated aliphatic molecules reacting with polycyclic aromatic hydrocarbon (PAH) molecules having a diradical character. We have found that these reactions follow the mechanism of carbon addition and hydrogen migration (CAHM) on both spin-triplet and open-shell singlet potential energy surfaces at a rate that is about ten times those of the hydrogen-abstraction-carbon-addition (HACA) reactions at 1500 K in the fuel-rich postflame region. The results also show that the most active reaction sites are in the center of the zigzag edges of the PAHs. Furthermore, the reaction products are more likely to form straight rather than branched aliphatic side chains in the case of reacting with diacetylene. The computed rate constants are also found to be independent of pressure at conditions of interest in soot formation, and the activation barriers of the CAHM reactions are linearly correlated with the diradical characters.

  2. Role of Carbon-Addition and Hydrogen-Migration Reactions in Soot Surface Growth.

    PubMed

    Zhang, Hong-Bo; Hou, Dingyu; Law, Chung K; You, Xiaoqing

    2016-02-11

    Using density functional theory and master equation modeling, we have studied the kinetics of small unsaturated aliphatic molecules reacting with polycyclic aromatic hydrocarbon (PAH) molecules having a diradical character. We have found that these reactions follow the mechanism of carbon addition and hydrogen migration (CAHM) on both spin-triplet and open-shell singlet potential energy surfaces at a rate that is about ten times those of the hydrogen-abstraction-carbon-addition (HACA) reactions at 1500 K in the fuel-rich postflame region. The results also show that the most active reaction sites are in the center of the zigzag edges of the PAHs. Furthermore, the reaction products are more likely to form straight rather than branched aliphatic side chains in the case of reacting with diacetylene. The computed rate constants are also found to be independent of pressure at conditions of interest in soot formation, and the activation barriers of the CAHM reactions are linearly correlated with the diradical characters. PMID:26799641

  3. tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon-Nitrogen Bond Forming Reactions.

    PubMed

    Ramirez Hernandez, Johana; Chemla, Fabrice; Ferreira, Franck; Jackowski, Olivier; Oble, Julie; Perez-Luna, Alejandro; Poli, Giovanni

    2016-01-01

    The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon-nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions. PMID:26931222

  4. The Reactions of Methanimine and Cyanogen with Carbon Monoxide in Prebiotic Molecular Evolution on Earth

    NASA Astrophysics Data System (ADS)

    Aylward, Nigel; Bofinger, Neville

    2001-12-01

    A primeval atmosphere is proposed containing simple molecules such as formaldehyde, ammonia, carbon monoxide, cyanogen and hydrogen cyanide, which have been detected in space. Chemical reactions are described for the formation of aziridine-2-one and di-azirine-3-one derivatives as potential precursors for the original synthesesis of amino-acids, proteins, pyrimidines, purines, nicotinamide and flavin. The reactions have been shown to be kinetically feasible from the overall enthalpy changes in the ZKE approximation at the MP2/6-31G^* level.

  5. Soil carbon cycle 13C responses in the decade following bark beetle and girdling disturbance

    NASA Astrophysics Data System (ADS)

    Maurer, G. E.; Chan, A. M.; Trahan, N. A.; Moore, D. J.; Bowling, D. R.

    2014-12-01

    Recent bark beetle outbreaks in western North America have impacted millions of hectares of conifer forests leading to uncertainty about whether these forests will become new sources of atmospheric CO2. In large part, this depends on whether enhanced respiration from the decomposition of newly dead organic matter will outpace the recovery of ecosystem carbon uptake by the ecosystems. To understand how rapidly conifer forest carbon pools turn over following these disturbances, we examined changes in the isotopic composition of soil respiration (δ13Cresp) following beetle and girdling mortality in two subalpine forests in Colorado, U.S.A. At the beetle-impacted forest δ13Cresp declined by ~1‰ between 3 and 8 years post-disturbance, but recovered in years 9-10. In the girdled forest, deep (<10 cm depth) soil respiration from plots at <1 to 2 years post-girdling was depleted by ~1‰ relative to ungirdled plots, but then gradually increased until there was a significant spike in δ13Cresp at 8-9 years post-girdling. Based on our understanding of isotopic composition in carbon pools and fluxes at these forests, we attribute these changes to removal of recently assimilated C in rhizosphere respiration (1-2 years) followed by the decomposition of litterfall (needles and roots) 8-10 years post-disturbance. Relative to ungirdled plots, there was also a transient enrichment in surface δ13Cresp from plots at <1 to 2 years post-girdling (~0.5‰, not statistically significant) and significant declines in microbial carbon in surface soils in 2-4 year post-girdling plots. Again, based on current understanding, we interpret these to signify the rapid turnover of mycorrhizal and rhizosphere microbial biomass in the 2 years following girdling. A potential confounding factor in this study is that seasonal variation in δ13Cresp was similar in magnitude to changes with time since disturbance and was significantly related to variation in soil temperature and water content.

  6. Recent Advances in Inverse-Electron-Demand Hetero-Diels-Alder Reactions of 1-Oxa-1,3-Butadienes.

    PubMed

    Pałasz, Aleksandra

    2016-06-01

    This review is an endeavor to highlight the progress in the inverse-electron-demand hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes in recent years. The huge number of examples of 1-oxadienes cycloadditions found in the literature clearly demonstrates the incessant importance of this transformation in pyran ring synthesis. This type of reaction is today one of the most important methods for the synthesis of dihydropyrans which are the key building blocks in structuring of carbohydrate and other natural products. Two different modes, inter- and intramolecular, of inverse-electron-demand hetero-Diels-Alder reactions of 1-oxadienes are discussed. The domino Knoevenagel hetero-Diels-Alder reactions are also described. In recent years the use of chiral Lewis acids, chiral organocatalysts, new optically active heterodienes or dienophiles have provided enormous progress in asymmetric synthesis. Solvent-free and aqueous hetero-Diels-Alder reactions of 1-oxabutadienes were also investigated. The reactivity of reactants, selectivity of cycloadditions, and chemical stability in aqueous solutions and under physiological conditions were taken into account to show the potential application of the described reactions in bioorthogonal chemistry. New bioorthogonal ligation by click inverse-electron-demand hetero-Diels-Alder cycloaddition of in situ-generated 1-oxa-1,3-butadienes and vinyl ethers was developed. It seems that some of the hetero-Diels-Alder reactions described in this review can be applied in bioorthogonal chemistry because they are selective, non-toxic, and can function in biological conditions taking into account pH, an aqueous environment, and temperature. PMID:27573264

  7. Recent Advances in Inverse-Electron-Demand Hetero-Diels-Alder Reactions of 1-Oxa-1,3-Butadienes.

    PubMed

    Pałasz, Aleksandra

    2016-06-01

    This review is an endeavor to highlight the progress in the inverse-electron-demand hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes in recent years. The huge number of examples of 1-oxadienes cycloadditions found in the literature clearly demonstrates the incessant importance of this transformation in pyran ring synthesis. This type of reaction is today one of the most important methods for the synthesis of dihydropyrans which are the key building blocks in structuring of carbohydrate and other natural products. Two different modes, inter- and intramolecular, of inverse-electron-demand hetero-Diels-Alder reactions of 1-oxadienes are discussed. The domino Knoevenagel hetero-Diels-Alder reactions are also described. In recent years the use of chiral Lewis acids, chiral organocatalysts, new optically active heterodienes or dienophiles have provided enormous progress in asymmetric synthesis. Solvent-free and aqueous hetero-Diels-Alder reactions of 1-oxabutadienes were also investigated. The reactivity of reactants, selectivity of cycloadditions, and chemical stability in aqueous solutions and under physiological conditions were taken into account to show the potential application of the described reactions in bioorthogonal chemistry. New bioorthogonal ligation by click inverse-electron-demand hetero-Diels-Alder cycloaddition of in situ-generated 1-oxa-1,3-butadienes and vinyl ethers was developed. It seems that some of the hetero-Diels-Alder reactions described in this review can be applied in bioorthogonal chemistry because they are selective, non-toxic, and can function in biological conditions taking into account pH, an aqueous environment, and temperature.

  8. Indirect study of the {sup 13}C({alpha},n){sup 16}O reaction via the {sup 13}C({sup 7}Li,t){sup 17}O transfer reaction

    SciTech Connect

    Pellegriti, M. G.; Hammache, F.; Roussel, P.; Audouin, L.; Beaumel, D.; Fortier, S.; Vilmay, M.; Descouvemont, P.; Gaudefroy, L.; Kiener, J.; Lefebvre-Schuhl, A.; Tatischeff, V.; Stanoiu, M.

    2008-04-15

    The {sup 13}C({alpha},n){sup 16}O reaction is considered the main neutron source for the s process in low mass asymptotic giant branch (AGB) stars. In the Gamow peak, the cross section sensitively depends on the 1/2{sup +} subthreshold state of {sup 17}O (E{sub x}=6.356 MeV). In this work, we determined the astrophysical S factor through an evaluation of the {alpha} spectroscopic factor and the corresponding asymptotic normalization factor (ANC) of the 6.356 MeV state using the transfer reaction {sup 13}C({sup 7}Li,t){sup 17}O at two different incident energies. Our result confirms that the contribution of the 1/2{sup +} state is dominant at astrophysical energies. Our reaction rate at T=0.09 GK is slightly lower than the value adopted in the Nuclear Astrophysics Compilation of REaction rates (NACRE), but two times larger than the one obtained in a recent ANC measurement.

  9. Protonation of carbon single-walled nanotubes studied using 13C and 1H-13C cross polarization nuclear magnetic resonance and Raman spectroscopies.

    PubMed

    Engtrakul, Chaiwat; Davis, Mark F; Gennett, Thomas; Dillon, Anne C; Jones, Kim M; Heben, Michael J

    2005-12-14

    The reversible protonation of carbon single-walled nanotubes (SWNTs) in sulfuric acid and Nafion was investigated using solid-state nuclear magnetic resonance (NMR) and Raman spectroscopies. Magic-angle spinning (MAS) was used to obtain high-resolution 13C and 1H-13C cross polarization (CP) NMR spectra. The 13C NMR chemical shifts are reported for bulk SWNTs, H2SO4-treated SWNTs, SWNT-Nafion polymer composites, SWNT-AQ55 polymer composites, and SWNTs in contact with water. Protonation occurs without irreversible oxidation of the nanotube substrate via a charge-transfer process. This is the first report of a chemically induced change in a SWNT 13C resonance brought about by a reversible interaction with an acidic proton, providing additional evidence that carbon nanotubes behave as weak bases. Cross polarization was found to be a powerful technique for providing an additional contrast mechanism for studying nanotubes in contact with other chemical species. The CP studies confirmed polarization transfer from nearby protons to nanotube carbon atoms. The CP technique was also applied to investigate water adsorbed on carbon nanotube surfaces. Finally, the degree of bundling of the SWNTs in Nafion films was probed with the 1H-13C CP-MAS technique. PMID:16332107

  10. Carbon isotope analysis in urea at high 13C-abundances using the 13/12CO2-breath test device FANci2.

    PubMed

    Schmidt, G

    2002-09-01

    The increasing application of 13C-labelled urea in medicine requires simple and reasonable methods for measuring highly enriched C in urea. The combination: ultimate organic analysis--mass spectrometry so far prescribed is complicated and expensive. For medical diagnosis, however, isotope selective nondispersive infrared spectrometers (NDIRS) have been available for many years. One of these tools is FANci2 which is very reasonable and easily to be operated. By means of such devices also urea highly enriched in 13C can be analysed, provided that the samples are first diluted with a defined amount of urea of natural isotopic composition and then transformed into carbon dioxide by means of urease. The relative abundance of 13C in this carbon dioxide, measured by nondispersive infrared spectrometry, is then a measure of the 13C abundance in the initial urea sample. Comparison of results of such measurements with those attained by mass spectrometry proves that this procedure is feasible and yields precis results.

  11. Active sites in Cu-SSZ-13 deNOx catalyst under reaction conditions: a XAS/XES perspective

    NASA Astrophysics Data System (ADS)

    Lomachenko, Kirill A.; Borfecchia, Elisa; Bordiga, Silvia; Soldatov, Alexander V.; Beato, Pablo; Lamberti, Carlo

    2016-05-01

    Cu-SSZ-13 is a highly active catalyst for the NH3-assisted selective catalytic reduction (SCR) of the harmful nitrogen oxides (NOx, x=1, 2). Since the catalytically active sites for this reaction are mainly represented by isolated Cu ions incorporated into the zeolitic framework, element-selective studies of Cu local environment are crucial to fully understand the enhanced catalytic properties of this material. Herein, we highlight the recent advances in the characterization of the most abundant Cu-sites in Cu-SSZ-13 upon different reaction-relevant conditions made employing XAS and XES spectroscopies, complemented by computational analysis. A concise review of the most relevant literature is also presented.

  12. Isoscapes of tree-ring carbon-13 perform like meteorological networks in predicting regional precipitation patterns

    NASA Astrophysics Data System (ADS)

    Castillo, Jorge; Aguilera, Mònica; Voltas, Jordi; Ferrio, Juan Pedro

    2013-03-01

    isotopes in tree rings provide climatic information with annual resolution dating back for centuries or even millennia. However, deriving spatially explicit climate models from isotope networks remains challenging. Here we propose a methodology to model regional precipitation from carbon isotope discrimination (Δ13C) in tree rings by (1) building regional spatial models of Δ13C (isoscapes) and (2) deriving precipitation maps from Δ13C-isoscapes, taking advantage of the response of Δ13C to precipitation in seasonally dry climates. As a case study, we modeled the spatial distribution of mean annual precipitation (MAP) in the northeastern Iberian Peninsula, a region with complex topography and climate (MAP = 303-1086 mm). We compiled wood Δ13C data for two Mediterranean species that exhibit complementary responses to seasonal precipitation (Pinus halepensis Mill., N = 38; Quercus ilex L.; N = 44; pooling period: 1975-2008). By combining multiple regression and geostatistical interpolation, we generated one Δ13 C-isoscape for each species. A spatial model of MAP was then built as the sum of two complementary maps of seasonal precipitation, each one derived from the corresponding Δ13C-isoscape (September-November from Q. ilex; December-August from P. halepensis). Our approach showed a predictive power for MAP (RMSE = 84 mm) nearly identical to that obtained by interpolating data directly from a similarly dense network of meteorological stations (RMSE = 80-83 mm, N = 65), being only outperformed when using a much denser meteorological network (RMSE = 56-57 mm, N = 340). This method offers new avenues for modeling spatial variability of past precipitation, exploiting the large amount of information currently available from tree-ring networks.

  13. Isoscapes of tree-ring carbon-13 perform like meteorological networks in predicting regional precipitation patterns

    NASA Astrophysics Data System (ADS)

    del Castillo, Jorge; Aguilera, Mònica; Voltas, Jordi; Ferrio, Juan Pedro

    2013-04-01

    Stable isotopes in tree rings provide climatic information with annual resolution dating back for centuries or even millennia. However, deriving spatially explicit climate models from isotope networks remains challenging. Here we propose a methodology to model regional precipitation from carbon isotope discrimination (Δ13C) in tree rings by (1) building regional spatial models of Δ13C (isoscapes), and (2) deriving precipitation maps from 13C-isoscapes, taking advantage of the response of Δ13C to precipitation in seasonally-dry climates. As a case study, we modeled the spatial distribution of mean annual precipitation (MAP) in the northeastern Iberian Peninsula, a region with complex orography and climate (MAP=303-1086 mm). We compiled wood Δ13C data for two Mediterranean species that exhibit complementary responses to seasonal precipitation (Pinus halepensis Mill., N=38; Quercus ilex L.; N=44; pooling period: 1975-2008). By combining multiple regression and geostatistical interpolation, we generated one 13C-isoscape for each species. A spatial model of MAP was then built as the sum of two complementary maps of seasonal precipitation, each one derived from the corresponding 13C-isoscape (September-November from Q. ilex; December-August from P. halepensis). Our approach showed a predictive power for MAP (RMSE=84 mm) nearly identical to that obtained by interpolating data directly from a similarly dense network of meteorological stations (RMSE=80-83 mm, N=65), being only outperformed when using a much denser meteorological network (RMSE=56-57 mm, N=340). This method offers new avenues for modeling spatial variability of past precipitation, exploiting the large amount of information currently available from tree-ring networks. Acknowledgements: This work was funded by MC-ERG-246725 (FP7, EU) and AGL 2012-40039-C02-02 (MINECO, Spain). JdC and JPF are supported by FPI fellowship (MCINN) and Ramón y Cajal programme (RYC-2008-02050, MINECO), respectively.

  14. Organocatalytic, enantioselective, intramolecular oxa-Michael reaction of alkoxyboronate: a new strategy for enantioenriched 1-substituted 1,3-dihydroisobenzofurans.

    PubMed

    Ravindra, Barnala; Das, Braja Gopal; Ghorai, Prasanta

    2014-11-01

    An unprecedented strategy for the synthesis of enantioenriched 1-substituted 1,3-dihydroisobenzofurans via an enantioselective oxa-Michael reaction of o-alkoxyboronate containing chalcone (II) has been accomplished employing cinchona alkaloid based squaramide bifunctional organocatalyst in the presence of proton source. The corresponding alkoxyboronate intermediates have been readily prepared in situ from o-formyl chalcones using neutral borane as hydride source and a tertiary amine moiety which is a counterpart of the catalyst.

  15. Synthesis and carbonic anhydrase inhibitory properties of 1,3-dicarbonyl derivatives of methylaminobenzene-sulfonamide.

    PubMed

    Demirci, Tuna; Arslan, Mustafa; Bilen, Çiğdem; Demir, Dudu; Gençer, Nahit; Arslan, Oktay

    2014-02-01

    Abstract 1,3-Dicarbonyl derivatives of methylaminobenzene-sulfonamide were synthesized and their inhibitory effects on the activity of purified human carbonic anhydrase (hCA) I and hCA II were evaluated. hCA I and hCA II from human erythrocytes were purified by a simple one-step procedure by using Sepharose 4B-L-tyrosine-sulfanilamide affinity column. Our results show that the synthesized compounds inhibited the activity of carbonic anhydrase (CA) I and CA II. Among them, 2b and 2e were found to be the most active (IC50=2.12 and 2.52 µM) for hCA I and hCA II, respectively. PMID:23356427

  16. Carbon-protected bimetallic carbide nanoparticles for a highly efficient alkaline hydrogen evolution reaction.

    PubMed

    Liu, Yipu; Li, Guo-Dong; Yuan, Long; Ge, Lei; Ding, Hong; Wang, Dejun; Zou, Xiaoxin

    2015-02-21

    The hydrogen evolution reaction (HER) is one of the two important half reactions in current water-alkali and chlor-alkali electrolyzers. To make this reaction energy-efficient, development of highly active and durable catalytic materials in an alkaline environment is required. Herein we report the synthesis of carbon-coated cobalt-tungsten carbide nanoparticles that have proven to be efficient noble metal-free electrocatalysts for alkaline HER. The catalyst affords a current density of 10 mA cm(-2) at a low overpotential of 73 mV, which is close to that (33 mV) required by Pt/C to obtain the same current density. In addition, this catalyst operates stably at large current densities (>30 mA cm(-1)) for as long as 18 h, and gives nearly 100% Faradaic yield during alkaline HER. The excellent catalytic performance (activity and stability) of this nanocomposite material is attributed to the cooperative effect between nanosized bimetallic carbide and the carbon protection layer outside the metal carbide. The results presented herein offer the exciting possibility of using carbon-armoured metal carbides for an efficient alkaline HER, although pristine metal carbides are not, generally, chemically stable enough under such strong alkaline conditions.

  17. Inhibiting the CO/CO/sub 2/ reaction between carbon and plutonia at elevated temperatures

    SciTech Connect

    Johnson, E.W.

    1981-01-01

    One of the problems associated with the sometimes protracted, ground storage of space PuO/sub 2/ RTG devices is the ingrowth of carbon dioxide and carbon monoxide in the gas phase due to the cyclical reaction established between the fuel (/sup 238/PuO/sub 2/) and the carbon impact body. This ingrowth proceeds according to the two equations: xCO + PuO/sub 2/ = xCO/sub 2/ + PuO/sub 2/-x (1) and xCO/sub 2/ + xC = 2xCO, etc. (2). This reaction stops after launch because the two solid-phase reactants are physically separated when the inside of the RTG is evacuated to space for performance reasons. When the RTG is stored on the ground, however, the product gases become established and can cause degradation of the solid-state thermoelectric elements. Controlling the reduction of the plutonia to such an extent that reaction (1) becomes thermodynamically unfavorable minimizes the continued generation of CO and CO/sub 2/. The conditions necessary to maintain plutonia at a substoichiometric level are being determined. These test conditions are described and are supported with data from previous heat source studies. Finally a facility to perform the necessary treatment is described.

  18. Reservoir-Condition Pore-Scale Imaging of Reaction in Carbonates using Synchrotron Fast Tomography

    NASA Astrophysics Data System (ADS)

    Menke, H. P.; Andrew, M. G.; Bijeljic, B.; Blunt, M. J.

    2015-12-01

    Carbon capture and storage in carbonate reservoirs is essential for mitigating climate change. Supercritical CO2 mixed with host brine is acidic and can dissolve the surrounding pore structure and change flow dynamics. However, the type, speed, and magnitude of the dissolution are dependent on both the reactive transport properties of the pore-fluid and the intrinsic properties of the rock. Understanding how changes in the pore structure, chemistry, and flow properties affect dissolution is vital for successful predictive modelling both on the pore-scale and for up-scaled reservoir simulations. Reaction in carbonates has been studied at the pore-scale but has never been imaged dynamically in situ. We present an experimental method whereby both lab-based benchtop instruments and 'Pink Beam' synchrotron radiation are used in X-ray microtomography to investigate pore structure changes during supercritical CO2 injection at reservoir conditions. Three types of pure limestone rock with broadly varying rock topology were imaged under the same reservoir conditions. Flow-rate and brine acidity was varied in successive experiments by half an order of magnitude to gain insight into the impact of flow, transport, and physical heterogeneity. The images were binarized and the magnitude of dissolution was identified on a voxel-by-voxel basis to extract pore-by-pore dissolution data. The impact of dissolution on flow characteristics was studied by computing the evolution of the pore-scale velocity fields with a flow solver. We found that increasing rock heterogeneity increased channelized flow [Figure 1] through preferential pathways and that higher flow rate increased total dissolution. Additionally, decreasing reaction rate lowered overall reaction rate and made axial flow less uniform. Experimentally measured reaction rates in real rocks are at least an order of magnitude lower when compared to batch experiments. We provide evidence that this can be due to transport limitations

  19. The chemistry of subcritical water reactions of a hardwood derived lignin and lignin model compounds with nitrogen, hydrogen, carbon monoxide and carbon dioxide

    NASA Astrophysics Data System (ADS)

    Hill Bembenic, Meredith A.

    collected solids from the CO reactions appeared to be the most reacted (i.e., the most changed from the unreacted lignin) according to solid state 13C-NMR analysis, and the widest variety of products (methoxy-substituted phenolic compounds) were obtained when using CO according to GC/MS analysis. Therefore, reactions with CO were completed that varied the initial reaction pressure (300, 500 and 800 psi) in order to elucidate the effects of CO pressure. Similar conversion (≈54--58%) and DCM-soluble liquid product yields (≈53--62%) were obtained for the different pressure reactions, but the reactions with an initial pressure of 500 psi had the greatest change in aromaticity from the unreacted lignin. Additional reactions between Organosolv lignin and H2O with CO (initial pressure of 500 psi) were conducted where the reaction time was varied (15, 30 and 60 min.) to determine the effect of reaction time. Longer reaction time (60 min.) appeared to inhibit conversion to low molecular weight compounds (i.e., conversion and DCM-soluble yields were lower at ≈53% and ≈28%, respectively). Solid state 13C-NMR of collected residues also showed that there are losses in carbons representative of both guaiacyl and syringyl components as reaction time increases, which may indicate that methoxy groups are being cleaved or the products are reacting with each other (i.e., repolymerization) to form high molecular weight compounds as reaction time is increased. The role of H2O and the gases during the baseline reactions and the expanded CO reactions is not intuitive based on the results, so reactions with lignin model compounds (i.e., aromatic aldehydes represented by vanillin and syringaldehyde, aromatic ketones represented by acetovanillone and acetosyringone, and aromatic ethers represented by dibenzyl ether and 2-phenethyl phenyl ether) were completed to study this. From these results, the suggested reaction pathway of Organosolv lignin reactions in subcritical H2O with and without

  20. Stable carbon isotope fractionation during trichloroethene degradation in magnetite-catalyzed Fenton-like reaction.

    PubMed

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Liu, Cunfu; Yu, Tingting; Li, Xiaoqian

    2013-02-01

    Mineral-catalyzed Fenton-like oxidation of chlorinated ethylenes is an attractive technique for in situ soil and groundwater remediation. Stable carbon isotope enrichment factors associated with magnetite-catalyzed Fenton-like oxidation of trichloroethylene (TCE) have been determined, to study the possibility of applying stable carbon isotope analysis as a technique to assess the efficacy of remediation implemented by Fenton-like oxidation. The carbon enrichment factors (ε values) ranged from -2.7‰ to -3.6‰ with a mean value of -3.3±0.3‰, and only small differences were observed for different initial reactive conditions. The ε values were robust and reproducible, and were relatively insensitive to a number of environmental factors such as ratios of reactants and PCE co-contamination, which can reduce the uncertainty associated with application of isotope enrichment factors for quantification of in situ remediation by Fenton-like reaction. ε values for Fenton-like oxidation of TCE were intermediate in those previously reported for aerobic biological processes (ε=-1.1 to -20.7‰). Thus, field-derived ε values that are more negative than those for Fenton-like oxidation, may indicate the occurrence of aerobic biodegradation at contaminated sites undergoing in situ remediation with Fenton-like reaction. However, stable carbon isotope analysis is unable to determine whether there is the occurrence of biodegradation processes if field-derived ε values are less negative than those for Fenton-like oxidation.

  1. An Image of the J=6-5 line of 13-carbon CO in Orion

    NASA Astrophysics Data System (ADS)

    Wilson, Thomas L.; Muders, D.; Dumke, M.

    2007-05-01

    An image of the J=6-5 line of the 13-carbon isotopomer of CO for the region toward and around the Orion KL region and the Orion-S region, about 90” to the south are presented. The measurements are made with the Heinrich-Hertz-Telescope on Mt. Graham, AZ in reasonably good weather. The line frequency is 661 GHz. At this frequency the FWHP beam size is 13”. The velocity result was about 0.5 km s-1. Pointing and focusing measurements were made on planets prior to and during the mapping. The resulting image is fairly similar to that obtained in the J=7-6 line of CO (Wilson, T.L. et al. 2001 ApJ 557, 240-9). Based on a comparison of CO lines, conclusions about the clumping of the molecular gas and the state of this gas are made

  2. Carbon Nitrogen Nanotubes as Efficient Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reactions.

    PubMed

    Yadav, Ram Manohar; Wu, Jingjie; Kochandra, Raji; Ma, Lulu; Tiwary, Chandra Sekhar; Ge, Liehui; Ye, Gonglan; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M

    2015-06-10

    Oxygen reduction and evolution reactions are essential for broad range of renewable energy technologies such as fuel cells, metal-air batteries and hydrogen production through water splitting, therefore, tremendous effort has been taken to develop excellent catalysts for these reactions. However, the development of cost-effective and efficient bifunctional catalysts for both reactions still remained a grand challenge. Herein, we report the electrocatalytic investigations of bamboo-shaped carbon nitrogen nanotubes (CNNTs) having different diameter distribution synthesized by liquid chemical vapor deposition technique using different nitrogen containing precursors. These CNNTs are found to be efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions. The electrocatalytic activity strongly depends on the nanotube diameter as well as nitrogen functionality type. The higher diameter CNNTs are more favorable for these reactions. The increase in nanotube diameter itself enhances the catalytic activity by lowering the oxygen adsorption energy, better conductivity, and further facilitates the reaction by increasing the percentage of catalytically active nitrogen moieties in CNNTs. PMID:25970133

  3. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    USGS Publications Warehouse

    Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

  4. Cross-coupling reaction of alkyl halides with grignard reagents catalyzed by Ni, Pd, or Cu complexes with pi-carbon ligand(s).

    PubMed

    Terao, Jun; Kambe, Nobuaki

    2008-11-18

    Transition metal-catalyzed cross-coupling reactions of organic halides and pseudo-halides containing a C-X bond (X = I, Br, Cl, OTf, OTs, etc.) with organometallic reagents are among the most important transformations for carbon-carbon bond formation between a variety of sp, sp(2), and sp(3)-hybridized carbon atoms. In particular, researchers have widely employed Ni- and Pd-catalyzed cross-coupling to synthesize complex organic structures from readily available components. The catalytic cycle of this process comprises oxidative addition, transmetalation, and reductive elimination steps. In these reactions, various organometallic reagents could bear a variety of R groups (alkyl, vinyl, aryl, or allyl), but the coupling partner has been primarily limited to sp and sp(2) carbon compounds: alkynes, alkenes, and arenes. With alkyl coupling partners, these reactions typically run into two problems within the catalytic cycle. First, oxidative addition of alkyl halides to a metal catalyst is generally less efficient than that of aryl or alkenyl compounds. Second, the alkylmetal intermediates formed tend to undergo intramolecular beta-hydrogen elimination. In this Account, we describe our efforts to overcome these problems for Ni and Pd chemistry. We have developed new catalytic systems that do not involve M(0) species but proceed via an anionic complex as the key intermediate. For example, we developed a unique cross-coupling reaction of alkyl halides with organomagnesium or organozinc reagents catalyzed by using a 1,3-butadiene as the additive. This reaction follows a new catalytic pathway: the Ni or Pd catalyst reacts first with R-MgX to form an anionic complex, which then reacts with alkyl halides. Bis-dienes were also effective additives for the Ni-catalyzed cross-coupling reaction of organozinc reagents with alkyl halides. This catalytic system tolerates a wide variety of functional groups, including nitriles, ketones, amides, and esters. In addition, we have extended

  5. Dynamic three-dimensional pore-scale imaging of reaction in a carbonate at reservoir conditions.

    PubMed

    Menke, Hannah P; Bijeljic, Branko; Andrew, Matthew G; Blunt, Martin J

    2015-04-01

    Quantifying CO2 transport and average effective reaction rates in the subsurface is essential to assess the risks associated with underground carbon capture and storage. We use X-ray microtomography to investigate dynamic pore structure evolution in situ at temperatures and pressures representative of underground reservoirs and aquifers. A 4 mm diameter Ketton carbonate core is injected with CO2-saturated brine at 50 °C and 10 MPa while tomographic images are taken at 15 min intervals with a 3.8 μm spatial resolution over a period of 2(1/2) h. An approximate doubling of porosity with only a 3.6% increase in surface area to volume ratio is measured from the images. Pore-scale direct simulation and network modeling on the images quantify an order of magnitude increase in permeability and an appreciable alteration of the velocity field. We study the uniform reaction regime, with dissolution throughout the core. However, at the pore scale, we see variations in the degree of dissolution with an overall reaction rate which is approximately 14 times lower than estimated from batch measurements. This work implies that in heterogeneous rocks, pore-scale transport of reactants limits dissolution and can reduce the average effective reaction rate by an order of magnitude. PMID:25738415

  6. Ambient solid-state mechano-chemical reactions between functionalized carbon nanotubes

    PubMed Central

    Kabbani, Mohamad A.; Tiwary, Chandra Sekhar; Autreto, Pedro A.S.; Brunetto, Gustavo; Som, Anirban; Krishnadas, K.R.; Ozden, Sehmus; Hackenberg, Ken P.; Gong, Yongi; Galvao, Douglas S.; Vajtai, Robert; Kabbani, Ahmad T.; Pradeep, Thalappil; Ajayan, Pulickel M.

    2015-01-01

    Carbon nanotubes can be chemically modified by attaching various functionalities to their surfaces, although harsh chemical treatments can lead to their break-up into graphene nanostructures. On the other hand, direct coupling between functionalities bound on individual nanotubes could lead to, as yet unexplored, spontaneous chemical reactions. Here we report an ambient mechano-chemical reaction between two varieties of nanotubes, carrying predominantly carboxyl and hydroxyl functionalities, respectively, facilitated by simple mechanical grinding of the reactants. The purely solid-state reaction between the chemically differentiated nanotube species produces condensation products and unzipping of nanotubes due to local energy release, as confirmed by spectroscopic measurements, thermal analysis and molecular dynamic simulations. PMID:26073564

  7. Experimental validation of environmental controls on the δ13C of Arctica islandica (ocean quahog) shell carbonate

    NASA Astrophysics Data System (ADS)

    Beirne, Erin C.; Wanamaker, Alan D.; Feindel, Scott C.

    2012-05-01

    The marine bivalve species, Arctica islandica, was reared under experimental conditions for 29 weeks in the Gulf of Maine in order to determine the relationship between the carbon isotope composition of shell carbonate13CS) and ambient seawater dissolved inorganic carbon13CDIC), as well as to approximate the metabolic contribution (CM) to shell material. Three experimental environments were compared: two flow-through tanks (one at ambient seawater conditions, one with a supplemental food source) and an in situ cage. Each environment contained 50 juveniles and 30 adults. Both juvenile (2-3 years) and adult (19-64 years) specimens displayed average percent CM of less than or equal to 10% when using three different proxies of respired carbon: digestive gland, adductor muscle and sediment. Hence, the primary control on δ13CS values is ambient DIC. The relationship between δ13CDIC and δ13CS for 114 individuals used in the study was: δ13C=δ13C-1.0‰(±0.3‰) No ontogenetic effect on δ13CS was observed, and growth rates did not generally impact δ13CS values. Based on the results of this study, shell material derived from the long-lived ocean quahog (A. islandica) constitutes a viable proxy for paleo-DIC from the extratropical Atlantic Ocean.

  8. Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscop

    SciTech Connect

    Kwak, Ja Hun; Hu, Jian Z.; Hoyt, David W.; Sears, Jesse A.; Wang, Chong M.; Rosso, Kevin M.; Felmy, Andrew R.

    2010-03-11

    Ex situ solid state NMR was used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration (GCS) using a model silicate mineral forsterite (Mg2SiO4)+supercriticalCO2 with and without H2O. Run conditions were 80 C and 96 atm. 29Si NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce dissolved Mg2+, and mono- and oligomeric hydroxylated silica species. Surface hydrolysis products contain only Q0 (Si(OH)4) and Q1(Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. 29Si NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. 13C MAS NMR identified a possible reaction intermediate as (MgCO3)4-Mg(OH)2-5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed.

  9. Anhydrous TEMPO-H: reactions of a good hydrogen atom donor with low-valent carbon centres.

    PubMed

    Giffin, Nick A; Makramalla, Miller; Hendsbee, Arthur D; Robertson, Katherine N; Sherren, Cody; Pye, Cory C; Masuda, Jason D; Clyburne, Jason A C

    2011-05-21

    In this paper, we report a novel synthesis of anhydrous 1-hydroxy-2,2,6,6-tetramethyl-piperidine (TEMPO-H). An X-ray crystal structure and full characterization of the compound are included. Compared to hydrated TEMPO-H, its anhydrous form exhibits improved stability and a differing chemical reactivity. The reactions of anhydrous TEMPO-H with a variety of low-valent carbon centres are described. For example, anhydrous TEMPO-H was reacted with 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), an unsaturated NHC. Crystals of [CHNC(6)H(2)(CH(3))(3)](2)C···HO(NC(5)H(6)(CH(3))(4)), IMes···TEMPO-H, were isolated and a crystal structure determined. The experimental structure is compared to the results of theoretical calculations on the hydrogen-bonded dimer. Anhydrous TEMPO-H was also reacted with the saturated NHC, 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr), giving the product [CH(2)Ni-Pr(2)C(6)H(3)](2)CH···O(NC(5)H(6)(CH(3))(4)). In contrast, the reaction of hydrated TEMPO-H with 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene gave small amounts of the hydrolysis product, N-(2,6-diisopropylphenyl)-N-[2-(2,6-diisopropylphenylamino)ethyl]formamide. Finally, anhydrous TEMPO-H was reacted with (triphenylphosphoranylidene)ketene to generate Ph(3)PC(H)C(=O)O(NC(5)H(6)(CH(3))(4)). A full characterization of the product, including an X-ray crystal structure, is described.

  10. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration – Literature Review

    SciTech Connect

    Krupka, Kenneth M.; Cantrell, Kirk J.; McGrail, B. Peter

    2010-09-01

    Permanent storage of anthropogenic CO2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO2 sequestration. A review of thermodynamic data for CO2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO2 and CH4 gases, carbonate aqueous species, and carbonate minerals. Values of ΔfG298° and/or log Kr,298° are available for essentially all of these compounds. However, log Kr,T° or heat capacity values at temperatures above 298 K exist for less than

  11. 13C-Depleted carbon microparticles in >3700-Ma sea-floor sedimentary rocks from west greenland

    PubMed

    Rosing

    1999-01-29

    Turbiditic and pelagic sedimentary rocks from the Isua supracrustal belt in west Greenland [more than 3700 million years ago (Ma)] contain reduced carbon that is likely biogenic. The carbon is present as 2- to 5-micrometer graphite globules and has an isotopic composition of delta13C that is about -19 per mil (Pee Dee belemnite standard). These data and the mode of occurrence indicate that the reduced carbon represents biogenic detritus, which was perhaps derived from planktonic organisms.

  12. Carbonate reactions in a natural CO2 Reservoir, Green River, Utah, USA

    NASA Astrophysics Data System (ADS)

    Chapman, H.; Bickle, M. J.; Kampman, N.; Maskell, A.; Busch, A.; Evans, J. P.

    2013-12-01

    Understanding the geochemical interaction of CO2 with minerals within a rock reservoir is vitally important to assess the long-term suitability of underground storage of anthropogenic carbon dioxide. This study investigates the complexities of changes in mineralogy, porosity and flow within a series of porous aquifers and caprocks within Jurassic sedimentary sequences flooded by natural CO2 at Green River in Utah. This study of a natural analogue will inform the processes to quantify the risk of leakage and evolution of stored CO2 over a range of time scales in a sequence of stacked aquifers separated by less permeable rock layers. A 325m well (CO2W55 diamond drilled by DOSECC in 2012) gave excellent recovery of 282m of core from two major CO2 reservoirs in the Entrada and Navajo Sandstones and from the intervening Carmel Formation caprock. Fluid samples were also taken at pressure downhole. Element and isotope geochemistry were used to constrain fluid sources, mixing and fluid-rock reactions. Comparisons were made with the geochemistry of an adjacent cold water CO2-geyser to investigate the upward leakage and horizontal flow from the Little Grand Wash normal Fault that both the geyser and borehole intersect. Here we report the geochemical and isotopic compositions of the various carbonate and silicate components of the CO2 reacted rocks to constrain fluid-mineral reactions. A series of leaching experiments investigating reagents and reaction times allowed measurement of cation and strontium isotopic compositions of the major components within this sedimentary sequence. Strontium isotopes offer a powerful constraint in the study of subsurface fluid-rock reactions as they can be measured to high precision and are not affected by mass dependent fractionations during reaction and fluid transport. Analysis of major cations (especially Ca, Mg and Fe), Sr and 87Sr/86Sr of leachates from sequential leaching experiments allows estimation of the chemical and Sr

  13. Protic-salt-derived nitrogen/sulfur-codoped mesoporous carbon for the oxygen reduction reaction and supercapacitors.

    PubMed

    Zhang, Shiguo; Ikoma, Ai; Ueno, Kazuhide; Chen, Zhengjian; Dokko, Kaoru; Watanabe, Masayoshi

    2015-05-11

    Nitrogen/sulfur-co-doped mesoporous carbon (Phen-HS) was obtained through direct carbonization of a single protic salt, that is, 1,10-phenanthrolinium dibisulfate ([Phen][2 HSO4 ]), in the presence of a colloidal silica template without the use of additional acid or metal catalysts for prepolymerization prior to carbonization. Phen-HS was prepared in a relatively high yield (30.0 %) and has a large surface area (1161 m(2)  g(-1) ), large pore volume (2.490 cm(3)  g(-1) ), large mesopores (≈12 nm), narrow pore-size distribution (7-16 nm), and high nitrogen (7.5 at %) and sulfur (1.3 at %) contents. The surface area/pore-size distribution is much higher/narrower than that of most reported carbon materials obtained from traditional precursors by using the same template. Phen-HS was directly used as an electrocatalyst for the oxygen reduction reaction (ORR) and as an electrode material for supercapacitors. As an efficient metal-free catalyst, Phen-HS exhibited good electrocatalytic activity toward the ORR in a 0.1 M KOH aqueous solution, which is comparable to the activity of a commercial Pt/C catalyst. Electrochemical measurements for Phen-HS used in a double-layer capacitor showed high specific capacitances of 160 and 140 F g(-1) in 1 M H2 SO4 and 6 M KOH, respectively, with good rate capabilities and high cycling stabilities. PMID:25855218

  14. Modification of multi-walled carbon nanotubes by Diels-Alder and Sandmeyer reactions.

    PubMed

    Gergely, A; Telegdi, J; Mészáros, E; Pászti, Z; Tárkanyi, G; Kármán, F H; Kálmán, E

    2007-08-01

    Random (L) and aligned (A) multi-walled carbon nanotubes (MWNTs) were modified by Diels-Alder (DA) [4+2] cycloaddition, Sandmeyer (SM) reaction and by catalytic oxidation (OX). The properties of modified carbon nanotubes were studied by dispersability tests, elemental analysis, thermogravimetry/mass spectrometry, X-ray photoelectron spectroscopy, and NMR spectroscopy. The cycloaddition reaction could only be successfully performed with the L-MWNTs in molten and in solution state by using an aluminum chloride homogeneous catalyst. The efficiency and thermal stability of the solution phase cycloaddition were much higher than in the case of modification in the molten phase. The functionalization of both types of MWNTs by Sandmeyer reaction was carried out by copper(I) and iron(ll) ions that helped in the radical decomposition of diazonium salts. Successful functionalization of nanotubes is achieved by a long decomposition time of the thermally activated diazonium salts. To the contrary, in the case of radical decomposition of diazonium salts, the time is not a decisive parameter. The dispersability tests have proved the changes in the physical features of modified carbon nanotubes depending on the hydrophobic and hydrophilic character of the solvents. The presence of the modifying groups and their fragments from the functionalized MWNTs has been demonstrated by thermogravimetry/mass spectrometry (TG/MS). Relatively high concentration of sulfur atoms was detected by X-ray photoelectron spectroscopy in nanotubes modified by sulfur substituent groups. In the case of catalytic oxidation, the X-ray photoelectron spectroscopic signal of oxygen bound to nanotubes showed considerable change as compared to pristine nanotubes. Due to the high thermal stability of modified multi-walled carbon nanotubes, the functionalized derivatives are applicable in several industrial fields. PMID:17685300

  15. Distribution of hydrogen peroxide-dependent reaction in a gelatin sample irradiated by carbon ion beam.

    PubMed

    Matsumoto, Ken-ichiro; Aoki, Ichio; Nakanishi, Ikuo; Matsumoto, Atsuko; Nyui, Minako; Endo, Kazutoyo; Anzai, Kazunori

    2010-01-01

    We investigated the amount and distribution of hydrogen peroxide (H(2)O(2)) generated in a solid gelatin sample irradiated by heavy ion (carbon) beam. We irradiated the gelatin sample, which contained a nitroxyl radical (4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, TEMPOL), with a 290-MeV/nucleon carbon beam (~128 Gy). To verify the distribution of H(2)O(2) generation in the irradiated sample, we employed both electron paramagnetic resonance (EPR) spectroscopic and magnetic resonance (MR) imaging methods based on H(2)O(2)-dependent paramagnetic loss of TEMPOL. We obtained a distribution profile of the H(2)O(2)-dependent reaction in the gelatin sample when we irradiated gelatin samples with carbon beams with several different linear energy transfer (LET) values. Because the profiles of oxygen consumption in the gelatin sample measured by L-band EPR oxymetry and of the H(2)O(2)-dependent reaction have almost the same shape, the profile of the H(2)O(2)-dependent reaction can be used as an estimation of the profile of the generation of H(2)O(2). The H(2)O(2) profile in one intact gelatin sample scanned by 7-tesla MR imaging showed a similar shape as a result of the EPR experiment. We obtained several hundreds of micromolars of H(2)O(2) generated in a gelatin sample irradiated by carbon beam when 200 Gy was given at the surface of the sample. H(2)O(2) distribution was almost flat, with only a slight peak just before the end of the beam.

  16. Electron transfer in reactions of ketones with organolithium reagents. A carbon-14 kinetic isotope effect probe

    SciTech Connect

    Yamataka, H.; Fujimura, N.; Kawafuji, Y.; Hanafusa, T.

    1987-07-08

    Kinetic isotope effects have been determined for reactions of ketones labeled with carbon-14 at the carbonyl carbon with MeLi and Me/sub 2/CuLi in diethyl ether at 0/sup 0/C. Observed isotope effects were as follows: (C/sub 6/H/sub 5/)/sub 2/C double bonds O + MeLi, /sup 12/k//sup 14/k = 1.000 +/- 0.002; (C/sub 6/H/sub 5/)/sub 2/C double bonds O + Me/sub 2/CuLi, 1.029 +/- 0.005; 2,4,6-Me/sub 3/C/sub 6/H/sub 2/COC/sub 6/H/sub 5/ + MeLi, 1.023 +/- 0.004. The relative reactivities of ortho-, meta-, and para-substituted benzophenones with these reagents were also determined by the competition experiments. These results are consistent with an electron-transfer step which is followed by a carbon-carbon bond-forming step that is or is not rate determining depending on the structure of ketones and reagents. The reaction of benzophenone with MeLi proceeds via rate-determining electron transfer; the change in nucleophile from MeLi to Me/sub 2/CuLi shifts the rate-determining step from electron transfer to recombination; the change in ketone from benzophenone to 2,4,6-trimethylbenzophenone also shifts the rate-determining step from electron transfer to recombination because the latter step becomes slower for the more hindered ketone. The extent of the geometrical change of the substrate at the electron-transfer transition state of the reaction of benzophenone with MeLi was estimated to be small on the basis of the magnitude of the KIE and the rho value of the Hammett correlation.

  17. Reactions of HCl and D2O with molten alkali carbonates.

    PubMed

    Krebs, Thomas; Nathanson, Gilbert M

    2011-02-01

    The acidic oxide SO₂ and protic acid HCl are among the gases released in the combustion of coal and the incineration of municipal waste. They are typically removed by wet or dry scrubbing involving calcium carbonate or calcium hydroxide. The molten alkali carbonate eutectic provides a liquid-state alternative that readily absorbs SO₂ and HCl and does not become covered with a passivating layer. Gas-liquid scattering experiments utilizing the eutectic mixture (44 mol % Li₂CO₃, 31 mol % Na₂CO₃, 25 mol % K₂CO₃) reveal that the reaction probability for HCl(g) + CO₃²⁻ → CO₂(g) + OH⁻ + Cl⁻ is 0.31 ± 0.02 at 683 K and rises to 0.39 at 783 K. Gaseous CO₂ is formed within 10⁻⁴ s or less, implying that the reaction takes place in a liquid depth of less than 1000 Å. When the melt is exposed to D₂O, the analogous reaction D₂O(g) + CO₃²⁻ → CO₂(g) + 2OD⁻ occurs too slowly to measure and no water uptake is observed. Together with previous studies of SO₂(g) + CO₃²⁻ → CO₂(g) + SO₃²⁻, these results demonstrate that molten carbonates efficiently remove both gaseous HCl and SO₂ while reacting at most weakly with water vapor. The experiments further highlight the remarkable ability of hot CO₃²⁻ ions to behave as a base in reactions with protic and Lewis acids.

  18. Reactions upstream of glycerate-1,3-bisphosphate drive Corynebacterium glutamicum (D)-lactate productivity under oxygen deprivation.

    PubMed

    Tsuge, Yota; Yamamoto, Shougo; Suda, Masako; Inui, Masayuki; Yukawa, Hideaki

    2013-08-01

    We previously demonstrated the simplicity of oxygen-deprived Corynebacterium glutamicum to produce D-lactate, a primary building block of next-generation biodegradable plastics, at very high optical purity by introducing heterologous D-ldhA gene from Lactobacillus delbrueckii. Here, we independently evaluated the effects of overexpressing each of genes encoding the ten glycolytic enzymes on D-lactate production in C. glutamicum. We consequently show that while the reactions catalyzed by glucokinase (GLK), glyceraldehyde 3-phosphate dehydrogenase (GAPDH), phosphofructokinase (PFK), triosephosphate isomerase (TPI), and bisphosphate aldolase had positive effects on D-lactate productivity by increasing 98, 39, 15, 13, and 10 %, respectively, in 10 h reactions in minimal salts medium, the reaction catalyzed by pyruvate kinase had large negative effect by decreasing 70 %. The other glycolytic enzymes did not affect D-lactate productivity when each of encoding genes was overexpressed. It is noteworthy that all reactions associated with positive effects are located upstream of glycerate-1,3-bisphosphate in the glycolytic pathway. The D-lactate yield also increased by especially overexpressing TPI encoding gene up to 94.5 %. Interestingly, overexpression of PFK encoding gene reduced the yield of succinate, one of the main by-products of D-lactate production, by 52 %, whereas overexpression of GAPDH encoding gene increased succinate yield by 26 %. Overexpression of GLK encoding gene markedly increased the yield of dihydroxyacetone and glycerol by 10- and 5.8-fold in exchange with decreasing the D-lactate yield. The effect of overexpressing glycolytic genes was also evaluated in 80 h long-term reactions. The variety of effects of overexpressing each of genes encoding the ten glycolytic enzymes on D-lactate production is discussed. PMID:23712891

  19. Analyzing power measurements for the (. pi. sup + ,. pi. sup 0 ) reaction on a polarized sup 13 C target

    SciTech Connect

    Goergen, J.J.

    1991-05-01

    The analyzing powers A{sub y} differential cross sections d{sigma}/d{Omega} for the reaction {sup 13}C({pi}{sup +},{pi}{sup 0}){sup 13}N have been measured for forward scattering angles at an incident pion kinetic energy of T{sub pi}{sup +} = 163 MeV by using a transversely polarized target. Analyzing powers and reaction cross sections impose stringent constrains on nuclear reaction models and can be used to test the present understanding of nuclear structure for 1p-shell nuclei. The resulting A{sub y} are compared to the predictions of first-order Distorted Wave Impulse Approximation (DWIA) calculations, which reproduce well the differential cross sections. Although there is qualitative agreement at forward angles, the quantitative agreement is poor, especially at scattering angles larger than 50{degrees}. Since the DWIA calculations do not appear to be strongly sensitive to the assumed nuclear structure model, the discrepancy in describing the analyzing powers suggests that the reaction mechanism may not yet be well understood and higher order corrections may be important. Also measured were the analyzing powers for the elementary charge exchange reaction {pi}{sup {minus}} {bar p} {yields} {pi}{degrees}n over the same angular range and at an incident pion kinetic energy of T{sub pi}{minus} = 161 MeV. The results are compared to the most recents phase shift predictions. Within the experimental uncertainties, phase shift calculations agree with the measured A{sub y} and no changes in the {pi}N phase shifts near the P{sub 33} resonance are needed to describe the data.

  20. Structures and sites of nonenzymatic glucosylation of protein: characterization by carbon-13 nuclear magnetic resonance spectroscopy

    SciTech Connect

    Fisher, C.I.

    1985-01-01

    Products of nonenzymatic glucosylation of protein were studied by carbon-13 NMR spectroscopy at 100 MHz in phosphate buffer. The anomeric region of the spectrum of glycated cytochrome c (blocked amino terminus) showed three signals representing the C-2 carbon of the alpha and beta-furanose (101.7 and 99.2 ppm) and beta pyranose (95.8 ppm) anomers of the Amadori rearrangement products (ARP) at lysine epsilon amino groups. The spectrum of glycated poly-L-lysine showed two distinct sets of three resonances; the second set, resonating to lower shielding than the first, was assigned to C-2 of the anomers of ARP at the alpha amino terminus. A third set of peaks was observed on glucation of RNase A corresponding to the ARP at lysine residue 41. The anomeric region of RNase denatured with urea at pH 7.4 was similar to that of glycated poly-L-lysine, while at pH 4.0 it was indistinguishable from that of glycated cytochrome c. The anomeric spectum of glycated hemoglobin was comparable to that of poly-L-lysine, and distinct resonances were observed for the ARP at the alpha amino terminal valine and epsilon amino groups. Because of the differences in chemical shift of C-2 of the ARP, we conclude that the pKa of the amino group influences the electronic environment of the anomeric carbon of the ARP.

  1. HYDROXYL RADICAL AND OZONE INITIATED PHOTOCHEMICAL REACTIONS OF 1,3-BUTADIENE. (R826247)

    EPA Science Inventory

    1,3-Butadiene, classified as hazardous in the 1990 Clean Air Act Amendments, is an important ambient air pollutant. Understanding its atmospheric transformation is useful for its own sake, and is also helpful for eliciting isoprene's fate in the atmosphere (isoprene dominates ...

  2. Analyzing and Assigning Carbon-13 Chemical-Shift Tensors in Fructose, Sorbose, and Xylose Single Crystals

    NASA Astrophysics Data System (ADS)

    Liu, Fang; Phung, Cu G.; Alderman, D. W.; Grant, David M.

    Complete carbon-13 chemical-shift tensors are measured in single crystals of the monosaccharides β- D-fructopyranose [57-48-7], α- L-sorbopyranose [87-79-6], and α- D-xylopyranose [58-86-6] using the two-dimensional chemical-shift correlation technique with a multiple-axis sample-reorientation mechanism. Symmetry-constrained fitting of the experimental data extracts the tensors for the four equivalent molecules in the P2 12 12 1unit cells and the directions of the three twofold axes in the orthorhombic crystals. The standard deviations of the symmetry fits to the data are 0.30, 0.40, and 0.29 ppm for the three monosaccharide molecules, respectively. Gauge-invariant atomic orbital (GIAO) computations using the D-95 double-zeta basis set are then used to assign the experimental tensors to the carbons in the molecules and to the molecules in the unit cell. All assignment permutations and combinations are explored, and that which minimizes the RMS deviation between the experimental and computed tensors is accepted as the best assignment. The GIAO results also identify the experimental twofold axes with the crystallographic axes. Because the hydroxymethyl hydroxyl group in sorbose jumps between two positions, it is necessary to compute the tensors for both molecular configurations and then to take a weighted average of the results for comparison with the experimental data. The D-95 GIAO results have RMS deviations from the experimental tensors of 1.90 ppm for fructose, 2.61 ppm for sorbose, and 2.66 ppm for xylose. Similar computations confirm a previous assignment of the carbon-13 tensors in sucrose and yield a 2.85 ppm RMS deviation.

  3. Nitrogen, carbon, and sulfur isotopic change during heterotrophic (Pseudomonas aureofaciens) and autotrophic (Thiobacillus denitrificans) denitrification reactions.

    PubMed

    Hosono, Takahiro; Alvarez, Kelly; Lin, In-Tian; Shimada, Jun

    2015-12-01

    In batch culture experiments, we examined the isotopic change of nitrogen in nitrate (δ(15)NNO3), carbon in dissolved inorganic carbon (δ(13)CDIC), and sulfur in sulfate (δ(34)SSO4) during heterotrophic and autotrophic denitrification of two bacterial strains (Pseudomonas aureofaciens and Thiobacillus denitrificans). Heterotrophic denitrification (HD) experiments were conducted with trisodium citrate as electron donor, and autotrophic denitrification (AD) experiments were carried out with iron disulfide (FeS2) as electron donor. For heterotrophic denitrification experiments, a complete nitrate reduction was accomplished, however bacterial denitrification with T. denitrificans is a slow process in which, after seventy days nitrate was reduced to 40% of the initial concentration by denitrification. In the HD experiment, systematic change of δ(13)CDIC (from -7.7‰ to -12.2‰) with increase of DIC was observed during denitrification (enrichment factor εN was -4.7‰), suggesting the contribution of C of trisodium citrate (δ(13)C=-12.4‰). No SO4(2-) and δ(34)SSO4 changes were observed. In the AD experiment, clear fractionation of δ(13)CDIC during DIC consumption (εC=-7.8‰) and δ(34)SSO4 during sulfur use of FeS2-S (around 2‰), were confirmed through denitrification (εN=-12.5‰). Different pattern in isotopic change between HD and AD obtained on laboratory-scale are useful to recognize the type of denitrification occurring in the field. PMID:26529303

  4. Nitrogen, carbon, and sulfur isotopic change during heterotrophic (Pseudomonas aureofaciens) and autotrophic (Thiobacillus denitrificans) denitrification reactions

    NASA Astrophysics Data System (ADS)

    Hosono, Takahiro; Alvarez, Kelly; Lin, In-Tian; Shimada, Jun

    2015-12-01

    In batch culture experiments, we examined the isotopic change of nitrogen in nitrate (δ15NNO3), carbon in dissolved inorganic carbon13CDIC), and sulfur in sulfate (δ34SSO4) during heterotrophic and autotrophic denitrification of two bacterial strains (Pseudomonas aureofaciens and Thiobacillus denitrificans). Heterotrophic denitrification (HD) experiments were conducted with trisodium citrate as electron donor, and autotrophic denitrification (AD) experiments were carried out with iron disulfide (FeS2) as electron donor. For heterotrophic denitrification experiments, a complete nitrate reduction was accomplished, however bacterial denitrification with T. denitrificans is a slow process in which, after seventy days nitrate was reduced to 40% of the initial concentration by denitrification. In the HD experiment, systematic change of δ13CDIC (from - 7.7‰ to - 12.2‰) with increase of DIC was observed during denitrification (enrichment factor εN was - 4.7‰), suggesting the contribution of C of trisodium citrate (δ13C = - 12.4‰). No SO42 - and δ34SSO4 changes were observed. In the AD experiment, clear fractionation of δ13CDIC during DIC consumption (εC = - 7.8‰) and δ34SSO4 during sulfur use of FeS2-S (around 2‰), were confirmed through denitrification (εN = - 12.5‰). Different pattern in isotopic change between HD and AD obtained on laboratory-scale are useful to recognize the type of denitrification occurring in the field.

  5. Nitrogen, carbon, and sulfur isotopic change during heterotrophic (Pseudomonas aureofaciens) and autotrophic (Thiobacillus denitrificans) denitrification reactions.

    PubMed

    Hosono, Takahiro; Alvarez, Kelly; Lin, In-Tian; Shimada, Jun

    2015-12-01

    In batch culture experiments, we examined the isotopic change of nitrogen in nitrate (δ(15)NNO3), carbon in dissolved inorganic carbon (δ(13)CDIC), and sulfur in sulfate (δ(34)SSO4) during heterotrophic and autotrophic denitrification of two bacterial strains (Pseudomonas aureofaciens and Thiobacillus denitrificans). Heterotrophic denitrification (HD) experiments were conducted with trisodium citrate as electron donor, and autotrophic denitrification (AD) experiments were carried out with iron disulfide (FeS2) as electron donor. For heterotrophic denitrification experiments, a complete nitrate reduction was accomplished, however bacterial denitrification with T. denitrificans is a slow process in which, after seventy days nitrate was reduced to 40% of the initial concentration by denitrification. In the HD experiment, systematic change of δ(13)CDIC (from -7.7‰ to -12.2‰) with increase of DIC was observed during denitrification (enrichment factor εN was -4.7‰), suggesting the contribution of C of trisodium citrate (δ(13)C=-12.4‰). No SO4(2-) and δ(34)SSO4 changes were observed. In the AD experiment, clear fractionation of δ(13)CDIC during DIC consumption (εC=-7.8‰) and δ(34)SSO4 during sulfur use of FeS2-S (around 2‰), were confirmed through denitrification (εN=-12.5‰). Different pattern in isotopic change between HD and AD obtained on laboratory-scale are useful to recognize the type of denitrification occurring in the field.

  6. Functionalization of Oxide Surfaces through Reaction with 1,3-Dialkylimidazolium Ionic Liquids.

    PubMed

    Schernich, Stefan; Laurin, Mathias; Lykhach, Yaroslava; Steinrück, Hans-Peter; Tsud, Nataliya; Skála, Tomáš; Prince, Kevin C; Taccardi, Nicola; Matolín, Vladimír; Wasserscheid, Peter; Libuda, Jörg

    2013-01-01

    Practical applications of ionic liquids (ILs) often involve IL/oxide interfaces, but little is known regarding their interfacial chemistry. The unusual physicochemical properties of ILs, including their exceptionally low vapor pressure, provide access to such interfaces using a surface science approach in ultrahigh vacuum (UHV). We have applied synchrotron radiation photoelectron spectroscopy (SR-PES) to the study of a thin film of the ionic liquid [C6C1Im][Tf2N] prepared in situ in UHV on ordered stoichiometric CeO2(111) and partially reduced CeO2-x. On the partially reduced surface, we mostly observe decomposition of the anion. On the stoichiometric CeO2(111) surface, however, a layer of surface-anchored organic products with high thermal stability is formed upon reaction of the cation. The suggested acid-base reaction pathway may provide well-defined functionalized IL/solid interfaces on basic oxides.

  7. The influence of carbon surface chemistry on supported palladium nanoparticles in heterogeneous reactions.

    PubMed

    Ding, Yuxiao; Zhang, Liyun; Wu, Kuang-Hsu; Feng, Zhenbao; Shi, Wen; Gao, Qiang; Zhang, Bingsen; Su, Dang Sheng

    2016-10-15

    The surface chemistry of nanocarbon support can tailor chemical properties of precious metal nanoparticle/nanocarbon hybrid catalyst in heterogeneous reactions. We report on modified reduced graphene oxide (rGO) support with ionic liquid-derived carbonaceous surface for palladium nanoparticle (Pd NPs) decoration and their actions in different heterogeneous reactions. The surface chemistry of support materials was characterized in detail, and the influence of which on the formation and distribution of metal particles was further investigated. Three different types of reactions including Suzuki-Miyaura coupling reaction, CO oxidation and phenol reduction were examined in terms of reactivity and selectivity. The roles of substituted nitrogen in graphitic lattice and grafted groups on the carbon surface were exploited. Nitrogen-doping can give rise to changes in electronic properties of supported metals, and the Lewis basicity of the doped nitrogen atoms can favor the adsorption of acidic reactants in phenol reduction. The grafted groups derived a negative impact to the Suzuki-Miyaura coupling reaction, due to the involvement of larger reactant molecules, despite that they could prevent significant sintering of Pd NPs in the CO oxidation.

  8. The influence of carbon surface chemistry on supported palladium nanoparticles in heterogeneous reactions.

    PubMed

    Ding, Yuxiao; Zhang, Liyun; Wu, Kuang-Hsu; Feng, Zhenbao; Shi, Wen; Gao, Qiang; Zhang, Bingsen; Su, Dang Sheng

    2016-10-15

    The surface chemistry of nanocarbon support can tailor chemical properties of precious metal nanoparticle/nanocarbon hybrid catalyst in heterogeneous reactions. We report on modified reduced graphene oxide (rGO) support with ionic liquid-derived carbonaceous surface for palladium nanoparticle (Pd NPs) decoration and their actions in different heterogeneous reactions. The surface chemistry of support materials was characterized in detail, and the influence of which on the formation and distribution of metal particles was further investigated. Three different types of reactions including Suzuki-Miyaura coupling reaction, CO oxidation and phenol reduction were examined in terms of reactivity and selectivity. The roles of substituted nitrogen in graphitic lattice and grafted groups on the carbon surface were exploited. Nitrogen-doping can give rise to changes in electronic properties of supported metals, and the Lewis basicity of the doped nitrogen atoms can favor the adsorption of acidic reactants in phenol reduction. The grafted groups derived a negative impact to the Suzuki-Miyaura coupling reaction, due to the involvement of larger reactant molecules, despite that they could prevent significant sintering of Pd NPs in the CO oxidation. PMID:27442144

  9. Tandem carbon-carbon bond insertion and intramolecular aldol reaction of benzyne with aroylacetones: novel formation of 4,4'-disubstituted 1,1'-binaphthols.

    PubMed

    Okuma, Kentaro; Itoyama, Ryoichi; Sou, Ayumi; Nagahora, Noriyoshi; Shioj, Kosei

    2012-11-21

    An efficient route to 4-aryl-2-naphthols from arynes and aroylacetones was developed by carbon-carbon bond insertion followed by an intramolecular aldol reaction and dehydration. Benzyne derived from 2-(trimethylsilyl)phenyl triflate reacted with benzoylacetones in refluxing acetonitrile to give 4-aryl-2-naphthols and 3-aryl-1-naphthols.

  10. /sup 13/C nuclear magnetic resonance studies of the biosynthesis by Microbacterium ammoniaphilum of L-glutamate selectively enriched with carbon-13

    SciTech Connect

    Walker, T.E.; Han, C.H.; Kollman, V.H.; London, R.E.; Matwiyoff, N.A.

    1982-02-10

    /sup 13/C NMR of isotopically enriched metabolites has been used to study the metabolism of Microbacterium ammoniaphilum, a bacterium which excretes large quantities of L-glutamic acid into the medium. Biosynthesis from 90% (1-/sup 13/C) glucose results in relatively high specificity of the label, with (2,4-/sup 13/C/sub 2/) glutamate as the major product. The predominant biosynthetic pathway for synthesis of glutamate from glucose was determined to be the Embden Meyerhof glycolytic pathway followed by P-enolpyruvate carboxylase and the first third of the Krebs cycle. Different metabolic pathways are associated with different correlations in the enrichment of the carbons, reflected in the spectrum as different /sup 13/C-/sup 13/C scalar multiplet intensities. Hence, intensity and /sup 13/C-/sup 13/C multiplet analysis allows quantitation of the pathways involved. Although blockage of the Krebs cycle at the ..cap alpha..-ketoglutarate dehydrogenase step is the basis for the accumulation of glutamate, significant Krebs cycle activity was found in glucose grown cells, and extensive Krebs cycle activity in cells metabolizing (1-/sup 13/C) acetate. In addition to the observation of the expected metabolites, the disaccharide ..cap alpha..,..cap alpha..-trehalose and ..cap alpha..,..beta..-glucosylamine were identified from the /sup 13/C NMR spectra.

  11. Effect Of Reaction Environments On The Reactivity Of PCB (2-Chlorobiphenyl) Over Activated Carbon Impregnated With Palladized Iron

    EPA Science Inventory

    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-...

  12. In Situ 13C NMR at Elevated-Pressures and -Temperatures Investigating the Conversion of CO2 to Magnesium and Calcium Carbonate Minerals

    NASA Astrophysics Data System (ADS)

    Surface, J. A.; Conradi, M. S.; Skemer, P. A.; Hayes, S. E.

    2013-12-01

    We have constructed specialized NMR hardware to conduct in situ elevated-pressure, elevated-temperature 13C NMR studies of unmixed heterogeneous mixtures of solids, liquids, gases, and supercritical fluids. Specifically, our aim is to monitor CO2 uptake in both ultramafic rocks and in more porous geological materials to understand the mechanisms of chemisorption as a function of temperature, pressure and pH. In this in situ NMR probe, we are able to simulate processes at geologically relevant fluid pressures and temperatures, monitoring the kinetics of CO2 conversion to carbonates. The in situ NMR experiments consist of heterogeneous mixtures of rock, salty brine solution, and moderate pressure CO2 gas at elevated temperatures. The purpose of studying these reactions is to determine efficacy of carbonate formation in various geological reservoirs. Via 13C NMR, we have spectroscopically characterized and quantified the conversion of CO2 to magnesium carbonate and calcium carbonate minerals. When CO2 reacts with the calcium or magnesium in a mineral or rock sample, the 13C chemical shift, linewidth, lineshape, and relaxation times change dramatically. This change can be monitored in situ and provide instantaneous and continuous characterization that maps the chemistry that is taking place. For example, on the pathway to MgCO3 formation, there are a number of phases of Mg(OH)x(H2O)y(CO3)z that are apparent via NMR spectroscopy. We will demonstrate that NMR can be used for quantitative characterization of multiple metastable mineral phases in pure forms and in mixtures. Results are confirmed via powder XRD and Raman spectroscopy of aquo- hydro- carbonato- magnesium species and calcium carbonate species. We also have monitored the 13C spectroscopy to analyze the phase of CO2 (liquid, supercritical, or gas) and its conversion into other forms, such as bicarbonate and carbonate species, providing a "window" into the in situ pH of the reacting system. Reference: 'In Situ

  13. Influence of matrix diffusion and exchange reactions on radiocarbon ages in fissured carbonate aquifers

    SciTech Connect

    Maloszewski, P. ); Zuber, A. )

    1991-08-01

    The parallel fissure model coupled with the equation of diffusion into the matrix and with exchange reaction equations has been used to derive a simple formula for estimating the influence of matrix porosity and reaction parameters on the determination of radiocarbon ages in fissured carbonate rocks. Examples of evidently too great radiocarbon ages in carbonate formations, which are not explainable by models for the initial {sup 14}C corrections, can easily be explained by this formula. Parameters obtained for a chalk formation from a known multitracer experiment combined with a pumping test suggest a possibility of {sup 14}C ages more than three orders of magnitude greater than the ages which would be observed if the radiocarbon transport took place only in the mobile water in the fissures. It is shown that contrary to the solute movement on a small scale and with a variable input, the large-scale movement, characteristic for the {sup 14}C dating, does not necessarily require the knowledge of kinetic parameters, because they may be replaced by the distribution coefficient. Discordant tritium and {sup 14}C concentrations are commonly interpreted as a proof of mixing either in the aquifer or at the discharge site. For fissured carbonate formations, however, an alternative explanation is given by the derived model showing a considerable delay of {sup 14}C with respect to nonsorbable tracers.

  14. Unique Sandwiched Carbon Sheets@Ni-Mn Nanoparticles for Enhanced Oxygen Evolution Reaction.

    PubMed

    Zhang, Yan; Zhang, Huijuan; Yang, Jiao; Bai, Yuanjuan; Qiu, Huajun; Wang, Yu

    2016-05-11

    A unique sandwich-like architecture, where Ni-Mn nanoparticles are enveloped in coupled carbon sheets (CS@Ni-Mn), has been successfully fabricated. In the synthesis process, a great quantity of uniform NiMnO3 nanosheets generated by a universal hydrothermal method acts as precursors and templates and the cheap, environmentally friendly and recyclable glucose functions as a green carbon source. Via subsequent hydrothermal reaction and thermal annealing, sandwiched nanocomposites with Ni-Mn nanoparticles embedded inside and carbon sheets encapsulating outside can be massively prepared. The novel sandwich-like CS@Ni-Mn possesses numerous advantages, such as an intrinsic porous feature, large specific surface area, and enhanced electronic conductivity. Moreover, as a promising NiMn-based oxygen evolution reaction (OER) catalyst, the special sandwiched nanostructure demonstrates improved electrochemical properties in 1 M KOH, including a low overpotential of about 250 mV, a modest Tafel slope of 40 mV dec(-1), excellent stability over 2000 cycles, and durability for 40 h. PMID:27101350

  15. Carbon incorporation effects and reaction mechanism of FeOCl cathode materials for chloride ion batteries

    PubMed Central

    Zhao, Xiangyu; Li, Qiang; Yu, Tingting; Yang, Meng; Fink, Karin; Shen, Xiaodong

    2016-01-01

    Metal oxychlorides are proved to be new cathode materials for chloride ion batteries. However, this kind of cathode materials is still in a very early stage of research and development. The obtained reversible capacity is low and the electrochemical reaction mechanism concerning chloride ion transfer is not clear. Herein, we report FeOCl/carbon composites prepared by mechanical milling of the as-prepared FeOCl with carbon nanotube, carbon black or graphene nanoplatelets as cathode materials for chloride ion batteries. The electrochemical performance of the FeOCl electrode is evidently improved by the incorporation of graphene into the cathode. FeOCl/graphene cathode shows a high reversible capacity of 184 mAh g−1 based on the phase transformation between FeOCl and FeO. Two stages of this phase transformation are observed for the FeOCl cathode. New insight into the reaction mechanism of chloride ion dissociation of FeOCl is investigated by DFT + U + D2 calculations. PMID:26777572

  16. Electrochemical activation of commercial polyacrylonitrile-based carbon fiber for the oxygen reduction reaction.

    PubMed

    Xu, Haibo; Xia, Guangsen; Liu, Haining; Xia, Shuwei; Lu, Yonghong

    2015-03-28

    Nitrogen (N)-doped carbon and its non-noble metal composite replacing platinum-based oxygen reduction reaction (ORR) electrocatalysts still have some fundamental problems that remain. Here the micron-sized commercial polyacrylonitrile-based carbon fiber (PAN-CF) electrode was modified using an electrochemical method, converting its inherent pyridinic-N into 2-pyridone (or 2-hydroxyl pyridine) functional group existing in three-dimensional active layers with remarkable ORR catalytic activity and stability. The carbon atom adjacent to the nitrogen and oxygen atoms is prone to act as an active site to efficiently catalyze a two-electron ORR process. However, after coordinating pyridone to the Cu(2+) ion, together with the electrochemical reaction, the chemical redox between Cu(+) and ORR intermediates synergistically tends towards a four-electron pathway in alkaline solution. In different medium, the complexation and dissociation can induce the charge transfer and reconstruction among proton, metal ion and pyridone functionalities, eventually leading to the changes of ORR performance. PMID:25712410

  17. Nitrogen-doped porous carbon nanosheets made from biomass as highly active electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Pan, Fuping; Cao, Zhongyue; Zhao, Qiuping; Liang, Hongyu; Zhang, Junyan

    2014-12-01

    The successful commercialization of fuel cells requires the efficient electrocatalyst to make the oxygen reduction reaction (ORR) fast because of the sluggish nature of ORR and the high cost of the platinum catalysts. In this work, we report the excellent performance of metal-free nitrogen-doped porous carbon nanosheets (NPCN) with hierarchical porous structure and a high surface area of 1436.02 m2 g-1 for catalyzing ORR. The active NPCN is synthesized via facile high-temperature carbonization of natural ginkgo leaves followed by purification and ammonia post-treatment without using additional supporting templates and activation processes. In O2-saturated 0.1 M KOH solution, the resultant NPCN exhibits a high kinetic-limiting current density of 13.57 mA cm-2 at -0.25 V (vs. Ag/AgCl) approaching that of the commercial Pt/C catalyst (14 mA cm-2) and long-term electrochemical stability. Notably, the NPCN shows a slightly negative ORR half-wave potential in comparison with Pt/C (ΔE1/2 = 19 mV). The excellent electrocatalytic properties of NPCN originate from the combined effect of optimal nitrogen doping, high surface area, and porous architecture, which induce the high-density distribution of highly active and stable catalytic sites.

  18. The composition of primary carbonate melts and their evolution through wallrock reaction in the mantle

    NASA Astrophysics Data System (ADS)

    Dalton, John A.; Wood, Bernard J.

    1993-10-01

    We have experimentally determined the composition of near-soldus melts from depleted natural Iherzolite at pressures greater than 25 kbar. The melts are carbontitic with low alkali contents and Ca/(Ca + Mg) ratios of 0.72-0.74. Primary carbonate melts from fertile mantle are more sodic with Ca/(Ca + Mg + Fe + Na) of 0.52 and Na/(Na + Ca + Mg + Fe) up to 0.15. The melt compositions are similar to many natural magnesio-carbonatites, but differ substantially from the more abundant calcio-carbonatites. Experimentally we find that calcio-carbonatites are produced by wallrock reaction of primary melts with harzburgite at pressures of less than 25 kbar. At 15 kbar we have obtained a Ca/(Ca + Mg + Fe + Na) ratio of up to 0.87 and very low Na contents generated by this process. Values of Ca/(Ca + Mg + Fe + Na) up to 0.95 are possible at lower pressures. Low pressure wallrock reaction of primary carbonate melt with fertile Iherzolite produces melts richer in Na2CO3, corresponding to possible parental magmas of natrocarbonatite. Wallrock reaction at low pressures transforms the bulk peridotite composition from that of a harzburgite or Iherzolite to wehrlite. Examples of such carbonatite metasomatism are now widely documented. Our experiments show that the calcium content of olivine and the jadeite content of clinopyroxene may be used to constrain the Ca and Na contents respectively of the cabonatite melt responsible for metasomatism.

  19. Totally stereoselective synthesis of 1,3-disaccharides through Diels-Alder reactions.

    PubMed

    Bartolozzi, Alessandra; Pacciani, Stefania; Benvenuti, Cecilia; Cacciarini, Martina; Liguori, Francesca; Menichetti, Stefano; Nativi, Cristina

    2003-10-31

    A nonclassical, totally stereoselective synthesis of orthogonally protected 1,3-disaccharides is reported. Enantiomerically pure beta-keto-delta-lactones, efficiently obtained from glucal and galactal, are transformed into electron-poor heterodienes and chemo-, regio-, and stereoselectively cycloadded to glycals as electron-rich dienophiles, to directly afford 2-thiodisaccharides. The reductive desulfurization of the latter smoothly gave the corresponding 2,2'-dideoxydisaccharides. PMID:14575481

  20. Delta13C analyses of calcium carbonate: Comparison between the GasBench and elemental analyzer techniques.

    PubMed

    Skrzypek, Grzegorz; Paul, Debajyoti

    2006-01-01

    Measurements of stable carbon isotopic composition (delta13C) of carbonates or carbonate-rich soils are seldom performed in a continuous-flow isotope ratio mass spectrometer (IRMS) using an elemental analyzer (EA) as an online sample preparation device. Such analyses are routinely carried out with an external precision better than 0.1 per thousand using a GasBench II (GB) sample preparation device coupled online with a continuous-flow IRMS. In this paper, we report and compare delta13C analyses (86 total analyses) of calcium carbonates obtained by using both the GB and the EA. Using both techniques, the delta13C compositions of two in-house carbonate standards (MERCK carbonate and NR calcite) and ten selected carbonate-rich paleosol samples (of variable CaCO3 content) were analyzed, and data are reported in the VPDB scale calibrated against international standards, NBS 18 and 19. For the in-house standards analyzed by both techniques, a precision better than 0.08 per thousand is achieved. The analytical errors (1sigma) computed from multiple analyses of the delta13C of both the MERCK and NR obtained by the above two techniques are nearly identical. In general, the 1sigma (internal error) of paleosol analyses obtained in the GB is better than 0.06 per thousand, whereas that for the analyses in the EA (three repetitive analyses of the same sample) varies in the range 0.05-0.21 per thousand. However, for paleosols having more than 85% CaCO3, 1sigma is better than 0.15 per thousand (similar to the instrument precision), and in this case the delta13C(VPDB) of samples obtained by the GB is similar to that obtained by the EA. Our results suggest that the delta13C of pure calcium carbonate samples can also be analyzed using the EA technique.

  1. {sup 13}C-enrichment at carbons 8 and 2 of uric acid after {sup 13}C-labeled folate dose in man

    SciTech Connect

    Baggott, Joseph E.; Gorman, Gregory S.; Morgan, Sarah L.; Tamura, Tsunenobu . E-mail: tamurat@uab.edu

    2007-09-21

    To evaluate folate-dependent carbon incorporation into the purine ring, we measured {sup 13}C-enrichment independently at C{sub 2} and C{sub 8} of urinary uric acid (the final catabolite of purines) in a healthy male after an independent oral dose of [6RS]-5-[{sup 13}C]-formyltetrahydrofolate ([6RS]-5-H{sup 13}CO-H{sub 4}folate) or 10-H{sup 13}CO-7,8-dihydrofolate (10-H{sup 13}CO-H{sub 2}folate). The C{sub 2} position was {sup 13}C-enriched more than C{sub 8} after [6RS]-5-H{sup 13}CO-H{sub 4}folate, and C{sub 2} was exclusively enriched after 10-H{sup 13}CO-H{sub 2}folate. The enrichment of C{sub 2} was greater from [6RS]-5-H{sup 13}CO-H{sub 4}folate than 10-H{sup 13}CO-H{sub 2}folate using equimolar bioactive doses. Our data suggest that formyl C of [6RS]-10-H{sup 13}CO-H{sub 4}folate was not equally utilized by glycinamide ribotide transformylase (enriches C{sub 8}) and aminoimidazolecarboxamide ribotide (AICAR) transformylase (enriches C{sub 2}), and the formyl C of 10-H{sup 13}CO-H{sub 2}folate was exclusively used by AICAR transformylase. 10-HCO-H{sub 2}folate may function in vivo as the predominant substrate for AICAR transformylase in humans.

  2. Base-dependent stereodivergent intramolecular aza-Michael reaction: asymmetric synthesis of 1,3-disubstituted isoindolines.

    PubMed

    Fustero, Santos; Herrera, Lidia; Lázaro, Ruben; Rodríguez, Elsa; Maestro, Miguel A; Mateu, Natalia; Barrio, Pablo

    2013-08-26

    The nucleophilic addition (A(N)) / intramolecular aza-Michael reaction (IMAMR) process on Ellman's tert-butylsulfinyl imines, bearing a Michael acceptor in the ortho position, is studied. This reaction affords 1,3-disubstituted isoindolines with a wide range of substituents in good yields and diastereoselectivities. Interestingly, careful choice of the base for the aza-Michael step allows either the cis or the trans diastereoisomers to be exclusively obtained. This stereodivergent cyclization has enabled the synthesis of C2-symmetric bisacetate-substituted isoindolines. In addition, bisacetate isoindolines bearing two well-differentiated ester moieties are also noteworthy because they may allow for the orthogonal synthesis of β,β'-dipeptides using a single nitrogen atom as a linchpin.

  3. Anaerobic reductive dechlorination of tetrachloroethene: how can dual Carbon-Chlorine isotopic measurements help elucidating the underlying reaction mechanism?

    NASA Astrophysics Data System (ADS)

    Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel

    2014-05-01

    Chlorinated ethenes (CEs) such as tetrachloroethene (PCE) are common persistent groundwater contaminants. Among clean-up strategies applied to sites affected by such pollution, bioremediation has been considered with a growing interest as it represents a cost-effective, environmental friendly approach. This technique however sometimes leads to an incomplete and slow biodegradation of CEs resulting in an accumulation of toxic metabolites. Understanding the reaction mechanisms underlying anaerobic reductive dechlorination would thus help assessing PCE biodegradation in polluted sites. Stable isotope analysis can provide insight into reaction mechanisms. For chlorinated hydrocarbons, carbon (C) and chlorine (Cl) isotope data (δ13C and δ37Cl) tend to show a linear correlation with a slope (m ≡ ɛC/ɛCl) characteristic of the reaction mechanism [1]. This study hence aims at exploring the potential of a dual C-Cl isotope approach in the determination of the reaction mechanisms involved in PCE reductive dechlorination. C and Cl isotope fractionation were investigated during anaerobic PCE dechlorination by two bacterial consortia containing members of the Sulfurospirillum genus. The specificity in these consortia resides in the fact that they each conduct PCE reductive dechlorination catalysed by one different reductive dehalogenase, i.e. PceADCE which yields trichloroethene (TCE) and cis-dichloroethene (cDCE), and PceATCE which yields TCE only. The bulk C isotope enrichment factors were -3.6±0.3 o for PceATCE and -0.7±0.1o for PceADCE. The bulk Cl isotope enrichment factors were -1.3±0.2 o for PceATCE and -0.9±0.1 o for PceADCE. When applying the dual isotope approach, two m values of 2.7±0.1 and 0.7±0.2 were obtained for the reductive dehalogenases PceATCE and PceADCE, respectively. These results suggest that PCE can be degraded according to two different mechanisms. Furthermore, despite their highly similar protein sequences, each reductive dehalogenase seems

  4. Investigation of the reaction of 1,3-dimethylurea with formaldehyde by quantitative on-line NMR spectroscopy: a model for the urea-formaldehyde system.

    PubMed

    Steinhof, Oliver; Scherr, Günter; Hasse, Hans

    2016-06-01

    Quantitative on-line NMR spectroscopy is applied to study equilibria and reaction kinetics of the reaction of formaldehyde with 1,3-dimethylurea. This reaction system serves as a model system for the much more complex but industrially relevant urea-formaldehyde system. The aim is to study individual reactions and intermediates. The 1,3-dimethylurea-formaldehyde system undergoes only four reactions and, unlike urea-formaldehyde, does not form polymers. The following reactions are studied in detail: (1) the hydroxymethylation, (2) the formation of hemiformals of the hydroxymethylated intermediate, and (3) two condensation reactions of which the first leads to methylene bridges, the other to ether bridges. NMR spectroscopic chemical shift data of the reacting species are provided for the (1) H, (13) C, and (15) N domains. Equilibrium data of reactions (1), (2), and (3) are determined by quantitative (1) H and (13) C NMR spectroscopy at molar ratios of formaldehyde to 1,3-dimethylurea between 1:2 and 16:1 at a pH value of 8.5. Reaction kinetic experiments using an NMR spectrometer coupled to a batch reactor led to a reaction kinetic model parametrized with true species concentrations. The model takes into account reactions (1), (2), and (3). It describes the reaction system well for molar ratios of 1:1, 2:1, and 4:1, temperatures of 303 to 333K, and pH values from 5.0 to 9.5. Dilution experiments with a micro mixer coupled to the NMR spectrometer are conducted to estimate the time to equilibrium of reaction (2) of which the time constant is significantly lower than those of reactions (1) and (3). Copyright © 2015 John Wiley & Sons, Ltd.

  5. Enhancing the Accuracy of Carbonate δ18O and δ13C Measurements by SIMS

    NASA Astrophysics Data System (ADS)

    Orland, I. J.; Kozdon, R.; Linzmeier, B.; Wycech, J.; Sliwinski, M.; Kitajima, K.; Kita, N.; Valley, J. W.

    2015-12-01

    The precision and accuracy of carbonate δ18O & δ13C analysis by multicollector SIMS is well established if standards match samples in structure and major/minor element chemistry. However, low-T- and bio-carbonates used to construct paleoclimate archives can include complex internal structures and some samples analyzed at WiscSIMS (and other SIMS labs) have a consistent, sample-dependent offset between average SIMS δ18O measurements and bulk δ18O analyses by phosphoric-acid digestion. The offset is typically <1‰, but recent work has discovered samples where the offset is greater — up to 1.8‰ (average SIMS δ18O values < corresponding conventional measurements). Notably, δ13C offsets have not been observed even in samples with a δ18O offset. We conducted tests to characterize the δ18O offset in different low-T carbonate materials. Multiple potential causes were examined: perhaps the measured offset is real and conventional analyses include material that SIMS excludes (and vice versa); analytical errors and inter-lab (mis)calibration; depth-profiling effects; porosity; and the effects of variable minor element composition. One explanation implicates water and/or organic matter within carbonate that is ionized during SIMS analysis, but sometimes removed for bulk analysis. Two diagnostic tools help monitor such contaminants during SIMS analysis: 1) simultaneous measurement of [16O1H], and 2) secondary ion yield. Offsets of 0.3 to 1.8‰ in δ18O correlate to [16O1H] for 7 studies of Nautilus, foraminifera, pteropods and speleothems. Offsets were not observed in all foraminifera. For Nautilus, foraminifera, otoliths, and speleothems we also tested pre-treatment techniques (e.g. vacuum roasting, hydrogen peroxide), for which there is no agreed procedure in conventional bulk analyses. For SIMS analyses, pre-treatments had varied influence on the δ18O value, [16O1H], the concentration of "organic markers" like 12C14N and 31P, and mineralogy (of aragonite

  6. Ammonia-treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction

    SciTech Connect

    Wang, Xiqing; Lee, Je Seung; Zhu, Qing; Liu, Jun; Wang, Yong; Dai, Sheng

    2010-04-13

    Polymer electrolyte membrane fuel cells (PEMFCs) have been considered as promising alternative power sources for many mobile and stationary applications. Compared to the fast hydrogen oxidation at the anode, the sluggish oxygen reduction reaction (ORR) at the cathode requires high-performance catalysts. Currently, platium (Pt) nanoparticles supported on high surface area carbons remain the best catalysts for ORR. However, both instability and high cost of Pt-based catalysts represent two main obstacles limiting the commercial applications of PEMFCs. The instability of supported Pt catalysts is mainly due to the corrosion of carbon support under operation conditions and the agglomation and detachment of Pt particles, leading to a decrease in catalytic surface areas. Development of corrosion resistant supports and enhancement of the interactions between Pt and supports are two strategies to improve the cathode long-term activity.

  7. Synergy among transition element, nitrogen, and carbon for oxygen reduction reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Li, Zhou Peng; Liu, Zi Xuan; Zhu, Kun Ning; Li, Zhuo; Liu, Bin Hong

    2012-12-01

    A series of M-doped polypyrrole (PPy)-modified BP2000 catalysts (M = Mn, Fe, Co, Ni, and Cu) are synthesized using the hydrothermal method. The synergy among a transition element, nitrogen, and carbon for oxygen reduction reaction (ORR) in alkaline medium is discussed based on the physical characterization and electrochemical analyses of the Co-doped PPy-modified BP2000. PPy is found to adhere carbon black particles together to form a porous 3D network during the PPy modification on BP2000. PPy reconfiguration occurs during the hydrothermal treatment process. The individual interactions between BP and PPy, BP and Co, and Co and PPy exhibit insignificant effects on the enhancement of ORR. The cooperative interaction among Co, N, and C plays a very important role in the enhancement of ORR. The doping effect of transition-metal salt on ORR enhancement depends on the nature of the transition element and the corresponding anion.

  8. Case Report of Focal Epithelial Hyperplasia (Heck's Disease) with Polymerase Chain Reaction Detection of Human Papillomavirus 13.

    PubMed

    Brehm, Mary A; Gordon, Katie; Firan, Miahil; Rady, Peter; Agim, Nnenna

    2016-05-01

    Focal epithelial hyperplasia (FEH), or Heck's disease, is an uncommon benign proliferation of oral mucosa caused by the human papillomavirus (HPV), particularly subtypes 13 and 32. The disease typically presents in young Native American patients and is characterized by multiple asymptomatic papules and nodules on the oral mucosa, lips, tongue, and gingiva. The factors that determine susceptibility to FEH are unknown, but the ethnic and geographic distribution of FEH suggests that genetic predisposition, particularly having the human lymphocytic antigen DR4 type, may be involved in pathogenesis. We report a case of FEH with polymerase chain reaction detection of HPV13 in a healthy 11-year-old Hispanic girl and discuss the current understanding of disease pathogenesis, susceptibility, and treatment.

  9. Case Report of Focal Epithelial Hyperplasia (Heck's Disease) with Polymerase Chain Reaction Detection of Human Papillomavirus 13.

    PubMed

    Brehm, Mary A; Gordon, Katie; Firan, Miahil; Rady, Peter; Agim, Nnenna

    2016-05-01

    Focal epithelial hyperplasia (FEH), or Heck's disease, is an uncommon benign proliferation of oral mucosa caused by the human papillomavirus (HPV), particularly subtypes 13 and 32. The disease typically presents in young Native American patients and is characterized by multiple asymptomatic papules and nodules on the oral mucosa, lips, tongue, and gingiva. The factors that determine susceptibility to FEH are unknown, but the ethnic and geographic distribution of FEH suggests that genetic predisposition, particularly having the human lymphocytic antigen DR4 type, may be involved in pathogenesis. We report a case of FEH with polymerase chain reaction detection of HPV13 in a healthy 11-year-old Hispanic girl and discuss the current understanding of disease pathogenesis, susceptibility, and treatment. PMID:27072123

  10. Comparative temporal analysis of multiwalled carbon nanotube oxidation reactions: Evaluating chemical modifications on true nanotube surface

    NASA Astrophysics Data System (ADS)

    Pacheco, Flávia G.; Cotta, Alexandre A. C.; Gorgulho, Honória F.; Santos, Adelina P.; Macedo, Waldemar A. A.; Furtado, Clascídia A.

    2015-12-01

    The influence of extensive purification on oxidized multiwalled carbon nanotube surface composition was studied through the characterization and differentiation of the actual surface submitted to three oxidation methods: microwave-assisted acid oxidation, hydrogen peroxide reflux, and Fenton reaction. The oxidized samples were purified by a multi-step procedure including the sequential use of basic reflux and dispersion in dimethylformamide (DMF). The results showed a significant increase in the amount of oxidation debris with hydrogen peroxide and Fenton reaction times longer than 8 h and strong surface characteristic modification. With regard to sample purification, basic reflux led to a reduction in oxygenated group concentration of only 10% in the samples treated by acid oxidation. On the other hand, the subsequent use of DMF led to a further decrease in concentration of 39%, proving to be a more efficient method for the removal of oxidation debris.

  11. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    SciTech Connect

    Nandan, Ravi Nanda, Karuna Kar

    2015-06-24

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  12. Coral skeletal carbon isotopes (δ13C and Δ14C) record the delivery of terrestrial carbon to the coastal waters of Puerto Rico

    USGS Publications Warehouse

    Moyer, R.P.; Grottoli, A.G.

    2011-01-01

    Tropical small mountainous rivers deliver a poorly quantified, but potentially significant, amount of carbon to the world's oceans. However, few historical records of land-ocean carbon transfer exist for any region on Earth. Corals have the potential to provide such records, because they draw on dissolved inorganic carbon (DIC) for calcification. In temperate systems, the stable- (δ13C) and radiocarbon (Δ14C) isotopes of coastal DIC are influenced by the δ13C and Δ14C of the DIC transported from adjacent rivers. A similar pattern should exist in tropical coastal DIC and hence coral skeletons. Here, δ13C and Δ14C measurements were made in a 56-year-old Montastraea faveolata coral growing ~1 km from the mouth of the Rio Fajardo in eastern Puerto Rico. Additionally, the δ13C and Δ14C values of the DIC of the Rio Fajardo and its adjacent coastal waters were measured during two wet and dry seasons. Three major findings were observed: (1) synchronous depletions of both δ13C and Δ14C in the coral skeleton are annually coherent with the timing of peak river discharge, (2) riverine DIC was always more depleted in δ13C and Δ14C than seawater DIC, and (3) the correlation of δ13C and Δ14C was the same in both coral skeleton and the DIC of the river and coastal waters. These results indicate that coral skeletal δ13C and Δ14C are recording the delivery of riverine DIC to the coastal ocean. Thus, coral records could be used to develop proxies of historical land-ocean carbon flux for many tropical regions. Such information could be invaluable for understanding the role of tropical land-ocean carbon flux in the context of land-use change and global climate change.

  13. Coral skeletal carbon isotopes (δ13C and Δ14C) record the delivery of terrestrial carbon to the coastal waters of Puerto Rico

    USGS Publications Warehouse

    Moyer, R.P.; Grottoli, A.G.

    2011-01-01

    Tropical small mountainous rivers deliver a poorly quantified, but potentially significant, amount of carbon to the world's oceans. However, few historical records of land-ocean carbon transfer exist for any region on Earth. Corals have the potential to provide such records, because they draw on dissolved inorganic carbon (DIC) for calcification. In temperate systems, the stable- (??13C) and radiocarbon (??14C) isotopes of coastal DIC are influenced by the ??13C and ??14C of the DIC transported from adjacent rivers. A similar pattern should exist in tropical coastal DIC and hence coral skeletons. Here, ??13C and ??14C measurements were made in a 56-year-old Montastraea faveolata coral growing ~1 km from the mouth of the Rio Fajardo in eastern Puerto Rico. Additionally, the ??13C and ??14C values of the DIC of the Rio Fajardo and its adjacent coastal waters were measured during two wet and dry seasons. Three major findings were observed: (1) synchronous depletions of both ??13C and ??14C in the coral skeleton are annually coherent with the timing of peak river discharge, (2) riverine DIC was always more depleted in ??13C and ??14C than seawater DIC, and (3) the correlation of ??13C and ??14C was the same in both coral skeleton and the DIC of the river and coastal waters. These results indicate that coral skeletal ??13C and ??14C are recording the delivery of riverine DIC to the coastal ocean. Thus, coral records could be used to develop proxies of historical land-ocean carbon flux for many tropical regions. Such information could be invaluable for understanding the role of tropical land-ocean carbon flux in the context of land-use change and global climate change. ?? 2011 United States Geological Survey.

  14. Incomplete fusion reactions at low energies in 13C+169Tm system

    NASA Astrophysics Data System (ADS)

    Sharma, Vijay R.; Yadav, Abhishek; Singh, Devendra P.; Singh, Pushpendra P.; Bala, Indu; Kumar, R.; Sharma, M. K.; Gupta, S.; Murlithar, S.; Singh, R. P.; Singh, B. P.; Prasad, R.

    2014-03-01

    Aiming to investigate the incomplete fusion processes at low projectile energies, experiments have been carried out for the 13C + 169Tm system at ≈ 4-7 MeV/A. Excitation functions for several heavy residues likely to be populated via complete and incomplete fusion processes have been measured using heavy recoil residue catcher technique followed by γ- ray spectroscopy. The measured cross-sections for the complete fusion (xn and pxn) channels are compared with the statistical model code PACE4, consistently using the same set of parameters. The complete fusion channels are found to be consistent with the model calculations. However, the cross-sections for all the measured α-emitting channels are found to be significantly enhanced over the calculations. Analysis of data indicate a significant fraction of incomplete fusion even at energies as low as 17% above barrier. The present results are discussed in light of the Morgenstern's systematics. Incomplete fusion strength function is found to be relatively large for alpha cluster projectile i.e. for 12C as compared to one neutron excess 13C projectile.

  15. Synthesis of ortho acid ester-type 1,3-dioxolanofullerenes: radical reaction of [60]fullerene with halocarboxylic acids promoted by lead(IV) acetate.

    PubMed

    You, Xun; Li, Fa-Bao; Wang, Guan-Wu

    2014-11-21

    A lead(IV) acetate-promoted radical reaction of [60]fullerene with halocarboxylic acids has been exploited to synthesize rare ortho acid ester-type 1,3-dioxolanofullerenes, the hydroxyl group of which can be further transformed to an ester or ether group. Intriguingly, an ortho acid ester-type 1,3-dioxolanofullerene can also be converted to a 1,4-dioxanonofullerene in the presence of a base or manipulated to another ortho acid ester-type 1,3-dioxolanofullerene by reaction with a stronger halocarboxylic acid. Moreover, two possible reaction pathways leading to the observed products are also proposed.

  16. Rapid uplift of the Altiplano revealed through 13C-18O bonds in paleosol carbonates.

    PubMed

    Ghosh, Prosenjit; Garzione, Carmala N; Eiler, John M

    2006-01-27

    The elevation of Earth's surface is among the most difficult environmental variables to reconstruct from the geological record. Here we describe an approach to paleoaltimetry based on independent and simultaneous determinations of soil temperatures and the oxygen isotope compositions of soil waters, constrained by measurements of abundances of 13C-18O bonds in soil carbonates. We use this approach to show that the Altiplano plateau in the Bolivian Andes rose at an average rate of 1.03 +/- 0.12 millimeters per year between approximately 10.3 and approximately 6.7 million years ago. This rate is consistent with the removal of dense lower crust and/or lithospheric mantle as the cause of elevation gain.

  17. A general rule for the assignment of the carbon-13 NMR peaks in fatty acid chains

    NASA Astrophysics Data System (ADS)

    Bengsch, E.; Perly, B.; Deleuze, C.; Valero, A.

    Complete assignments of the carbon-13 NMR signals in long fatty acid chains up to C 19 and C 22 were obtained from relaxation behavior studies, from specific isotope labeling, and from studies of analogies between homologous compounds. Results lead to a pyramidal representation which offers a very surprising systematic ordering. From high to low field, signals are ordered in triads with increasing number like C 3C 4C 5, C 6C 7C 8. The triads are interrupted by a signal from the chain end position in decreasing order like C n-3 , C n-4 , and so on. This rule allows complete line assignments for unknown aliphatic fatty acid chains. The rule should be important for studies of lipid compounds and for motional models in biological membrane material.

  18. 13 nm Exciton Size in (6,5) Single-Wall Carbon Nanotubes.

    PubMed

    Mann, Christoph; Hertel, Tobias

    2016-06-16

    Electron-hole correlation lengths, also termed exciton size, for (6,5) single-wall carbon nanotubes (SWNTs) are determined using femtosecond time-resolved pump-probe spectroscopy. The phase space filling model is used to obtain the sizes of the first subband exciton in samples of isolated and of bundled SWNTs. The experiments indicate that the exciton size of (13 ± 3) nm is a factor of 6 higher than previous experimental estimates and theoretical predictions for vacuum suspended SWNTs. This surprising result may be attributed at least in part to the effect of the dielectric environment on exciton sizes and supports recent theoretical findings predicting that screening in SWNTs may enhance rather than reduce electron-hole interactions for separations larger than the tube diameter. Thereby, the work also points to the unique nature of screening and electronic correlations in one-dimensional semiconductors. PMID:27249311

  19. Dissolved inorganic carbon (DIC) and its δ13C in the Ganga (Hooghly) River estuary, India: Evidence of DIC generation via organic carbon degradation and carbonate dissolution

    NASA Astrophysics Data System (ADS)

    Samanta, Saumik; Dalai, Tarun K.; Pattanaik, Jitendra K.; Rai, Santosh K.; Mazumdar, Aninda

    2015-09-01

    In this study, we present comprehensive data on dissolved Ca, dissolved inorganic carbon (DIC) and its carbon isotope composition (δ13CDIC) of (i) the Ganga (Hooghly) River estuary water sampled during six seasons of contrasting water discharge over 2 years (2012 and 2013), (ii) shallow groundwater from areas adjacent to the estuary and (iii) industrial effluent water and urban wastewater draining into the estuary. Mass balance calculations indicate that processes other than the conservative mixing of seawater and river water are needed to explain the measured DIC and δ13CDIC. Results of mixing calculations in conjunction with the estimated undersaturated levels of dissolved O2 suggest that biological respiration and organic carbon degradation dominate over biological production in the estuary. An important outcome of this study is that a significant amount of DIC and dissolved Ca is produced within the estuary at salinity ⩾10, particularly during the monsoon period. Based on consideration of mass balance and a strong positive correlation observed between the "excess" DIC and "excess" Ca, we contend that the dominant source of DIC generated within the estuary is carbonate dissolution that is inferred to be operating in conjunction with degradation of organic carbon. Calculations show that groundwater cannot account for the observed "excess" Ca in the high salinity zone. Estimated DIC contributions from anthropogenic activity are minor, and they constitute ca. 2-3% of the river water DIC concentrations. The estimated annual DIC flux from the estuary to the Bay of Bengal is ca. (3-4) × 1012 g, of which ca. 40-50% is generated within the estuary. The monsoon periods account for the majority (ca. 70%) of the annual DIC generation in the estuary. The annual DIC flux from the Hooghly estuary accounts for ca. 1% of the global river DIC flux to the oceans. This is disproportionately higher than the water contribution from the Hooghly River to the oceans, which

  20. Surface-specific deposition of catalytic metal nanocrystals on hollow carbon nanospheres via galvanic replacement reactions of carbon-encapsulated MnO nanoparticles.

    PubMed

    Lee, Dong-Gyu; Kim, Soo Min; Jeong, Hwakyeung; Kim, Jongwon; Lee, In Su

    2014-05-27

    This paper reports the findings of our efforts toward gaining a more complete understanding and utilization of galvanic replacement reactions involving manganese oxide with noble metals. It was revealed that the site of metal deposition is significantly affected by the variable oxidation state of manganese oxide. The use of carbon-encapsulated MnO nanoparticles as a reaction template led to metal growth specifically on the outermost surfaces of the carbon shells rather than on the MnO cores, which allowed for the selective decoration of the external surfaces of hollow carbon nanospheres with catalytic nanocrystals of various noble metals, including Pt, Pd, Rh, and Ir. By rearranging the sequence between carbon-shell coating and galvanic replacement processes, the deposited metal nanocrystals could be placed on the interior surfaces of hollow carbon nanospheres and, moreover, separately on the internal and the external surfaces, which may enable the respective control of the catalytic functionalities of each specific surface.

  1. Study of 16O(12C,α20Ne)α for the investigation of carbon-carbon fusion reaction via the Trojan Horse Method

    NASA Astrophysics Data System (ADS)

    Rapisarda, G. G.; Spitaleri, C.; Bordeanu, C.; Hons, Z.; Kiss, G. G.; La Cognata, M.; Mrazek, J.; Nita, C.; Pantelica, D.; Petrascu, H.; Pizzone, R. G.; Romano, S.; Szücs, T.; Trache, L.; Tumino, A.; Velisa, G.

    2016-04-01

    Carbon-carbon fusion reaction represents a nuclear process of great interest in astrophysics, since the carbon burning is connected with the third phase of massive stars (M > 8 M⊙) evolution. In spite of several experimental works, carbon-carbon cross section has been measured at energy still above the Gamow window moreover data at low energy present big uncertainty. In this paper we report the results about the study of the 16O(12C,α 20Ne)α reaction as a possible three-body process to investigate 12C(12C,α)20Ne at astrophysical energy via Trojan Horse Method (THM). This study represents the first step of a program of experiments aimed to measure the 12C+12C cross section at astrophysical energy using the THM.

  2. Design of Zeolitic Imidazolate Framework Derived Nitrogen-Doped Nanoporous Carbons Containing Metal Species for Carbon Dioxide Fixation Reactions.

    PubMed

    Toyao, Takashi; Fujiwaki, Mika; Miyahara, Kenta; Kim, Tae-Ho; Horiuchi, Yu; Matsuoka, Masaya

    2015-11-01

    Various N-doped nanoporous carbons containing metal species were prepared by direct thermal conversion of zeolitic imidazolate frameworks (ZIFs; ZIF-7, -8, -9, and -67) at different temperatures (600, 800, and 1000 °C). These materials were utilized as bifunctional acid-base catalysts to promote the reaction of CO2 with epoxides to form cyclic carbonates under 0.6 MPa of CO2 at 80 °C. The catalyst generated by thermal conversion of ZIF-9 at 600 °C (C600-ZIF-9) was found to exhibit a higher catalytic activity than the other ZIFs, other conventional catalysts, and other metal-organic framework catalysts. The results of various characterization techniques including elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and transmission electron microscopy show that C600-ZIF-9 contains partly oxidized Co nanoparticles and N species. Temperature-programmed desorption measurements by using CO2 and NH3 as probe molecules revealed that C600-ZIF-9 has both Lewis acid and Lewis base catalytic sites. Finally, the substrate scope was extended to seven other kinds of epoxides.

  3. Phenotyping hepatocellular metabolism using uniformly labeled carbon-13 molecular probes and LC-HRMS stable isotope tracing.

    PubMed

    Meissen, John K; Pirman, David A; Wan, Min; Miller, Emily; Jatkar, Aditi; Miller, Russell; Steenwyk, Rick C; Blatnik, Matthew

    2016-09-01

    Metabolite stable isotope tracing is a powerful bioanalytical strategy that has the potential to unravel phenotypic markers of early pharmaceutical efficacy by monitoring enzymatic incorporation of carbon-13 atoms into targeted pathways over time. The practice of probing biological systems with carbon-13 labeled molecules using broad MS-based screens has been utilized for many years in academic laboratories but has had limited application in the pharmaceutical R&D environment. The goal of this work was to establish a LCMS analytical workflow that was capable of monitoring carbon-13 isotope changes in glycolysis, the TCA and urea cycles, and non-essential amino acid metabolism. This work applies a standardized protein precipitation with 80% cold methanol and two distinct reverse-phase ion-pair liquid chromatography methods coupled to either a positive- or negative-ion mode high-resolution accurate mass spectrometry screening method. The data herein combines thousands of single-point peak integrations into a novel metabolite network map as a visualization aid to probe and monitor stable isotope incorporation in murine hepatocytes using uniformly labeled (13)C6 glucose, (13)C3 lactate, and (13)C5 glutamine. This work also demonstrates that nitrogen metabolism may have a large influence on the TCA cycle and gluconeogenic carbon fluxes in hepatocyte cell culture. PMID:27343766

  4. Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles.

    PubMed

    Trillo, Paz; Baeza, Alejandro; Nájera, Carmen

    2012-09-01

    The direct allylic substitution reaction using allylic alcohols in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE) as reaction media is described. The developed procedure is simple, works under mild conditions (rt, 50 and 70 °C), and proves to be very general, since different nitrogenated nucleophiles and carbon nucleophiles can be used achieving high yields, especially when HFIP is employed as solvent and aromatic allylic alcohols are the substrates. Thus, sulfonamides, carbamates, carboxamides, and amines can be successfully employed as nitrogen-based nucleophiles. Likewise, silylated nucleophiles such as trimethylsilylazide, allyltrimethylsilane, trimethylsilane, and trimethylsilylphenylacetylene give the corresponding allylic substitution products in high yields. Good results for the Friedel-Crafts adducts are also achieved with aromatic compounds (phenol, anisole, indole, and anilines) as nucleophiles. Particularly interesting are the results obtained with electron-rich anilines, which can behave as nitrogenated or carbon nucleophiles depending on their electronic properties and the solvent employed. In addition, 1,3-dicarbonyl compounds (acetylacetone and Meldrum's acid) are also successfully employed as soft carbon nucleophiles. Studies for mechanism elucidation are also reported, pointing toward the existence of carbocationic intermediates and two working reaction pathways for the obtention of the allylic substitution product.

  5. EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides

    PubMed Central

    Bencivenni, Giorgio; Cesari, Riccardo; Nanni, Daniele; El Mkami, Hassane

    2010-01-01

    Summary The reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium, gallium and indium trichlorides with phenyl azides containing a variety of substituents. Analysis of the spectra showed that 4-methoxy-, 3-methoxy- and 2-methoxyphenyl azides all gave ‘dimer’ radical cations [ArNHC6H4NH2]+• and trimers [ArNHC6H4NHC6H4NH2]+• followed by polymers. 4-Azidobenzonitrile, with its electron-withdrawing substituent, did not react. In general the aromatic azides appeared to react most rapidly with AlCl3 but this reagent tended to generate much polymer. InCl3 was the least reactive group 13 halide. DFT computations of the radical cations provided corroborating evidence and suggested that the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposed. PMID:21049080

  6. Characterisation of black carbon-rich samples by (13)C solid-state nuclear magnetic resonance.

    PubMed

    Novotny, Etelvino H; Hayes, Michael H B; Deazevedo, Eduardo R; Bonagamba, Tito J

    2006-09-01

    There are difficulties in quantifying and characterising the organic matter (OM) in soils that contain significant amounts of partially oxidised char or charcoal materials. The anthropogenic black carbon (BC), such as that found in the Terra Preta de Indio soils of the Amazon region, is a good example of the OM that is difficult to analyse in such soils. (13)C direct polarisation/magic angle spinning (DP/MAS) at high MAS frequency, (1)H-(13)C cross polarisation (CP)/MAS with total suppression of spinning sidebands (TOSS), and chemical shift anisotropy (CSA) filter nuclear magnetic resonance techniques have been applied successfully for quantifying the different components of OM. However, because pyrogenic materials present strong local magnetic susceptibility heterogeneities, the use of CSA-filter and TOSS make the pulse sequences very sensitive to imperfections in the pi pulses. In this study, the DP/MAS pulse sequence was replaced by a CP with a radio frequency ramp--variable amplitude CP (VACP)--VACP/MAS pulse sequence, and composite pi pulses were used in the CSA-filter and TOSS pulse sequences. In that way, the component functionalities in a humic acid from a BC soil were successfully determined. The spectrometer time needed was greatly decreased by employing this VACP/MAS technique. This development provides an accurate method for characterising BC-rich samples from different origins. PMID:16688435

  7. Characterisation of black carbon-rich samples by 13C solid-state nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Novotny, Etelvino H.; Hayes, Michael H. B.; Deazevedo, Eduardo R.; Bonagamba, Tito J.

    2006-09-01

    There are difficulties in quantifying and characterising the organic matter (OM) in soils that contain significant amounts of partially oxidised char or charcoal materials. The anthropogenic black carbon (BC), such as that found in the Terra Preta de Índio soils of the Amazon region, is a good example of the OM that is difficult to analyse in such soils. 13C direct polarisation/magic angle spinning (DP/MAS) at high MAS frequency, 1H-13C cross polarisation (CP)/MAS with total suppression of spinning sidebands (TOSS), and chemical shift anisotropy (CSA) filter nuclear magnetic resonance techniques have been applied successfully for quantifying the different components of OM. However, because pyrogenic materials present strong local magnetic susceptibility heterogeneities, the use of CSA-filter and TOSS make the pulse sequences very sensitive to imperfections in the π pulses. In this study, the DP/MAS pulse sequence was replaced by a CP with a radio frequency ramp—variable amplitude CP (VACP)—VACP/MAS pulse sequence, and composite π pulses were used in the CSA-filter and TOSS pulse sequences. In that way, the component functionalities in a humic acid from a BC soil were successfully determined. The spectrometer time needed was greatly decreased by employing this VACP/MAS technique. This development provides an accurate method for characterising BC-rich samples from different origins.

  8. Carbon-Free Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions.

    PubMed

    Yang, Yang; Fei, Huilong; Ruan, Gedeng; Li, Lei; Wang, Gunuk; Kim, Nam Dong; Tour, James M

    2015-09-23

    A nanoporous Ag-embedded SnO2 thin film was fabricated by anodic treatment of electrodeposited Ag-Sn alloy layers. The ordered nanoporous structure formed by anodization played a key role in enhancing the electrocatalytic performance of the Ag-embedded SnO2 layer in several ways: (1) the roughness factor of the thin film is greatly increased from 23 in the compact layer to 145 in the nanoporous layer, creating additional active sites that are involved in oxygen electrochemical reactions; (2) a trace amount of Ag (∼1.7 at %, corresponding to a Ag loading of ∼3.8 μg cm(-2)) embedded in the self-organized SnO2 nanoporous matrix avoids the agglomeration of nanoparticles, which is a common problem leading to the electrocatalyst deactivation; (3) the fabricated nanoporous thin film is active without additional additives or porous carbon that is usually necessary to support and stabilize the electrocatalyst. More importantly, the Ag-embedded SnO2 nanoporous thin film shows outstanding bifunctional oxygen electrochemical performance (oxygen reduction and evolution reactions) that is considered a promising candidate for use in metal-air batteries. The present technique has a wide range of applications for the preparation of other carbon-free electrocatalytic nanoporous films that could be useful for renewable energy production and storage applications. PMID:26320368

  9. Reaction with DNA and mutagenic specificity of syn-benzo[g]chrysene 11,12-dihydrodiol 13,14-epoxide

    SciTech Connect

    Szeliga, J.; Page, J.E.; Ross, H.L.; Routledge, M.N.; Dipple, A.; Lee, H.; Harvey, R.G.; Hilton, B.D.

    1994-05-01

    The spectroscopic characterization of purine deoxyribonucleoside adducts derived from the fjord-region syn-benzo[g]chrysene 11,12-dihydrodiol 13,14-epoxide and the mutagenic specificity of the latter compound for the supF gene in the pSP189 shuttle vector are described. This dihydrodiol epoxide preferentially forms adducts with deoxyadenosine residues in DNA and is preferentially opened trans in reactions with DNA or with deoxyribonucleotides. In common with other fjord-region syn-dihydrodiol epoxides, the most frequently observed mutational changes were A {yields} T and G {yields} T changes. This hydrocarbon dihydrodiol epoxide is structurally similar to syn-benzo[c]phenanthrene 3,4-dihydrodiol 1,2-epoxide but has an additional benzene ring annelated distant from the reaction center. As anticipated, there were some common features in the chemistry and mutagenicities of these two compounds, but there were also substantive differences which indicate factors of importance in controlling reactions of these kinds of compounds with DNA. 38 refs., 11 figs., 2 tabs.

  10. Evidence for a secular variation in the C-13/C-12 ratio of carbon implanted in lunar soils

    NASA Technical Reports Server (NTRS)

    Becker, R. H.

    1980-01-01

    A curve of delta(C-13) vs delta(N-15) for lunar soils and breccias shows that the previously recorded 30% change in delta(N-15) is associated with a change in delta(C-13). The correlation represents concurrent changes in the isotope ratios of both elements at their source, and does not result from maturation effects or nonselective sample contamination. A computation of the relative production rates of C-13 and N-15 shows that spallation reactions in the sun could produce the observed ratio of the delta(C-13) to delta (N-15) variations.

  11. The use of natural abundance carbon-13 to identify and quantify sources of emitted carbon dioxide in a calcareous southern Ontario Luvisolic soil

    NASA Astrophysics Data System (ADS)

    Wilton, Meaghan

    Three studies Were conducted at the Elora Research Station (ERS) on a Luvisolic soil to investigate the soil inorganic carbon (SIC) and soil organic carbon (SOC) components contributing to the CO2 flux (FC) using natural 13C abundance. SIC contributed to the FC in intact soil incubations. Soil disruption exacerbated the release of CO2 from both pedogenic and lithogenic carbonates. Field and laboratory techniques to obtain the delta13C of respired CO2 (delta13CR) were compared. Short-term deployment of non flow-through non steady-state chambers and the use of the simple two-ended mass balance approach to derive delta 13CR were found acceptable to apply to the ERS site. The delta13CR from a corn field at ERS with a history of multiple C4 and C3 crop rotations was partitioned into SIC and SOC components using two approaches. Root respiration contributed 2% - 64% and carbonates contribute up to 20% to the FC.

  12. Ammonia fixation by humic substances: A nitrogen-15 and carbon-13 NMR study

    USGS Publications Warehouse

    Thorn, K.A.; Mikita, M.A.

    1992-01-01

    The process of ammonia fixation has been studied in three well characterized and structurally diverse fulvic and humic acid samples. The Suwannee River fulvic acid, and the IHSS peat and leonardite humic acids, were reacted with 15N-labelled ammonium hydroxide, and analyzed by liquid phase 15N NMR spectrometry. Elemental analyses and liquid phase 13C NMR spectra also were recorded on the samples before and after reaction with ammonium hydroxide. The largest increase in percent nitrogen occurred with the Suwannee River fulvic acid, which had a nitrogen content of 0.88% before fixation and 3.17% after fixation. The 15N NMR spectra revealed that ammonia reacted similarly with all three samples, indicating that the functional groups which react with ammonia exist in structural configurations common to all three samples. The majority of nitrogcn incorporated into the samples appears to be in the form of indole and pyrrole nitrogen, followed by pyridine, pyrazine, amide and aminohydroquinone nitrogen. Chemical changes in the individual samples upon fixation could not be discerned from the 13C NMR spectra.

  13. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    NASA Astrophysics Data System (ADS)

    Senanayake, Sanjaya D.; Pappoe, Naa Adokaley; Nguyen-Phan, Thuy-Duong; Luo, Si; Li, Yuanyuan; Xu, Wenqian; Liu, Zongyuan; Mudiyanselage, Kumudu; Johnston-Peck, Aaron C.; Frenkel, Anatoly I.; Heckler, Ilana; Stacchiola, Dario; Rodriguez, José A.

    2016-10-01

    We have studied the catalytic carbon monoxide (CO) oxidation (CO + 0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5 wt.% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including transmission electron microscopy (TEM), the local catalyst morphology and structure were also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggest that surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.

  14. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    DOE PAGESBeta

    Senanayake, S. D.; Pappoe, N. A.; Nguyen-Phan, T. -D.; Luo, S.; Li, Y.; Xu, W.; Liu, Z.; Mudiyanselage, K.; Johnston-Peck, A. C.; Frenkel, A. I.; et al

    2016-10-01

    We have studied the catalytic carbon monoxide (CO) oxidation (CO+0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5wt% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray Diffraction (XRD), X-ray Absorption Fine Structure (XAFS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface statesmore » or intermediates of this reaction. With the aid of several ex situ characterization techniques including Transmission Electron Microscopy (TEM), the local catalyst morphology and structure was also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggests that a surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.« less

  15. Concerted two-dimensional NMR approaches to hydrogen-1, carbon-13, and nitrogen-15 resonance assignments in proteins

    SciTech Connect

    Stockman, B.J.; Reily, M.D.; Westler, W.M.; Ulrich, E.L.; Markley, J.L. )

    1989-01-10

    When used in concert, one-bond carbon-carbon correlations, one-bond and multiple-bond proton-carbon correlations, and multiple-bond proton-nitrogen correlations, derived from two-dimensional (2D) NMR spectra of isotopically enriched proteins, provide a reliable method of assigning proton, carbon, and nitrogen resonances. In contrast to procedures that simply extend proton assignments to carbon or nitrogen resonances, this technique assigns proton, carbon, and nitrogen resonances coordinately on the basis of their integrated coupling networks. Redundant spin coupling pathways provide ways of resolving overlaps frequently encountered in homonuclear {sup 1}H 2D NMR spectra and facilitate the elucidation of complex proton spin systems. Carbon-carbon and proton-carbon couplings can be used to bridge the aromatic and aliphatic parts of proton spin systems; this avoids possible ambiguities that may result from the use of nuclear Overhauser effects to assign aromatic amino acid signals. The technique is illustrated for Anabaena 7120 flavodoxin and cytochrome c-553, both uniformly enriched with carbon-13 (26%) or nitrogen-15 (98%).

  16. Curing chemistry of phenylethynyl-terminated imide oligomers: Model compounds, carbon-13 labeling and cure analysis

    NASA Astrophysics Data System (ADS)

    Roberts, Christopher Chad

    1998-11-01

    cyclotrimers and linear oligomers (polyenes) were also synthesized from PEPA/An and analyzed in terms of spectroscopic and thermal properties. The conversion of alpha,beta-sp{13}C-acetophenone to alpha,beta-sp{13}C-phenylacetylene using a LDA/phosphate ester procedure was readily accomplished, and following a silver salt purification, the labeled enylacetylene was immediately reacted with 4-bromophthalic anhydride under Heck coupling conditions. A 29% yield of recrystallized 4-(phenylethynyl-alpha,beta-sp{13}Csb2)phthalic anhydride was obtained based on acetophenone. By adjusting the stoichiometry, sp{13}C labeled phenylethynyl-terminated imide oligomers (PETI) were synthesized with Msb{n} of 2,000 to 9,000 daltons. The thermal curing of PETI's and model compounds was monitored via solid state sp{13}C nuclear magnetic resonance, electron spin resonance spectroscopy and differential scanning calorimetry. Using solid state sp{13}C NMR, several cure products were identified. The effects of post-curing and oligomer chain length on the final structure of the cured resins were also examined. Electron spin resonance spectra were obtained on unlabeled PETI's before and after heating at 250-410sp°C. ESR signals suggest that the curing of these resins involves a carbon centered radical. The cure parameters of model compounds as determined by DSC were tabulated and compared. Molecular mechanics and semi-empirical calculations were employed to calculate theoretical bond orders, ionization potentials, HOMO-LUMO gaps, point charges and molecular volumes. The cure profiles of the model compounds were rationalized using these molecular parameters. All of the present data is consistent with the proposed curing mechanisms and cure products. The dominant factors include the chain length of the reactive oligomer, the backbone structure and steric hindrance around the ethynyl group. Although less defined, the electronics and flexibility around the ethynyl group also appear to be factors in

  17. Development of palladium-based nanocatalysts on carbon support for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Arroyo Ramirez, Lisandra

    Direct methanol fuel cell (DMFC) promises to be a power source for space application, transportation and portable devices. However, platinum catalysts, the methanol crossover and the sluggish kinetics of the oxygen reduction reaction (ORR) limit their commercialization. DMFC has the challenge to find a catalyst with high methanol tolerance and simple synthesis methodology. We proposed the development of palladium-based nanostructures on carbon supports as electrocatalyst for the oxygen reduction reaction. The working hypothesis is that the use of different methodologies and carbon supports will lead the formation of different palladium catalytic nanostructures with high methanol tolerance. A new single source approach was used to synthesize Pd-Co nanostructures on a highly ordered pyrolytic graphite (HOPG) surface using a bimetallic molecular precursor. Then, synthesis of palladium and palladium-cobalt nanoparticles on Vulcan XC-72R by chemical and thermal reduction using organometallic complexes as precursors was done. The palladium thin films and nanoshells were synthesized on HOPG and carbon cloth using sputtering deposition and electrospinning techniques. The morphology and composition were characterized by surface analysis techniques, such as: atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscope with energy-dispersive X-ray fluorescence spectroscopy (SEM/EDS), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), among others. ORR electrocatalytic activity and methanol tolerance was determined for the Pd/C, Pd2Co/C and PdCo 2/C catalysts. The rotating ring-disk electrode technique was used to determine the ORR mechanism and kinetics. Pd2Co nanorings were formed on a HOPG surface by self-assembly with humidity control. Also, a single precursor was used for the synthesis of palladium-cobalt nanocatalysts on carbon supports by thermal reduction with ORR electrocatalytic activity and higher methanol

  18. Nitrogen-doped carbon nanotubes as catalysts for the oxygen reduction reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Yang, Mei; Yang, Duangguang; Chen, Hongbiao; Gao, Yong; Li, Huaming

    2015-04-01

    A novel electrocatalyst for the oxygen reduction reaction (ORR) is fabricated by directly annealing oxidized carbon nanotubes and tripyrrolyl[1,3,5]triazine in nitrogen. The structural and chemical properties of the resultant N-doped carbon nanotubes (NCNTs) are systematically investigated. The electrocatalytic activity of the NCNTs towards ORR in O2-saturated 0.1 M KOH electrolyte is evaluated using rotating disk electrode voltammetry. The results demonstrate that the as-prepared NCNT-900 (annealed at 900 °C) exhibits excellent electrochemical performance towards ORR in alkaline medium with an onset potential of -0.038 V (vs Ag/AgCl), a high kinetic current density of 31.26 mA cm-2 at -0.25 V, a dominant four-electron transfer mechanism (n = 3.88 at -0.25 V), and excellent methanol tolerance and durability. The results obtained are significant for the development of N-doped carbon-based electrocatalysts for alkaline fuel cells.

  19. Cu,N-codoped Hierarchical Porous Carbons as Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Yu, Haiyan; Fisher, Adrian; Cheng, Daojian; Cao, Dapeng

    2016-08-24

    It remains a huge challenge to develop nonprecious electrocatalysts with high activity to substitute commercial Pt catalysts for oxygen reduction reactions (ORR). Here, the Cu,N-codoped hierarchical porous carbon (Cu-N-C) with a high content of pyridinic N was synthesized by carbonizing Cu-containing ZIF-8. Results indicate that Cu-N-C shows excellent ORR electrocatalyst properties. First of all, it nearly follows the four-electron route, and its electron transfer number reaches 3.92 at -0.4 V. Second, both the onset potential and limited current density of Cu-N-C are almost equal to those of a commercial Pt/C catalyst. Third, it exhibits a better half-wave potential (∼16 mV) than a commercial Pt/C catalyst. More importantly, the Cu-N-C displays better stability and methanol tolerance than the Pt/C catalyst. All of these good properties are attributed to hierarchical structure, high pyridinic N content, and the synergism of Cu and N dopants. The metal-N codoping strategy can significantly enhance the activity of electrocatalysts, and it will provide reference for the design of novel N-doped porous carbon ORR catalysts. PMID:27490846

  20. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells.

    PubMed

    Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

    2015-02-01

    The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells.

  1. WO3-x Nanoplates Grown on Carbon Nanofibers for an Efficient Electrocatalytic Hydrogen Evolution Reaction.

    PubMed

    Chen, JiaDong; Yu, DanNi; Liao, WeiSha; Zheng, MengDan; Xiao, LongFei; Zhu, Han; Zhang, Ming; Du, MingLiang; Yao, JuMing

    2016-07-20

    The search for non-noble metal catalysts with high activity for the hydrogen evolution reaction (HER) is crucial for efficient hydrogen production at low cost and on a large scale. Herein, we report a novel WO3-x catalyst synthesized on carbon nanofiber mats (CFMs) by electrospinning and followed by a carbonization process in a tubal furnace. The morphology and composition of the catalysts were tailored via a simple method, and the hybrid catalyst mats were used directly as cathodes to investigate their HER performance. Notably, the as-prepared catalysts exhibit substantially enhanced activity for the HER, demonstrating a small overpotential, a high exchange current density, and a large cathodic current density. The remarkable electrocatalytic performances result from the poor crystallinity of WO3-x, the high electrical conductivity of WO3-x, and the use of electrospun CNFs. The present work outlines a straightforward approach for the synthesis of transition metal oxide (TMO)-based carbon nanofiber mats with promising applications for the HER. PMID:27356101

  2. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells

    PubMed Central

    Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

    2015-01-01

    The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells. PMID:26601132

  3. Cu,N-codoped Hierarchical Porous Carbons as Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Yu, Haiyan; Fisher, Adrian; Cheng, Daojian; Cao, Dapeng

    2016-08-24

    It remains a huge challenge to develop nonprecious electrocatalysts with high activity to substitute commercial Pt catalysts for oxygen reduction reactions (ORR). Here, the Cu,N-codoped hierarchical porous carbon (Cu-N-C) with a high content of pyridinic N was synthesized by carbonizing Cu-containing ZIF-8. Results indicate that Cu-N-C shows excellent ORR electrocatalyst properties. First of all, it nearly follows the four-electron route, and its electron transfer number reaches 3.92 at -0.4 V. Second, both the onset potential and limited current density of Cu-N-C are almost equal to those of a commercial Pt/C catalyst. Third, it exhibits a better half-wave potential (∼16 mV) than a commercial Pt/C catalyst. More importantly, the Cu-N-C displays better stability and methanol tolerance than the Pt/C catalyst. All of these good properties are attributed to hierarchical structure, high pyridinic N content, and the synergism of Cu and N dopants. The metal-N codoping strategy can significantly enhance the activity of electrocatalysts, and it will provide reference for the design of novel N-doped porous carbon ORR catalysts.

  4. Carbonized nanoscale metal-organic frameworks as high performance electrocatalyst for oxygen reduction reaction.

    PubMed

    Zhao, Shenlong; Yin, Huajie; Du, Lei; He, Liangcan; Zhao, Kun; Chang, Lin; Yin, Geping; Zhao, Huijun; Liu, Shaoqin; Tang, Zhiyong

    2014-12-23

    The oxygen reduction reaction (ORR) is one of the key steps in clean and efficient energy conversion techniques such as in fuel cells and metal-air batteries; however, several disadvantages of current ORRs including the kinetically sluggish process and expensive catalysts hinder mass production of these devices. Herein, we develop carbonized nanoparticles, which are derived from monodisperse nanoscale metal organic frameworks (MIL-88B-NH3), as the high performance ORR catalysts. The onset potential and the half-wave potential for the ORR at these carbonized nanoparticles is up to 1.03 and 0.92 V (vs RHE) in 0.1 M KOH solution, respectively, which represents the best ORR activity of all the non-noble metal catalysts reported so far. Furthermore, when used as the cathode of the alkaline direct fuel cell, the power density obtained with the carbonized nanoparticles reaches 22.7 mW/cm2, 1.7 times higher than the commercial Pt/C catalysts. PMID:25426850

  5. Cobalt nanoparticles embedded in nitrogen-doped carbon for the hydrogen evolution reaction.

    PubMed

    Fei, Huilong; Yang, Yang; Peng, Zhiwei; Ruan, Gedeng; Zhong, Qifeng; Li, Lei; Samuel, Errol L G; Tour, James M

    2015-04-22

    There is great interest in renewable and sustainable energy research to develop low-cost, highly efficient, and stable electrocatalysts as alternatives to replace Pt-based catalysts for the hydrogen evolution reaction (HER). Though nanoparticles encapsulated in carbon shells have been widely used to improve the electrode performances in energy storage devices (e.g., lithium ion batteries), they have attracted less attention in energy-related electrocatalysis. Here we report the synthesis of nitrogen-enriched core-shell structured cobalt-carbon nanoparticles dispersed on graphene sheets and we investigate their HER performances in both acidic and basic media. These catalysts exhibit excellent durability and HER activities with onset overpotentials as low as ∼70 mV in both acidic (0.5 M H2SO4) and alkaline (0.1 M NaOH) electrolytes, and the overpotentials needed to deliver 10 mA cm(-2) are determined to be 265 mV in acid and 337 mV in base, further demonstrating their potential to replace Pt-based catalysts. Control experiments reveal that the active sites for HER might come from the synergistic effects between the cobalt nanoparticles and nitrogen-doped carbon. PMID:25826236

  6. The influence of diet on the δ 13C of shell carbon in the pulmonate snail Helix aspersa

    NASA Astrophysics Data System (ADS)

    Stott, Lowell D.

    2002-02-01

    The influence of diet and atmospheric CO 2 on the carbon isotope composition of shell aragonite and shell-bound organic carbon in the pulmonate snail Helix aspersa raised in the laboratory was investigated. Three separate groups of snails were raised on romaine lettuce (C3 plant, δ 13C=-25.8‰), corn (C4 plant, δ 13C=-10.5‰), and sour orange ( 12C-enriched C3 plant, δ 13C=-39.1‰). The isotopic composition of body tissues closely tracked the isotopic composition of the snail diet as demonstrated previously. However, the isotopic composition of the acid insoluble organic matrix extracted from the aragonite shells does not track diet in all groups. In snails that were fed corn the isotopic composition of the organic matrix was more negative than the body by as much as 5‰ whereas the matrix was approximately 1‰ heavier than the body tissues in snails fed a diet of C3 plant material. These results indicate that isotopic composition of the organic matrix carbon cannot be used as an isotopic substrate for paleodietary reconstructions without first determining the source of the carbon and any associated fractionations. The isotopic composition of the shell aragonite is offset from the body tissues by 12.3‰ in each of the culture groups. This offset was not influenced by the consumption of carbonate and is not attributable to the diffusion of atmospheric CO 2 into the hemolymph. The carbon isotopic composition of shell aragonite is best explained in terms of equilibrium fractionations associated with exchange between metabolic CO 2 and HCO 3 in the hemolymph and the fractionation associated with carbonate precipitation. These results differ from previous studies, based primarily on samples collected in the field, that have suggested atmospheric carbon dioxide contributes significantly to the shell δ 13C. The culture results indicate that the δ 13C of aragonite is a good recorder of the isotopic composition of the snail body tissue, and therefore a better

  7. Synthesis of 5-aryl-1,3-dimethyl-6-(alkyl- or aryl-amino) furo [2,3-d]pyrimidine derivatives by reaction between isocyanides and pyridinecarbaldehydes in the presence of 1,3-dimethylbarbituric acid.

    PubMed

    Maghsoodlou, Malek Taher; Marandi, Ghasem; Hazeri, Nourallah; Habibi-Khorassani, Sayyed Mostafa; Mirzaei, Ali Akbar

    2011-02-01

    5-Aryl-6-(alkyl- or aryl-amino)-1,3-dimethylfuro [2,3-d]pyrimidine derivatives were obtained by in situ reaction alkyl or aryl isocyanides and pyridinecarbaldehyde derivatives in the presence of 1,3-dimethylbarbituric acid in dichloromethane without any prior activation or modifications.

  8. Large odd-numbered carbon clusters from fullerene-ozone reactions. (Reannouncement with new availability information). Technical report

    SciTech Connect

    McElvany, S.W.; Callahan, J.H.; Ross, M.M.; Lamb, L.D.; Huffman, D.R.

    1993-06-11

    The odd-numbered carbon clusters C119, C129 and C139 have been observed in the mass spectra of toluene extracts of fullerene soots and of the products of ozone-fullerene reactions. Specifically, ozone-C60 reactions yield C119, and ozone-C70 reactions yield C139, and ozone-(C60/C70) reactions produce C119, C129, and C139. These unexpected species correspond to dimers of C60, C60/C70, and C70, respectively, less one carbon atom, and are stable gas-phase ions with behavior similar to that of fullerenes. The results suggest a new route to functionalization and derivatization of fullerenes through controlled ozone-catalyzed cage-opening reactions.

  9. Structural effects in the reaction between carbon dioxide and coke doped with various potassium bearing catalytic precursors

    NASA Astrophysics Data System (ADS)

    Alam, M.; Debroy, T.

    1986-09-01

    The rate of reaction between carbon dioxide and coke with and without the additions of KCN, KOCN, and K2CO3 was studied using thermogravimetry. Since both potassium and carbon are lost during the reaction, the concentration of potassium in the coke samples was determined as a function of the extent of the reaction by atomic absorption spectrometry. The changes in the specific surface area due to the reaction were studied by the nitrogen adsorption technique. The changes in the pore structure of coke were investigated by mercury porosimetry and scanning electron microscopy. The distribution of potassium in the coke structure was examined as a function of the reaction time by the energy dispersion X-ray technique. Furthermore, since sulfur is known to influence the rate of the C-CO2 reaction, the sulfur content of the coke samples with or without the addition of catalytic precursors was monitored as a function of the extent of reaction. The influences of the structural parameters and the concentration of potassium on the rate of the coke-CO2 reaction were determined. The rate data were analyzed on the basis of a structural model to examine the contributions of the chemical reaction and the pore diffusion on the overall rate of the coke-CO2 reaction.

  10. Revealing Brown Carbon Chromophores Produced in Reactions of Methylglyoxal with Ammonium Sulfate

    SciTech Connect

    Lin, Peng; Laskin, Julia; Nizkorodov, Sergey A.; Laskin, Alexander

    2015-12-15

    Atmospheric brown carbon (BrC) is an important contributor to light absorption and climate forcing by aerosols. Reactions between small water-soluble carbonyls and ammonia or amines have been identified as one of the potential pathways of BrC formation. However, detailed chemical characterization of BrC chromophores has been challenging and their formation mechanisms are still poorly understood. Understanding BrC formation is impeded by the lack of suitable methods which can unravel the variability and complexity of BrC mixtures. This study applies high performance liquid chromatography (HPLC) coupled to photodiode array (PDA) detector and high resolution mass spectrometry (HRMS) to investigate optical properties and chemical composition of individual BrC components produced through reactions of methylglyoxal (MG) and ammonium sulfate (AS), both of which are abundant in the atmospheric environment. A direct relationship between optical properties and chemical composition of 30 major BrC chromophores was established. Nearly all of these chromophores are nitrogen-containing compounds that account for >70% of the overall light absorption by the MG+AS system in the 300-500 nm range. These results suggest that reduced-nitrogen organic compounds formed in reactions between atmospheric carbonyls and ammonia/amines are important BrC chromophores. It is also demonstrated that improved separation of BrC chromophores by HPLC will significantly advance understanding of BrC chemistry.

  11. Revealing Brown Carbon Chromophores Produced in Reactions of Methylglyoxal with Ammonium Sulfate.

    PubMed

    Lin, Peng; Laskin, Julia; Nizkorodov, Sergey A; Laskin, Alexander

    2015-12-15

    Atmospheric brown carbon (BrC) is an important contributor to light absorption and climate forcing by aerosols. Reactions between small water-soluble carbonyls and ammonia or amines have been identified as one of the potential pathways of BrC formation. However, detailed chemical characterization of BrC chromophores has been challenging and their formation mechanisms are still poorly understood. Understanding BrC formation is impeded by the lack of suitable methods which can unravel the variability and complexity of BrC mixtures. This study applies high performance liquid chromatography (HPLC) coupled to photodiode array (PDA) detector and high resolution mass spectrometry (HRMS) to investigate optical properties and chemical composition of individual BrC components produced through reactions of methylglyoxal (MG) and ammonium sulfate (AS), both of which are abundant in the atmospheric environment. A direct relationship between optical properties and chemical composition of 30 major BrC chromophores is established. Nearly all of these chromophores are nitrogen-containing compounds that account for >70% of the overall light absorption by the MG+AS system in the 300-500 nm range. These results suggest that reduced-nitrogen organic compounds formed in reactions between atmospheric carbonyls and ammonia/amines are important BrC chromophores. It is also demonstrated that improved separation of BrC chromophores by HPLC will significantly advance understanding of BrC chemistry. PMID:26505092

  12. Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

    PubMed Central

    Jouffroy, Matthieu; Gramage-Doria, Rafael; Sémeril, David; Oberhauser, Werner; Toupet, Loïc

    2014-01-01

    Summary The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. PMID:25383109

  13. Revealing Brown Carbon Chromophores Produced in Reactions of Methylglyoxal with Ammonium Sulfate.

    PubMed

    Lin, Peng; Laskin, Julia; Nizkorodov, Sergey A; Laskin, Alexander

    2015-12-15

    Atmospheric brown carbon (BrC) is an important contributor to light absorption and climate forcing by aerosols. Reactions between small water-soluble carbonyls and ammonia or amines have been identified as one of the potential pathways of BrC formation. However, detailed chemical characterization of BrC chromophores has been challenging and their formation mechanisms are still poorly understood. Understanding BrC formation is impeded by the lack of suitable methods which can unravel the variability and complexity of BrC mixtures. This study applies high performance liquid chromatography (HPLC) coupled to photodiode array (PDA) detector and high resolution mass spectrometry (HRMS) to investigate optical properties and chemical composition of individual BrC components produced through reactions of methylglyoxal (MG) and ammonium sulfate (AS), both of which are abundant in the atmospheric environment. A direct relationship between optical properties and chemical composition of 30 major BrC chromophores is established. Nearly all of these chromophores are nitrogen-containing compounds that account for >70% of the overall light absorption by the MG+AS system in the 300-500 nm range. These results suggest that reduced-nitrogen organic compounds formed in reactions between atmospheric carbonyls and ammonia/amines are important BrC chromophores. It is also demonstrated that improved separation of BrC chromophores by HPLC will significantly advance understanding of BrC chemistry.

  14. Evaluation and characterization of the methane-carbon dioxide decomposition reaction

    NASA Technical Reports Server (NTRS)

    Davenport, R. J.; Schubert, F. H.; Shumar, J. W.; Steenson, T. S.

    1975-01-01

    A program was conducted to evaluate and characterize the carbon dioxide-methane (CO2-CH4) decomposition reaction, i.e., CO2 + CH4 = 2C + 2H2O. The primary objective was to determine the feasibility of applying this reaction at low temperatures as a technique for recovering the oxygen (O2) remaining in the CO2 which exits mixed with CH4 from a Sabatier CO2 reduction subsystem (as part of an air revitalization system of a manned spacecraft). A test unit was designed, fabricated, and assembled for characterizing the performance of various catalysts for the reaction and ultraviolet activation of the CH4 and CO2. The reactor included in the test unit was designed to have sufficient capacity to evaluate catalyst charges of up to 76 g (0.17 lb). The test stand contained the necessary instrumentation and controls to obtain the data required to characterize the performance of the catalysts and sensitizers tested: flow control and measurement, temperature control and measurement, product and inlet gas analysis, and pressure measurement. A product assurance program was performed implementing the concepts of quality control and safety into the program effort.

  15. Applications of carbon-13 and sodium-23 NMR in the study of plants, animal, and human cells

    SciTech Connect

    Sillerud, L.O.; Heyser, J.W.; Han, C.H.; Bitensky, M.W.

    1984-01-01

    Carbon-13 and sodium-23 NMR have been applied to the study of a variety of plant, animal and human cell types. Sodium NMR, in combination with dysprosium shift reagents, has been used to monitor sodium transport kinetics in salt-adapted, and non-adapted cells of P. milliaceum and whole D. spicata plants. The sodium content of human erythrocytes and leukemic macrophages was measured. Carbon-13 NMR was used to determine the structure and metabolism of rat epididymal fat pad adipocytes in real time. Insulin and isoproterenol-stimulated triacylglycerol turnover could be monitored in fat cell suspensions. (1-/sup 13/C) glucose was used as a substrate to demonstrate futile metabolic cycling from glucose to glycerol during lypolysis. Cell wall polysaccharide synthesis was followed in suspensions of P. milliaceum cells using (1-/sup 13/C) glucose as a precursor. These results illustrate the wide range of living systems which are amenable to study with NMR. 14 refs., 21 figs.

  16. The 'Nuts and Bolts' of 13C NMR Spectroscopy at Elevated-Pressures and -Temperatures for Monitoring In Situ CO2 Conversion to Metal Carbonates

    NASA Astrophysics Data System (ADS)

    Moore, J. K.; Surface, J. A.; Skemer, P. A.; Conradi, M. S.; Hayes, S. E.

    2013-12-01

    We will present details of newly-constructed specialized NMR designed to conduct in situ elevated-pressure, elevated-temperature 13C NMR studies on unmixed slurries of minerals in the presence of CO2 or other gases. This static probe is capable of achieving 300 bar, 300C conditions, and it is designed to spectroscopically examine 13C signals in mixtures of solids, liquids, gases, and supercritical fluids. Ultimately, our aim is to monitor CO2 uptake in both ultramafic rocks and in more porous geological materials to understand the mechanisms of chemisorption as a function of temperature, pressure and pH. We will give details of the hardware setup, and we will show a variety of static in situ NMR, as well as ex situ 'magic-angle spinning' NMR to show the analyses that are possible of minerals in pure form and in mixtures. In addition, specific NMR pulse sequences, techniques, and modeling will be described in detail. In this in situ NMR probe, we are able to simulate processes at geologically relevant fluid pressures and temperatures, monitoring the kinetics of CO2 conversion to carbonates. The in situ NMR experiments consist of heterogeneous mixtures of rock, salty brine solution, and moderate pressure CO2 gas at elevated temperatures. The purpose of studying these reactions is to determine conditions that affect the efficacy of carbonate formation in various targeted geological reservoirs (i.e., peroditite, or others). Via 13C NMR, we have spectroscopically characterized and quantified the conversion of CO2 to magnesium carbonate and calcium carbonate minerals, including metastable intermediates (such as hydromagnesite, or dypingite in the case of magnesium carbonate species, or vaterite in the case of calcium carbonate species). Such species are distinguishable from a combination of the 13C isotropic chemical shift, the static 13C lineshape, and changes in spin-lattice (T1) relaxation times. We will demonstrate that NMR can be used for quantitative

  17. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    SciTech Connect

    Dixon, David Adams

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  18. Differentiation of Pigment in Eggs Using Carbon ((13)C/(12)C) and Nitrogen ((15)N/(14)N) Stable Isotopes.

    PubMed

    Sun, Feng M; Shi, Guang Y; Wang, Hui W

    2016-07-01

    Consumers prefer natural and healthy food, but artificial pigments are often abused in egg products. The study aimed at differentiating the origin of pigments in eggs by applying the technique of carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) stable isotope analysis. Five hundred sixty laying hens were randomly distributed into 14 treatments, which were divided into four groups: maize, carophyll red pigment, carophyll yellow pigment, and a mixture of carophyll red and yellow pigments. Eggs were collected and pretreated to determe the values of the Roche Yolk Color Fan (RCF), δ(13)C, and δ(15)N. With increasing maize content, the RCF and δ(13)C values of yolks increased. Moreover, the RCF values in the three pigment groups were significantly influenced by the artificial colors, but δ(13)C values were not significantly different, regardless of the existence of pigment. The δ(15)N values in all treatments did not vary as regularly as the carbon stable isotope. A strong positive correlation was found between RCF and δ(13)C in the maize group, but no such correlation was be observed in the pigment groups. It is concluded that carbon stable isotope ratio analysis (δ(13)C) of the yolk can be used to differentiate the origin of the pigment added to eggs. PMID:27302905

  19. Differentiation of Pigment in Eggs Using Carbon ((13)C/(12)C) and Nitrogen ((15)N/(14)N) Stable Isotopes.

    PubMed

    Sun, Feng M; Shi, Guang Y; Wang, Hui W

    2016-07-01

    Consumers prefer natural and healthy food, but artificial pigments are often abused in egg products. The study aimed at differentiating the origin of pigments in eggs by applying the technique of carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) stable isotope analysis. Five hundred sixty laying hens were randomly distributed into 14 treatments, which were divided into four groups: maize, carophyll red pigment, carophyll yellow pigment, and a mixture of carophyll red and yellow pigments. Eggs were collected and pretreated to determe the values of the Roche Yolk Color Fan (RCF), δ(13)C, and δ(15)N. With increasing maize content, the RCF and δ(13)C values of yolks increased. Moreover, the RCF values in the three pigment groups were significantly influenced by the artificial colors, but δ(13)C values were not significantly different, regardless of the existence of pigment. The δ(15)N values in all treatments did not vary as regularly as the carbon stable isotope. A strong positive correlation was found between RCF and δ(13)C in the maize group, but no such correlation was be observed in the pigment groups. It is concluded that carbon stable isotope ratio analysis (δ(13)C) of the yolk can be used to differentiate the origin of the pigment added to eggs.

  20. Reactions of atomic hydrogen with formic acid and carbon monoxide in solid parahydrogen II: Deuterated reaction studies.

    PubMed

    Wonderly, William R; Anderson, David T

    2014-09-11

    It is difficult to determine whether the measured rate constant for reaction of atomic hydrogen with formic acid reported in Part 1 reflects the H atom quantum diffusion rate or the rate constant for the tunneling reaction step. In Part 2 of this series, we present kinetic studies of the postphotolysis H atom reactions with deuterated formic acid (DCOOD) to address this ambiguity. Short duration 193 nm in situ photolysis of DCOOD trapped in solid parahydrogen results in partial depletion of the DCOOD precursor and photoproduction of primarily CO, CO2, DOCO, HCO and mobile H atoms. At 1.9 K we observe post-irradiation growth in the concentrations of DOCO and HCO that can be explained by H atom tunneling reactions with DCOOD and CO, respectively. Conducting experiments with different deuterium isotopomers of formic acid (DCOOD, DCOOH, HCOOD and HCOOH) provides strong circumstantial evidence the reaction involves H atom abstraction from the alkyl group of formic acid. Further, the anomalous temperature dependence measured for the H + HCOOH reaction in Part 1 is also observed for the analogous reactions with deuterated formic acid. The rate constants extracted for H atom reactions with DCOOD and HCOOH are equivalent to within experimental uncertainty. This lack of a kinetic isotope effect in the measured rate constant is interpreted as evidence the reactions are diffusion limited; the measured rate constant reflects the H atom diffusion rate and not the tunneling reaction rate. Whether or not H atom reactions with chemical species in solid parahydrogen are diffusion limited is one of the outstanding questions in this field, and this work makes significant strides toward showing the reaction kinetics with formic acid are diffusion limited.

  1. Carbon capture by sorption-enhanced water-gas shift reaction process using hydrotalcite-based material

    SciTech Connect

    van Selow, E.R.; Cobden, P.D.; Verbraeken, P.A.; Hufton, J.R.; van den Brink, R.W.

    2009-05-15

    A novel route for precombustion decarbonization is the sorption-enhanced water-gas shift (SEWGS) process. In this process carbon dioxide is removed from a synthesis gas at elevated temperature by adsorption. Simultaneously, carbon monoxide is converted to carbon dioxide by the water-gas shift reaction. The periodic adsorption and desorption of carbon dioxide is induced by a pressure swing cycle, and the cyclic capacity can be amplified by purging with steam. From previous studies is it known that for SEWGS applications, hydrotalcite-based materials are particularly attractive as sorbent, and commercial high-temperature shift catalysts can be used for the conversion of carbon monoxide. Tablets of a potassium promoted hydrotalcite-based material are characterized in both breakthrough and cyclic experiments in a 2 m tall fixed-bed reactor. When exposed to a mixture of carbon dioxide, steam, and nitrogen at 400{sup o}C, the material shows a breakthrough capacity of 1.4 mmol/g. In subsequent experiments the material was mixed with tablets of promoted iron-chromium shift catalyst and exposed to a mixture of carbon dioxide, carbon monoxide, steam, hydrogen, and nitrogen. It is demonstrated that carbon monoxide conversion can be enhanced to 100% in the presence of a carbon dioxide sorbent. At breakthrough, carbon monoxide and carbon dioxide simultaneously appear at the end of the bed. During more than 300 cycles of adsorption/reaction and desorption, the capture rate, and carbon monoxide conversion are confirmed to be stable. Two different cycle types are investigated: one cycle with a CO{sub 2} rinse step and one cycle with a steam rinse step. The performance of both SEWGS cycles are discussed.

  2. Aqueous-Medium Carbon-Carbon Bond-Forming Radical Reactions Catalyzed by Excited Rhodamine B as a Metal-Free Organic Dye under Visible Light Irradiation.

    PubMed

    Yoshioka, Eito; Kohtani, Shigeru; Jichu, Takahisa; Fukazawa, Takuya; Nagai, Toyokazu; Kawashima, Akira; Takemoto, Yoshiji; Miyabe, Hideto

    2016-08-19

    The utility of rhodamine B as a water-soluble organic photocatalyst was studied in the cascade radical addition-cyclization-trapping reactions under visible light irradiation. In the presence of (i-Pr)2NEt, the electron transfer from the excited rhodamine B to perfluoroalkyl iodides proceeded smoothly to promote the carbon-carbon bond-forming radical reactions in aqueous media. When i-C3F7I was employed as a radical precursor, the aqueous-medium radical reactions proceeded even in the absence of (i-Pr)2NEt. In these reactions, the direct electron transfer from the excited singlet state of rhodamine B would take place. Furthermore, the cleavage of the C-I bond in less reactive i-PrI could be achieved by the reductive electron transfer from the excited rhodamine B, which was confirmed by the fluorescence quenching of rhodamine B with the addition of i-PrI.

  3. Up-Scaling Geochemical Reaction Rates for Carbon Dioxide (CO2) in Deep Saline Aquifers

    SciTech Connect

    Peters, Catherine A

    2013-02-28

    Geochemical reactions in deep subsurface environments are complicated by the consolidated nature and mineralogical complexity of sedimentary rocks. Understanding the kinetics of these reactions is critical to our ability to make long-term predictions about subsurface processes such as pH buffering, alteration in rock structure, permeability changes, and formation of secondary precipitates. In this project, we used a combination of experiments and numerical simulation to bridge the gap between our knowledge of these reactions at the lab scale and rates that are meaningful for modeling reactive transport at core scales. The focus is on acid-driven mineral dissolution, which is specifically relevant in the context of CO2-water-rock interactions in geological sequestration of carbon dioxide. The project led to major findings in three areas. First, we modeled reactive transport in pore-network systems to investigate scaling effects in geochemical reaction rates. We found significant scaling effects when CO2 concentrations are high and reaction rates are fast. These findings indicate that the increased acidity associated with geological sequestration can generate conditions for which proper scaling tools are yet to be developed. Second, we used mathematical modeling to investigate the extent to which SO2, if co-injected with CO2, would acidify formation brines. We found that there exist realistic conditions in which the impact on brine acidity will be limited due to diffusion rate-limited SO2 dissolution from the CO2 phase, and the subsequent pH shift may also be limited by the lack of availability of oxidants to produce sulfuric acid. Third, for three Viking sandstones (Alberta sedimentary basin, Canada), we employed backscattered electron microscopy and energy dispersive X-ray spectroscopy to statistically characterize mineral contact with pore space. We determined that for reactive minerals in sedimentary consolidated rocks, abundance alone is not a good predictor of

  4. Carbon cycling in floodplain ecosystems: excess pCO2, extreme δ13C, and snail shell proxies

    NASA Astrophysics Data System (ADS)

    Gray, D. P.; Horton, T. W.

    2010-12-01

    Braided river floodplains typically possess high vertical hydrological/hydrogeological connectivity. This surface-subsurface exchange is highly important in the overall function and structure of these complex 4-dimensional systems, including the ecosystems they support. Spring-fed streams on the floodplain are often hotspots of benthic invertebrate diversity and productivity. Here, δ13C values of both dissolved inorganic carbon (DIC) and food-web components from five braided fluvial floodplain spring-fed streams in New Zealand, are used to assess the source of carbon in spring-fed food-webs. Partial pressures of CO2 in spring water ranged from 2-7 times atmospheric pressure, but rapidly approached equilibrium with the atmosphere downstream commensurate with an increase in DIC δ13C. Survey results demonstrate that both out-gassing and photosynthetic draw-down by aquatic plants controlled the net flux of CO2. The gradient in DIC δ13C was transmitted through three trophic levels of spring food-webs. These findings suggest highly productive spring-fed ecosystems are ‘fertilized’ by excess carbon dioxide dissolved in subsurface source waters. Furthermore, the stable carbon isotope composition of gastropod shells and soft tissue can serve as proxies for groundwater derived carbon in spring-fed braided fluvial ecosystems.

  5. Identification of secondary phases formed during unsaturated reaction of UO{sub 2} with EJ-13 water

    SciTech Connect

    Bates, J.K.; Tani, B.S.; Veleckis, E.

    1989-11-01

    A set of experiments, wherein UO{sub 2} has been contacted by dripping water, has been conducted over a period of 182.5 weeks. The experiments are being conducted to develop procedures to study spent fuel reaction under unsaturated conditions that are expected to exist over the lifetime of the proposed Yucca Mountain repository site. One half of the experiments have been terminated, while one half are ongoing. Analyses of solutions that have dripped from the reacted UO{sub 2} have been performed for all experiments, while the reacted UO{sub 2} surfaces have been examined for the terminated experiments. A pulse of uranium release from the UO{sub 2} solid, combined with the formation of schoepite on the surface of the UO{sub 2}, was observed between 39 and 96 weeks of reaction. Thereafter, the uranium release decreased and a second set of secondary phases was observed. The latter phases incorporated cations from the EJ-13 water and included boltwoodite, uranophane, sklodowskite, compreignacite, and schoepite. The experiments are continuing to monitor whether additional changes in solution chemistry or secondary phase formation occurs. 6 refs., 2 figs., 2 tabs.

  6. Gas-Phase Reactions of Glyceraldehyde and 1,3-Dihydroxyacetone as Models for Levoglucosan Conversion during Biomass Gasification.

    PubMed

    Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro

    2016-04-01

    Levoglucosan, the major intermediate in wood gasification, is decomposed selectively to C1/C2 fragments at 550-600 °C. Kinetic analyses suggest that radical chain mechanisms with the involvement of short-lived carbonyl intermediates explain the lower production of larger fragments. To address this hypothesis, the gas-phase reactivities of glyceraldehyde (Gald), 1,3-dihydroxyacetone (DHA), and glycerol, as simple C3 model compounds, were compared at 400-800 °C under N2 flow at residence times of 0.9-1.4 s. Retro-aldol fragmentation and dehydration proceeded for the pyrolysis of Gald/DHA at 400 °C, far below the 600 °C decomposition point of glycerol. Pyrolysis of Gald/DHA generated exclusively syngas (CO and H2). On the basis of the results of theoretical calculations, the effects of carbonyl intermediates on reactivity were explained by postulating uni- and bimolecular reactions, although the bimolecular reactions became less effective at elevated temperatures. PMID:26893057

  7. Cobalt diselenide nanoparticles embedded within porous carbon polyhedra as advanced electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wu, Renbing; Xue, Yanhong; Liu, Bo; Zhou, Kun; Wei, Jun; Chan, Siew Hwa

    2016-10-01

    Highly efficient and cost-effective electrocatalyst for the oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications. Herein, strongly coupled hybrid composites composed of cobalt diselenide (CoSe2) nanoparticles embedded within graphitic carbon polyhedra (GCP) as high-performance ORR catalyst have been rationally designed and synthesized. The catalyst is fabricated by a convenient method, which involves the simultaneous pyrolysis and selenization of preformed Co-based zeolitic imidazolate framework (ZIF-67). Benefiting from the unique structural features, the resulting CoSe2/GCP hybrid catalyst shows high stability and excellent electrocatalytic activity towards ORR (the onset and half-wave potentials are 0.935 and 0.806 V vs. RHE, respectively), which is superior to the state-of-the-art commercial Pt/C catalyst (0.912 and 0.781 V vs. RHE, respectively).

  8. The reduction of carbon dioxide in iron biocatalyst catalytic hydrogenation reaction: a theoretical study.

    PubMed

    Yang, Longhua; Wang, Hongming; Zhang, Ning; Hong, Sanguo

    2013-08-21

    The reaction mechanism of CO₂ hydrogenation catalyzed by [FeH(PP₃)]BF₄ (PP₃ = P(CH₂CH₂PPh₂)₃) had been investigated by DFT calculations. Our calculations indicated that the reduction of carbon dioxide could be carried out via two spin states, the high-spin (HS) triplet state and the low-spin (LS) singlet state. The minimum energy crossing points (MECPs) on the seam of two intersecting PESs (potential energy surfaces) were searched out. Some interesting phenomena, such as the open-loop phenomenon, and the O-rebound process, were demonstrated to be the important causes of the spin crossover. All these calculations gave us insight into the essence of the related experiment from the macro point of view, and helped to verify which spin states the related complexes pertinent were in. All of these researches would help advance the development of efficient and structurally tailorable CO₂ hydrogenation catalysts.

  9. Continuum reaction field calculation of dielectric constant and vapor pressures for water and carbon disulfide.

    PubMed

    Nir, S

    1976-01-01

    Continuum reaction field theory is applied to calculations of dielectric constant, contribution of intermolecular interactions to the free energy of a liquid, and heat of vaporization. Introduction of repulsive interactions and the use of one adjustable parameter, the free volume, enables prediction of vapor pressures. The calculations are illustrated for a simple nonpolar liquid, carbon disulfide, and for liquid water. It is shown that when Onsager's equation is rearranged to a quadratic equation, and a recently found value of the polarizability is employed, its solutions for liquid water yield good agreement with experimental values throughout the whole temperature range. The decrease of the dielectric constant with temperature is essentially linear with the inverse of absolute temperature, but there is additional significant decrease due to the decrease of density with temperature. The relatively high value of the heat of vaporization of liquid water is expressed in terms of large dipolar interaction of a water molecule with the environment, which is due to polarization effects.

  10. Strong near-infrared carbon in the Type Ia supernova iPTF13ebh

    DOE PAGESBeta

    Hsiao, E. Y.; Burns, C. R.; Contreras, C.; Höflich, P.; Sand, D.; Marion, G. H.; Phillips, M. M.; Stritzinger, M.; González-Gaitán, S.; Mason, R. E.; et al

    2015-05-22

    We present near-infrared (NIR) time-series spectroscopy, as well as complementary ultraviolet (UV), optical, and NIR data, of the Type Ia supernova (SN Ia) iPTF13ebh, which was discovered within two days from the estimated time of explosion. The first NIR spectrum was taken merely 2.3 days after explosion and may be the earliest NIR spectrum yet obtained of a SN Ia. The most striking features in the spectrum are several NIR C I lines, and the C Iλ1.0693 μm line is the strongest ever observed in a SN Ia. Interestingly, no strong optical C II counterparts were found, even though themore » optical spectroscopic time series began early and is densely cadenced. Except at the very early epochs, within a few days from the time of explosion, we show that the strong NIR C I compared to the weaker optical C II appears to be general in SNe Ia. iPTF13ebh is a fast decliner with Δm15(B) = 1.79 ± 0.01, and its absolute magnitude obeys the linear part of the width-luminosity relation. It is therefore categorized as a “transitional” event, on the fast-declining end of normal SNe Ia as opposed to subluminous/91bg-like objects. iPTF13ebh shows NIR spectroscopic properties that are distinct from both the normal and subluminous/91bg-like classes, bridging the observed characteristics of the two classes. These NIR observations suggest that composition and density of the inner core are similar to that of 91bg-like events, and that it has a deep-reaching carbon burning layer that is not observed in more slowly declining SNe Ia. Furthermore, there is also a substantial difference between the explosion times inferred from the early-time light curve and the velocity evolution of the Si II λ0.6355 μm line, implying a long dark phase of ~4 days.« less

  11. Strong near-infrared carbon in the Type Ia supernova iPTF13ebh

    SciTech Connect

    Hsiao, E. Y.; Burns, C. R.; Contreras, C.; Höflich, P.; Sand, D.; Marion, G. H.; Phillips, M. M.; Stritzinger, M.; González-Gaitán, S.; Mason, R. E.; Folatelli, G.; Parent, E.; Gall, C.; Amanullah, R.; Anupama, G. C.; Arcavi, I.; Banerjee, D. P. K.; Beletsky, Y.; Blanc, G. A.; Bloom, J. S.; Brown, P. J.; Campillay, A.; Cao, Y.; De Cia, A.; Diamond, T.; Freedman, W. L.; Gonzalez, C.; Goobar, A.; Holmbo, S.; Howell, D. A.; Johansson, J.; Kasliwal, M. M.; Kirshner, R. P.; Krisciunas, K.; Kulkarni, S. R.; Maguire, K.; Milne, P. A.; Morrell, N.; Nugent, P. E.; Ofek, E. O.; Osip, D.; Palunas, P.; Perley, D. A.; Persson, S. E.; Piro, A. L.; Rabus, M.; Roth, M.; Schiefelbein, J. M.; Srivastav, S.; Sullivan, M.; Suntzeff, N. B.; Surace, J.; Woźniak, P. R.; Yaron, O.

    2015-05-22

    We present near-infrared (NIR) time-series spectroscopy, as well as complementary ultraviolet (UV), optical, and NIR data, of the Type Ia supernova (SN Ia) iPTF13ebh, which was discovered within two days from the estimated time of explosion. The first NIR spectrum was taken merely 2.3 days after explosion and may be the earliest NIR spectrum yet obtained of a SN Ia. The most striking features in the spectrum are several NIR C I lines, and the C Iλ1.0693 μm line is the strongest ever observed in a SN Ia. Interestingly, no strong optical C II counterparts were found, even though the optical spectroscopic time series began early and is densely cadenced. Except at the very early epochs, within a few days from the time of explosion, we show that the strong NIR C I compared to the weaker optical C II appears to be general in SNe Ia. iPTF13ebh is a fast decliner with Δm15(B) = 1.79 ± 0.01, and its absolute magnitude obeys the linear part of the width-luminosity relation. It is therefore categorized as a “transitional” event, on the fast-declining end of normal SNe Ia as opposed to subluminous/91bg-like objects. iPTF13ebh shows NIR spectroscopic properties that are distinct from both the normal and subluminous/91bg-like classes, bridging the observed characteristics of the two classes. These NIR observations suggest that composition and density of the inner core are similar to that of 91bg-like events, and that it has a deep-reaching carbon burning layer that is not observed in more slowly declining SNe Ia. Furthermore, there is also a substantial difference between the explosion times inferred from the early-time light curve and the velocity evolution of the Si II λ0.6355 μm line, implying a long dark phase of ~4 days.

  12. Developing high-resolution carbon-13 and silicon-29 MRI of solids in sedimentary rocks

    NASA Astrophysics Data System (ADS)

    Blum, Robert; Barrett, Sean; Viswanathan, Ravinath; Song, Yi-Qiao

    2014-03-01

    Mapping pore structure and flow properties of sedimentary rock is directly relevant to current challenges in geophysics like carbon sequestration and oil/gas exploration. Such applications require detailed information about both structure and composition of porous rocks. However, existing scanning methods tend to be limited to gathering one or the other type of information. MRI could be used to measure both composition and structure simultaneously, but conventional MRI in such systems, which targets the proton signal of interstitial fluid, is severely limited by signal losses due to magnetic susceptibility inhomogeneity. Our lab has recently made advances in obtaining high spatial resolution (sub-400 μm)3 three-dimensional 31P MRI of bone through use of the quadratic echo line-narrowing sequence (1). In this talk, we describe our current work applying these methods to sedimentary rock, targeting the isotopes 13C and 29Si. We describe the results of characterization of limestone and shale samples, and we discuss our progress with producing MRI of these systems. (1) M. Frey, et al. PNAS 109: 5190 (2012)

  13. Metal-Organic Framework Derived Hierarchically Porous Nitrogen-Doped Carbon Nanostructures as Novel Electrocatalyst for Oxygen Reduction Reaction

    SciTech Connect

    Fu, Shaofang; Zhu, Chengzhou; Zhou, Yazhou; Yang, Guohai; Jeon, Ju Won; Lemmon, John P.; Du, Dan; Nune, Satish K.; Lin, Yuehe

    2015-10-01

    The hierarchically porous nitrogen-doped carbon materials, derived from nitrogen-containing isoreticular metal-organic framework-3 (IRMOF-3) through direct carbonization, exhibited excellent electrocatalytic activity in alkaline solution for oxygen reduction reaction (ORR). This high activity is attributed to the 10 presence of high percentage of quaternary and pyridinic nitrogen, the high surface area as well as good conductivity. When IRMOF-3 was carbonized at 950 °C (CIRMOF-3-950), it showed four-electron reduction pathway for ORR and exhibited better stability (about 78.5% current density was maintained) than platinum/carbon (Pt/C) in the current durability test. In addition, CIRMOF-3-950 presented high selectivity to cathode reactions compared to commercial Pt/C.

  14. Mafic enclaves in Caucasian granitoids: generation of mantle-looking lamprophyre nodules by reaction with (meta)-sedimentary carbonates

    NASA Astrophysics Data System (ADS)

    Aranovich, Leonid; Dubinina, Elena; Nosova, Anna; Avdeenko, Anna

    2010-05-01

    The occurrence of mafic enclaves in granitic plutons is a very common feature, particularly in the late- to post-collision granites. Origin of the enclaves is conventionally ascribed to the magma mingling processes, with the mafic component being derived from an "enriched" mantle source. Here we report geochemical and petrological data on the late-Miocene granitoid stocks and laccolites of the Caucasian Spring Waters region (CSW), which indicate principal involvement of contamination by (meta)-sedimentary carbonates in the origin of mafic nodules. The stocks and laccolites are composed of amphibole-bearing (Amph) granite, granosyenite, syenite and leucogranite varieties. Mafic nodules are rather abundant in granosyenite and syenite, and almost entirely absent in Amph- and leucogranite. All granitoids except for the leucogranites, which are believed to represent late differentiates of the Amph-granites not contaminated by the carbonates, are enriched in Ba and Sr (1227-1766 and 899-1143 ppm, correspondingly). 87Sr/86Sr ratio in the granitoids, recalculated to the intrusion age (8.3 Myr), falls in a narrow range from 0.7083-0.7086, while epsilon Nd(T) varies from -4.2 to -2.1. The epsilon Nd(T) values point to the crustal precursor for the granitoid melts, while the nearly constant 87Sr/86Sr ratio indicates derivation of all granitoid bodies from the same magma reservoir. Mafic nodules in granosyenite and syenite consist of fluorine-rich phlogopite (Phl, up to 5 wt.% F) + clinopyroxene (Cpx) + subordinate plagioclase (Pl, An14-16) + minor carbonate (Carb, 0.2-0.4 wt.% SrO) and apatite. Rare, up to 100 micron sized Sr-rich (up to 2 wt.% SrO) barite (Brt) grains have been identified in the nodules. Stable isotope composition of both Carb (delta 18O = +18.8 per mille, delta 13C = -13.4 per mille) and Brt (delta 34S = +13.5 per mille) indicate (meta)-sedimentary origin of the carbonate precursor rock. Jurassic dolomite-rich evaporates with the required Sr- and S

  15. Sucrose octabenzoate: assignment of 13C and 1H resonances of the sucrose moiety and the 13C resonances of the carbonyl carbons. Use of 13C-n.m.r. spectroscopy for the study of selective deacylation.

    PubMed

    Colquhoun, I J; Haines, A H; Konowicz, P A; Jones, H F

    1990-09-19

    Assignment of the 1H and 13C signals arising from the carbohydrate portion of sucrose octabenzoate has been achieved using homonuclear shift correlation experiments (COSY) and one-bond 1H-13C heteronuclear shift correlation measurements, respectively. The 13C resonances of the carbonyl carbon atoms of the eight benzoyl groups are readily distinguished for solutions in benzene-d6-pyridine-d5 (1:1), and have been assigned by means of three-bond 1H-13C shift correlation studies coupled with measurement of the 13C-n.m.r. spectrum of a sucrose octabenzoate specifically labelled with 13C in some of the carbonyl groups. With this assignment, products of partial deacylation of the octabenzoate may readily be identified by treatment with excess of benzoyl-carbonyl-13C chloride followed by measurement of the 13C-n.m.r. spectrum of the labelled sucrose octabenzoate, so prepared, in the carbonyl region. PMID:2276151

  16. Seasonal variations of belowground carbon transfer assessed by in situ 13CO2 pulse labelling of trees

    NASA Astrophysics Data System (ADS)

    Epron, D.; Ngao, J.; Dannoura, M.; Bakker, M. R.; Zeller, B.; Bazot, S.; Bosc, A.; Plain, C.; Lata, J. C.; Priault, P.; Barthes, L.; Loustau, D.

    2011-02-01

    Soil CO2 efflux is the main source of CO2 from forest ecosystems and it is tightly coupled to the transfer of recent photosynthetic assimilates belowground and their metabolism in roots, mycorrhiza and rhizosphere microorganisms feeding on root-derived exudates. The objectives of our study were to assess patterns of belowground carbon allocation among tree species and along seasons. Pure 13CO2 pulse labelling of the entire crown of three different tree species (beech, oak and pine) was carried out at distinct phenological stages. Excess 13C in soil CO2 efflux was tracked using tunable diode laser absorption spectrometry to determine time lags between the start of the labelling and the appearance of 13C in soil CO2 efflux and the amount of 13C allocated to soil CO2 efflux. Isotope composition (δ13C) of CO2 respired by fine roots and soil microbes was measured at several occasions after labelling, together with δ13C of bulk root tissue and microbial carbon. Time lags ranged from 0.5 to 1.3 days in beech and oak and were longer in pine (1.6-2.7 days during the active growing season, more than 4 days during the resting season), and the transfer of C to the microbial biomass was as fast as to the fine roots. The amount of 13C allocated to soil CO2 efflux was estimated from a compartment model. Seasonal patterns of carbon allocation to soil CO2 efflux differed markedly between species, with pronounced seasonal variations in pine and beech. In beech, it may reflect competition with other sinks (aboveground growth in late spring and storage in late summer) that were not observed in oak.

  17. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte.

    PubMed

    Zhuang, Zhongbin; Giles, Stephen A; Zheng, Jie; Jenness, Glen R; Caratzoulas, Stavros; Vlachos, Dionisios G; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

  18. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte.

    PubMed

    Zhuang, Zhongbin; Giles, Stephen A; Zheng, Jie; Jenness, Glen R; Caratzoulas, Stavros; Vlachos, Dionisios G; Yan, Yushan

    2016-01-01

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

  19. Formation of tungsten carbide nanoparticles on graphitized carbon to facilitate the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yan, Zaoxue; He, Guoqiang; Cai, Mei; Meng, Hui; Shen, Pei Kang

    2013-11-01

    Tungsten carbide nanoparticles with the average size less than 5 nm uniformly dispersed on the graphitized carbon matrix have been successfully synthesized by a one-step ion-exchange method. This route is to locally anchor the interested species based on an ionic level exchange process using ion-exchange resin. The advantage of this method is the size control of targeted nanomaterial as well as the graphitization of resin at low temperatures catalyzed by iron salt. The Pt nanoparticles coupled with tungsten carbide nanoparticles on graphitized carbon nanoarchitecture form a stable electrocatalyst (Pt/WC-GC). The typical Pt/WC-GC electrocatalyst gives a Pt-mass activity of 247.7 mA mgPt-1, which is much higher than that of commercial Pt/C electrocatalyst (107.1 mA mgPt-1) for oxygen reduction reaction due to the synergistic effect between Pt and WC. The presented method is simple and could be readily scaled up for mass production of the nanomaterials.

  20. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    PubMed Central

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-01

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

  1. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    DOE PAGESBeta

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

  2. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-01

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

  3. One-pot synthesis of S-alkyl dithiocarbamates via the reaction of N-tosylhydrazones, carbon disulfide and amines.

    PubMed

    Sha, Qiang; Wei, Yun-Yang

    2013-09-14

    A new, convenient and efficient transition metal-free synthesis of S-alkyl dithiocarbamates through one-pot reaction of N-tosylhydrazones, carbon disulfide and amines is reported. Tosylhydrazones derived from various aromatic and aliphatic ketones or aldehydes were tested and gave dithiocarbamates in good to excellent yields. The tosylhydrazones can be generated in situ without isolation, which provides a simpler one-pot method to synthesize dithiocarbamates via the reaction of carbonyl compounds, carbon disulfide and amines in the presence of 4-methylbenzenesulfonohydrazide. PMID:23863979

  4. Bio-mass derived mesoporous carbon as superior electrode in all vanadium redox flow battery with multicouple reactions

    NASA Astrophysics Data System (ADS)

    Ulaganathan, Mani; Jain, Akshay; Aravindan, Vanchiappan; Jayaraman, Sundaramurthy; Ling, Wong Chui; Lim, Tuti Mariana; Srinivasan, Madapusi P.; Yan, Qingyu; Madhavi, Srinivasan

    2015-01-01

    We first report the multi-couple reaction in all vanadium redox flow batteries (VRFB) while using bio-mass (coconut shell) derived mesoporous carbon as electrode. The presence of V3+/V4+ redox couple certainly supplies the additional electrons for the electrochemical reaction and subsequently provides improved electrochemical performance of VRFB system. The efficient electro-catalytic activity of such coconut shell derived high surface area mesoporous carbon is believed for the improved cell performance. Extensive power and electrochemical studies are performed for VRFB application point of view and described in detail.

  5. Strongly Coupled CoCr2 O4 /Carbon Nanosheets as High Performance Electrocatalysts for Oxygen Evolution Reaction.

    PubMed

    Al-Mamun, Mohammad; Su, Xintai; Zhang, Haimin; Yin, Huajie; Liu, Porun; Yang, Huagui; Wang, Dan; Tang, Zhiyong; Wang, Yun; Zhao, Huijun

    2016-06-01

    A strongly coupled CoCr2 O4 /carbon nanosheet composite is concurrently grown via a facile one-step molten-salt calcination approach. The strong coupling between carbon and CoCr2 O4 has improved the electrical conductivity and preserved the active sites in catalysts. These results may pave the way to improve the performance of spinel oxides as electrocatalysts for oxygen evolution reactions. PMID:27087475

  6. Dual-face nucleoside scaffold featuring a stereogenic all-carbon quaternary center. Intramolecular silicon tethered group-transfer reaction.

    PubMed

    Tambutet, Guillaume; Becerril-Jiménez, Fabiola; Dostie, Starr; Simard, Ryan; Prévost, Michel; Mochirian, Philippe; Guindon, Yvan

    2014-11-01

    The design of a novel nucleoside scaffold that exhibits an all-carbon quaternary center is reported. This allows for both α- and β-anomers of a given 2'-deoxy-2',2'-difluoro nucleoside analog (NA) to have potential biological activity. Using an intramolecular atom-transfer reaction, an all-carbon quaternary center was obtained without the use of heavy metals and/or harsh conditions. The chemistry developed is efficient, easily scalable and leads to novel libraries of molecules.

  7. Fe/SSZ-13 as an NH3-SCR Catalyst: A Reaction Kinetics and FTIR/Mössbauer Spectroscopic Study

    SciTech Connect

    Gao, Feng; Kollar, Marton; Kukkadapu, Ravi K.; Washton, Nancy M.; Wang, Yilin; Szanyi, Janos; Peden, Charles H.F.

    2015-03-01

    Using a traditional aqueous solution ion-exchange method under a protecting atmosphere of N2, an Fe/SSZ-13 catalyst active in NH3-SCR was synthesized. Mössbauer and FTIR spectroscopies were used to probe the nature of the Fe sites. In the fresh sample, the majority of Fe species are extra-framework cations. The likely monomeric and dimeric ferric ions in hydrated form are [Fe(OH)2]+ and [HO-Fe-O-Fe-OH]2+, based on Mössbauer measurements. During the severe hydrothermal aging (HTA) applied in this study, a majority of cationic Fe species convert to FeAlOx and clustered FeOx species, accompanied by severe dealumination of the SSZ-13 framework. The clustered FeOx species do not give a sextet Mössbauer spectrum, indicating that these are highly disordered. However, some Fe species in cationic positions remain after aging as determined from Mössbauer measurements and CO/NO FTIR titrations. NO/NH3 oxidation reaction tests reveal that dehydrated cationic Fe are substantially more active in catalyzing oxidation reactions than the hydrated ones. For NH3-SCR, enhancement of NO oxidation under ‘dry’ conditions promotes SCR rates below ~300 • C. This is due mainly to contribution from the “fast” SCR channel. Above ~300 • C, enhancement of NH3 oxidation under ‘dry’ conditions, however, becomes detrimental to NOx conversions. The HTA sample loses much of the SCR activity below ~300 • C; however, above ~400 • C much of the activity remains. This may suggest that the FeAlOx and FeOx species become active at such elevated temperatures. Alternatively, the high-temperature activity may be maintained by the remaining extra-framework cationic species. For potential practical applications, Fe/SSZ-13 may be used as a co-catalyst for Cu/CHA as integral aftertreatment SCR catalysts on the basis of the stable high temperature activity after hydrothermal aging. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy

  8. A Theoretical Study on Stepwise- and Concertedness of the Mechanism of 1,3-Dipolar Cycloaddition Reaction Between Tetra Amino Ethylene and Trifluoro Methyl Azide.

    PubMed

    Siadati, Seyyed Amir

    2016-01-01

    The order of reaction, especially in 1,3-dipolar cycloadditions directly affects the products' stereo selectivity. Due to this fact that a wide range of heterocyclic rings of natural products and biologically active molecules are synthesizing via this valuable procedure, understanding about the order of this reaction is so useful in designing the synthesis of different types of heterocyclic species. Therefore, the order of 1, 3-dipolar reaction has been carefully studied by many researchers but it seems that this question is still open despite many valuable answers. Considering this, in the present work, it is attempted to pursue this subject by theoretical investigation of any possible pathway of 1, 3-dipolar reaction of tetra amino ethylene as a highly electron rich dipolarophile and trifluoro methyl azide as an electron poor 1,3-dipole. During the calculations, one, two, and three step mechanism(s) have been found to be possible for the present 1, 3-dipolar reaction.

  9. 3D Printing Carbonate Microstructures: Preliminary Porosity-Permeability Trends with Applications to the Decarbonation Reaction

    NASA Astrophysics Data System (ADS)

    Head, D. A.; Vanorio, T.

    2015-12-01

    The advent of modern 3D printing has provided an unprecedented opportunity to combine the strengths of two of the main approaches used in rock physics analysis - digital and experimental. In the laboratory we can explore still unknown frontiers of rock behaviour, and in digital rock physics each sample and experiment is fully reproducible at a minute, detailed scale. Bringing these two techniques together and applying both to the same rock volumes has become more important than ever as we add layers of complexity to both models and experiments in an attempt understand the coupled thermo-chemo-mechanical changes controlling transport and elastic properties of carbonate diagenesis. In this study, we take a two-pronged approach. First, we investigate the effect of changing the size of a specific natural carbonate pore geometry on the frame independent properties porosity and permeability and compare the laboratory measurements to the results of numerical simulations. These preliminary tests show that it is possible to use an iterative, grain-scale geometry modification and measurement workflow that utilizes 3D printing. Second, we induce the decarbonation reaction in a carbonate deposit injected with silicate-bearing fluids in a temperature-pressure space not previously explored. These results show that we can quantify changes to the acoustic and transport properties of the sample when exposed to such diagenetic conditions. Ultimately we will use a workflow designed to iteratively combine baseline CT-scanned rock volumes, experimentally derived boundary conditions for and modifications to the digital rock volumes, and measurements on 3D printed rock models in order to test hypotheses about grain-scale changes on bulk sample properties.

  10. Heteropoly Acid/Nitrogen Functionalized Onion-like Carbon Hybrid Catalyst for Ester Hydrolysis Reactions.

    PubMed

    Liu, Wei; Qi, Wei; Guo, Xiaoling; Su, Dangsheng

    2016-02-18

    A novel heteropoly acid (HPA)/nitrogen functionalized onion-like carbon (NOLC) hybrid catalyst was synthesized through supramolecular (electrostatic and hydrogen bond) interactions between the two components. The chemical structure and acid strength of the HPA/NOLC hybrid have been fully characterized by thermogravimetric analysis, IR spectroscopy, X-ray photoelectron spectroscopy, NH3 temperature-programmed desorption and acid-base titration measurements. The proposed method for the fabrication of the HPA/NOLC hybrid catalyst is a universal strategy for different types of HPAs to meet various requirements of acidic or redox catalysis. The hydrophobic environment of NOLC effectively prevents the deactivation of HPA in an aqueous system, and the combination of uniformly dispersed HPA clusters and the synergistic effect between NOLC and HPA significantly promotes its activity in ester hydrolysis reactions, which is higher than that of bare PWA as homogeneous catalyst. The kinetics of the hydrolysis reactions indicate that the aggregation status of the catalyst particles has great influence on the apparent activity. PMID:26606266

  11. Heteropoly Acid/Nitrogen Functionalized Onion-like Carbon Hybrid Catalyst for Ester Hydrolysis Reactions.

    PubMed

    Liu, Wei; Qi, Wei; Guo, Xiaoling; Su, Dangsheng

    2016-02-18

    A novel heteropoly acid (HPA)/nitrogen functionalized onion-like carbon (NOLC) hybrid catalyst was synthesized through supramolecular (electrostatic and hydrogen bond) interactions between the two components. The chemical structure and acid strength of the HPA/NOLC hybrid have been fully characterized by thermogravimetric analysis, IR spectroscopy, X-ray photoelectron spectroscopy, NH3 temperature-programmed desorption and acid-base titration measurements. The proposed method for the fabrication of the HPA/NOLC hybrid catalyst is a universal strategy for different types of HPAs to meet various requirements of acidic or redox catalysis. The hydrophobic environment of NOLC effectively prevents the deactivation of HPA in an aqueous system, and the combination of uniformly dispersed HPA clusters and the synergistic effect between NOLC and HPA significantly promotes its activity in ester hydrolysis reactions, which is higher than that of bare PWA as homogeneous catalyst. The kinetics of the hydrolysis reactions indicate that the aggregation status of the catalyst particles has great influence on the apparent activity.

  12. Use of carbon-13 as a population marker for Anopheles arabiensis in a sterile insect technique (SIT) context

    PubMed Central

    Hood-Nowotny, Rebecca; Mayr, Leo; Knols, Bart GJ

    2006-01-01

    Background Monitoring of sterile to wild insect ratios in field populations can be useful to follow the progress in genetic control programmes such as the Sterile Insect Technique (SIT). Of the numerous methods for marking insects most are not suitable for use in mass rearing and mass release. Suitable ones include dye marking, genetic marking and chemical marking. Methods The feasibility of using the stable isotope of carbon, 13C, as a potential chemical marker for Anopheles arabiensis was evaluated in the laboratory. Labeled-13C glucose was incorporated into the larval diet in a powder or liquid form. The contribution of adult sugar feeding to the total mosquito carbon pool and the metabolically active carbon pool was determined by tracing the decline of the enrichment of the adult male mosquito as it switched from a labeled larval diet to an unlabeled adult diet. This decline in the adult was monitored by destructive sampling of the whole mosquito and analyzed using isotope ratio mass spectrometry. Results A two-pool model was used to describe the decline of the 13C-enrichment of adult mosquitoes. The proportion of the total adult carbon pool derived from the adult sugar diet over the life span of mosquitoes was determined and the ratio of structural carbon, with a low turnover rate to metabolically active non-structural carbon was assessed. The uptake and turnover of sugar in the metabolically active fraction suggests that after 3 days >70% of the active fraction carbon is derived from sugar feeding (increasing to >90% by day 7), indicating the high resource demand of male mosquitoes. Conclusion It was possible to "fix" the isotopic label in adult An. arabiensis and to detect the label at an appropriate concentration up to 21 days post-emergence. The optimum labeling treatment would cost around 250 US$ per million mosquitoes. Stable isotope marking may thus aid research on the fate of released insects besides other population-based ecological studies. PMID

  13. Reactions of recoil nitrogen-13 atoms in the ethanol-water system. Formation of [{sup 13}N]NH{sub 3} upon irradiation of water and dilute aqueous solutions of ethanol under a pressure of various gases

    SciTech Connect

    Korsakov, M.V.; Krasikova, R.N.; Fedorova, O.S.

    1995-07-01

    The influence of the nature and pressure of a gas (helium, hydrogen) contacting with a solution on radiochemical yield of the {sup 13}N-labeled products of nuclear-chemical and radiolytic reactions occurring upon irradiation of water and dilute aqueous solution of ethanol by 17-MeV protons was examined. It was shown that irradiation of water under hydrogen pressure, about 50% of recoil nitrogen-13 atoms are stabilized in the gas phase in the form of [{sup 13}N]N{sub 2}, and the main product in the liquid phase is ammonia-{sup 13}N.

  14. Seasonal variations of belowground carbon transfer assessed by in situ 13CO2 pulse labelling of trees

    NASA Astrophysics Data System (ADS)

    Epron, D.; Ngao, J.; Dannoura, M.; Bakker, M. R.; Zeller, B.; Bazot, S.; Bosc, A.; Plain, C.; Lata, J. C.; Priault, P.; Barthes, L.; Loustau, D.

    2011-05-01

    Soil CO2 efflux is the main source of CO2 from forest ecosystems and it is tightly coupled to the transfer of recent photosynthetic assimilates belowground and their metabolism in roots, mycorrhiza and rhizosphere microorganisms feeding on root-derived exudates. The objective of our study was to assess patterns of belowground carbon allocation among tree species and along seasons. Pure 13CO2 pulse labelling of the entire crown of three different tree species (beech, oak and pine) was carried out at distinct phenological stages. Excess 13C in soil CO2 efflux was tracked using tuneable diode laser absorption spectrometry to determine time lags between the start of the labelling and the appearance of 13C in soil CO2 efflux and the amount of 13C allocated to soil CO2 efflux. Isotope composition (δ13C) of CO2 respired by fine roots and soil microbes was measured at several occasions after labelling, together with δ13C of bulk root tissue and microbial carbon. Time lags ranged from 0.5 to 1.3 days in beech and oak and were longer in pine (1.6-2.7 days during the active growing season, more than 4 days during the resting season), and the transfer of C to the microbial biomass was as fast as to the fine roots. The amount of 13C allocated to soil CO2 efflux was estimated from a compartment model. It varied between 1 and 21 % of the amount of 13CO2 taken up by the crown, depending on the species and the season. While rainfall exclusion that moderately decreased soil water content did not affect the pattern of carbon allocation to soil CO2 efflux in beech, seasonal patterns of carbon allocation belowground differed markedly between species, with pronounced seasonal variations in pine and beech. In beech, it may reflect competition with the strength of other sinks (aboveground growth in late spring and storage in late summer) that were not observed in oak. We report a fast transfer of recent photosynthates to the mycorhizosphere and we conclude that the patterns of carbon

  15. Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implication for PM2.5

    NASA Astrophysics Data System (ADS)

    Jaoui, M.; Lewandowski, M.; Docherty, K.; Offenberg, J. H.; Kleindienst, T. E.

    2014-06-01

    Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivative-based methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography-mass spectrometry (GC-MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, d-threonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM2.5 samples and could potentially serve as organic markers of 1,3-butadiene (13BD). Furthermore, a series of oligoesters were detected and found to be produced from esterification reactions among compounds bearing alcoholic groups and compounds bearing acidic groups. Time profiles are provided for selected compounds. SOA was analyzed for organic mass to organic carbon (OM / OC) ratio, effective enthalpy of vaporization (ΔHvapeff), and aerosol yield. The average OM / OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average ΔHvapeff was 26.1 ± 1.5 kJ mol-1, a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 μg m-3 was 0.025 ± 0.011, a value consistent with the literature (0.021-0.178). While the focus of this study has been examination of the particle-phase measurements, the gas

  16. Reproducibly creating hierarchical 3D carbon to study the effect of Si surface functionalization on the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zeng, Yuze; Flores, Jose F.; Shao, Yu-Cheng; Guo, Jinghua; Chuang, Yi-De; Lu, Jennifer Q.

    2016-06-01

    We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This investigation reveals for the first time that non-conductive Si with an appropriate electronic structure distorts the carbon electronic structure and consequently enhances ORR electrocatalysis. The strong interface provides excellent electron connectivity according to electrochemical analysis. This highly reproducible and stable 3D platform can serve as a stepping-stone for the investigation of the effect of carbon surface functionalization on electrochemical reactions in general.We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This

  17. 13C Metabolic Flux Analysis Identifies an Unusual Route for Pyruvate Dissimilation in Mycobacteria which Requires Isocitrate Lyase and Carbon Dioxide Fixation

    PubMed Central

    Beste, Dany J. V.; Bonde, Bhushan; Hawkins, Nathaniel; Ward, Jane L.; Beale, Michael H.; Noack, Stephan; Nöh, Katharina; Kruger, Nicholas J.; Ratcliffe, R. George; McFadden, Johnjoe

    2011-01-01

    Mycobacterium tuberculosis requires the enzyme isocitrate lyase (ICL) for growth and virulence in vivo. The demonstration that M. tuberculosis also requires ICL for survival during nutrient starvation and has a role during steady state growth in a glycerol limited chemostat indicates a function for this enzyme which extends beyond fat metabolism. As isocitrate lyase is a potential drug target elucidating the role of this enzyme is of importance; however, the role of isocitrate lyase has never been investigated at the level of in vivo fluxes. Here we show that deletion of one of the two icl genes impairs the replication of Mycobacterium bovis BCG at slow growth rate in a carbon limited chemostat. In order to further understand the role of isocitrate lyase in the central metabolism of mycobacteria the effect of growth rate on the in vivo fluxes was studied for the first time using 13C-metabolic flux analysis (MFA). Tracer experiments were performed with steady state chemostat cultures of BCG or M. tuberculosis supplied with 13C labeled glycerol or sodium bicarbonate. Through measurements of the 13C isotopomer labeling patterns in protein-derived amino acids and enzymatic activity assays we have identified the activity of a novel pathway for pyruvate dissimilation. We named this the GAS pathway because it utilizes the Glyoxylate shunt and Anapleurotic reactions for oxidation of pyruvate, and Succinyl CoA synthetase for the generation of succinyl CoA combined with a very low flux through the succinate – oxaloacetate segment of the tricarboxylic acid cycle. We confirm that M. tuberculosis can fix carbon from CO2 into biomass. As the human host is abundant in CO2 this finding requires further investigation in vivo as CO2 fixation may provide a point of vulnerability that could be targeted with novel drugs. This study also provides a platform for further studies into the metabolism of M. tuberculosis using 13C-MFA. PMID:21814509

  18. The kinetics of the O2/CO2 reaction in molten carbonate - Reaction orders for O2 and CO2 on NiO. [in fuel cells

    NASA Technical Reports Server (NTRS)

    Winnick, J.; Ross, P. N.

    1980-01-01

    The kinetics of the O2/CO2 reaction in molten carbonate is investigated using paste electrolytes and nickel sinter electrodes. A two-step approach to the determination of reaction orders is employed. First, exchange currents at various P(CO2) and P(O2) were measured using the low polarization method. Second, alpha(+) and alpha(-) values were obtained from the slope of the Allen-Hickling plot for current densities low enough so that concentration polarization within the electrode can be neglected. The reaction orders are + 1/4 in CO2 and + 5/8 in O2 in the cathodic direction, and - 3/4 in CO2 and + 1/8 in O2 in the anodic direction.

  19. Degradation pathways of dissolved carbon in landfill leachate traced with compound-specific (13)C analysis of DOC.

    PubMed

    Mohammadzadeh, Hossein; Clark, Ian

    2008-09-01

    The isotopic compositions of carbon compounds in landfill leachate provide insights into the biodegradation pathways that dominate the different stages of waste decomposition. In this study, the carbon geochemistry of different carbon pools, environmental stable isotopes and compound-specific isotope analysis (CSIA) of leachate dissolved organic carbon (DOC) fractions and gases show distinctions in leachate biogeochemistry and methane production between the young area of active waste emplacement and the old area of historical emplacement at the Trail Road Landfill (TRL). The active area leachate has low DOC concentrations (<200 mg l(-1)) dominated by fulvic acid (FA=160 mg l(-1)), and produces CH(4) dominantly by CO(2) reduction (D- excess=20.6 per thousand). Leachate generated in the area of older waste has high DOC (>4770 mg l(-1)) dominated by FA (4482 mg l(-1)) and simple fatty acids (acetic=1008 mg l(-1) and propionic=608 mg l(-1)), and produces CH(4) by the acetate fermentation pathway (D- excess=9.8 per thousand). CSIA shows an advanced degradation and a progressive accumulation of (13)C of fatty acids in leachate from the older area. The enriched (13)C value of FA (-20 and-26 per thousand for the older and active parts, respectively,) and of low molecular weight DOC (-8 and-27 per thousand) as well as of the bulk DOC (-21 and-25 per thousand) shows more advanced degradation in the older part of the landfill, which is consistent with the shift in the humic/FA ratios (0.05 and 0.18). The (13)C enrichment of acetate (-12 per thousand) above the (13)C of DOC (-21 per thousand) and of propionic acid (-19 per thousand), in older leachate, suggests that this acetate has not evolved from the simple degradation of larger organic molecules, but by homoacetogenesis from the enriched dissolved inorganic carbon (DIC) pool (8 per thousand) and H(2,) which produce a more enriched (13)C of acetate. In contrast, the (13)C of the minor acetate in the active area (-17 per

  20. Tracing carbon assimilation in endosymbiotic deep-sea hydrothermal vent Mytilid fatty acids by 13C-fingerprinting

    NASA Astrophysics Data System (ADS)

    Riou, V.; Bouillon, S.; Serrão Santos, R.; Dehairs, F.; Colaço, A.

    2010-09-01

    Bathymodiolus azoricus mussels thrive at Mid-Atlantic Ridge hydrothermal vents, where part of their energy requirements are met via an endosymbiotic association with chemolithotrophic and methanotrophic bacteria. In an effort to describe phenotypic characteristics of the two bacterial endosymbionts and to assess their ability to assimilate CO2, CH4 and multi-carbon compounds, we performed experiments in aquaria using 13C-labeled NaHCO3 (in the presence of H2S), CH4 or amino-acids and traced the incorporation of 13C into total and phospholipid fatty acids (tFA and PLFA, respectively). 14:0; 15:0; 16:0; 16:1(n - 7)c+t; 18:1(n - 13)c+t and (n - 7)c+t; 20:1(n - 7); 20:2(n - 9,15); 18:3(n - 7) and (n - 5,10,13) PLFA were labeled in the presence of H13CO3- (+H2S) and 13CH4, while the 12:0 compound became labeled only in the presence of H13CO3- (+H2S). In contrast, the 17:0; 18:0; 16:1(n - 9); 16:1(n - 8) and (n - 6); 18:1(n - 8); and 18:2(n - 7) PLFA were only labeled in the presence of 13CH4. Some of these symbiont-specific fatty acids also appeared to be labeled in mussel gill tFA when incubated with 13C-enriched amino acids, and so were mussel-specific fatty acids such as 22:2(n - 7,15). Our results provide experimental evidence for the potential of specific fatty acid markers to distinguish between the two endosymbiotic bacteria, shedding new light on C1 and multi-carbon compound metabolic pathways in B. azoricus and its symbionts.

  1. Modelling the 13C and 12C isotopes of inorganic and organic carbon in the Baltic Sea

    NASA Astrophysics Data System (ADS)

    Gustafsson, Erik; Mörth, Carl-Magnus; Humborg, Christoph; Gustafsson, Bo G.

    2015-08-01

    In this study, 12C and 13C contents of all carbon containing state variables (dissolved inorganic and organic carbon, detrital carbon, and the carbon content of autotrophs and heterotrophs) have for the first time been explicitly included in a coupled physical-biogeochemical Baltic Sea model. Different processes in the carbon cycling have distinct fractionation values, resulting in specific isotopic fingerprints. Thus, in addition to simulating concentrations of different tracers, our new model formulation improves the possibility to constrain the rates of processes such as CO2 assimilation, mineralization, and air-sea exchange. We demonstrate that phytoplankton production and respiration, and the related air-sea CO2 fluxes, are to a large degree controlling the isotopic composition of organic and inorganic carbon in the system. The isotopic composition is further, but to a lesser extent, influenced by river loads and deep water inflows as well as transformation of terrestrial organic carbon within the system. Changes in the isotopic composition over the 20th century have been dominated by two processes - the preferential release of 12C to the atmosphere in association with fossil fuel burning, and the eutrophication of the Baltic Sea related to increased nutrient loads under the second half of the century.

  2. Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma-atomic emission spectrometry

    NASA Astrophysics Data System (ADS)

    Grindlay, Guillermo; Gras, Luis; Mora, Juan; de Loos-Vollebregt, Margaretha T. C.

    2016-01-01

    In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma-atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w- 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

  3. Rh(I)-catalyzed Pauson-Khand-type cycloaddition reaction of ene-vinylidenecyclopropanes with carbon monoxide (CO)

    PubMed Central

    Yuan, Wei; Dong, Xiang; McDowell, Patrick

    2012-01-01

    An intramolecular Pauson-Khand type cycloaddition reaction of ene-vinylidenecyclopropanes with carbon monoxide has been established by using [Rh(COD)Cl]2 as the catalyst. The reaction was found to be highly efficient in solvents of 1,2-dichloroethane and 1,1,2,2-tetrachloroethane to give excellent yields of 90 – 99%. The reaction provides easy access to a series of fused 6,5-ring structures containing spiro-cyclopropane units that are useful for drug design and development. A mechanism of this cycloaddition process has been proposed accounting for structures of resulting products that were unambiguously assigned by X-ray diffractional analysis. PMID:23098194

  4. Flow-injection analysis for the determination of total inorganic carbon and total organic carbon in water using the H2O2-luminol-uranine chemiluminescent reaction.

    PubMed

    Fan, Shun-Li; Qu, Fang; Zhao, Lixia; Lin, Jin-Ming

    2006-12-01

    In the presence of carbonate and uranine, the chemiluminescent intensity from the reaction of luminol with hydrogen peroxide was dramatically enhanced in a basic medium. Based on this fact and coupled with the technique of flow-injection analysis, a highly sensitive method was developed for the determination of carbonate with a wide linear range. The method provided the determination of carbonate with a wide linear range of 1.0 x 10(-10)-5.0 x 10(-6) mol L(-1) and a low detection limit (S/N = 3) of carbonate of 1.2 x 10(-11) mol L(-1). The average relative standard deviation for 1.0 x 10(-9)-9.0 x 10(-7) mol L(-1) of carbonate was 3.7% (n = 11). Combined with the wet oxidation of potassium persulfate, the method was applied to the simultaneous determination of total inorganic carbon (TIC) and total organic carbon (TOC) in water. The linear ranges for TIC and TOC were 1.2 x 10(-6)-6.0 x 10(-2) mg L(-1) and 0.08-30 mg L(-1) carbon, respectively. Recoveries of 97.4-106.4% for TIC and 96.0-98.5% for TOC were obtained by adding 5 or 50 mg L(-1) of carbon to the water samples. The relative standard deviations (RSDs) were 2.6-4.8% for TIC and 4.6-6.6% for TOC (n = 5). The mechanism of the chemiluminescent reaction was also explored and a reasonable explanation about chemical energy transfer from luminol to uranine was proposed.

  5. Sequential Diels–Alder/[3,3]-sigmatropic rearrangement reactions of β-nitrostyrene with 3-methyl-1,3-pentadiene

    PubMed Central

    Pipic, Alma; Zeller, Matthias; Tsetsakos, Panagiota

    2013-01-01

    Summary The tin(IV)-catalyzed reaction of β-nitrostyrene with (E)-3-methyl-1,3-pentadiene in toluene afforded two major nitronic ester cycloadducts in 27% and 29% yield that arise from the reaction at the less substituted diene double bond. Also present were four cycloadducts from the reaction at the higher substituted diene double bond, two of which were the formal cycloadducts of (Z)-3-methyl-1,3-pentadiene. A Friedel–Crafts alkylation product from the reaction of the diene, β-nitrostyrene, and toluene was also obtained in 10% yield. The tin(IV)-catalyzed reaction of β-nitrostyrene with (Z)-3-methyl-1,3-pentadiene in dichloromethane afforded four nitronic ester cycloadducts all derived from the reaction at the higher substituted double bond. One cycloadduct was isolated in 45% yield and two others are formal adducts of the E-isomer of the diene. The product formation in these reactions is consistent with a stepwise mechanism involving a zwitterionic intermediate. The initially isolated nitronic ester cycloadducts underwent tin(IV)-catalyzed interconversion, presumably via zwitterion intermediates. Cycloadducts derived from the reaction at the less substituted double bond of (E)-3-methyl-1,3-pentadiene underwent a [3,3]-sigmatropic rearrangement on heating to afford 4-nitrocyclohexenes. Cycloadducts derived from the reaction at the higher substituted diene double bond of either diene failed to undergo a thermal rearrangement. Rates and success of the rearrangement are consistent with a concerted mechanism possessing a dipolar transition state. An initial assessment of substituent effects on the rearrangement process is presented. PMID:24204426

  6. Monitoring Time-Dependent Formation of Oligomers and Brown Carbon in Reactions of Glycolaldehyde, Methylglyoxal, and Amines

    NASA Astrophysics Data System (ADS)

    Espelien, B.; Galloway, M. M.; De Haan, D. O.

    2012-12-01

    Authors: Brenna Espelien, Melissa Galloway, and David De Haan The brown carbon components of atmospheric aerosol exhibit strong UV absorbance with a featureless 'tail' that extends into the visible range. Recent work has shown that brown carbon (or HULIS) is formed at least in part by aqueous-phase chemical reactions in the atmosphere. Reactions between aldehydes (such as glycolaldehyde and methylglyoxal) and amines create brown products that have similar light-absorbing spectra as HULIS extracted from atmospheric aerosol. However, the structures of these products have not been well-characterized. Bulk-phase reactions were monitored using LCMS and UV-Vis spectroscopy over a period of 2-3 weeks to see what products formed, whether oligomerization is occurring, and how this correlates with the development of absorbance peaks in the visible range. UV-Vis data shows that these reactions generally take several days to reach maximum absorbance in the visible range. For the glycolaldehyde/glycine reaction, the appearance of a strong absorber at about 400 nm correlated with the appearance of high-mass products at m/z 227, 363, 393, and 431. Additional reactions between aldehydes and amines that quickly produce brown products are being studied. We suggest that imine oligomers are major products of these reactions.

  7. Enzymatic synthesis and carbon-13 nuclear magnetic resonance conformational studies of disaccharides containing. beta. -D-galactopyranosyl and. beta. -D-(1-/sup 13/C)Galactopyranosyl residues

    SciTech Connect

    Nunez, H.A.; Barker, R.

    1980-02-05

    Partially purified UDPgalactosyltransferase (EC 2.4.1.22) from bovine milk has been used to synthesize millimolar amounts of compounds such as Gal..beta..(1..-->..4)Glc, Gal..beta..(1..-->..4)GlcNAc-..beta..-hexanolamine, and Gal..beta..(1..-->..4)-GlcNAc..beta..(1..-->..4)GlcNAc. The same method has been used to prepare similar compounds containing /sup 13/C-enriched galactopyranosyl moieties. Gal..beta..(1..-->..4)GlcNAc-..beta..-hexanolamine was also synthesized in a solid-phase system in which the GlcNAc-..beta..-hexanolamine glycoside was covalently linked to agarose beads. At pH 7.0 and at 1 to 5 mM Mn/sup 2 + +/ the yields of the galactosyl saccharides are greater than 90% by using 10% excess of UDPGal donor. The use of a 90% enriched (1-/sup 13/C)galactosyl residue allowed the determination of the most abundant conformer about the galactopyranosyl-glycoside linkage by analysis of the carbon-carbon coupling constants from Cl to Gal to the C3', C4', and C5' of GlcNAc or Glc. 3 figures, 1 table.

  8. Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implications for PM2.5

    NASA Astrophysics Data System (ADS)

    Jaoui, M.; Lewandowski, M.; Docherty, K.; Offenberg, J. H.; Kleindienst, T. E.

    2014-12-01

    Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivative-based methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography-mass spectrometry (GC-MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, d-threonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM2.5 samples, and could potentially serve as organic markers of 13BD. Furthermore, a series of oligoesters were detected and found to be produced through chemical reactions occurring in the aerosol phase between compounds bearing alcoholic groups and compounds bearing acidic groups. SOA was analyzed for organic mass to organic carbon (OM /OC) ratio, effective enthalpy of vaporization (Δ Hvapeff), and aerosol yield. The average OM /OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average Δ Hvapeff was -26.08 ± 1.46 kJ mol-1, a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 μg m-3 was 0.025 ± 0.011, a value consistent with the literature (0.021-0.178). While the focus of this study has been examination of the particle-phase measurements, the gas-phase photooxidation products have also been

  9. Vapor-phase reaction of acetophenone with methanol or dimethyl carbonate on magnesium oxide and magnesium phosphates

    SciTech Connect

    Aramendia, M.A.; Borau, V.; Jimenez, C.; Marinas, J.M.; Romero, F.J.

    1999-04-01

    The vapor-phase reaction of acetophenone with methanol on magnesium oxide, various magnesium phosphates, and combinations of the two types of catalysts was studied. The process was found to involve the Meerwein-Ponndorf-Verley reaction, aldol condensations, dehydrations, and hydrogenations. The presence of basic sites is indispensable for the reaction to develop; however, acid sites also play an active role. The selectivity for each reaction product depends on the particular catalyst used. The total conversion is maximal with the catalysts containing the largest populations of acid and basic sites. Also, catalysts with large numbers of acid sites exhibit an increased selectivity towards the corresponding alkenes. The use of dimethyl carbonate instead of methanol alters the reaction selectivity to an extent dependent on the particular catalyst and operating conditions. However, this also results in markedly decreased total conversion in some instances.

  10. Carbon-13 NMR study of switch variant anti-dansyl antibodies: Antigen binding and domain-domain interactions

    SciTech Connect

    Kato, Koichi; Matsunaga, Chigusa; Odaka, Asano; Yamato, Sumie; Takaha, Wakana; Shimada, Ichio; Arata, Yoji )

    1991-07-02

    A {sup 13}C NMR study is reported of switch variant anti-dansyl antibodies, which possess the identical V{sub H}, V{sub L}, and C{sub L} domains in conjunction with highly homologous but not identical heavy-chain constant regions. Each of the antibodies has been selectively labeled with {sup 13}C at the carbonyl carbon of Trp, Tyr, His, or Cys residue by growing hybridoma cells in serum-free medium. Spectral assignments have been made by folowing the procedure described previously for the switch variant antibodies labeled with (1-{sup 13}C)Met. On the basis of the spectral data collected for the antibodies and their proteolytic fragments, the authors discuss how {sup 13}C NMR spectroscopy can be used for the structural analyses of antigen binding and also of domain-domain interactions in the antibody molecule.

  11. Reversibility of electrochemical reactions of sulfur supported on inverse opal carbon in glyme-Li salt molten complex electrolytes.

    PubMed

    Tachikawa, Naoki; Yamauchi, Kento; Takashima, Eriko; Park, Jun-Woo; Dokko, Kaoru; Watanabe, Masayoshi

    2011-07-28

    Electrochemical reactions of sulfur supported on three-dimensionally ordered macroporous carbon in glyme-Li salt molten complex electrolytes exhibit good reversibility and large capacity based on the mass of sulfur, which suggests that glyme-Li salt molten complexes are suitable electrolytes for Li-S batteries.

  12. One-Carbon Homologation of Primary Alcohols to Carboxylic Acids, Esters, and Amides via Mitsunobu Reactions with MAC Reagents.

    PubMed

    Kagawa, Natsuko; Nibbs, Antoinette E; Rawal, Viresh H

    2016-05-20

    A method is reported for the one-carbon homologation of an alcohol to the extended carboxylic acid, ester, or amide. The process involves the Mitsunobu reaction with an alkoxymalononitrile, followed by unmasking in the presence of a suitable nucleophile. The homologation and unmasking can even be performed in a one-pot process in high yield. PMID:27135854

  13. Metal-catalyzed coupling reactions on an olefin template: the total synthesis of (13E,15E,18Z,20Z)-1-hydroxypentacosa- 13,15,18,20-tetraen-11-yn-4-one 1-acetate.

    PubMed

    Organ, Michael G; Ghasemi, Haleh

    2004-02-01

    The naturally occurring ant venom (13E,15E,18Z,20Z)-1-hydroxypentacosa-13,15,18,20-tetraen-11-yn-4-one 1-acetate was synthesized stereospecifically using a series of metal-mediated cross-coupling reactions. The use of the difunctional olefin template (E)-1-chloro-2-iodoethylene as the central, pseudosymmetrical building block facilitated a fully convergent and, thus, efficient strategy to prepare this polyunsaturated natural product.

  14. CO2-brine-mineral Reactions in Geological Carbon Storage: Results from an EOR Experiment

    NASA Astrophysics Data System (ADS)

    Chapman, H.; Wigley, M.; Bickle, M.; Kampman, N.; Dubacq, B.; Galy, A.; Ballentine, C.; Zhou, Z.

    2012-04-01

    Dissolution of CO2 in brines and reactions of the acid brines ultimately dissolving silicate minerals and precipitating carbonate minerals are the prime long-term mechanisms for stabilising the light supercritical CO2 in geological carbon storage. However the rates of dissolution are very uncertain as they are likely to depend on the heterogeneity of the flow of CO2, the possibility of convective instability of the denser CO2-saturated brines and on fluid-mineral reactions which buffer brine acidity. We report the results of sampling brines and gases during a phase of CO2 injection for enhanced oil recovery in a small oil field. Brines and gases were sampled at production wells daily for 3 months after initiation of CO2 injection and again for two weeks after 5 months. Noble gas isotopic spikes were detected at producing wells within days of initial CO2 injection but signals continued for weeks, and at some producers for the duration of the sampling period, attesting to the complexity of gas-species pathways. Interpretations are complicated by the previous history of the oil field and re-injection of produced water prior to injection of CO2. However water sampled from some producing wells during the phase of CO2 injection showed monotonic increases in alkalinity and in concentrations of major cations to levels in excess of those in the injected water. The marked increase in Na, and smaller increases in Ca, Mg, Si, K and Sr are interpreted primarily to result from silicate dissolution as the lack of increase in S and Cl concentrations preclude additions of more saline waters. Early calcite dissolution was followed by re-precipitation. 87Sr/86Sr ratios in the waters apparently exceed the 87Sr/86Sr ratios of acetic and hydrochloric acid leaches of carbonate fractions of the reservoir rocks and the silicate residues from the leaching. This may indicate incongruent dissolution of Sr or larger scale isotopic heterogeneity of the reservoir. This is being investigated

  15. Engineering Studies of a Pilot Plant for Laser Isotope Separation of CARBON-13 by Multiphoton Dissociation of Chlorodifluoromethane

    NASA Astrophysics Data System (ADS)

    Mehmetli, Bulent Ahmet

    Recent research in laser isotope separation by multiphoton dissociation (LISMPD) of ^{13 }C suggests that an LISMPD commercial process is more economical than the cryogenic CO distillation technology currently used to meet most of the world's ^ {13}C demand. In this dissertation, experimental studies of an engineering process for LISMPD of polyatomic molecules is examined. The experimental results have been obtained by MPD of chlorodifluoromethane (CF_2 HCl) to yield ^{13}C -enriched tetrafluoroethylene rm(C_2F _4). Emphasis is on research leading to the development of a practical chemical plant for the preparation of stable isotopes by this method. The experimental program has achieved the design, construction, and operation of a laboratory-scale ^{13}C separation apparatus and parametric dependences of enrichment factors and dissociated fractions. In this experiment, the reactant gas, industrial grade CF_2HCl, flows continuously along the axis of a stainless steel reaction cell. The beam of a commercial CO_2 TEA laser, delivering up to 3 J/pulse at a single wavelength, is focused into the cell to induce isotope-selective multiphoton dissociation. The ^{13}C-enriched reaction product, rm C_2F_4, is analyzed by mass spectroscopy for its isotopic content. Typical production rates of the setup are about 10 g/year ^{13}C at an enrichment of 15% or 1 g/year at an enrichment of 65%. The results of a detailed cost analysis, which takes into account different reaction conditions and laser types, showed that at production rates of 7,000 kg per year, the cost of ^{13}C can be as low as 4/g. This figure is about an order of magnitude less than the cost of ^13 C obtained by cryogenic distillation of CO. The design, construction, and operation of a CO _2 MOPA (Master Oscillator/ Power Amplifier) laser is proposed because a MOPA combines the advantages of favorable isotope separation reaction conditions of TEA lasers and the cheaper photons of cw discharges. Analytical

  16. The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents.

    PubMed

    Mojica, Martha; Méndez, Francisco; Alonso, Julio A

    2016-02-12

    The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH₂, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF₃, CHO, CN, NO₂). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO₂ substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

  17. Amorphous Molybdenum Sulfide on Graphene-Carbon Nanotube Hybrids as Highly Active Hydrogen Evolution Reaction Catalysts.

    PubMed

    Pham, Kien-Cuong; Chang, Yung-Huang; McPhail, David S; Mattevi, Cecilia; Wee, Andrew T S; Chua, Daniel H C

    2016-03-01

    In this study, we report on the deposition of amorphous molybdenum sulfide (MoSx, with x ≈ 3) on a high specific surface area conductive support of Graphene-Carbon Nanotube hybrids (GCNT) as the Hydrogen Evolution Reaction (HER) catalysts. We found that the high surface area GCNT electrode could support the deposition of MoSx at much higher loadings compared with simple porous carbon paper or flat graphite paper. The morphological study showed that MoSx was successfully deposited on and was in good contact with the GCNT support. Other physical characterization techniques suggested the amorphous nature of the deposited MoSx. With a typical catalyst loading of 3 mg cm(-2), an overpotential of 141 mV was required to obtain a current density of 10 mA cm(-2). A Tafel slope of 41 mV decade(-1) was demonstrated. Both measures placed the MoSx-deposited GCNT electrode among the best performing molybdenum sulfide-based HER catalysts reported to date. The electrode showed a good stability with only a 25 mV increase in overpotential required for a current density of 10 mA cm(-2), after undergoing 500 potential sweeps with vigorous bubbling present. The current density obtained at -0.5 V vs SHE (Standard Hydrogen Electrode potential) decreased less than 10% after the stability test. The deposition of MoSx on high specific surface area conductive electrodes demonstrated to be an efficient method to maximize the catalytic performance toward HER. PMID:26864503

  18. Direct uptake of organic carbon by grass roots and allocation in leaves and phytoliths: 13C labeling evidence

    NASA Astrophysics Data System (ADS)

    Alexandre, A.; Balesdent, J.; Cazevieille, P.; Chevassus-Rosset, C.; Signoret, P.; Mazur, J.-C.; Harutyunyan, A.; Doelsch, E.; Basile-Doelsch, I.; Miche, H.; Santos, G. M.

    2015-12-01

    In the rhizosphere, the uptake of low molecular weight carbon (C) and nitrogen (N) by plant roots has been well documented. While organic N uptake relatively to total uptake is important, organic C uptake is supposed to be low relatively to the plant's C budget. Recently, radiocarbon analyses demonstrated that a fraction of C from the soil was occluded in amorphous silica micrometric particles that precipitate in plant cells (phytoliths). Here, we investigated whether and in which extent organic C absorbed by grass roots, under the form of either intact amino acids (AAs) or microbial metabolites, can feed the organic C occluded in phytoliths. For this purpose we added 13C- and 15N-labeled AAs to the silicon-rich hydroponic solution of the grass Festuca arundinacea. The experiment was designed to prevent C leakage from the labeled nutritive solution to the chamber atmosphere. After 14 days of growth, the 13C and 15N enrichments (13C-excess and 15N-excess) in the roots, stems and leaves, and phytoliths, as well as the 13C-excess in AAs extracted from roots and stems and leaves, were quantified relatively to a control experiment in which no labelled AAs were added. The net uptake of 13C derived from the labeled AAs supplied to the nutritive solution (AA-13C) by Festuca arundinacea represented 4.5 % of the total AA-13C supply. AA-13C fixed in the plant represented only 0.13 % of total C. However, the experimental conditions may have underestimated the extent of the process under natural and field conditions. Previous studies showed that 15N and 13C can be absorbed by the roots in several organic and inorganic forms. In the present experiment, the fact that phenylalanine and methionine, that were supplied in high amount to the nutritive solution, were more 13C-enriched than other AAs in the roots and stems and leaves strongly suggested that part of AA-13C was absorbed and translocated in its original AA form. The concentration of AA-13C represented only 0.15 % of the

  19. Role of reaction resistance in limiting carbon monoxide uptake in rabbit lungs.

    PubMed

    Heller, H; Schuster, K

    1998-06-01

    The contribution of reaction resistance to overall resistance to pulmonary carbon monoxide (CO) uptake [DLCO/(ThetaCO . Vc), where DLCO is lung CO diffusing capacity, ThetaCO is CO uptake conductance of erythrocytes, and Vc is pulmonary capillary blood volume] was determined in 10 anesthetized, paralyzed, and artificially ventilated rabbits. On the basis of the classical double-reciprocal equation of F. G. W. Roughton and R. E. Forster (J. Appl. Physiol. 11: 290-302, 1957), DLCO/(ThetaCO . Vc) was obtained by solving the relation DLCO/(ThetaCO . Vc) = 1 - 2/(DLNO/DLCO), where DLNO/DLCO represents the ratio between the respective single-breath diffusing capacities (DL) of nitric oxide (NO) and CO pulmonary capillary blood. The lungs of eight rabbits were inflated, starting from residual volume, by using 55 ml of indicator gas mixture (0.2% CO and 0.05% NO in nitrogen). DL values were calculated by taking the end-tidal partial pressures of CO and NO as analyzed by using a respiratory mass spectrometer. The overall value was DLCO/(ThetaCO . Vc) = 0.4 +/- 0.025 (mean +/- SD). Because of the use of O2-free indicator gas mixtures, the end-tidal O2 partial pressures were approximately 21 Torr. In one other rabbit, the application of 0.2% CO and 0.001% NO yielded DLCO/(ThetaCO . Vc) = 0.39; in the tenth rabbit, however, inspiratory volume was varied, and an identical value was found at functional residual capacity. We conclude that the contribution of reaction resistance to overall resistance to pulmonary CO uptake is independent of the inspiratory NO concentration used, including, with respect to the pertinent literature, the conclusion that in rabbits, dogs, and humans this contribution amounts to 40% when determined at functional residual capacity.

  20. Highly vibrationally excited CO generated in a low-temperature chemical reaction between carbon vapor and molecular oxygen

    NASA Astrophysics Data System (ADS)

    Jans, E.; Frederickson, K.; Yurkovich, M.; Musci, B.; Rich, J. W.; Adamovich, I. V.

    2016-08-01

    A chemical flow reactor is used to study the vibrational population distribution of CO produced by a reaction between carbon vapor generated in an arc discharge and molecular oxygen. The results demonstrate formation of highly vibrationally excited CO, up to vibrational level v = 14, at low temperatures, T = 400-450 K, with population inversion at v = 4-7, in a collision-dominated environment, 15-20 Torr. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of reaction enthalpy. The results show feasibility of development of a new CO chemical laser using carbon vapor and oxygen as reactants.

  1. Tracing source, mixing and uptaking processes of carbon in an epikarst spring-pond system in southeastern Guizhou of China by carbon isotopes (13C-14C)

    NASA Astrophysics Data System (ADS)

    Zhao, M.; Chen, B.; Liu, Z.; Li, H. C.; Yang, R.

    2015-12-01

    δ13C and Δ14C of dissolved inorganic carbon (DIC), particulate organic carbon (POC) and aquatic plants from a karst spring and two spring-fed ponds in Laqiao, Maolan County, Guizhou Province in January, July and October of 2013 were measured to understand the roles of aquatic photosynthesis through DIC uptake in karst surface waters. The mean Δ14C and δ13C values of DIC for the spring pool, midstream and downstream ponds are -60.6±26.3‰ and -13.53±1.97‰, -62.8±62.9‰ and -11.72±2.72‰, and -54.2±56.5‰ and -9.40±2.03‰, respectively. Both Δ14C and δ13C show seasonal variations, with lower Δ14C values but heavier δ13C values in dry season and vice versa in summer rainy season. This observation indicates that (1) the main carbon source of the spring DIC is from limestone bedrock dissolution and soil CO2 with higher contribution in summer due to higher productivity; and (2) 13C and 14C have different behaviors during DIC uptake by aquatic plants and during CO2 exchange between DIC and the atmospheric CO2. Biological uptake of CO2 will not affect the Δ14C of DIC, but lead to δ13CDIC enrichment. CO2 exchange between DIC and the atmospheric CO2 should elevate both the Δ14C and δ13C of DIC. In Laqiao spring-pond system, it seems that the effect of biological uptake on the Δ14C and δ13C of DIC is much stronger than that of CO2 exchange with the atmosphere. The mean Δ14C values of POC from the spring pool, midstream and downstream ponds are -308.1 ±64.3‰, -164.4±84.4‰ and -195.1±108.5‰, respectively, indicating mixture of aquatic algae and detrital particle (clay and dust). More aquatic algae were formed in the stream ponds especially in the summer. SEM results of the POC samples support this conclusion. Furthermore, the Δ14C values of the submerged aquatic plants range from -200.0‰ to -51.3 ‰ and were similar to those of the DIC, indicating that the aquatic plants used DIC for photosynthesis. The Δ14C value of an emergent plant

  2. A Study of the Abundance and 13C/12C Ratio of Atmospheric Carbon Dioxide to Advance the Scientific Understanding of Terrestrial Processes Regulating the Global Carbon Cycle

    SciTech Connect

    Stephen C. Piper

    2005-10-15

    The primary goal of our research program, consistent with the goals of the U.S. Climate Change Science Program and funded by the terrestrial carbon processes (TCP) program of DOE, has been to improve understanding of changes in the distribution and cycling of carbon among the active land, ocean and atmosphere reservoirs, with particular emphasis on terrestrial ecosystems. Our approach is to systematically measure atmospheric CO2 to produce time series data essential to reveal temporal and spatial patterns. Additional measurements of the 13C/12C isotopic ratio of CO2 provide a basis for distinguishing organic and inorganic processes. To pursue the significance of these patterns further, our research also involved interpretations of the observations by models, measurements of inorganic carbon in sea water, and of CO2 in air near growing land plants.

  3. Tetramethylallene and 2,4-dimethyl-1,3-pentadiene as hydrogen atom acceptors in reactions with HMn(CO)/sub 5/ and HCo(CO)/sub 4/

    SciTech Connect

    Garst, J.F.; Bockman, T.M.; Batlaw, R.

    1986-04-02

    The authors report evidence that reactions of tetramethylallene with HMn(CO)/sub 5/ or HCo(CO)/sub 4/ proceed by initial hydrogen atom transfer (Scheme I), providing the first examples of such reactions of nonconjugated alkenes. 2,4-Dimethyl-1,3-pentadiene also reacts with HCo(CO)/sub 4/, and probably HMn(CO)/sub 5/, through a similar mechanism.

  4. Nonequilibrium neutron emission from /sup 12/C + /sup 158/Gd and /sup 13/C + /sup 157/Gd reactions. [103 to 160 MeV

    SciTech Connect

    Plasil, F.; Beene, J.R.; Ferguson, R.L.

    1981-01-01

    The energy dependence of nonequilibrium neutron emission (NNE) and the effects of projectile structure were investigated in these reactions between 103 and 160 MeV. Neutron energy spectra and angular distributions were measured. Typical spectra show no projectile structure effect. The absence of difference in NNE between /sup 12/C- and /sup 13/C-induced reactions was also noted. The Wilczynski model agrees well with the data. 5 figures, 1 table. (RWR)

  5. Geminal bis(silane)-controlled regio- and stereoselective oxidative Heck reaction of enol ethers with terminal alkenes to give push-pull 1,3-dienes.

    PubMed

    Li, Linjie; Chu, Yang; Gao, Lu; Song, Zhenlei

    2015-11-01

    A geminal bis(silane)-controlled regio- and stereoselective oxidative Heck reaction of enol ethers with terminal alkenes has been developed. The reaction proceeds with α,β-coupling regioselectivity to give push-pull Z,E-1,3-dienes in good yields. The product showed valuable utility in Sakurai homoallylation with acetals to generate α-substituted-γ-keto esters with good anti-selectivity.

  6. Reproducibly creating hierarchical 3D carbon to study the effect of Si surface functionalization on the oxygen reduction reaction.

    PubMed

    Zeng, Yuze; Flores, Jose F; Shao, Yu-Cheng; Guo, Jinghua; Chuang, Yi-De; Lu, Jennifer Q

    2016-06-01

    We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This investigation reveals for the first time that non-conductive Si with an appropriate electronic structure distorts the carbon electronic structure and consequently enhances ORR electrocatalysis. The strong interface provides excellent electron connectivity according to electrochemical analysis. This highly reproducible and stable 3D platform can serve as a stepping-stone for the investigation of the effect of carbon surface functionalization on electrochemical reactions in general. PMID:27217228

  7. Colloidal and micro-carbon spheres derived from low-temperature polymerization reactions.

    PubMed

    Moreno-Castilla, Carlos

    2016-10-01

    Carbon spheres (CSs) have recently attracted major interest due to their new applications, mainly in energy storage and conversion but also in hard-templating, sorption/catalysis processes, and drug delivery systems. This is attributable to their physico-chemical properties, including their tunable morphology (solid, hollow and core-shell), size, surface area/porosity, good electrical conductivity, low external surface-to-volume ratio, high packing density, enhanced mass transport, robust mechanical stability, low cytotoxicity, and excellent biocompatibility. They can be obtained from a wide variety of carbon precursors and methods. This review covers their production by carbonization of polymer spheres from low-temperature polymerization reactions, considered here as below 250°C. This is a very important method because it allows the synthesis of CSs with different morphologies and doped with other elements or chemical compounds. The preparation of polymer spheres by this technique is well documented in the literature, and the objective of this review is to summarize and give an overview of the most significant publications, proposing a novel classification based on the formation mechanism of the polymer spheres. This classification includes the following polymerization processes: emulsion polymerization and its derivatives, seeded emulsion and inverse emulsion polymerization; precipitation polymerization and its derivative, dispersion polymerization; hard-templating; spray-drying; and hydrothermal or solvothermal treatment of carbohydrates and biomass in general. This review also reports on the morphology and surface characteristics of the CSs obtained by different synthetic approaches. The final section of the review describes the current applications of these CSs, notably in energy storage (supercapacitors and rechargeable batteries) and energy conversion (fuel cells and dye-sensitized solar cells). Besides the numerous applications listed above, they are

  8. Colloidal and micro-carbon spheres derived from low-temperature polymerization reactions.

    PubMed

    Moreno-Castilla, Carlos

    2016-10-01

    Carbon spheres (CSs) have recently attracted major interest due to their new applications, mainly in energy storage and conversion but also in hard-templating, sorption/catalysis processes, and drug delivery systems. This is attributable to their physico-chemical properties, including their tunable morphology (solid, hollow and core-shell), size, surface area/porosity, good electrical conductivity, low external surface-to-volume ratio, high packing density, enhanced mass transport, robust mechanical stability, low cytotoxicity, and excellent biocompatibility. They can be obtained from a wide variety of carbon precursors and methods. This review covers their production by carbonization of polymer spheres from low-temperature polymerization reactions, considered here as below 250°C. This is a very important method because it allows the synthesis of CSs with different morphologies and doped with other elements or chemical compounds. The preparation of polymer spheres by this technique is well documented in the literature, and the objective of this review is to summarize and give an overview of the most significant publications, proposing a novel classification based on the formation mechanism of the polymer spheres. This classification includes the following polymerization processes: emulsion polymerization and its derivatives, seeded emulsion and inverse emulsion polymerization; precipitation polymerization and its derivative, dispersion polymerization; hard-templating; spray-drying; and hydrothermal or solvothermal treatment of carbohydrates and biomass in general. This review also reports on the morphology and surface characteristics of the CSs obtained by different synthetic approaches. The final section of the review describes the current applications of these CSs, notably in energy storage (supercapacitors and rechargeable batteries) and energy conversion (fuel cells and dye-sensitized solar cells). Besides the numerous applications listed above, they are

  9. A 13C labelling study on carbon fluxes in Arctic plankton communities under elevated CO2 levels

    NASA Astrophysics Data System (ADS)

    de Kluijver, A.; Soetaert, K.; Czerny, J.; Schulz, K. G.; Boxhammer, T.; Riebesell, U.; Middelburg, J. J.

    2012-07-01

    The effect of CO2 on carbon fluxes in Arctic plankton communities was investigated during the 2010 EPOCA mesocosm study in Ny Ålesund, Svalbard. Nine mesocosms were set up with initial pCO2 levels ranging from 185 to 1420 μatm for 5 weeks. 13C labelled bicarbonate was added at the start of the experiment to follow the transfer of carbon from dissolved inorganic carbon (DIC) into phytoplankton, bacteria, total particulate organic carbon (POC), zooplankton, and settling particles. Polar lipid derived fatty acids (PLFA) were used to trace carbon dynamics of phytoplankton and bacteria and allowed distinction of two groups of phytoplankton: phyto I (autotrophs) and phyto II (mixotrophs). Nutrients were added on day 13. A nutrient-phytoplankton-zooplankton-detritus model amended with 13C dynamics was constructed and fitted to the data to quantify uptake rates and carbon fluxes in the plankton community during the phase prior to nutrient addition (phase 1, days 0-12). During the first 12 days, a phytoplankton bloom developed that was characterized by high growth rates (0.87 days-1) for phyto I and lower growth rates (0.18 days-1) for phyto II. A large part of the carbon fixed by phytoplankton (~31%) was transferred to bacteria, while mesozooplankton grazed only ~6% of the production. After 6 days, the bloom collapsed and part of the organic matter subsequently settled into the sediment traps. The sedimentation losses of detritus in phase 1 were low (0.008 days-1) and overall export was only ~7% of production. Zooplankton grazing and detritus sinking losses prior to nutrient addition were sensitive to CO2: grazing decreased with increasing CO2, while sinking increased. Phytoplankton production increased again after nutrient addition on day 13. Although phyto II showed initially higher growth rates with increasing CO2 (days 14-22), the overall production of POC after nutrient addition (phase 2, days 14-29) decreased with increasing CO2. Significant sedimentation occurred

  10. Carbon isotopic composition (δ(13)C and (14)C activity) of plant samples in the vicinity of the Slovene nuclear power plant.

    PubMed

    Sturm, Martina; Vreča, Polona; Krajcar Bronić, Ines

    2012-08-01

    δ(13)C values of various plants (apples, wheat, and maize) collected in the vicinity of the Krško Nuclear Power Plant (Slovenia) during 2008 and 2009 were determined. By measuring dried samples and their carbonized counterparts we showed that no significant isotopic fractionation occurs during the carbonization phase of the sample preparation process in the laboratory. The measured δ(13)C values of the plants were used for δ(13)C correction of their measured (14)C activities.

  11. Carbon solids in oxygen-deficient explosives (LA-UR-13-21151)

    NASA Astrophysics Data System (ADS)

    Peery, Travis

    2013-06-01

    The phase behavior of excess carbon in oxygen-deficient explosives has a significant effect on detonation properties and product equations of state. Mixtures of fuel oil in ammonium nitrate (ANFO) above a stoichiometric ratio demonstrate that even small amounts of graphite, on the order of 5% by mole fraction, can substantially alter the Chapman-Jouget (CJ) state properties, a central ingredient in modeling the products equation of state. Similar effects can be seen for Composition B, which borders the carbon phase boundary between graphite and diamond. Nano-diamond formation adds complexity to the product modeling because of surface adsorption effects. I will discuss these carbon phase issues in our equation of state modeling of detonation products, including our statistical mechanics description of carbon clustering and surface chemistry to properly treat solid carbon formation. This work is supported by the Advanced Simulation and Computing Program, under the NNSA.

  12. Tracing carbon assimilation in endosymbiotic deep-sea hydrothermal vent Mytilid fatty acids by 13C-fingerprinting

    NASA Astrophysics Data System (ADS)

    Riou, V.; Bouillon, S.; Serrão Santos, R.; Dehairs, F.; Colaço, A.

    2010-05-01

    Bathymodiolus azoricus mussels thrive at Mid-Atlantic Ridge hydrothermal vents, where part of their energy requirements are met via an endosymbiotic association with chemolithotrophic and methanotrophic bacteria. In an effort to describe phenotypic characteristics of the two bacterial endosymbionts and to assess their ability to assimilate CO2, CH4 and multi-carbon compounds, we performed experiments in aquaria using 13C-labeled NaHCO3 (in the presence of H2S), CH4 or amino-acids and traced the incorporation of 13C into total and phospholipid fatty acids (tFA and PLFA, respectively). 14:0, 15:0, 16:1(n-7)c+t and 18:1(n-7)c+t PLFA were labeled in the presence of H13CO3- (+H2S) and 13CH4, while the 12:0 compound became labeled only in the presence of H13CO3- (+H2S). In contrast, the 16:1(n-9), 16:1(n-8) and (n-6), 18:1(n-8)c and (n-7), 20:1(n-7) and 18:2(n-7) PLFA were only labeled in the presence of 13CH4. Some of these symbiont-specific fatty acids also appeared to be labeled in mussel gill tFA when incubated with 13C-enriched amino acids, and so were mussel-specific fatty acids such as 22:2(n-7,15). Our results provide experimental evidence for the potential of specific fatty acid markers to distinguish between the two endosymbiotic bacteria, shedding new light on C1 and multi-carbon compound metabolic pathways in B. azoricus and its symbionts.

  13. A theoretical thermodynamic investigation of cascade reactions in dinuclear octa-azacryptates involving carbon dioxide.

    PubMed

    El-Hendawy, Morad M; English, Niall J; Mooney, Damian A

    2011-12-01

    This paper investigates the thermodynamics of gas-phase CO(2) cascade uptake-reactions in the form of carbonate or monomethylcarbonate anions in the host cavity of various dinuclear octa-azacryptates of m-CH(2)C(6)H(4)CH(2) and 2,5-furano-spaced hosts, L (1) and L (2) cryptands, using density functional theory (DFT). The cascade process involves two stages, namely the formation of dinuclear cryptate complexes, and the subsequent formation of either μ-carbonato cryptate complexes or μ-monomethylcarbonato cryptates. The geometric and electronic structures were also investigated to determine the parameters that affect the stability of the complexes. Natural bond orbital (NBO) analysis was used to investigate the interactions between the trapped anion and its host. Ion selectivity was studied in terms of the formation of dinuclear cryptate complexes, while the basicity and nucleophilicity of cryptands towards Lewis acids was also studied, and good agreement was found vis-à-vis available experimental data. PMID:21360180

  14. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    DOE PAGESBeta

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; Sohn, Young-Jun; Cheon, Jae Yeong; Joo, Sang Hoon; Yim, Sung-Dae; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.; et al

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities comparedmore » to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.« less

  15. One-step synthesis of nitrogen-iron coordinated carbon nanotube catalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Choi, Woongchul; Yang, Gang; Kim, Suk Lae; Liu, Peng; Sue, Hung-Jue; Yu, Choongho

    2016-05-01

    Prohibitively expensive precious metal catalysts for oxygen reduction reaction (ORR) have been one of the major hurdles in a wide use of electrochemical cells. Recent significant efforts to develop precious metal free catalysts have resulted in excellent catalytic activities. However, complicated and time-consuming synthesis processes have negated the cost benefit. Moreover, detailed analysis about catalytically active sites and the role of each element in these high-performance catalysts containing nanomaterials for large surface areas are often lacking. Here we report a facile one-step synthesis method of nitrogen-iron coordinated carbon nanotube (CNT) catalysts without precious metals. Our catalysts show excellent long-term stability and onset ORR potential comparable to those of other precious metal free catalysts, and the maximum limiting current density from our catalysts is larger than that of the Pt-based catalysts. We carry out a series of synthesis and characterization experiments with/without iron and nitrogen in CNT, and identify that the coordination of nitrogen and iron in CNT plays a key role in achieving the excellent catalytic performances. We anticipate our one-step process could be used for mass production of precious metal free electrocatalysts for a wide range of electrochemical cells including fuel cells and metal-air batteries.

  16. Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

    2014-12-01

    Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

  17. Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

    PubMed Central

    Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

    2013-01-01

    The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

  18. Use of Position-Specific 13C Isotopomers to Examine Central Carbon Metabolism in the Thermophile 'Thermoflexus hugenholtzii'

    NASA Astrophysics Data System (ADS)

    Thomas, S.; Tamadonfar, K. O.; Dijkstra, P.; Dodsworth, J. A.; Hedlund, B. P.

    2013-12-01

    'Thermoflexus hugenholtzii' is a member of a newly discovered class of Chloroflexi. It is the dominant microorganism in certain hot springs; however, very little is known about its physiology, and it is unable to grow on defined media. In order to examine central carbon metabolism in 'T. hugenholtzii', the genome was annotated for genes encoding enzymes for central carbon metabolism, revealing complete pathways for glycolysis, the tricarboxylic acid (TCA) cycle, and the pentose phosphate pathway (PPP). Isotope experiments were conducted to test predicted activities by adding position-specific carbon-13 (13C)-labeled metabolites of glucose, pyruvate, acetate, TCA metabolites, and amino acids and measuring the production of 13CO2 during exponential growth. Use of these metabolites demonstrated broad heterotrophic activity of 'T. hugenholtzii,' despite its inability to grow on defined media. Use of glucose-U demonstrated an active glycolytic pathway and pyruvate-1 demonstrated the functioning of the pyruvate oxidation pathway after glycolysis. Use of the TCA cycle intermediates citrate and succinate demonstrated an active TCA cycle. Production of CO2 from alanine and cysteine demonstrated oxidation of amino acids. However, lack of activity on glucose-1 failed to reveal an active PPP suggesting 'T. hugenholtzii' may rely on exogenous sources of pentoses for nucleic acid biosynthesis.

  19. ATOMIC-LEVEL MODELING OF CO2 DISPOSAL AS A CARBONATE MINERAL: A SYNERGETIC APPROACH TO OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    A.V.G. Chizmeshya; M.J. McKelvy; J.B. Adams

    2001-11-01

    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar hydroxide mineral carbonation is a leading process candidate, which generates the stable naturally occurring mineral magnesite (MgCO{sub 3}) and water. Key to process cost and viability are the carbonation reaction rate and its degree of completion. This process, which involves simultaneous dehydroxylation and carbonation is very promising, but far from optimized. In order to optimize the dehydroxylation/carbonation process, an atomic-level understanding of the mechanisms involved is needed. In this investigation Mg(OH){sub 2} was selected as a model Mg-rich lamellar hydrocide carbonation feedstock material due to its chemical and structural simplicity. Since Mg(OH){sub 2} dehydroxylation is intimately associated with the carbonation process, its mechanisms are also of direct interest in understanding and optimizing the process. The aim of the current innovative concepts project is to develop a specialized advanced computational methodology to complement the ongoing experimental inquiry of the atomic level processes involved in CO{sub 2} mineral sequestration. The ultimate goal is to integrate the insights provided by detailed predictive simulations with the data obtained from optical microscopy, FESEM, ion beam analysis, SIMS, TGA, Raman, XRD, and C and H elemental analysis. The modeling studies are specifically designed to enhance the synergism with, and complement the analysis of, existing mineral-CO{sub 2} reaction process studies being carried out under DOE UCR Grant DE-FG2698-FT40112. Direct contact between the simulations and the experimental

  20. A multiplex allele-specific real-time polymerase chain reaction assay for HLA-B*13:01 genotyping in four Chinese populations.

    PubMed

    Liu, Z; Chen, G; Kang, X; Han, M; Chen, R; Chen, C; Wang, H

    2016-10-01

    Human leukocyte antigen HLA-B*13:01 is identified currently as a marker of individual susceptibility to drug-induced hypersensitivity reaction, such as dapsone-induced hypersensitivity reactions (DIHRs) and trichloroethylene-induced dermatitis. Therefore, screening for the HLA-B*13:01 allele can assist clinics in identifying patients at risk of developing DIHRs. By combining the allele-specific primers with TaqMan probes, we established a single tube, triplex real-time PCR to detect HLA-B*13:01. The reliability of this assa